OXIDATIVE DEGRADATION OF TEXTILE DYES WITH …

OXIDATIVE DEGRADATION OF TEXTILE DYES WITH

HYPOCHLORITE AND CHLORINE DIOXIDE

By

SRINIVASU NADUPALLI

Submitted in fulfillment of the academic requirements for the degree of Doctor of

Philosophy in the School of Chemistry University of KwaZulu-Natal Durban

11 October 2010

ii

DECLARATION

The experimental work described in this thesis was carried out in the School of Chemistry

University of KwaZulu-Natal Durban under the supervision of Professor SB Jonnalagadda and

co-supervisor Dr N Koorbanally

These studies represent original work by the author and have not otherwise been submitted in

any form for any degree or diploma to any tertiary institution Where use has been made of the

work of others it is duly acknowledged in the text

Signed ______________________ Name _____________________ Date ___________

As the candidatersquos supervisor I havehave not approved this thesisdissertation for submission

Signed ______________________ Name _____________________ Date ___________

iii

DECLARATION - PLAGIARISM

I helliphelliphellipS Nadupallihelliphellip declare that

1 The research reported in this thesis except where otherwise indicated and is my original research

2 This thesis has not been submitted for any degree or examination at any other university

3 This thesis does not contain other personsrsquo data pictures graphs or other information unless specifically acknowledged as being sourced from other persons

4 This thesis does not contain other persons writing unless specifically acknowledged as being sourced from other researchers Where other written sources have been quoted then a Their words have been re-written but the general information attributed to them

has been referenced b Where their exact words have been used then their writing has been placed in

italics and inside quotation marks and referenced

5 This thesis does not contain text graphics or tables copied and pasted from the Internet unless specifically acknowledged and the source being detailed in the thesis and in the References sections

Signed helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip

iv

ACKNOWLEDGEMENTS

First and foremost I want to express my sincere gratitude to my supervisor Professor SB

Jonnalagadda and Co-supervisor Dr N Koorbanally for their guidance time encouragement of

ideas and their collaborative involvement through their helpful discussions to make my PhD

experience productive and stimulating

I would like to acknowledge National Research Foundation for the financial support through

their Doctoral scholarship programme

My parents Mr N Ramakrishna Rao and Mrs Nagamani who instilled in me the values of faith

and hard work and afforded me every opportunity to further myself with their love and support

throughout this period of study

I would like to thank Dr A Ramakrishna Dr CS Vasam and Dr R Pullabhotla for the

numerous discussions that substantially improved the quality of my research and their

encouragement

I would like to thank my wife Madhuri and Mr V Dasireddy for their enthusiasm patience

and help

Mr Mark Pritchard TGK Scientific Ltd UK for his prompt replies even at late nights for my

emails regarding issues with Stopped Flow system

I would like to express my gratitude to my fellow researchers colleagues and lab technicians at

School of Chemistry for their help in promoting a stimulating and welcoming academic and

social environment

Not to be forgotten Ms L Govender and my colleagues at Corporate Relations for the

inspiration and support during my endeavors

v

PUBLICATIONS

S B Jonnalagadda and S Nadupalli Effluent treatment using electrochemically bleached

seawater-oxidative degradation of pollutants Talanta 2004 64(1) p 18-22

CONFERENCE CONTRIBUTIONS ORALPOSTER PRESENTATIONS

Oral Presentations

35th Convention of South African Chemical Institute (SACI) June 2001 University of Natal

Durban entitled ldquoOxidative degradation of Industrial effluents using Hypochlorite and Chlorine

Dioxiderdquo

36th Convention of South African Chemical Institute (SACI) July 2002 University of Port

Elizabeth entitled ldquoOxidation of Amaranth with Hypochloriterdquo

Poster Presentations

Local

SACI annual postgraduate colloquium University of Durban Westville 2001 October Durban

entitled ldquoOxidative degradation of industrial effluents using Hypochloriterdquo

Convention of South African Chemical Institute (SACI) CATSA 2001 November Pilanesburg

entitled ldquoOxidation of Brilliant blue-R with Hypochloriterdquo

International

CHEMCON December 2002 Osmania University Hyderabad India entitled ldquoOxidative

Degradation of Industrial Effluent with Hypochloriterdquo

vi

TABLE OF CONTENTS

Abstract xiv

List of figures xvii

List of tables xxvi

Symbols and abbreviations xxx

CHAPTER 1

11 Introduction 1

12 Water pollution and treatment methods 4

121 Ozonation 5

122 Chlorination 6

123 Hypochlorination-history of hypochlorite 7

13 Methods for the preparation of hypochlorite 8

14 Advantages and uses of hypochlorination 9

15 Limitations of hypochlorination 10

16 History of chlorine dioxide 11

161 Methods of preparation of chlorine dioxide 12

162 Advantages and uses of chlorine dioxide 14

163 Limitations of chlorine dioxide 15

17 Dyes and classification of dyes 15

171 Acid dyes 16

vii

172 Direct dyes 17

173 Disperse dyes 17

174 Sulfur dyes 18

175 Reactive dyes 19

176 Basic dyes 20

177 Vat dyes 20

178 Literature survey 21

18 Classes of the dyes studied 25

181 Azo dyes 25

182 Triarylmethane dyes 26

183 Azine dyes 26

19 Chemistry of hypochlorite 27

191 Hypochlorite decomposition 27

192 Bleaching action of hypochlorite ion 28

193 Oxidising action of hypochlorite 29

194 Hypochlorite and hypochlorous acid distribution 29

110 Chemistry of chlorine dioxide 30

111 Chemical kinetics 32

112 Classification of reaction rates 33

1121 Factors influencing reaction rates 33

viii

1122 First-order reactions 34

1123 Reversible first-order reactions 35

1124 Second-order reactions 38

1125 Reversible second-order reactions 40

1126 Consecutive first-order reactions 42

113 Kinetic salt effect 44

114 Kinetic simulations 45

1141 Simulations 45

1142 Importance of simulation as a tool 46

1143 Requirements for kinetics simulation 47

115 Kinetic measurements - fast reactions 47

1151 Analysis of kinetic data 49

116 Scope and Objectives of the study 50

CHAPTER 2

21 Experimental 52

211 Three dyes - amaranth brilliant blue-R safranine-O 52

212 Hypochlorite solution 56

2121 Preparation method 56

2122 Calculation of molarity of the hypochlorite arsenite method 58

213 Chlorine dioxide 59

ix

2131 Chlorine dioxide preparation 59

2132 Calculation of molarity of the chlorine dioxide - iodometric method 61

214 General reagents 62

215 Kinetic measurements 62

216 Simulations and software used 68

217 Product analysis 68

218 Precision calculations 70

219 Standard deviation (s) 71

2110 Variance (s2) 72

CHAPTER 3

OXIDATION OF DYES WITH HYPOCHLORITE

31 Reaction between amaranth and hypochlorite 73

311 Order with respect to amaranth 73

312 Analysis of kinetic data using KinetAsystTM Fit software 74

313 Order with respect to hypochlorite 75

314 Effect of pH on the reaction rate 78

315 Primary salt effect 86

316 Kinetic salt effect at acidic pH 88

317 Effect of chloride on reaction rate 89

318 Activation parameters 90

x

319 Product identification and characterization 92

3110 Stoichiometric equation 95

3111 Reaction scheme 95

3112 Proposed mechanism 98

3113 Rate law 99

3114 Simulations 100

32 Reaction between brilliant blue and hypochlorite 103

321 Order with respect to brilliant blue-R 103











3212 Proposed reaction mechanism 125

3213 Rate law 125

xi


33 Reaction of hypochlorite with safranine-O 130

331 Order with respect to safranine-O 130



334 Effect of acid concentration on the reaction rate 134


336 Kinetic Salt Effect at acidic pH 144




3310 Stoichiometry equation 149



3313 Rate law 152


CHAPTER 4

OXIDATION OF DYES WITH CHLORINE DIOXIDE

41 Oxidation of amaranth and chlorine dioxide 156


xii


413 Order with respect to chlorine dioxide 158

414 Effect of pH on reaction rate and reaction order with respect to OH- 161

415 Effect on pH on the order with respect to chlorine dioxide 168




419 Products identification and characterisation 174




4113 Rate law 179


42 Reaction of brilliant blue and chlorine dioxide 183

421 Order with repect to brilliant blue-R 183



424 Effect of pH on reaction rate and reaction order with respect to hydroxide ion 188

425 Effect of pH on the order with respect to chlorine dioxide 193


xiii


428 Effect of temperature on rate of reaction 197

429 Products identification and characterization 200




4213 Rate law 204


43 Oxidation of safranine-O with chlorine dioxide 208

431 Reaction of safranine-O and chlorine dioxide 209



434 Effect of pH 213



437 Effect of chloride on rate of reaction 221

438 Effect of temperature 222




xiv


4313 Rate law 228


CHAPTER 5

Conclusions 231

References 237

Appendix 248

xv

ABSTRACT

The oxidation reaction mechanisms of water soluble textile dyes amaranth (an azo dye) brilliant

blue-R (a triaryl dye) and safranine-O (an azine dye) with oxidants- hypochlorite and chlorine

dioxide were investigated The detailed kinetics of the reactions of the three dyes was studied

under excess concentrations of the oxidant and other reagents The depletion of concentration of

the chosen dye taken at low concentration was monitored using a Hi-Tech SF-61 DX2 double

mixing micro volume stopped-flow apparatus

The hypochlorite initiated oxidations were investigated as function of varying concentration of

oxidant and hydrogen ion ionic strength and temperature For the chosen dyes and reaction

conditions the depletion of dye followed pseudo first-order kinetics and the rate constants were

estimated using KinetAsystTM software All the three reactions had first-order dependence on the

oxidant concentration and the reaction rates increased by varied extent with increase in [H+]0

The role of acid in their reaction mechanisms was established The kinetic data was analysed to

evaluate the rate constants for the competitive pathways initiated by hypochlorite ion and

hypochlorous acid The overall second-order rate coefficients for the OCl- and HOCl initiated

reactions were estimated for all the three reactions Major oxidation products for the reactions

were separated and characterized by 1H NMR and 13C NMR and GC-MS techniques and the

stoichiometry was established The energy parameters inclusive of Arrhenius factor enthalpy

entropy and energy of activations for the oxidation of three dyes both by OCl- and HOCl species

were estimated Based on the experimental findings the probable rate laws mechanisms and

reaction schemes were described Simulations studies were conducted to validate the proposed

xvi

mechanisms using SIMKINE2 computer programme The rate of oxidation of safranine-O is

greater than that of amaranth and brilliant blue-R with OCl- HOCl reaction

Following similar protocol the oxidations of the chosen dyes with chlorine dioxide were

investigated by monitoring the depletion kinetics of dye as function of varying concentration of

ClO2 and OH- ion ionic strength and temperature All the three dyes exhibited pseudo first-

order kinetics and the rate constants were estimated using KinetAsystTM software All the three

reactions had first-order dependence on the oxidant concentration at pH conditions 70 80 and

90 suggesting that reaction mechanism remains unaltered with pH variation The effect of

hydroxide ion on the reaction rate revealed that it acts as catalyst All the three reactions had

first-order dependence on [OH-]0 when its concentration was low but the order with respect to

[OH-] decreased as [OH-] increased stoichiometry proportion to reactants The catalytic constant

for hydroxide catalysed reaction was estimated for all the three reactions Kinetic salt effect

experiments were conducted to identify the possible reaction species involved in the reactions

The major reaction products were characterized by 1H NMR 13C NMR and GC-MS techniques

The stoichiometry ratios were established and energy parameters were estimated The rate laws

and probable reaction mechanisms were proposed and appropriate reaction schemes for all the

reactions were described The elucidated mechanisms were confirmed by simulation studies

using SIMKINE2 software At neutral pH the rate of oxidation of amaranth is greater than

safranine-O and brilliant blue-R and brilliant blue R being the slowest

xvii

LIST OF FIGURES

Figure 111 Structure of acid dye-brilliant blue-R 18

Figure 112 Structure of direct dye-direct fast red 8B 18

Figure 113 Structure of disperse dye-reactive orange 4 19

Figure 114 Structure of sulphur dye-soluble sulphur black 1 20

Figure 115 Structure of reactive dye-reactive red 22 20

Figure 116 Structure of basic dye-safranine-O 21

Figure 117 Structure of vat dye-vat brown 1 22

Figure 118 Schematic diagram of a continuous flow kinetic system The

quantity d is the distance from the mixer to the point of observation 49

Figure 119 KinetAsystTM single-exponential equation fit (green) and the

experimental curve (red) with residuals shown in the (lower curve)

and the rate parameters in the adjacent box for the reaction of

[AM-]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 51

Figure 211 Structure of amaranth 53

Figure 212 UV-Visible spectrum of amaranth [AM-]0 (1 x 10-6 M) 54

Figure 213 Structure of brilliant blue-R 55

Figure 214 UV- Visible spectrum of brilliant blue-R [BB+]0 (1 x 10-6 M) 55

Figure 215 Structure of safranine-O 56

Figure 216 UV- Visible spectrum of safranine-O [SO+]0 (1 x 10-6 M) 56

Figure 217 Baird amp Tatlock hypochlorite generator 58

Figure 218 Chlorine dioxide generation and absorption system 61

Figure 219 Flow circuit diagram 65

Figure 2110 Hi-Tech Stopped flow apparatus-Typical bench setup 66

Figure 2111 Hi-Tech Stopped flow apparatus - Sample handling unit 67

Figure 2112 Hi-Tech Stopped flow apparatus- Optical setup 68

Figure 311 Typical kinetic curve absorbance versus time plot for the reaction of

[AM-]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M) at pH = 90 and 520 nm 74

Figure 312 KinetAsystTM single-exponential equation fit(green) and the

experimental curve (red) with residuals shown in the (lower curve) and the

rate parameters in the adjacent box for the reaction of [AM-]0

(70 x 10-5 M) with [OCl-]t (15 x 10-3 M)) 75

xviii

Figure 313 Depletion of amaranth with various hypochlorite concentrations for the

reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t x 10-3M (a = 0085

b = 170 c = 255 d = 340 and e = 510) at pH = 90 76

Figure 314 Fits using KinetAsyst TM single - exponential equation and rate equation

1 Exp + C y = -A exp (-k x) + C (where ks-1 a = 0041 b = 0093

c = 0145 d = 0175 and e = 0322)) 77

Figure 315 Plot of ln [OCl-]t versus ln k for the reaction of [AM-]0 (70 x 10-5 M)

with [OCl-]t (085 x 10-4 - 51 x 10-3 M) at pH = 900 and I = 0128 M 78

Figure 316 Plot of k versus pH for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t

(145 x 10-3 M) [H+]eq (199x10-9- 7752 x 10-4 M) 79

Figure 317 Plot of ln k versus ln H+ for the reaction of [AM-]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 81

Figure 318 KinetAsystTM single-exponential equation fit of two curves and residuals

(lower sketch) using the first-order equation for the reaction of

[AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M)

and I (012 M)) 82

Figure 319 KinetAsystTM double-exponential equation fit of two curves and

residuals (lower sketch) for the two competitive first-order reactions

for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M)

[H+]0 (996 x 10-9 M) and I (012 M) 83

Figure 3110 Plot of ln k versus ln [OCl-]eq for the reaction of [AM-]0

(70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at [H+]eq (397 x 10-6 -

775 x 10-3 M) [OCl-]eq (114 x 10-3 -153 x 10-6 M) 85

Figure 3111 Plot of ln k versus ln [HOCl]eq for the reaction of [AM-]0 (70 x 10-5 M)

with [OCl-]t (145 x 10-3 M) at [H+]eq (199x10-9- 998 x 10-7 M)

[OCl-]eq (276 x 10-2 -33 x 10-6 M) 85

Figure 3112 Plot of log k1 versus I (ionic strength) for the reaction of

[AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at pH 90 ionic

strength (I = 0009 - 0039 M) 87

xix

Figure 3113 Plot of k versus I (ionic strength) for the reaction of

[AM-]0 (70 x 10-4 M) with [OCl-]t (145 x 10-3 M) at varying ionic

strength I(0009-0039M) at fixed acid [H+]0 (45 x 10-3 M) and pH 40 89

Figure 3114 Plot of ln k versus 1T for the reaction of [AM-]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) at different temperatures (TK = 283-303) 91

Figure 3115 Mechanistic scheme for the oxidation of amaranth with hypochlorite 97

Figure 3116 Experimental curves versus simulated curves for reaction of [AM-]0

(70 x 10-5 M) with [OCl-]t (145x10-3 M) 101

Figure 3117 Intermediates and product formation for the reaction of amaranth with

hypochlorite 102

Figure 321 Typical kinetic curve-absorbance versus time plot for the reaction of

[BB+]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3) at pH = 90 and 555 nm 103

Figure 322 KinetAsystTM single - exponential equation fit (green) and the

experimental curve (red) with residuals shown in the (lower curve) and

the rate parameters in the adjacent box for the reaction of [BB+]0

(70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 104

Figure 323 Depletion of brilliant blue with various hypochlorite concentrations for

the reaction of [BB+]0 (70 x 10-5 M) with OClˉ] x 10-3M (a = 073 b =

145 c = 218 d = 290 and e = 435) at pH 90 105

Figure 324 Fits using KinetAsystTM single-exponential equation and rate equation


c = 0037 d = 0046 and e = 0086) 106

Figure 325 Plot of ln [OCl-]t versus ln k for the reaction of [BB+]0 (70 x 10-5M)

with [OCl-]t (0725 x 10-3 -435 x 10-3 M) at pH = 90 and I = 0128 M 107

Figure 326 Plot of k versus pH for the reaction of [BB+]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) with [H+]e (199 x 10-9- 7752 x 10-4 M) 108

Figure 327 Plot of ln k versus ln [H+] for the reaction of [OCl-]t (145 x 10-3M)

with [BB+]0 (70 x 10-5M) at [H+]eq (199 x 10-9- 7752 x 10-3 M) 110

Figure 328 KinetAsystTM single-exponential equation fit of two curves and

residuals (lower sketch) for the reaction of [BB+]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (013 M) 111

xx

Figure 329 KinetAsystTM double-exponential eqn fit of two curves and residuals

for two competitive first-order reactions (lower sketch) for the reaction

of [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]0

(996 x 10-9M) and I (012 M) 112

Figure 3210 Plot of ln k versus ln [OCl-]eq for the reaction of [BB+]0 (70 x 10-5M)

with [OCl-]t (145 x 10-3 M) at [H+]eq (397 x 10-6 - 775 x 10-3M)

[OCl-]eq (114 x 10-3 -153 x 10-6M) 114

Figure 3211 Plot of ln k versus ln [HOCl]eq for the reaction of [BB+]0 (70 x 10-5 M)

with [OCl-]t (145 x 10-3 M) at [H+]eq (199 x 10-9- 998 x 10-7 M)

[HOClˉ]eq (276 x 10-2 -33 x 10-6 M) 114

Figure 3212 Plot of log k versus ionic strength (I) for the reaction of [OCl-]t (145 x

10-3 M) with [BB+]0 (70 x 10-5M) at pH = 90 ionic strength (I = 001-

003 M) (A - OCl initiated B - HOCl initiated reaction) 116

Figure 3213 Plot of k versus radicI (ionic strength) for the reaction of [BB+]0

(70 x 10-5 M) with [OClˉ]t (145 x 10-3 M) at varying ionic strength

I (0051- 0069 M) at fixed acid [H+] (45 x 10-3 M) pH 40 117

Figure 3214 Plot of ln k versus 1T for the reaction of with [BB+]0 (70 x 10-5M)

with [OCl-]t (145 x 10-3 M) at varying temperature conditions (A - OCl

initiated B - HOCl initiated reaction) 119

Figure 3215 Mechanistic scheme for the oxidation of brilliant blue-R with

hypochlorite 124

Figure 3216 Experimental curves versus simulated curves for reaction of

[BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 128

Figure 3217 Intermediates and product formation for the reaction of brilliant blue-R

with hypochlorite 129

Figure 331 Typical kinetic curve - absorbance versus time plot for the reaction of

[SO+]0 (30 x 10-5 M) with [OCl-]t (15 x 10-3 M) at pH = 90 wavelength

519 nm 130

Figure 332 KinetAsystTM single-exponential equation fit (green) and the experimental

curve (red) with residuals shown in the (lower curve) and the rate

xxi

parameters box for the reaction of [SO+]0 (30 x 10-5 M) with

[OCl-]t (15 x 10-3 M) 131

Figure 333 Depletion of safranine-O with various hypochlorite concentrations for

the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t x 10-3 M (a = 085 b =

170 c = 255 d = 340 and e = 510) at pH = 90 132


1 Exp + C y = -A exp (-k x) + C where ks-1 (a= 0010 b =

0027 c = 0034 d = 0043 and e = 0052) 133

Figure 335 Plot of ln [OCl-]t versus ln k for the reaction of [OCl-]t (085 x 10-4 -

51 x 10-3 M) with [SO+]0 (30 x 10-5M) at pH = 90 and I = 0128 M 134

Figure 336 Plot of k versus pH for the reaction of [SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 135

Figure 337 Plot of ln k versus ln [H+] for the reaction of [SO+]0 (3x 10-5 M) with

[OCl-]t (145 x 10-3 M) [H+]eq (199x 10-9- 7752 x 10-4 M) 136


(lower sketch) for the reaction of [SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10- 3M) [H+] (996 x 10-9 M) and I (0128 M) 138

Figure 339 KinetAsystTM double-exponential equation fit of two curves and residuals

(lower part) for the reaction of [SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10-3 M) [H+] (996 x 10-9 M) and I (0128M) 138

Figure 3310 Plot of ln k versus ln [HOCl]eq for the reaction [SO+]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) with at [H+]eq (186 x 10-9 - 141 x 10-5 M) 139

Figure 3311 Plot of ln k versus ln [OCl]eq for the reaction of [SO+]0 (30 x 10-5 M)

with [OClˉ]t (145 x 10-3 M) at [H+]e (186x 10-9- 141 x 10-5 M) 139

Figure 3312 Plot of k versus [H+]eq below pH = 60 143

Figure 3313 Plot of log k1 and log k2 versus radicI for the reaction of [SO+]0 (30 x 10-5

M) with [OCl-]t (145 x 10-3M) at pH = 90 ionic strength (I = 0009 to

0039 M) 144

Figure 3314 Plot of k versus radicI for the reaction of[SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10-3 M) at varying ionic strength I (00092 - 00392 M) at

fixed acid [H+] (45 x 10-3 M) 145

xxii

Figure 3315 Plot of ln k versus 1T for the reaction of [SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10-3 M) at different temperatures (TK = 283 - 303)

(A= OCl- reaction B = HOCl reaction) 147

Figure 3316 Possible reaction pathway for the oxidation of safranine-O 151


[SO+]0 (30 x10-5M) with [OCl-]t (145 x 10-3 M) 154

Figure 3318 Product and intermediate formation for the reaction of safranine-O with

hypochlorite 155

Figure 411 Typical kinetic curve absorbance versus Time plot for the reaction

of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) pH = 90 157


residuals (lower sketch) for the reaction of [AM]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) using the first-order equation (Eqn 1 Exp +

C y = -A exp (-k x) + C) 157

Figure 413 Depletion of amaranth with various chlorine dioxide concentrations for

the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t 10-3 M (a = 252 b =

379 c = 505 d = 631 and e = 757) at pH = 90 158


1 Exp + C y = -A exp (-k x) + C for the reaction for amaranth with

chlorine dioxide where k s-1 (a = 332 b = 374 c = 399 d = 422 and

e = 480) 159

Figure 415 Plot of ln [ClO2]t versus ln k for the reaction of [AM]0 (70 x 10-5 M)

with [ClO2]t(25x 10-3 - 75 x 10-3 M) at pH = 90 and I = 0128 M 160

Figure 416 Plot of k versus pH for the reaction of [AM]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 162

Figure 417 Plot of ln [OH-] versus ln k for the reaction of [AM]0 (70 x 10-5 M)

with [ClO2]t (115 x 10-3 M)[OH-]eq(1 x 10-8 - 195 x 10 -7 M) 163

Figure 418 Plot of log [OH-] versus log k at different pH conditions 164

Figure 419 Plot of [OH-] versus k[ClO2] for the reaction [AM]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) [OH-]eq (10 x 10-8- 631 x 10-7 M) 166

xxiii

Figure 4110 Plot of ln k versus ln [ClO2] for the reaction of [AM]0 (70 x 10-5 M)

with [ClO2]t (115 x 10-3 M) a (pH = 90) b (pH = 80) and c (pH = 70) 170

Figure 4111 Plot of log k versus radicI for the reaction of [AM]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) at varying ionic strength I (00096 - 003) 171

Figure 4112 Plot of ln k versus 1T for the reaction of amaranth with ClO2 at

different temperatures 173

Figure 4113 Plausablie mechanistic scheme for the oxidation of amaranth with

chlorine dioxide 177


(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 181



Figure 421 Typical kinetic curve curve absorbance versus time plot for the reaction

of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) pH = 90 183


(lower sketch) for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t

(115 x 10-3 M) using the first-order equation 184

Figure 423 Depletion of brilliant blue with various chlorine dioxide concentrations

for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t 10-3 M at

pH = 90 I (0128 M) with [ClO2]t 10-3 M (a = 252 b = 278

c = 303 d = 328 and e = 353) 185

Figure 424 Fits using Kinet AsystTM single-exponential equation and rate equation

y = - A exp(-k x) + C for the reaction of [BB+]0 (70 x 10-5 M) where

k s (a = 332 b = 374 c = 399 d = 422 and e = 467) 186

Figure 425 Plot of ln [ClO2]t versus ln k for the reaction of [BB+]0 (70 x 10-5 M)

with [ClO2]t (25 x 10-3 -35 x 10-3 M) at pH = 90 and I = 0128 M 187


[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 189

Figure 427 Plot of ln [OH-] versus ln k [BB+]0 (70 x 10-5 M) with [ClO2]t

(115 x 10-3 M) 190

xxiv


Figure 429 Plot of [OH-] versus k[ClO2] for the reaction [BB+]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) [OH-]eq(10 x 10-8 M to 195 x 10-7 M) 193

Figure 4210 Plot of ln k versus ln [ClO2] for the reaction of [BB+]0 (70 x 10-5 M)

with [ClO2]t (115 x 10-3 M) A (pH = 90) B (pH = 80) C (pH = 70) 195

Figure 4211 Plot of log k versus radicI for the reaction of [BB+]0 (70 x 10-5 M)

with [ClO2]t (115 x 10-3 M) at varying ionic strength I (0005 - 0056) 196

Figure 4212 Plot of ln krsquo versus 1T for the reaction of brilliant blue with ClO2 at


Figure 4213 Mechanistic scheme for oxidation of brilliant blue-R with


Figure 4214 Experimental curves versus simulated curves for reaction of [BB+]0

(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 206

Figure 4215 Intermediates and product formation for selected typical kinetic curve

(E2 S2) 207

Figure 431 Typical absorbance versus time plot for the reaction of

[SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) at pH = 90 208



[ClO2]t (115 x 10-3 M) using the first-order equation 209

Figure 433 Depletion of safranine-O with various chlorine dioxide concentrations

for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t 10-3 M

(a = 252 b= 278 c= 303 d = 328 and e = 353) 210

Figure 434 Experimental and computed fits using KinetAsystTM single- exponential

equation for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t 10-3 M

(a = 252 b= 278 c = 303 d = 328 and e = 353) 211

Figure 435 Plot of ln [ClO2] versus ln k for the reaction of [SO+]0 (30 x 10-5 M) with

[ClO2]t (25 x 10-3 -75 x10-3 M) at pH = 90 and I = 0128 M 212


[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 214

xxv

Figure 437 Plot of ln [OH-] versus ln k for the reaction of [SO+]0 (30 x 10-5M)

with [ClO2]t (115 x 10-3 M) 214


Figure 439 Plot of [OH-] versus k[ClO2] for the reaction [SO+]0 (30 x 10-5 M) with

[ClO2]t (115 x 10-3 M) [OH-]eq (18 x 10-8- 251 x 10-7 M) 217

Figure 4310 Plot of ln k versus ln [ClO2] for the reaction of [SO+]0 (30 x 10-5 M)

with [ClO2]t (115 x 10-3 M) a (pH = 90) b (pH = 80) c (pH = 70) 219

Figure 4311 Plot of log k versus radicI for the reaction of [SO+]0 (30 x 10-5 M) with

[ClO2]t (115 x 10-3 M) at I (0009 - 004 M) 221

Figure 4312 Plot of ln k versus 1T for the reaction of [SO+]0 (3 x 10-5 M) with [ClO2]t

(115 x 10-3 M) 223

Figure 4313 Mechanistic scheme for the oxidation of safrainine-O with chlorine

dioxide 226


[SO+]0 (70 x 10-5 M) with [ClO2ˉ]t (145x10-3 M) intermediates and

product formation 229



xxvi

LIST OF TABLES

Table 111 Percentage distribution of OCl- and HOCl 30

Table 311 Reaction between amaranth and hypochlorite at constant ionic strength

[AM-]0 (70 x 10-5 M) [OCl-]t (085 x 10-4 -51 x 10-3 M) pH = 90 and

ionic strength (I = 0128 M) 79

Table 312 Effect of pH on reaction rate for the reaction of [AM-]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) 81

Table 313 Effect of acid on the speciation of hypochlorite and reaction rate 84

Table 314 Effect of ionic strength on the reaction rate [OCl-]t (145 x 10-3 M)

[AM-]0 (70 x 10-5 M) pH = 90 87

Table 315 Effect of ionic strength on the reaction rate for the reaction of

[AM-]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) pH = 310 88

Table 316 Effect of addition of chloride ions for the reaction of [AM-]0 (70 x 10-5 M)

with [OCl-]t (145 x 10-3 M) [Cl-] = 1x10-1M 89

Table 317 Varied temperature and observed rate constants for the reaction of [AM-]0

(70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 90

Table 318 Energy parameters 91

Table 3110 Forward and reverse rate constants obtained from literature and

Simulations 107

Table 321 The reaction between brilliant blue and hypochlorite at constant ionic

[BB+]0 (70 x 10-5 M) [OCl-]t (0725 x 10-3 -435 x 10-3 M) pH = 90 107

Table 322 Effect of pH on the reaction rate 109



[BB+]0 (70 x 10-5 M) pH = 90 116


[BB+]0 (70 x10-5 M) [OCl-]t (145 x 10-3 M) pH = 31 117

Table 326 Effect of addition of chloride ions on the reaction [BB+]0 (70 x 10-5 M)

[OCl-]t (145 x 10-3 M) [Cl-] (1x10-1 M) 118

Table 327 Rate constants for the BB+ oxidation as function of temperature for the

reaction of [BB+]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) with at pH 90 119


xxvii

Table 329 Plausible oxidation products 122


simulations 126

Table 331 The reaction between safranine-O and hypochlorite at constant ionic

strength 134

Table 332 Effect of pH on reaction rate for the reaction of [SO+]0 (30 x 10-5 M)

[OCl-]t (145 x 10-3) 135

Table 333 Effect of acid on the speciation of hypochlorite and reaction rates 140

Table 334 Effect of ionic strength on the reaction rate [SO+]0 (30 x 10-5 M)

[OCl-]t (145 x 10-3 M) pH =90 143

Table 335 Effect of ionic strength on the reaction rate [SO+]0 (30 x 10-5 M) with

[OCl-]t (145 x 10-3M) pH = 40 145

Table 336 Effect of addition of chloride ions for the reaction of [SO+]0

(30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146

Table 337 Varied temperature and observed rate constants for the reaction of

[SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146

Table 338 Data analysis 147



simulations 153

Table 411 Reaction between amaranth and chlorine dioxide at constant ionic strength

[ClO2]t (25 x 10-3 -75 x10-3 M) with [AM-]0 (70 x 10-5 M)

pH = 90 and ionic strength (I = 0128) 160

Table 412 Effect of pH on reaction rate for the reaction 162

Table 413 Calculated [OH-]eq values and corresponding second order constants

reaction of [AM-]0 (70 x 10-5M) with [ClO2]t (115 x 10-3 M) 165

Table 414 Observed rate constants at pH 70 80 and 90 [AM]0 (70 x 10-5 M) with

[ClO2]t (115 x10-3 M) 169

Table 415 Effect of ionic strength on the reaction rate [AM-]0 (70 x 10-5M) with

[ClO2]t (115 x 10-3 M) pH = 80 171

Table 416 Varied chloride concentration and observed rate constant for the reaction

of [AM-]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 172

xxviii

Table 417 Varied temperature in presence of chlorine dioxide and observed rate

constant constant for the reaction of [AM-]0 (70 x 10-5 M) with [ClO2]t

(115 x 10-3 M) 173


Table 419 Possible major oxidation products 175

Table 421 Reaction between brilliant blue and chlorine dioxide at constant ionic

strength [ClO2]t (25 x 10- 3-35 x10-3 M) with [BB+]0 (70 x 10-5 M)


Table 422 Effect of pH on reaction rate for the reaction of [BB+]0 (70 x 10-5 M) with

[ClO2]t (25 x 10- 3-35 x10-3 M) 188

Table 423 Calculated [OH]eq values and corresponding second-order constants for

the reaction of [BB+]0 (70 x 10-5M) with [ClO2]t (115 x 10-3 M) 192

Table 424 Observed rate constants at pH 70 80 and 90 regions for the reaction of

[BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 194

Table 425 Effect of ionic strength on the reaction rate [BB+]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) pH = 90 196

Table 426 Varied chloride concentration and observed rate constants for the reaction

of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 197


constant for the reaction of [BB+]0 (70 x 10-5 M) with

[ClO2]t (115 x 10-3 M) 198


Table 429 Plausible major oxidation products 201


simulations 205

Table 431 Reaction between safranine-O and chlorine dioxide at constant ionic

strength [SO+]0 (30 x 10-5 M) with [ClO2]t (25 x 10-3 -75 x10-3 M)


Table 432 Effect of pH on reaction rate 213

xxix


their reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) 217


[SO+]0 (30 x 10-5 M) with [ClO2]t (115 x10-3 M) 218


[ClO2]t (115 x 10-3 M) pH = 80) 220

Table 436 Varied chloride concentration and observed rate constants 222

Table 437 Varied temperature in presence of chlorine dioxide and observed rate 222


Table 439 Major oxidation products 225


simulations 229

xxx

SYMBOLS AND ABBREVIATIONS

R2 correlation coefficient

ε molar absorbtivity coefficient degC degrees centigrade

I ionic strength

microM micro molar concentration 13C NMR carbon thirteen nuclear magnetic resonance 1H NMR proton nuclear magnetic resonance

A Debye-Hűckel constant

AM- amaranth

A h dm-3 amperes in hour per volume

BB+ brilliant blue-R

ClO2 chlorine dioxide

ClO2- chlorite

ClO3- chlorate

cm centimetre

activation enthalpy

activation entropy

e- electron

Ea activation energy

Exp exponential

g gram

gL gram per litre

GC gas chromatography

GC-MS gas chromatography-mass Spectrometry

HOCl hypochlorite

K Kelvin

k pseudo first-order rate constant

k second or third-order rate constant

K J mol-1 Kilo Joule per mol

k1 k2 rate constants

kobs observed pseudo first-order rate constant

L litre

M molar concentration (molL)

M-1 s-1 mol L sec

mg milligrams

mL millilitre

MS mass spectrometry

ng nano gram

nm nano metre

xxxi

NMR nuclear magnetic resonance

pH potential hydrogen

ppm parts per million

R Universal gas constant 83145 J K-1 mol-1

RSD relative standard deviation

s second

SO+ safranine-O dye

t time

TLC thin layer chromatography

TM trade mark

UV ultraviolet

V volt

z ionic charge

γ activity coefficients

1

CHAPTER 1

11 Introduction

With the phenomenal decline in water quality resulting from indiscriminate anthropogenic

activities access to potable water is at the forefront of the global agenda

Virtually all human activities require clean water Water is a renewable resource yet the

worlds supply of clean and drinkable water is steadily decreasing Half of the worlds

population and most of the worlds economic output is located in urban areas Water demand

already exceeds supply in many parts of the world1 Today 41 percent of the worldrsquos

population lives in river basins that are under water stress The control of water pollution has

become increasing importance in recent years The textile industry in particular faces a

severe pollution problem The World Bank estimates that 17 to 20 percent of industrial water

pollution comes from textile dyeing and treatment Many of the dye chemical substances

which are produced are toxic2

Treatment of highly-coloured dye effluent streams has attracted the attention of

environmentalists technologists and entrepreneurs because of its socio-economic and

political dimensions Water consumption in the textile dye house is very high Water as a

utility is becoming more and more costly and its availability is becoming increasingly

scarce3 The nature of the pollution that accompanies the dyeing industry is primarily due to

the non-biodegradable nature of the dyes along with the strong presence of toxic

metalsacidalkalicarcinogenic aromatic amines traceable in the effluents4

Wastewater generated by the dye production industry and many other industries which use

dyes and pigments is high in both color and organic content There are more than 100 000

2

commercially available dyes with over 7 x 105 tons of dye materials produced annually5 It

has been estimated that 10-15 of these dyes are released as effluent during the dyeing

process6 The discharge of highly colored waste is not only aesthetically displeasing but also

impedes light penetration thus upsetting biological processes within a stream In addition

many dyes are toxic to some organisms and may cause direct destruction of aquatic life The

removal of dyes from such wastewaters is therefore a major environmental problem and is

extremely necessary because dyes are visible even at low concentrations7

Dye pollutants produced from the textile industries are becoming a major source of

environmental contamination89 It is estimated that more than 60 of the worldrsquos dye

production is consumed by the textile industry 15 of the total world production of dyes is

lost during the dyeing and finishing operations10 and more than half of this is discharged into

receiving water bodies more or less without proper treatment thus hampering the functioning

of the ecological process11 The treatment of spent dye wastewater effluent is a growing

concern for the textile industry because of aesthetic conditions as well as eco-toxicological

issues regarding colored rinsing and processing wastewater and the impact of that wastewater

on the receiving streams As regulations become more stringent the effectiveness and cost of

the treatment processes have become more significant Conventional biological treatment can

be ineffective for color removal but chemical oxidative processes seem to provide an

opportunity for future use in industrial wastewater12 Examples of such potentially effective

chemical oxidants for oxidative processes include hydrogen peroxide (H2O2) ozone (O3)

chlorine dioxide (ClO2) ultraviolet irradiation following ClO2 (UVClO2) and

H2O2ultrasonication and Advanced oxidation processes (AOPs) include UVH2O2 UVO3

O3H2O2 Fentonrsquos reagent and the wet-air oxidation processes13

3

Wastewaters that are generated at various stages of dyeing differ in strength and temperature

The high pollution load is caused mainly by spent dyeing baths Their constituents are

untraced dyeing compounds dispersing agents (surfactants) and salts and organics washed

out of the material which undergoes dyeing14 The wastewaters are characterized by high

color and high chemical oxygen demand content and pH varying from 20 to 1201516

Liquid pollutants of the dyeing industries include effluents discharged from batch operations

as the equipment is cleaned and they usually contain toxic organic residues which affect the

parameters such as pH Biological Oxidation Demand (BOD) and Chemical Oxygen

Demand (COD)1718 Direct dyes will have pollutants such as salt unfixed dyes copper salts

and cationic fixing agents Reactive dyes will have salts unfixed dyes and alkalis Vat dyes

will have alkalis oxidising agents and reducing agents Sulfur dyes will have alkalis

oxidising agents reducing agents and unfixed dyes Acid dyes will have unfixed dyes and

organic dyes and disperse dyes will have carriers reducing agents and organic acids19

Several methods are used to decolorise textile wastewater but they cannot be effectively

applied for all dyes20 Synthetic dyes often receive considerable attention from researchers

interested in textile wastewater treatment processes Initial environmental efforts with dyes

dealt with color pollution which has a strong psychological effect More recently interest has

shifted to the potential toxicity of dyes dye precursors (eg certain aromatic amines used in

the production of azo dyes) and their degradation products especially the suspected

carcinogenicity of potential intermediate products As toxicity standards are becoming more

common and stringent the development of technological systems for minimizing the

concentration of dyes and their breakdown products in wastewater is now necessary21

4

In the textile industries the chemical reagents used are very diverse in their chemical

composition which include inorganic compounds polymers and organic products22 Due to

their chemical structure dyes are resistant to fading on exposure to light water and many

chemicals23 Many dyes are difficult to decolorise due to their complex structure and

synthetic origin There are many structural varieties such as acidic basic disperse azo

diazo anthroquinone-based and metal complex dyes Decolorisation of textile dye effluent

does not occur when treated aerobically by municipal sewerage systems24 Currently the main

method of textile wastewater treatment is by physical and chemical means with research

concentrating on cheaper and effective alternatives

12 Water pollution and treatment methods

The causes of water pollution are located at municipal industrial and agricultural level

Municipal causes are related to waste water from homes and commercial establishments

Industrial causes vary as per the biochemical demand suspended solids inorganic and

organic substances Agricultural causes include commercial livestock and poultry farming

These lead to organic and inorganic pollutants in surface waters and groundwater25 Water

pollution is caused by the emission of domestic or urban sewage agricultural waste

pollutants and industrial effluents into water bodies

One of the main sources of water pollution is the waste material discharged by industrial

units known as industrial water pollution it produces pollutants that are extremely harmful to

people and the environment26 Many industrial facilities use freshwater to carry waste away

from the plant and into rivers lakes and oceans Pollutants from industrial sources include

waste materials such as acids alkalis toxic metals oil grease dyes pesticides and even

radioactive materials that are poured into the water bodies27 Other important pollutants

5

include polychlorinated biphenyl (PCB) compounds lubricants and hot water discharged by

power plants The pollutants unloaded into the water bodies usually dissolve or remain

suspended in water Sometimes they also accumulate on the bottom of the water bodies28

Wastewater treatment consists of applying known technology to improve or upgrade the

quality of wastewater Usually wastewater treatment will involve collecting the wastewater

in a central segregated location (Wastewater Treatment Plant) and subjecting the wastewater

to various treatment processes Most municipal wastewater treatment plants have primary

and secondary treatment facilities followed by a tertiary processing plant29

Wastewater treatment however can also be organised or categorised by the nature of the

treatment process being used Primary treatment involves physical separation of floatable and

settleable solids Secondary treatment involves biological removal of dissolved solids

Tertiary treatment involves physical chemical and biological treatment30

121 Ozonation

Advanced oxidation is one of the potential alternatives to decolorise and reduce recalcitrant

wastewater loads from textile dyeing and finishing effluents This process implies generation

and subsequent reaction of hydroxyl radicals which are the most powerful oxidising species

after fluorine Advanced oxidation processes including ozonation UVH2O2 TiO2UV

Fentons reagent photo-Fenton and photo-electrocatalytic oxidation have been used for the

purification of water and wastewater Among these methods ozonation is very popular An

easy-operated oxidation technology it is very effective in treating wastewaters containing

harmful compounds31

6

Ozone and hydroxyl radicals generated by ozone in the aqueous solution are able to break

aromatic rings of dyes32 Ozonation provides no germicidal or disinfection residual to inhibit

or prevent regrowth33 Some disadvantages of ozone include higher equipment and

operational costs and the fact that it may be more difficult to find professionals proficient in

ozone treatment and system maintenance Ozonation by-products are still being evaluated and

it is possible that some by-products may be carcinogenic These may include brominated

byproducts aldehydes ketones and carboxylic acids34 This is one reason that the post-

filtration system may include an activate carbon filter in the ozonation process

Ozonation of water treatment may require pre-treatment for hardness reduction or the

addition of polyphosphate preventing the formation of carbonate scale Ozone is less soluble

in water compared to chlorine and therefore special mixing techniques are needed Potential

fire hazards and toxicity issues are associated with ozone generation Typically ozonation of

dye effluents rarely leads to the complete mineralization but the partial oxidation of dyes to

organic acids aldehydes and ketones35 It is quite efficient in decolorising solutions but

considerably less efficient in terms of total organic carbon (TOC) removal

Ozonation is fairly effective in water treatment However the technology is relatively

expensive Another disadvantage of ozonation is its short half-life typically being 20 min

This time can be further shortened if dyes are present with stability being affected by the

presence of salts pH and temperature36 In alkaline conditions ozone decomposition is

accelerated and so careful monitoring of the effluent pH is required37 and in general ozone

has to be generated in-situ which restricts its wider use to use it in remote locations38

7

122 Chlorination

The most commonly used chemical process in water treatment is chlorination This is a very

effective technology Its effectiveness depends on the quality of the water that is being

chlorinated and the method of chlorination used Normally gas chlorination is a more

efficient method of disinfection although a system based on the use of hypochlorite tablets is

easier to operate and maintain and is preferred by individual users39 The advantages of

chlorination systems include the fact that these systems are extremely reliable The

hypochlorite system is easier to operate than the gas system because the operators need not be

as skilled or as cautious Chlorination is also less costly than other disinfection systems and is

generally easier to implement Chlorine (Cl2) can be made easily in-situ and safety

considerations for its production transportation and uses are well-known40

123 Hypochlorination history of hypochlorite

Sodium hypochlorite is one of the most versatile chemicals to which humankind is

constantly exposed It is a powerful oxidising agent bleaching agent disinfectant and

deodorizer41 Itrsquos low cost and versatility makes it very desirable in industry and households

alike42 In 1774 Scheele first reported that chlorine water was able to bleach vegetable

colors43 In 1785 Berthelot a French chemist suggested that this property could be useful

commercially He noted that solutions of chlorine in potash lye proved more concentrated and

powerful bleaches In addition this particular combination did not have the deleterious

effects on workers and materials caused by excess chlorine The high cost of alkalis prompted

Tennant in 1789 to develop bleaching solutions by dissolving chlorine in aqueous

suspensions of lime [Ca(OH)2] strontia [Sr(OH)2] and baryta [Ba(OH)2] In 1789 he patented

a process for the manufacture of ldquobleaching powderrdquo by saturating dry calcium hydroxide

with chlorine gas44

8

By the end of the nineteenth century Louis Pasteur had discovered sodium hypochloritersquos

potent effectiveness against disease-causing bacteria which led to it being widely used as a

disinfectant To this day sodium hypochlorite remains one of the most effective bleaches

around Daily millions of households worldwide rely on sodium hypochlorite for their

disinfection deodorizing and cleaning needs The world consumer market for sodium

hypochlorite bleach is in excess of 4 million tons This does not include the large quantities

used for industrial purposes such as waste water treatment and drinking water disinfection45

In the light of the above the current study focus on dye chemical treatments using two

commonly-used oxidants - hypochlorite4647 and chlorine dioxide 48

13 Methods for the preparation of hypochlorite

The literature survey shows that various methods have been adopted for the preparation of

aqueous sodium hypochlorite A few of the important methods are outlined here Cl2 may be

reacted directly with sodium hydroxide and water49 The presence of excess base stabilizes

the solutions to some extent A small excess of sodium hydroxide is allowed as residue to

maintain the pH between 110 and 130 and minimize the decomposition of hypochlorite

formed

2 NaOH + Cl2 NaCl + NaOCl + H2O (11)

Electrolysis of a cold sodium chloride solution is another method in which the brine solution

in an iron cell is electrolyzed with iron serving as the cathode The anode and cathode

products are allowed to mix at low temperatures to minimize the decomposition caused by a

temperature increase50

Sodium hypochlorite can be obtained in solution by passing chlorine into a cold dilute

solution of sodium carbonate51

9

Na2CO3 + Cl2 NaCl + NaOCl + CO2 (12)

Hypochlorite solutions are prepared by the neutralization of hypochlorous acid or dichlorine

monoxide52 With alkalis hypochlorous acid forms salts which are largely hydrolysed

HOCl + OH- H2O + OCl- (13)

Gaseous chlorine is bubbled through aqueous slurry of yellow HgO at room temperature53

For every mol of chlorine dissolved in the slurry 30 mol HgO is added to provide an

adequate excess The slurry is mixed for 45 min at which time all of the Cl2 is converted to

HOCl and all the chloride ion is precipitated as HgCl2 This HOClHgCl2HgO slurry is

distilled under a reduced-pressure nitrogen atmosphere into a 010 M NaOH solution and the

HOCl is collected as NaOCl The nitrogen atmosphere is utilized so that no CO2 is present to

form carbonate ion as a contaminant in the final NaOCl solution54

14 Advantages and uses of hypochlorination

Sodium hypochlorite has long been recognized as having outstanding disinfection properties

Hypochlorite compounds are non-flammable It does not present the same hazards as gaseous

chlorine and is therefore safer to handle It can be easily stored and transported when it is

produced on-site

Hypochlorite spills can be cleaned up with large volumes of water Sodium hypochlorite

effectively destroys disease-causing bacteria and is thus a major contributor to efforts to stem

the debilitating consequences of cholera dysentery typhoid and other waterborne biotic

diseases In hospitals and health care facilities bleach is used to disinfect surfaces against

fatal viruses like Human Immunodeficiency Virus (HIV) and Hepatitis-B It is used

extensively in the area of water treatment to disinfect municipal drinking water and drinking

water from wells55 It is widely used for swimming pool water disinfection both as a daily

10

regimen and as a shock treatment It is a bactericidal and has good solvent properties for vital

necrotic and fixed tissues56

Hypochlorite is used for industrial and institutional applications It is used for the treatment

of sewage to reduce odours and to increase digesting efficiency as an irrigating solution for

endodontic treatment57 as well as in the treatment of the cyanide effluent in gold mining and

in cyanide waste treatment in metal finishing In food processing it is used for sanitizing dairy

equipment fruit and vegetable processing mushroom production hog beef and poultry

production maple syrup production fish processing and to effectively control algae in open

reservoirs Hypochlorite is used in cooling water and boiler water treatment to prevent

fouling58 It is used for the oxidative degradation of residual dyes present in waste water

streams5960

It can be safely used on many washable color fast fabrics including cotton polyester nylon

acetate linen rayon and permanent press It is highly effective in removing a wide range of

stains and soils which are not totally removed by laundry detergents eg blood body soiling

coffee grass mustard red wine etc Hypochlorite can provide a significant boost to the

whitening and cleaning power of laundry detergents even in cold or hard water

Hypochloritersquos unique disinfecting properties assure sanitization which is of particular

importance in hospital linens to reduce the possible transmission of disease6162

15 Limitations of hypochlorination

The use of chlorine in gaseous form or as a solution can cause safety hazards All operating

personnel should be made aware of these hazards and trained in handling Chlorine is reactive

and interacts with certain chemicals present in the product water depending on pH and water

11

temperature resulting in the depletion of the chlorine concentration leaving only residual

amounts of chlorine for disinfection (over-chlorination may result in the formation of

chlorinated hydrocarbons such as trihalomethanes which are known to be carcinogenic)63

Chlorine will also oxidise ammonia hydrogen sulfide and metals present in the product

water to their reduced states Chlorine gas is heavier than air and is extremely toxic and

corrosive in moist atmospheres Dry chlorine can be safely handled in steel containers and

piping but where moisture is present (as it is in most treatment plants) corrosion-resistant

materials such as silver glass pressurized gas Teflon and certain other plastics must be

used64 Hypochlorite may cause damage to the eyes and skin upon contact because it is a

powerful oxidant and may cause fires if it comes into contact with organic or other easily

oxidisable substances65

16 History of chlorine dioxide

Among the different chemical agents that can be used as chlorine alternatives for water

potabilisation chlorine dioxide has attracted considerable attention66 The discovery of ClO2

has largely been credited to Sir Humphrey Davy who in the 1800s created the compound by

mixing sulfuric acid with potassium chlorate67 Since its discovery researchers have found

that ClO2 shares some common characteristics with chlorine Specifically ClO2 is a greenish-

yellowish gas with a chlorine-like odor that is irritating to the eyes nose and throat Apart

from these very limited similarities however it has been learned that ClO2 exhibits physical

and chemical properties that are dramatically different from those of chlorine even though it

contains a chlorine atom in its molecular structure

12

ClO2 is unstable as a gas and will undergo decomposition into chlorine gas (Cl2) and oxygen

gas (O2) and produces heat However ClO2 is stable and soluble in an aqueous solution For

example solutions of approximately one percent ClO2 (10 gL) may be safely stored if the

solution is protected from light and kept chilled In solution form ClO2 exists as a true gas

Chlorine dioxide is commonly used as a pre-oxidant and primary disinfectant during

treatment of drinking water As a pre-oxidant it is used mainly as an alternative to chlorine

for tri-halomethane (THM) control6869 It is also used for taste-and-odor control manganese

and iron oxidation and color removal In the United States over 500 water treatment plants

use ClO2 full time and as many as 900 use it either part time or seasonally70

161 Methods of preparation of chlorine dioxide

Chlorine dioxide is a highly endothermic compound that can decompose when separated

from diluting substances As a result preparation methods that involve producing solutions of

it without going through a gas phase stage are often preferred

Most commercial generators use sodium chlorite (NaClO2) as the common feedstock

chemical to generate chlorine dioxide for drinking water application Recently production of

chlorine dioxide from sodium chlorate (NaClO3) has been introduced as a generation method

wherein NaClO3 is reduced by a mixture of concentrated hydrogen peroxide (H2O2) and

concentrated sulfuric acid (H2SO4) More than 95 of the sodium chlorate produced today is

used in the pulp and paper industry where it is a primary raw material for the production of

chlorine dioxide Chlorine dioxide is a strong and selective oxidiser and is used in the pulp

bleaching process7172

13

The most common methods for the generation of ClO2 for water treatment involve sodium

chlorite (NaClO2) either as a solid or in solution73 Sodium chlorite is reacted with either

chlorine gas (Cl2) hypochlorous acid (HOCl) or hydrochloric acid (HCl) in the following

reactions 74 This method was used to generate the chlorine dioxide in the current study

2NaClO2 + Cl2(g) rarr 2ClO2(g) + 2NaCl (14)

2NaClO2 + HOCl rarr NaCl + NaOH + 2ClO2(g) (15)

5NaClO2 + 4HCl rarr 4ClO2(g) + 2H2O + 5NaCl (16)

In the first two reactions an unstable intermediate Cl2O2 is formed if the reactants are in

high concentrations When chlorite ion (ClO2-) concentrations are low the intermediate

decays to chlorate ion (ClO3-) The chlorate ion production can also occur when initial

reactant concentrations are low or when chlorine (or hypochlorous acid) is in excess When

initial reactant concentrations are high or when ClO2- concentrations are in excess the

intermediate decays to ClO275

During the generation of ClO2 it is desirable to minimize or eliminate unwanted by-products

such as ClO2- and ClO3

- as well as excess chlorine The production of unwanted by-products

can occur when there is feedstock contamination improper generator control or excess

chlorine7677 In reaction 15 only 80 percent conversion of NaClO2 to ClO2 is possible and

therefore this method is not popular Pure chlorine dioxide can also be produced by

electrolysis of a chlorite solution

2NaClO2 + 2H2O rarr 2ClO2(g) + 2NaOH + H2 (17)

High purity chlorine dioxide gas (77 percent in air or nitrogen atmosphere) can be produced

by the Gas Solid method which reacts dilute chlorine gas with solid sodium chlorite

14

2NaClO2 + Cl2 rarr 2ClO2(g) + 2NaCl (18)

Another method for generating high-purity ClO2 by reaction of solid NaClO2 with chlorine

gas has become available75 The chlorine gas is first mixed with humidified air and then

passed through a series of drums containing solid NaClO2 No unreacted NaClO2 enters the

system because the generated ClO2 is in the gas phase and ClO3- is not produced

162 Advantages and uses of chlorine dioxide

Chlorine dioxide is less expensive than other disinfection methods such as ozone Chlorine

dioxide is used primarily (gt95) for bleaching of wood pulp as an oxidiser chlorine dioxide

is very selective It has this ability due to unique one-electron exchange mechanisms

Chlorine dioxide attacks the electron-rich centers of organic molecules By comparing the

oxidation strength and oxidation capacity of different disinfectants chlorine dioxide is

effective at low concentrations It can be effectively used when a large amount of organic

matter is present in the effluents It is also used for the bleaching of flour and for the

disinfection of municipal drinking water

New Yorkrsquos water treatment plant first used chlorine dioxide for drinking water treatment in

1944 for phenol destruction Itrsquos most common use in water treatment is as a pre-oxidant

prior to chlorination of drinking water to destroy natural water impurities that produce

trihalomethanes to free chlorine7879 Chlorine dioxide is also superior to chlorine when

operated above pH 70 in the presence of ammonia and amines andor for the control of

biofilms in water distribution systems Chlorine dioxide is used in many industrial water

treatment applications as a biocide including cooling towers process water and food

processing Chlorine dioxide is less corrosive than chlorine and superior for the control of

15

legionella bacteria It is more effective as a disinfectant in most circumstances than chlorine

against waterborne pathogenic microbes such as viruses bacteria and protozoa80 At a low

concentration level chlorine dioxide gas can be used as a precaution against Influenza A virus

infection81 It can also be used for air disinfection and was the principal agent used in the

decontamination of buildings in the United States after the 2001 anthrax attacks82 After the

disaster of Hurricane Katrina in New Orleans Louisiana and the surrounding Gulf Coast

chlorine dioxide has been used to eradicate dangerous mold from houses inundated by water

from massive flooding83 Chlorine dioxide is used as an oxidant for phenol destruction in

waste water streams control of zebra and quagga mussels in water intakes and for odor

control in the air scrubbers of animal by-product plants Stabilized chlorine dioxide can also

be used in an oral rinse to treat oral disease and malodor84

163 Limitations of chlorine dioxide

When using chlorine dioxide with sodium chlorite and chlorine gas safety measures must be

taken both during its transportation and usage Sufficient ventilation and gas masks are

required for handling Chlorine dioxide is a very unstable substance and it decomposes when

exposed to sunlight During chlorine dioxide production processes a large amount of chlorine

is formed85 Free chlorine reacts with organic matter to form halogenated disinfection by-

products Chlorine dioxide and its disinfection by-products chlorite and chlorate if present in

water can create health problems for dialysis patients To control pathogenic micro-

organisms chlorine dioxide is generally effective but it is less effective for the deactivation

of rota viruses and E coli bacteria Chlorine dioxide is about 5 to 10 times more expensive

than chlorine86 Chlorine dioxide is usually made on site The costs depend upon the price of

the chemicals that are used to produce it

16

17 Dyes and classification of dyes

A wide range of dyes exists to meet the demands of industry An aromatic ring structure

coupled with a side chain is usually required for resonance and to impart its color The color

is usually given by the chromophore group such as azo (ndashN=Nndash) carbonyl (gtC=O) carbon

(ndashCndashCndash) carbon-nitrogen (gtC=NH or ndashCH=Nndash) nitroso (ndashNO or NndashOH) nitro (ndashNO2 or

=NOndashOH) and sulfur (gtC=S and other carbon-sulfur groups) which also form a basis for

the chemical classification of dyes87 All commercial textile dyes are classified by their

generic name and chemical constitution They are assigned a Color Index classification

number by Color Index (CI)88 a journal published by the Society of Dyers and Colorists

(United Kingdom) in association with the American Association of Textile Chemists and

Colorists (AATC) Every commercial dye and pigment in it is given a CI Generic Name

which includes its application class its hue and a number which indicates its chronological

discovery Most of the dyes and pigments in the Color Index are placed in one of the 25

structural classes according to their chemical type Azo dyes the largest class are subdivided

into four sections89 However if we take color index as one of the basis for classification the

typical dyes most used widely in the textile industry include acid dyes basic dyes direct

dyes disperse dyes sulfur dyes reactive dyes oxidation dyes and vat dyes9091

171 Acid dyes

Acid dyes are typically used to dye acrylics wool nylon and nyloncotton blends and are

also used in the paper and leather industries They are called acid dyes because they are

normally applied to the nitrogenous fibers of fabrics in organic or inorganic acid solutions

The three most commercially important acid dyes are azo anthraquinone and triarylmethane

These dyes are generally applied as a liquid at elevated temperatures of greater than 39 degC

17

In general these dyes have poor wet fastness and their molecular weights range from 200 to

900 g mol-1 The structure of typical acid dye brilliant blue-R is illustrated in Figure 11192

NSO3

-

NN

O

SO3-

H

Figure 111 Structure of acid dye-brilliant blue R

172 Direct dyes

Direct dyes are commonly used on cotton fibers These dyes are mixed with all purpose dyes

along with the acid dyes The color of direct dyes on cotton fibers is not bright in comparison

with other dyes These dyes are normally used to dye cotton and other cellulosic fibers they

bond to fibers by electrostatic forces Direct dyes are applied in an aqueous bath containing

ionic salts and electrolytes these can be also used to stain silk and wool Few direct dyes like

direct orange 39 and direct blue 86 are considered as having very high light fastness capacity

The structure of typical acid dye direct fast red 8B is illustrated in Figure 11293

OH

H2N

N

SO3Na

N NHCONH N N

OH

SO3NaNaO3S

NH2

Figure 112 Structure of direct dye-direct fast red 8B

18

173 Disperse dyes

Disperse dyes are colloidal and have very low water solubility These dyes were originally

developed for the dyeing of cellulose acetate and are substantially water insoluble They are

finely grounded in the presence of a dispersing agent and then sold as a paste or spray-dried

and sold as powder Most of these dyes are used for polyester nylon acetate and triacetate

fibers and surface dyeing of plastics They are usually applied from a dye bath as dispersions

by direct colloidal absorption Dye bath conditions (temperature use of carrier) are varied

based on the degree of difficulty encountered by the dyes in penetrating the fiber being dyed

They are sometimes applied dry at high temperatures by means of a sublimation process

followed by colloidal absorption A typical disperse dye reactive orange 4 is shown in

Figure 11394

NaO3SSO3Na

N

NOH

N

CH3

NaO3S N

N

Cl

N

Cl

Figure 113 Structure of disperse dye-reactive orange 4

174 Sulfur dyes

Sulfur dyes are used primarily for cotton and rayon The main characteristics of sulfur dyes

are that they have lustrous grains and make a complete black shade with a slight reddish or

greenish impact These dyes are used for jigger cotton and viscose rayon From the name it is

clear that these dyes contain a small amount of sulfuric acid The fibers that can be dyed by

these dyes are viscous staple fibers yarn any materials which give a resin finish silk etc

19

These dyes have excellent light fastness properties The structure of typical sulfur dye

soluble sulfur black is illustrated in Figure 11495

NO-O

N

O-

O

OH

Figure 114 Structure of sulfur dye-soluble sulfur black

175 Reactive dyes

Reactive dyes or fiber reactive dyes are basically a class of highly colored organic

substances Reactive dye uses a chromophore that contains a substituent that is quite capable

of a direct reaction with a fiber substrate Fiber reactive dyes derive their name from the fact

that they form covalent bonds with the fiber molecules to be dyed Cold reactive dyes like

cibacron F procion MX and drimarene K are very easy to use as they can be applied at

room temperature Reactive dyes are very good for dyeing cotton and other cellulose fibers

They are primarily used for tinting textiles These dyes also have outstanding wet fastness

An example of a reactive dye reactive red 22 is shown in Figure 115 96

NaO3SOCH2CH2O2S

OCH3

N N

OH

SO3Na

Figure 115 Structure of reactive dye-reactive red 22

20

176 Basic dyes

Basic dyes are the class of dyes that are most commonly synthetic Their primary nature is to

act as bases and they are actually aniline dyes Initially their color base prevents them from

being water soluble They can be made with the base being converted into a salt At the

chemical level basic dyes are typically cationic or positively charged Basic dyes display

cationic functional groups like -NR3+ or =NR2

+ Basic dye is a stain that is cationic or

positively charged and this is the reason that it reacts well with material that is anionic or

negatively charged Basic dyes consist of amino groups or alkyl amino groups as their

auxochromes Some prominent examples of basic dyes are methylene blue crystal violet

basic fuchsin and safranin etc The structure of typical basic dye safranine-O is illustrated in

Figure 11697

N

N CH3

NH2H2N

H3C

Figure 116 Structure of basic dye-safranine-O

177 Vat dyes

Vat dyes are based on an original Indigo dye that is a kind of natural dye Vat dyes are an

ancient class of dye Indigo dyes (parent of vat dyes) are manufactured synthetically Various

kinds of fibers can be washed by using vat dyes and the main categories of fibers are cotton

and wool In the dyeing process the vat dyes are not directly used The major application is

the dyeing and printing of cotton Such are the outstanding fastness properties of this group

that special methods for the dyeing and printing of substrates other than cotton eg wool silk

21

and cellulose acetate have been developed The structure of typical vat dye vat brown 1 is

illustrated in Figure 11798

O

O HN

O

ONH

OO

Figure 117 Structure of vat dye-vat brown 1

178 Literature survey

Effluent from most textile dyeing operations generally has a dark reddish-brown hue that is

aesthetically unpleasing when discharged in receiving waters In typical dyeing and printing

processes 50 to 100 percent of the color is discarded in the form of spent dye-baths or in

wastewater from washing operations In recent years the oxidation of dyes has attracted much

attention Many methods of color removal exists using different oxidants Because of the

difficulties and expense in treating color due to the large variability of the composition of

textile wastewater most of the traditional methods are becoming inadequate89-99 There is a

need to investigate the best approach for minimizing colour discharges as a measure of

pollution prevention

The literature survey suggests that some azo and anthraquinone dyes were non-degradable by

the conventional activated sludge process100 Muruganandham et al studied the

22

photochemical oxidation of reactive orange 4 in the presence of H2O2 and UV-light and

concluded that the dye follows pseudo first-order kinetics with the UV-H2O2 and solar-H2O2

processes and efficient at pH 30101 Oakes et al studied the kinetics of the heterogeneous

oxidation (by hypochlorite) of an azo dye (Remazol Red RB) reactively bound to cotton102

and reported that the physical state of bound dye (eg its pKa and tautomeric form) and its

oxidation profile with pH are similar to those of dye in a homogeneous solution The analysis

presented suggested that the mechanism of oxidation in the two environments is similar The

oxidation of azo dyes of pyrazolone and pyridone types occurred at similar rates to

arylazonaphthol dyes and oxidation kinetics were independent of groups attached to either

side of the azo linkage confirming that the site of attack is the more nucleophilic nitrogen

atom of the azo group of the common anion

Oakes and Gratton investigated the oxidation of orange I and orange II103 and also a series

of substituted azo dyes with hypochlorite peracids and hydrogen peroxide in aqueous media

They concluded that the observed second-order rate constants exhibit maxima in alkaline

media at a pH equal to the midpoint of the pKa values of dye and oxidant They also reported

that substituents upon the aryl ring ortho to the azo group suppress dye reactivity towards

hypochlorite and peracids In contrast oxidation by hydrogen peroxide is enhanced by ortho

substituents suggesting that it functions via a different mechanism The dye common anion

has been identified as the form of the dye most susceptible to oxidation by peracids and

hypochlorite with the undissociated oxidant molecules acting as electrophiles In contrast

dye oxidation by hydrogen peroxide proceeds via the perhydroxyl anion and the hydrazone

tautomeric form of the dye The main function of ortho substituents was to increase the dye

pKa thereby influencing observed rates by changing the equilibrium concentration of

reactive species Reactive oxygen species eg singlet oxygen superoxide or hydroxyl

23

radicals were not implicated in the rate-controlling step of their reaction

Rauf et al studied the photolytic degradation of Amaranth azo dye104 Coomassie brilliant

blue105 and safranine-O using H2O2 and UV light106 They observed the first-order kinetics

with the respective dyes and concluded that the reaction of the dye is due to the hydroxyl

radicals generated in solution and UV oxidation degradation of the dye was less in the

presence of bromide chloride acetate sulfite silver and bicarbonate ions The results

showed that mere UV light or H2O2 alone were not sufficient for degradation of this dye

Szpyrkowicz et al studied the oxidation of pollutants in synthetic textile wastewater

containing partially soluble disperse dyes In their study the removal of pollutants was

mediated by active chlorine generated by electro-oxidation of chloride ions or by other

mediators generated in situ and not by a direct discharge of pollutants at the anode They

achieved 39 percent removal of chemical oxygen demand after 40 min of electrolysis They

reported that the apparent pseudo first-order rate constant for the removal of color was equal

to 254 times 10-4 s-1 and it increased to 823 times 10-4 s-1 under pH control at the value of 45

resulting in 90 percent removal of color after the passage of 19A h dm3 They reported that

in comparative studies on the chemical oxidation of pollutants by hypochlorite far lower

efficiency was obtained107

Hastie et al studied the electrochemical methods for degradation of orange II108 They

concluded that in divided flow-through cells reductive electrolysis of orange II was first-

order in both substrate and applied current and gave the products reductive cleavage at the

azo linkage in essentially quantitative yield Oxidative electrolysis was also pseudo first-order

and led to mineralization At a boron-doped diamond anode the rate of disappearance of dye

24

is closely tracked through the loss of total organic carbon from solution In undivided cells

oxidation and reduction occurred simultaneously under acidic conditions the reduction

products (anilines) were rather persistent because they were present as ammonium ions but

under alkaline conditions the anilines were mineralized along with the starting material

When chloride ion was present in the supporting electrolyte electrochemical oxidation

afforded hypochlorite and the disappearance of dye proceeded by way of hypochlorination

Sergio et al studied the chlorine dioxide reaction with selected amino acids in water and

reported that chlorine dioxide can attack the electron-rich aromatic moieties as well as the

nitrogen atom lone electron pair109 However very little is known about the chlorine dioxide

reactivity with dyes

Any type of chlorine that is added to water during the treatment process will result in the

formation of hypochlorous acid (HOCl) and hypochlorite ions (OCl-) which are the main

disinfecting species in chlorinated water The literature survey revealed that little is known

about the role of HOCl and OCl- and their speciation behavior towards the oxidation of the

dyes There are only a few studies of the reaction of chlorine dioxide with organic

compounds especially with dyes It is a strong oxidant and surface waters exhibit a chlorine

dioxide demand similar to that for chlorine110 Chlorine dioxide destroys phenolic compounds

when the oxidant is used for taste and odor control in water supplies111 Houmligne et al

demonstrated the reactivity of ClO2 with inorganic and organic compounds and established

first-order kinetics with respect to ClO2 and also first-order with respect to the compound112

In the current study the oxidation of three selected dyes ie amaranth (azo dye) brilliant

blue-R (triarylmethane dye) and safranine-O (azine dye) with hypochlorite and chlorine

25

dioxide were carried out by kinetic approach The outline is further supported by other

spectroscopic studies A brief summary of these dyes based on their chemical class and uses

is given below

18 Classes of the dyes studied

181 Azo dyes

The azo dyes are also broadly used in the textile color solvent ink paint varnish paper

plastic food drug and cosmetic industries More than two thousand azo dyes are known to

exist and over half of commercial dyestuffs are azo dyes with some of them and azo

precursors and their degraded products (like aromatic amines) being carcinogens113 It is for

this reason that amaranth was chosen as the representative dye It is also commonly referred

to as red no 2 food red 9 acid red 27 and azorubin S Amaranth is an anionic dye

Azoic dyes are also called azoic or napthol dyes These azo dyes consist of a group called the

azo group which has two nitrogen atoms This group (covalent bond) connects atomic ring

compounds The two Nitrogen atoms are bonded with each other and forms -N=N- as part of

their molecular structure Azoic dyes are found mainly in three colors - red brown and

yellow They are manufactured from aromatic amines Azoic dyes are applied by combining

two soluble components impregnated in the fiber to form an insoluble colour molecule These

dye components sold as paste-like dispersions and powders are used chiefly for cellulosics

especially cotton giving shades of a high standard of fastness to light and wet processing

They give bright intense hues particularly in the yellow orange and red ranges114

Amaranth is made from amaranth plants Its leaves range from purple and red to gold There

are about sixty Amaranthus species Several of them are cultivated as leaf vegetables cereals

26

or ornamental plants It is a dark red to purple azo dye used in many countries as a food dye

and to color cosmetics It usually comes as a trisodium salt It has the appearance of reddish-

brown dark red to purple and is water-soluble Its water-based solution has absorption

maximum at about 520 nm It is banned in some countries such as the United States by the

Food and Drug Administration (FDA) as it is a suspected carcinogen115

182 Triarylmethane dyes

Tri aryl dyes are the derivatives of triphenylmethane They have poor resistance to light and

to chemical bleaches and are used extensively in the textile paper leather and plastic

industry and also in large applications in food and beverages Brilliant blue - R was selected

for the study as it is often found in ice cream tinned processed peas dairy products sweets

and drinks It is also used in soaps shampoos syrups and other hygiene and cosmetics

applications It is one of the colorants that has been suggested should be eliminated from the

diet of children116 It is commonly referred as basic red 2 cotton red gossypimine

183 Azine dyes

Azine dyes are widely used in the textile industry and also in combination with other dyes as

color additives Safranin (also safranin-O or basic red 2) (38-diamino-47-dimethylphenyl

phenazinium chloride) was selected as the model compound for this study because of its wide

application in various textile industries either on its own or in combination with other dyes as

color additives117118 Safranin is used as a counter stain in some staining protocols coloring

all cell nuclei red Safranin is also used as redox indicator in analytical chemistry

27

19 Chemistry of hypochlorite ion

191 Hypochlorite decomposition

Commercially produced bleach is normally kept at a pH between 110 and 130 as it contains

between 0001 M and 0100 M hydroxide ion (OH-) to minimize its decomposition119

Hypochlorite ion decomposition in basic solution is a slow second order process120 in the 40 -

60 degC range with the following stoichiometry and rate law

3 OCl- = ClO3- + 2 Cl- (19)

OCl (110)

The decomposition of OCl- reported involves its disproportionation and chlorite ion (ClO2-)

as an intermediate leading to formation of chlorite and chloride ions18121122

OCl- + OCl- ClO2- + Cl- (slow) (111)

OCl- + ClO2- ClO3

- + Cl- (fast) (112)

Because reaction (112) is the fast process the concentration of ClO2- remains relatively

low123 Chlorate ion often present in drinking water that has been treated with OCl- is

foundin three possible sources124125 The first is from the raw (untreated) water itself and the

second source of ClO3- is the decomposition of residual hypochlorous acid (HOCl) during the

the disinfection process It has been shown that in the dark decomposition of HOCl at mg per

litre level between pH 50 and pH 80 is relatively slow In the presence of UV light

(sunlight) HOCl decomposes with a photolysis half life126 of 12 mins at pH 80 and increases

as the ratio of OCl- to HOCl increases The third possible source of ClO3- is the

decomposition of OCl- in liquid bleach during storage prior to application The formation of

oxygen from the decomposition of OCl- is a very slow side reaction127 in solutions of pure

OCl- and is considered to be only a minor decomposition pathway (lt 10)

28

OCl- + OCl- O2 + 2 Cl- (very slow) (113)

The liquid bleach stored with a pH between 120 and 130 is the most stable As the pH of the

bleach stock solution is lowered the pH of the OCl- stock solution will continue to decrease

over time because of a competing acid-producing decomposition pathway with the following

stoichiometry128

2 HOCl + OCl- ClO3- + 2 H+ + 2 Cl- (114)

This could be a serious problem because the high HOCl in the stored liquid bleach will lead

to a large ClO3- residual in the storage tank and eventually in the finished water Dilution of

the stock bleach can be an effective strategy for minimizing OCl- decomposition and

concomitant ClO3- formation To minimize ClO3

- formation the pH of the liquid bleach

should be adjusted and maintained at a pH 110129 Commercial bleach contains enough

caustic soda to maintain a pH 120 even after 50 percent dilution It has also been shown

that increasing the temperature of liquid bleach increases its rate of decomposition Thus in

summer months and in unventilated storage sheds the decomposition of liquid bleach will be

rapid130 The rate constants for the decomposition pathways are affected not only by

temperature but also by the ionic strength ionic media present and the presence of UV light

192 Bleaching action of hypochlorite ion

Bleach is a chemical that removes color or whitens often via oxidation Color in most dyes

and pigments is produced by molecules such as beta carotene which contain chromophores

Chemical bleaches work in one of two ways an oxidising bleach works by breaking the

chemical bonds that make up the chromophore this changes the molecule into a different

substance that either does not contain a chromophore or contains a chromophore that does

29

not absorb visible light A reducing bleach works by converting double bonds in the

chromophore into single bonds This eliminates the ability of the chromophore to absorb

visible light131132

The bleaching action of hypochlorite ion depends on three main reactions133 ie disruptive

oxidation of colored molecules addition of halogen oxides across olefinic functions and

halogenations of saturated compounds

193 Oxidising action of hypochlorite ion

The oxidation reaction with hypochlorite normally involves two electron oxidations both

under basic and acidic pH conditions

The oxidising action of hypochlorite may be expressed by the ion electron equations134

In alkali

OCl- + H2O + 2e- Cl- + 2OH- (115)

In acid

OCl- + 2H+ + 2e- Cl- + H2O (116)

194 Hypochlorite and hypochlorous acid distribution

The decomposition of hypochlorite (HOCl and OC1-) has been studied initially by Chapin et

al in the pH range 10 to 130135 The pKa value of hypochlorite is 746136 He further

reported that maximum decomposition rate of hypochlorite is in the neutral pH range Based

on its pKa value the speciation of hypochlorite and hypochlorous acid as function of pH is

calculated and the data is summarized in Table111

30

Table 111 Percentage distribution of OCl- and HOCl

pH [OCl-] [HOCl]

20 045 9955

30 121 9879

40 323 9677

50 832 9168

60 1978 8022

70 4013 5987

80 6457 3543

90 8320 1680

100 9309 691

calculated values using pKa 74 up to four significant figures

110 Chemistry of chlorine dioxide

Chlorine dioxide (ClO2) exists as a volatile energetic free radical and is quite reactive Due

to its explosive nature ClO2 cannot be compressed or stored and must be generated on-site

Solutions with concentrations greater than 100 gL can poses an explosive hazard137 and its

ignition temperature is about 130 degC Chlorine dioxide concentrations used in the water

treatment are generally in the range of 01 mgL to 50 mgL

One of the most important physical properties of chlorine dioxide is its high solubility in

water particularly in chilled water Chlorine dioxide does not hydrolyze in water but remains

a highly soluble gas above 11degC over a broad range of pH (20 to 100) Solutions are

greenish-yellow and smell strongly chlorinous75 Aqueous solutions must be protected from

light as chlorine dioxide is subject to photolysis by ultraviolet light138 and even fluorescent

lights

31

The main reaction product of ClO2 in water is the chlorite ion Its reduction occurs by an

electron transfer forming ClO2- as shown in this half-reaction74139

ClO2 + eminus rarr ClO2minus (117)

Masschelein140 reported ldquoIn aqueous solution chlorination by chlorine dioxide is not a direct

reaction However indirect chlorination by dioxide having undergone a previous reaction

may not necessary be excludedrdquo He attributed reports of chlorinated organic by-products

produced to the presence of chlorine in the ClO2 solution that was used Chlorine on the

other hand reacts with organic compounds to form chlorinated organic by-products141142

Chlorite ion which also is an oxidant reacts at a much slower rate than ClO2 under

conditions generally encountered in water treatment Chlorite ion is reduced to chloride ion

(Cl-) by the following reaction74137140

ClO2 + 4H+ + 4e- rarr Cl- + 2H2O (118)

This reaction does not occur however unless reduced compounds such as ferrous ion (Fe2+)

phenol or humic materials are present143 Typically from 50 to 70 percent of the reacted

ClO2 appears as ClO2- with the balance forming either Cl- or ClO3

-144145

In basic solutions ClO2 disproportionates to form ClO2-and ClO3

- 137

2ClO2 + 2OH- rarr ClO2- + ClO3

- + H2O (119)

Under certain conditions chlorine and ClO2 can react to form ClO3-

2ClO2 + HOCl + H2O rarr 2 ClO3- + 2H+ + HCl (120)

When chlorine dioxide is subject to photochemical decomposition through a series of

reactions to Cl- and ClO3- 146147 there was significant formation of ClO3

- (036 to 097 mgL)

when water containing from 356 mgL to 399 mgL of ClO2 was exposed to fluorescent

32

light In controlled experiments when water was treated with ClO2 and kept in the dark it did

not contain ClO3-

Chlorite ion reacts with chlorine in treated water to reform ClO2 in the same manner that

ClO2 is generated (Reaction 15) This reaction however depends heavily on pH and relative

reactant concentrations In basic solutions when the hypochlorite ion (OCl-) is present greater

amounts of ClO3- are formed by the following reaction144148

ClO2- + HOCl + OH-rarr H2O + Cl- + ClO3

- (121)

In acidic conditions more ClO2 than ClO3- is formed

2ClO2- + HOCl + H+ rarr 2 ClO2 + Cl- + H2O (122)

In neutral solutions also chlorine and ClO2 react to form ClO3-and Cl-

2ClO2 + HOCl + H2O rarr 2ClO3- + Cl- + 3H+ (123)

111 Chemical kinetics

The chemical kinetics is the study of rates of chemical processes as a function of time

Chemical kinetics includes investigations of how different experimental conditions can

influence the speed of a chemical reaction and yield information about the reactions

mechanism and transition states as well as the construction of mathematical models that can

describe the characteristics of a chemical reaction149150

The reaction kinetics can be applied to the optimization of process conditions as in organic

synthesis analytical reactions and chemical manufacturing The chemical kinetics is used for

the determination and control of the stability of commercial products such as pharmaceutical

dosage forms foods paints and metals Further uses of kinetics less sweeping in their scope

than the preceding application are for the testing of rate theories the measurement of

33

equilibrium constants the analysis of solutions including mixtures of solutes and the

measurement of solvent properties that depend upon rates151

1111 Classification of reaction rates

The rates of chemical reactions are found to be a function of the extent to which the reaction

has proceeded152 Some reactions are roughly classified as fast reactions and the rest are slow

reactions But in general a lsquofastrsquo reaction is one which is over in one second or less

A very rough general classification of rates can also be given in terms of the time taken for

reaction to appear to be virtually complete or in terms of half-lives These will include very

fast reaction fast rate moderate rate slow rate and very slow rate reactions Typically the

reactions in the current study can be classified into moderate (1 to 103 s) and fast rate

reactions (10-6 to 1 s) Hence to monitor the reaction rates for such reactions a Hi-Tech

stopped flow instrument was used

The study of the reaction rates can be explained in terms of the reaction mechanism involving

elementary reactions153 A complete reaction mechanism would involve knowledge of all

molecular details of the reaction including the energetic and stereochemistry eg interatomic

distances and angles throughout the course of the reaction of individual molecular stems

involved in a mechanism154

1112 Factors influencing reaction rates

A number of variables are recognized that influence the rate of a reaction The major factors

are concentrations of reactants products and possibly catalysts physical conditions such as

34

temperature and pressure the intensity of absorbed radiation for reactions in solution

properties of the solvent such as viscosity dielectric constant and ionic strength155

Each of the variables will be considered in turn and emphasis will be placed particularly on

the concentration variables They are the variables which provide the most direct connection

between chemical kinetics and reaction mechanism The minimum goal of a kinetic study is

to establish a possible mechanism for the reaction in the sense in which the term was used

earlier to learn whether it proceeds by a single pathway whether a sequence of reactions

occurs whether equilibria precede the rate-limiting step and whether one or more reaction

intermediates is involved

Variation of temperature and pressure can provide additional information particularly about

the energetic and volume relations of reaction steps in the mechanism The quantities

deduced from the variations are collectively termed ldquoactivation parametersrdquo and they include

such values as entropy of activation ∆Sǂ and the volume of activation ∆Vǂ156

1113 First-order reactions

Most reactions are either first-order or are carried out under conditions that approximate first-

order For a first-order reaction of the type

rarr (124)

where is rate of the reaction

the rate of the reaction is as follows

(125)

where are the concentrations of A initial and at time t = t respectively

35

It can be rearranged as

(126)

Integrating from t = 0 [A]0 to t = [A]t gives

(127)

here trations of A at time t = 0 and t = t respectively which

ln

(128)

Equivalent forms of the integrated first-order rate Equation (128) are shown below (Equation

129 to 130)

ln ln (129)

or

(130)

Thus for a first-order reaction a plot of ln [A]t versus t should be linear with the first-order

rate constant being represented by the slope The dimension of a first-order rate constant is

time-1 usually represented as s-1

1114 Reversible first-order reactions

In principle all reactions are reversible and although simple considerations suggest ways of

driving many reactions in one direction only there are systems where reversibility cannot be

ignored The simplest of these is the reversible first-order reaction

36

(131)

Where and are that the rate constants for forward and back reactions

Recognizing that the loss of a reagent corresponds to a negative rate and that the gain of a

reagent corresponds to a positive rate the rate law applicable to this system is

(132)

(133)

where [A] and [B] express the concentration of the species A and B and

and are the concentrations of A and B at time t = 0 and t = t respectively

At time t = 0 [B]t=0 = 0 and [A]t=0 = [A]0 consequently at any given time

(134)

Substitution of (134) into (133) gives

(135)

No net reaction occurs at equilibrium and hence

0 (136)

Applying equation (136) to (135) and (133) affords the following equilibrium expression

(137)

where and are equilibrium concentrations of A and B

which implies that

(138)

Substitution of (138) into (134) affords the following term

37

(139)

Subsequent separation of variables

(140)

Integration of (140) gives

(141)

which affords

(142)

An equivalent form of equation (141) is shown in equation (142)

ln ln (143)

A plot of ln ([A]t ndash [A]eq) versus time should give a straight slope that corresponds to

ndash (kf + kb)

Evaluation of the equilibrium constants allows one to determine the individual rate constants

kf and kb respectively

(144)

With the observed rate constant kobs

(145)

The most difficult problem encountered in treating reversible first-order reactions is in

accurately measuring [A]eq157

38

1115 Second-order reactions

Second-order reactions can be divided into two types The first type is when the rate is

second-order with respect to one of the reactants and zero-order with respect to the second

reactant The second type that will be analyzed in further detail is when the second-order

reaction is first-order with respect to each reagent

For the reaction

rarr

(146)

where is rate constant upon the rate equation can be written as

(147)

Upon separation of the variables equation (147) can be written as (where [A] and [B] and

and express the concentrations of A and B at time t = 0 and t = t respectively)

Separation of the two leads to

(148)

In order to integrate Equation 148 one must first relate the concentration of B to that of A If

then the initial concentrations of A and B are and respectively it follows from the

reaction Stoichiometry that when the concentrations of A have fallen to ndashx the

concentration of B has fallen into ndash x

Equation 148 can be written as

ndash x ndashx (149)

Since = ndash x it follows that and thus Equation 149 can be written as


39

Separation of the variables results in an alternate version of Equation 148

ndash ndash

(151)

Integrating Equation 151 under the condition that x=0 when t=0 gives

x

ndash x ndash x

(152)

Which affords Equation 152 in the form of y=mx

ln ndash

(153)

1ln (154)

In order to evaluate the second-order rate constant k2 (M-1 s-1) for the reaction one needs to

know the concentrations of both A and B both initially and at any time t ie [A]0 [B]0 [A]t

and [B]t However this represents a complicated and time-consuming process for most

kinetic experiments As a result of this these experiments are often conducted with either

reactant A or B in large excess ie [B]0 gtgt [A]0 (at least 10-fold excess) Under these

conditions the concentration of B remains constant throughout the course of the reaction and

the reaction may be treated as a first-order reaction These conditions whereby one reactant is

present in a large excess over the other are commonly referred to as pseudo first-order

conditions

Therefore Equation 147 may be written as

=

where kobs is the observed rate constant with units s-1

(155)

40

A plot of ln [A] versus time will result in a straight line with a slope equal to kobs Monitoring

the reactions for several concentrations of B whilst simultaneously ensuring that B is in a

large excess over A generates a series of kobs for different [B] With reference to Equation

(155) a plot of kobs vs [B]0 will be linear with a slope of k2 having units of M-1 s-1

1116 Reversible second-order reactions

Reactions may not go to completion at times Instead equilibrium between the reactants may

be reached These types of reactions may be represented as follows

(156)

This assumes that the reverse reaction is first-order whilst the forward reaction is second-

order Due to this the reaction in general exhibits a mixed-order behavior To eliminate the

complexity of the problem pseudo first-order conditions are often selected for the forward

reaction ie [B]0 gtgt [A]0 This result is in the equation now being treated as if it were a

reversible first-order reaction

The rate of formation of C can be written as

(157)

(where [A] and [B] and and express the concentration of the species A and B at

time t = 0 and t = t respectively)

for the given stoichiometry of 111 applying t mass balance at any time t gives

(158)

and

(159)

41

At equilibrium

(160)

The rates of the two opposing reactions at equilibrium are equal ie

0 (161)

This implies that

(162)

However [C]t = [A]0 ndash [A]t and [C]eq = [A]0 ndash [A]eq and equation (157) may now be written

as

(163)

Resulting in

(164)

Substituting [C]t = [A]0 ndash [A]t and Equation (164) into (157) results in

(165)

Since [B]0 gtgt [A]0 Equation (165) can be expressed as

(166)

Separation of variables and integration gives

(167)

Which results in

42

ln

(168)

For a second-order reversible reaction a plot of kobs versus [B]0 will be linear with a slope

equal to kf and an intercept equal to kb The equilibrium constant K can be obtained from the

ratio of kfkb and may also be determined thermodynamically

1117 Consecutive first-order reactions

Frequently a product of one reaction becomes a reactant in a subsequent reaction This is true

in multi-step reaction mechanisms A simple case involving two consecutive irreversible

first-order reactions is represented by equation (169)

rarr rarr

(169)

The rates of change of at time t [A] [B] and [C] are as follows

(170)

(171)

(172)

Since B is formed by the first reaction and is destroyed by the second reaction the expression

for has two terms

Let only A be present in the system at t = 0

[A] [A]0 [B]0 = 0 [C]0 = 0 (173)

and at any time t

43

(174)

subsequent integration of Equation (170) yields

(175)

Equation 175 is substituted into Equation (171) thus

(176)

Equation 176 can be integrated using the integrating factor method

Noting that at time t = 0 [B]0 = 0 application of product rule and subsequent integration of

(176) yields

(177)

Using conservation of matter enables one to determine [C] The total number of moles

present is constant with time so [A] + [B] + [C] = [A]0 Substituting Equations (175) and

(177) into Equation (174) yields

1

(178)

112 Kinetic salt effect

In aqueous solutions ionic strength plays an important role in the rates of the reaction The

effect of primary salt can be studied by varying the ionic strength of the reaction by

employing an inert electrolyte solution The kinetic salt effect gives an insight into the

charges and nature of the reacting species involved in the rate-limiting step

44

The Bronsted equation predicts the influence of the concentration of ions and their charges on

the rate constant k when the reaction occurs between two charged species A and B The rate

constant k of a bimolecular reaction is defined by the following equation

k = koγAγB γǂ (179)

where ko is the limiting value of the rate constant for zero value of all ion concentrations in

the mixture γA γB and γǂ the activity coefficients of A B and the activated complex

respectively7 The Debye-Huckel theory states that ldquoelectrolytes in solution as fully

dissociated assuming that each ion is surrounded by an ionic atmosphere of opposite charges

The behavior of this atmosphere is assumed to retard the motion of ions moving through itrdquo

Combining the Bronsted equation and Debye-Huckel limiting law a relationship between

the rate constant and ionic strength can be established158

log k = log ko ndash AZA2ZB

2 ndash (ZA+ZB)2I12 (180)

log k = log ko + 2AZAZB I12

(181)

where ZA and ZB are the valences and I is the ionic strength

If the Bronsted equation holds good in dilute solutions a plot of log k versus I12 should be

linear with slope equal to 102 ZAZB and intercept equal to log ko8 In aqueous solutions the

gradient indicates the product of charges on the species involved in rate-limiting step If both

the reactive species are like charges a positive slope is expected and a negative slope is

expected if they are oppositely charged

45

113 Kinetic simulations

Kinetic simulations are a good tool to provide insight into complex chemical reactions They

give information which is often inaccessible experimentally such as details of unstable

species (transition rates and reaction intermediates)159 Kinetic simulations are the initiation

of experimental behavior with respect to time and they also involve determination and

investigation of various species with respect to time

1131 Simulations

Simulation is the imitation of real world processes over time Simulation involves the

generation of a system with the properties that draw inferences concerning the operation

characteristics of the real system The simulation model is developed to study the behavior of

the system over time based on a set of assumptions that are expressed mathematically

logically and symbolically160 The simulation model can be used to investigate the

performance of a system by simulating the potential changes to it It can be used as an

analytic tool for predicting the effect of changes to the existing system It can also be used to

as a design tool to predict the performance of new systems under varying sets of

circumstances161

In some instances a model can be developed which is simple enough to be solved by

mathematical methods Such a solution may be reached by the use of differential calculus

probability theory algebraic methods or other mathematical techniques The solution usually

consists of one or more numerical measures of performance of the system Many real world

systems are so complex that their models are virtually impossible to solve mathematically162

In these instances numerical computer-based simulation can be used to imitate the behavior

46

of the system over time Simulation data is collected as if a real system is observed The

simulated data is used to estimate the measures of performance of the system

1132 Importance of simulation as a tool

Simulation enables the study of complex reaction mechanisms and experimentation with the

internal action of a complex system or of a subsystem within a complex one Informational

organizational and environmental changes can be simulated and the effect of these alterations

on the behavior of the model can be observed The knowledge gained in designing a

simulation model may be of great value towards suggesting improvement in the system under

investigation By changing simulation inputs and observing the resulting outputs valuable

insight may be obtained into which variables are most important and how they interact

Simulation can be used to experiment with new designs or policies prior to implementation so

as to prepare for what may happen Simulation can be used to verify analytic solutions It can

help in understanding how the system operates rather than how individuals think the system

operates Time can be compressed or expanded to allow for a speeded-up or slow-down of

the phenomena under investigation163164 Simulation can provide hypothesis about how or

why certain phenomena occur and these can be tested for feasibility Simulation and

modeling have been used in the motor industry controlling of traffic during peak hours in

the army in the designing and testing of new weapons and biological processes and in the

building industry to mention a few

1133 Requirements for kinetics simulation

The requirements for kinetic simulation are proposed mechanisms for a reaction rate

constants for each reaction step involved in a proposed mechanism and initial concentrations

of the starting species There are different kinds of software available for kinetics simulation

47

The most frequently used is the FitAll software developed by MTR Software165 Easy-Fit

developed by Schittkowski166 the Kaps and Rentrop program167 and Simkine 2 software168

To simulate the kinetic profile of reactants a proposed mechanism is essential To propose

the mechanism the reaction kinetics and other aspects needs to be studied experimentally In

any mechanism there is a slowest step and a reaction cannot progress slower than its slowest

reaction step The slowest reaction step is thus the rate-determining step Practical

experiments involve determination of an average rate of reaction of a large number of

molecules for the rate-determining step169

114 Kinetic measurements-fast reactions

Kinetic studies are accomplished by studying the time dependence of some variable that is

proportional to the concentration of reactant or product Subsequent fitting of the

concentration-time data to an appropriate model allows for the determination of the rate

constant

Flow methods are the best way of following fast reactions in which the reagents cannot be

prematurely mixed All fast flow methods are based on the pioneering work of Hartridge and

Roughton170171 Flow methods involve the fast together of separate solutions of the reactants

The rapid mixing of reactants is usually coupled to a rapid-response method for monitoring

the progress of the reaction flowing With such methods one can determine the rate constants

in the order of 5 x 102 s-1 (ie t12 gt 1 ms) The advantage of these methods over conventional

techniques is the ability of mixing the reactants rapidly

48

The continuous flow method operates on the principle whereby solutions of two reactants are

forced by pistons into a mixing chamber whose design contributes to rapid mixing The

mixed solutions then flows into an observation tube where detection by spectroscopy takes

place at a specific distance downstream from the mixer A schematic representation of the

continuous flow method is given in Figure 118

Figure 118 Schematic diagram of a continuous flow kinetic system (where d is the

distance from the mixer to the point of observation)

The stopped flow technique operates on the same principles as the continuous flow method

and is very popular in studying reactions having a half-life range of 100-103 s The apparatus

whose schematic diagram is illustrated in Figure 2111 consists of the four drive syringes

which are reagent filled through separate valves from the reagent reservoir syringes

containing the individual reactants The drive syringes are usually maintained at a specific

temperature by immersion in a water bath with a thermostated jacket Once filled the

solutions are allowed to equilibrate at the specified temperature The drive mechanism which

is usually piston driven either mechanically or by a compressed gas drives the reactant

solutions into a mixing chamber in such a manner that the solutions impinge on one another

and give very rapid mixing within 0001 s The mixed solution then flows into a reaction

cuvette or alternately the two solutions may be combined in the reaction chamber which in

49

turn triggers the recording device which might be an oscilloscope a transient scope or a

digital sensitizer The solution is now stationary and this marks the beginning of the

collection of kinetic data163

The usual method of detection is UV-Visible spectrophotometry and once the recording

device is triggered the amount of light at a predetermined wavelength setting of the

monochromator is transmitted through the mixed solution in the cuvette will change as the

reaction proceeds in the static mixed solution A photomultiplier then converts this

transmitted light into the electric current and a signal is fed through to a computer acquisition

system over an appropriate time interval The kinetic data is then processed and the rate

constant evaluated172173174

1141 Analysis of kinetic data

KinetAsystTM software package (Hi-Tech Ltd) was used for data collection Figure 119

represents the analysis of the data accomplished using the KinetAsystTM Fit Asystant

software for a typical kinetic curve obtained from the stopped-flow instrument Data were fit

with models including a single or sum of exponential phases as appropriate In each case the

residuals indicate the best fit assigned as the simplest one giving the smallest deviation in a

least-squares fit analysis and random residuals over the whole time course175 The upper

region indicates the fit between the fitted and experimental curves obtained whilst the lower

portion indicates the residuals (deviation between the two curves)

50

Figure 119 KinetAsystTM single-exponential equation fit (green) and the experimental curve (red) with residuals (lower curve) and the rate parameters for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M)

115 Scope and objectives of the study

Although the literature survey shows that considerable attention has been paid to understand

the chemistry of dyes not much is known about their reactions with various materials and

chemical reagents and their reaction mechanisms with bleaching agents which are

commonly used in industry and in water treatment processes The literature review indicates

that little information is available about the kinetics of degradation of the dyes and the

mechanisms of their oxidation by hypochlorite and chlorine dioxide The role of acid in such

reactions and possible intermediates are still not completely understood

The objective of the current study is to investigate the oxidation reaction mechanisms of

selected three water soluble dyes from three different classes amaranth (Azo dye) brilliant

blue-R (Triarylmethane dye) safranine-O (Azine dye) by hypochlorite and chlorine dioxide

51

which are the most widely used oxidants in the water treatment under varied reaction

conditions The study focuses on the reaction rates with emphasis on their decolorisation

kinetics Different factors influencing the reactive rates will be examined and the elucidated

mechanisms and proposed rate laws for the chosen dyes will be described

52

CHAPTER 2

21 Experimental

All the solutions were prepared with double distilled water using lsquoArsquo grade glassware All the

reagents were of analytical grade or of high purity All acid and base stock solutions were

standardized by the prescribed methods

Absorbance measurements

Absorbance readings were recorded using a Cary II-Varian double beam spectrophotometer

The instrument is equipped with a thermostated cuvette holder and data capturing facilities

interfaced with a computer Quartz cuvettes were used for absorbance measurements so as to

extend measurements into the ultraviolet region of the electromagnetic spectrum

211 Three dyes-amaranth brilliant blue-R safranine-O

Amaranth (Sigma-Aldrich USA 95 purity) was used with no further purification Since the

dye was sparingly soluble in water a stock solution of 1 x 10-2 M was prepared by dissolving

0604 g of amaranth dye in distilled water and making up to the mark in a 1 L standard

volumetric flask The stock solution was further diluted requisite to the need of experiments

The structure of azo dye amaranth is presented in Figure 211

N N SO3-

O-

-O3S

-O3S

Figure 211 Structure of amaranth

53

A typical spectrum obtained in the visible range and using UV-Visible Cary 100 double beam

spectrophotometer with data interval of 1 nm and average time interval of 01 s showed

maxima absorbance at 520 nm (Figure 212)

Figure 212 UV-Visible spectrum of amaranth [AM-]0 (1 x 10-6 M)

From five replicate measurements the absorption coefficient at the absorption maxima for this

dye was estimated to be (198 plusmn 002) x 104 dm3 molminus1 cmminus1 (Figure 212) No peak shift was

registered due to changes in pH

Brilliant blue-R (Aldrich USA 95 purity) was used with no further purification Since the


0802 g of brilliant blue - R in water and making up to the mark in a 1 L standard volumetric

flask The stock solution was further diluted requisite to the need of experiments The

structure of the dye is shown in Figure 213

‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

54

NSO3

-

NN

O

SO3-

H

Figure 213 Structure of brilliant blue-R

A typical spectrum obtained in the visible range obtained using UV-Visible Cary 100 Double

beam Spectrophotometer with data interval of 1 nm average time interval 01 s showed

maxima absorbance at 555 nm

Figure 214 UV- Visible spectrum of brilliant blue-R [BB+]0 (1 x 10-6 M)




0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorabnce

Wavelength (nm)

55

Safranine-O (Aldrich USA 95 purity) was used with no further purification since the dye

was sparingly soluble in water a stock solution of 1 x 10-2 M was prepared by weighing out

0315 gL of the dye in distilled water into a standard volumetric flask The stock solution

was further diluted requisite to the need of experiments176 Figure 215 represents the

structure of the dye

N

N CH3

NH2H2N

H3C

Figure 215 Structure of safranine-O




Figure 216 UV- Visible spectrum of safranine-O [SO]0 (1 x 10-6 M)

‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

56




212 Hypochlorite solution

Sodium hypochlorite solutions were prepared by electrolysis of sodium chloride solutions

The instrument used to generate these solutions was the Baird amp Tatlock electrolytic analysis

apparatus (Figure 217)

2141 Preparation method

The instrument comprises a single compact unit containing its own low voltage DC (direct

current) supply unit capable of giving an output of 0 to 10 amperes (A) at up to 12 V The

electrodes consists of ldquounimeshrdquo inner and outer platinum electrodes The inner platinum

electrode has a cylinder height and diameter of 32 mm with its overall height measuring 145

mm The outer platinum electrode has a cylinder height and diameter of 45 mm with an

overall height of 130 mm The polarity of the central electrode can be changed to positive or

negative by means of a ldquopolarity changerdquo switch (Figure 217)

57

Figure 217 Baird amp Tatlock hypochlorite generator

100 mL of a 5 (wv) NaCl solution was refrigerated for an hour prior to electrolysis to

avoid sodium hypochlorite decomposition caused by a temperature increase during the

electrolytic process The chilled NaCl solution was then electrolyzed at 2 amperes (A) for a

period of 45 minutes The operating conditions for the generation of OCl- are discussed at the

end of this chapter A number of researchers have used the Baird amp Tatlock apparatus for the

generation of sodium hypochlorite solutions The generated hypochlorite solutions were

stored in brown bottles left away from light to minimize decomposition caused by light and

air

The reactions involved in the electrolysis of NaCl are

Anode 2Cl- (aq) Cl2 (g) + 2e- (21)

Cathode 2 H2O (l) + 2e- H2(g) + 2OH- (aq) (22)

Overall 2H2O (l) + 2Cl- (aq) H2(g) + Cl2(g) + 2OH-(aq) (23)

58

The Cl2 (g) thereafter reacts with the H2O (l) to form hypochlorite

Cl2(g) + H2O(l) 2 H+(aq) + OCl-(aq) + Cl-(aq) (24)

In order to minimize Cl2 (g) escaping into the atmosphere the vessel containing the sodium

chloride solution is sealed with parafilm during the electrolytic procedure The hypochlorite

ion generation conditions were optimized by establishing suitable reaction conditions such as

(wv) of NaCl duration of electrolysis and temperature

After electrolysis the solution was neutralized with 10 M sulfuric acid to prevent the further

disproportionation of hypochlorite to the corresponding chlorate ions The solution was then

standardized by the arsenite method In the arsenite method the sample is titrated against

standard sodium arsenite solution An external indicator potassium iodide-starch paper is

employed The neutralization with acid also facilitates the effective oxidation of arsenite

since optimum conditions for its oxidation lie between pH 40 and 90 the best value being

65177 Since NaOCl is degraded by light and air normally solutions were kept in diffused

light in air tight flasks and fresh stock solutions were prepared whenever required

2142 Calculation of molarity of the hypochlorite-arsenite method

Two methods for OCl- ion determination commonly employed in the laboratories are the

arsenite and iodometric methods Of the two methods the arsenite method is preferred

because it is more accurate The reagents involved in the iodometric method include KIO3

KI and starch which have to be freshly prepared and standardized Solid As2O3 on the other

hand is stable and readily available in a high degree of purity

59

Preparation of As2O3 solution

Arsenic trioxide (As2O3) is a colorless crystalline solid formed when arsenic or a sulfide of

arsenic burns in air Arsenic trioxide sublimes on heating Up to 800 C the molecules are

As4O6 but by 1800 C dissociation to As2O3 is complete Sublimation gives a very pure

product which is used as a primary standard in volumetric analysis 0025 M As2O3 solution

was prepared by dissolving 2473 g finely powdered arsenious oxide in a 10 (wv) sodium

hydroxide (NaOH) solution178 The solution was then diluted to 200 mL and neutralized with

1 M HCl using litmus paper as indicator The neutralized solution was then quantitatively

transferred to a 500 mL volumetric flask 20 g of pure NaHCO3 was added and when all the

salt was dissolved the solution as made up to the mark

A volume of the generated OCl- solution was titrated with 0025 M As2O3 solution and the

end point was determined using KI-starch paper which serves as an external indicator As

long as OCl- is present the sample solution turns the KI-starch paper blue At the end point

the sample solution no longer produces a blue stain on the starch paper

2 OCl- + As2O3 As2O5 + 2 Cl- (25)

Thus 2 x (Volume of As2O3) x (0025 M) = (Molarity OCl-) x (Volume of OCl-)

(Molarity of OCl-) = 2 x (0025) x (Volume of As2O3) (Volume of OCl-)

213 Chlorine dioxide

2151 Chlorine dioxide preparation

A pure solution of chlorine dioxide is prepared by slowly adding dilute sulfuric acid to a

sodium chlorite solution removing any contaminants such as chlorine by means of a sodium

chlorite scrubber and passing the gas into distilled water by means of a steady stream of air

60

Figure 218 Chlorine dioxide generation and absorption system179

The experimental setup to generate the chlorine dioxide is described below An aspirator

flask A of 500 mL capacity as illustrated in Figure 218 was attached by means of rubber

tubing to a source of compressed air The air was bubbled through a layer of 300 mL of

distilled water and then passed over and down through a glass tube to within 5 mm of the

bottom of the 1-1 gas-generating bottle B The evolved gas passed via glass tubing through a

scrubber into bottle C containing saturated sodium chlorite solution or a tower packed with

flaked sodium chlorite and finally via glass tubing into a 2-1 Pyrex collecting bottle D

where the gas is absorbed in 1500 mL distilled water An air outlet tube on bottle D provided

for escape of the moving air A bottle was selected for gas generation which was constructed

of strong Pyrex glass and having a mouth wide enough to permit the insertion of three

separate glass tubes the first leading almost to the bottom for admitting air the second

reaching below the liquid surface for the gradual introduction of the H2SO4 and the third near

the top for exit of the evolved gas and air A graduated cylinder E containing H2SO4 was

fitted to the second tube

100 g sodium chlorite NaClO2 was dissolved in 740 mL distilled water and a smooth current

of air through the system as evidenced by the bubbling rate in all bottles A 5 mL increments

61

of sulfuric acid from cylinder E into bottle B at 5 min interval was introduced The generated

chlorine dioxide which was absorbed was kept in a refrigerator

2152 Calculation of molarity of the chlorine dioxide - iodometric method

Chlorine dioxide releases free iodine from a potassium iodide solution acidified with acetic or

sulfuric acid Chlorine dioxide solution was allowed prior to the titration to react in the dark

with the acid and the potassium iodide for 5 minutes The liberated iodine is titrated with a

standard solution of sodium thiosulfate with starch as the indicator The required volume of

stock chlorine dioxide solution was diluted to the desired strength with chlorine-demand-free

water prepared The stock solution is standardized by titrating with standard 0010 M or

0025 M sodium thiosulfate solution in the presence of KI acid and starch indicator

Chlorine dioxide concentrations were expressed in terms of chlorine dioxide alone or

available chlorine content The available chlorine is defined as the total oxidising power of

the chlorine dioxide measured by titrating the iodine released by the chlorine dioxide from an

acidic solution of KI The following expressions were used for standardizing chlorine

dioxide stock solution

mgmL ClO

A B N 1349

mL sample titrated

(26)

mgmL Cl

A B N 3545

mL sample titrated

(27)

For determining chlorine dioxide in temporary standards

mgL ClO

A B N 13490

mL sample

(28)

62

mgL Cl

A B N 35450

mL sample

(29)

Where A represents the sample volume in mL B is the volume of the blank in mL obtained

from titration for blank (positive or negative) and N is normality of Na2S2O3

214 General reagents

1000 M stock solutions of sulfuric acid sodium hydroxide and sodium chloride were

prepared by dissolving AR grade (Merck) in triple distilled water as per standard methods of

preparations The solutions were further diluted to suitable concentration The strength of

these solutions was determined by standard procedures

215 Kinetic measurements

All the kinetic measurements for the consumption of the organic dyes were conducted with

low concentration of dye and excess concentrations of all the other reagents The kinetic

measurements for all the reactions were conducted under pseudo first-order conditions and

the reactions were completed in few milliseconds at certain given conditions Therefore they

were monitored using the stopped-flow spectrophotometer which is designed to follow the

fast signal changes with a rapid mixing system

All kinetic measurements for amaranth-hypochlorite brilliant blue-R-hypochlorite or

safranine-O-hypochlorite reactions as well as amaranth-chlorine dioxide brilliant blue-R-

chlorine dioxide and safranine-O-chlorine dioxide reactions were conducted using the HI-

TECH (SF-61DX2) stopped-flow apparatus The high performance stopped-flow

spectrometer has a double mixing facility Flow circuit diagram Figure 219 Bench Setup

(Figure 2110) Sample handling unit (Figure 2111) and optical setup (Figure 2112) are

63

shown respectively To prepare the reagent mixtures for the reactions the requisite volumes

of reagents were added to bring the final volume to 10 mL The experiments were performed

by using conventional single mixing Only drive 2 (Figure 219) was used so that reagents C

and D are delivered to mixer 2 and the A and B reagent pathway was filled with water and

not used The rapid mixing initiated the study reaction The flow displaced aged solutions

(from previous runs) as the reaction mixture was driven into the observation cell A stop

syringe used to set the driven volume stops the flow The stop syringe plunger travel was set

by a rigid stop block causing rapid cessation of flow of the solution and thus triggering the

data acquisition system It should be noted at this point that the concentrations of the reagents

in the mixing chamber are half that of the reagent in the syringe

64

Figure 219 Hi-Tech Stopped flow apparatus - Flow circuit diagram180

65


66

Figure 2111 Hi-Tech Stopped flow apparatus-Sample Handling Unit 174

67

Figure 2112 Hi-Tech Stopped flow apparatus-Optical setup181

68

The rapid scanning single mixing mode technique was used to acquire multi-wavelength data

for reactions in the current study

216 Simulations and software used

In the current study ldquoSimkine2rdquo software was used due to its advantages of being efficient

less time consuming and it can handle most of the errors its flexibility and the fact that it

provides more options Simkine2 was an improved version of the original software developed

called Simkine182 Simkine2 software was rewritten using Delphi professional 5 that met the

needs of the various operating systems The advantage of using Delphi was that the software

could be operated at a good speed

The available softwares only plots the generated data and experimental data separately and

gives a plot for comparison at a later stage Simkine2 has the ability to plot the generated data

as it gets is generated The Simkine2 gives the user an option to plot the generated and

experimental data simultaneously and separately183 While doing simulations it is useful to

see how close the experimental and generated data agrees184 and also in order to see how the

generated and experimental data matches both plots need to be in the same set of axis

217 Product analysis

The characterisation of the reaction products is esesential postulating probable reaction

mechanism To obtain sufficient quantities of the reaction products reactants were taken in

large quantities but approximately in relative proportions to that used in the kinetic

experiments Then an attempt is made to isolate and characterize the products of each

reaction The products were characterized using 1H NMR and 13C NMR with Bruker

Avance III 400 MHz and 600 MHz NMR instruments with Probe BBO-2 gradient and the

69

lsquoTop spin 21rsquo software was used to analyse the spectras Thermo Finnigan Trace GC coupled

to a Polaris Q- MS was used for GC-MS analysis with column size 30 m x 02 mm internal

diameter with 025 μm 5 phenyl(equivalent) 95 methyl polysilphenylene siloxane

stationary phase film with mobile phase helium gas

Hypochlorite initiated reactions

The products of the reaction are analysed to propose the plausible reaction mechanism and

the rate law To commence the reaction 060 g of amaranth 080 g of brilliant blue 040 g of

safranine-O was dissolved in 100 mL of water and 400 mL of 0010 M hypochlorite was

added The mixture was allowed to stand for 24 hours with constant stirring at room

temperature The reaction mixture was extracted with dichloromethane using batch separation

technique The extracted filtrate was evaporated using rotavapor The filtrate was allowed to

evaporate and dissolved in ethyl acetate The separation of compounds was carried out using

column chromatography and thin layer chromatography (TLC) techniques using the

procedure outlined below

Chlorine dioxide initiated reactions

To initiate the reaction 060 g of amaranth 080 g of brilliant blue 040 g of safranine-O were

dissolved in 100 mL of water to which 400 mL of 0012 M chlorine dioxide was added The

mixture was allowed to stand for 24 h with constant stirring at room temperature The

reaction mixture was extracted and evaporated in the same manner as mentioned above The

filtrate was allowed to evaporate and dissolved in ethyl acetate A silica gel column was used

for the separation of the compounds The products were characterised using 1H NMR and 13C

spectroscopy on Varian 400 MHz NMR and the GC-MS spectrometer

70

Column and thin layer chromatography

The separation isolation and purification of compounds were carried out by gravity column

chromatography and monitored by thin layer chromatography (TLC) For column

chromatography all crude extracts were dry packed onto a 45 cm crude column and fractions

of 10 mL were collected Merck silica gel 60 (0040-0063 mm) was used for column

chromatography and Merck 20 times 20 cm silica gel 60 F254 aluminum sheets were used for

thin-layer chromatography The TLC plates were analysed under UV (254 nm and 366 nm)

before being sprayed with reagent (spray reagent is developed with a [1297] anisaldehyde

concentrated sulfuric acid methanol) and the plates are subjected to heat Varying ratios of

hexane dichloromethane and ethyl acetate were used for both column chromatography and

thin layer chromatography

218 Precision calculations

It is seldom easy to estimate the precision and accuracy of experimental data Attempts must

be made however to satisfy such estimates because data of unknown precision and accuracy

are worthless A tenfold increase in accuracy may take hours days or even weeks of added

labor Time to generate such accurate results is generally not available thus most chemists

usually carry out two to five replicates of an entire analytical procedure

Most of the experiments in this project were performed in triplicate and the data generated

were subjected to precision calculations Precision may be defined as the concordance of a

series of measurements of the same quantity Generally the precision of a measurement is

determined by simply repeating the measurement Three terms are used to describe the

precision of a set of replicate data standard deviation (s) variance (s2) relative standard

deviation (RSD) and coefficient of variation (CV)

71

219 Standard deviation (s)

In analytical chemistry one of the most common statistical terms employed is the standard

deviation of a population of observations

If we consider a series of n observations arranged in ascending order of magnitude

x1 x2 x3 xn-1 xn

The arithmetic mean is given by

ā = x1 + x2 + x3 + + xn-1 + xn

n (210)

The spread of the values is measured most efficiently by the standard deviation defined by

s = (x1 ndash ā)2 + (x2 ndash ā)2 + hellip (xn ndash ā)2 12

n ndash 1 (211)

In this equation the denominator is (n ndash 1) rather than n when the number of values is small

The equation 211 may also be written as

s = ( x ndash ā)2 12

n ndash 1

The equation for computing a pooled standard deviation from several sets of data takes the

form

12

N1 N2 N3

sp = (xi ndash ā1)2 + (xj ndash ā2)

2 + (xk ndash ā3)2 + hellip

i=1 j=1 k=1

N1 + N2 + N3 + - Ns

(212)

where sp represents pooled standard deviation N1 is the number of data in set1 N2 is the

number in set 2 and so forth The term Ns is the number of data sets that are pooled

72

2110 Variance (s2)

The variance is the square of the standard deviation The standard deviation has the same

units as the data whereas the variance has the units of the data squared Scientists tend to use

standard deviation rather than variance as a measure of precision It is easier to relate the

precision of a measurement to the measurement itself if they both have the same units The

advantage of using variance is that variances are additive

Standard deviations are frequently quoted in relative rather than absolute terms The relative

standard deviation multiplied by 100 is called the coefficient of variation (CV)

CV = (s ā) x 100

Relative standard deviations often give a clearer picture of data quality than do absolute

standard deviations The relative standard deviation (s) and coefficient of variation (CV) will

serve as measures of precision for all data obtained in this project

Kinetic data acquisition is done by KinetAsystTM 2 which allows single wave length-single

shot or single wave length- multishot to give the most meaningful data A series of shots were

conducted automatically for each experiment in three replicates The observed coefficient of

variation is always less than 4 unless otherwise specified

73

CHAPTER 3


The sodium hypochlorite is a strong oxidising agent Its bleaching reaction typically is one of

oxidative cleavage of a double bond breaking the delocalization and hence the moleculersquos

ability to absorb light in the visible region resulting in a colorless solution The kinetics of

oxidation of amaranth brilliant blue-R and safranine-O dyes with hypochlorite in an aqueous

solution was investigated as a function of pH Speciation profiles of the oxidant were utilized

to estimate the rate constants of the dyes over a wide pH range The kinetic investigations

were complemented by product analysis energy parameters and simulations to propose

plausible reaction mechanisms for the reactions

31 Reaction between amaranth and hypochlorite

311 Order with respect to amaranth

The kinetics and mechanism of oxidation of amaranth (AM-) an anionic azo dye by

hypochlorite was studied under diverse reaction conditions All the experimental runs were

conducted with low concentrations of dye and excess concentrations of the other reagents

Unless otherwise stated all the experiments were carried out at (25 plusmn 01) degC The rate of

depletion of AM- was monitored at 520 nm corresponding to the absorption maximum of the

dye At 520 nm no interferences from the products or intermediates were observed The

reaction was monitored using the Hi-Tech SF-61 DX2 double mixing micro volume stopped-

flow equipment Figure 311 shows the typical depletion curve of amaranth as a function of

time A perusal of the curve shows that depletion of the dye is completed in less than 100 s

74

Figure 311 Typical kinetic curve absorbance versus time plot for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t

(15 x 10-3 M) at pH = 90 and 520 nm

The kinetic data acquired at single wavelength was analysed using the KinetAsystTM software

which allows the matching of experimental results with different rate equations and to

estimate the rate constants by choosing appropriate integrated rate equations

312 Analysis of kinetic data using KinetAsystTM Fit software

The analysis of the data was accomplished using the KinetAsystTM Fit Asystant software The

data traces were selected to analyse with the KinetAsystTM Fit Asystant for the first-order

reaction using the rate equation 1 Exp + C y = -A exp (-k x) + C and the matching

simulated curve was generated Figure 312 represents the illustration of the typical

experimental curve with the fitted simulated curve The upper curve shows the fit between

the theoretical and experimental curves whilst the lower plot indicates the residuals

illustrating the agreement or variation between the two curves

‐01

0

01

02

03

04

05

06

07

08

0 20 40 60 80 100 120 140

Absorban

ce

Times

75

Figure 312 KinetAsystTM single-exponential equation fit (green) and the experimental curve (red) with residuals shown in the (lower curve) and the rate parameters in the adjacent box for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t

(15 x 10-3 M)

An observation of Figure 312 shows that using a first-order rate equation 1 Exp + C y = -

A exp (-k x) + C a fair agreement occurred between the experimental and computed

curves with small residuals The software fit analysis results for the curve displayed in the

box show that the rate constant is (320 plusmn 002 x 10-3) s-1 showing small standard deviation

The curve and data also suggest that for the chosen conditions the reaction follows pseudo

first-order kinetics and reaction order with respect to AM- is unity

313 Order with respect to hypochlorite

To establish the reaction order with respect to oxidant a series of experiments were

conducted with different initial concentrations of hypochlorite at pH 90 and fixed ionic

strength using sodium sulfate as a neutral salt Typical curves showing depletion of AM- as

function of time monitored at different initial concentrations of hypochlorite are shown in

Figure 313 In presence of varying initial excess concentrations of hypochlorite the

absorbance of dye decreased exponentially

76

Figure 313 Depletion of amaranth with various hypochlorite concentrations for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t x 10-3M (a = 0085 b = 170 c = 255 d = 340 and e = 510) at pH = 90

The typical plots of absorbance versus time showing the effect of variation of hypochlorite

concentration are shown in Figure 313 while the traces obtained using KinetAsystTM

software and the respective obtained pseudo first-order rate coefficients k(s-1) values are


‐01

0

01

02

03

04

05

06

0 20 40 60 80 100 120

Absorban

ce

Time s

a

b

c

de

77

(a) (b)

(c) (d)

(e)

Figure 314 Fits using KinetAsystTM single-exponential equation and rate equation 1 Exp + C y = -A exp (-k x) + C (where ks-1 a = 0041 b = 0093 c = 0145 d = 0175 and e = 0322)

78

The k values obtained by analyzing the respective experimental kinetic curves for different

initial hypochlorite concentrations are also shown in Table 311 at constant ionic strength

and pH equals to 90

Table 311 Reaction between amaranth and hypochlorite at constant ionic strength [AM-]0 (70 x 10-5 M) [OCl-]t (085 x 10-4 ndash 51 x 10-3 M) pH = 90 and ionic strength (I = 0128 M)

[OCl-]t 10-3 M ks-1

050 0041

170 0093

255 0145

340 0175

510 0322

Mean of four replicate experiments with relative standard deviation lt 4

Figure 315 Plot of ln [OCl-]t versus ln k for the reaction of [AM-]0 (70 x 10-5 M) with [OClˉ]t (085 x 10-4 ndash 51 x 10-3 M) at pH = 900 and I = 0128 M

y = 11072x + 46582Rsup2 = 09928

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4

lnk`

ln [OCl‐]t

79

From Figure 315 the plot of ln k versus ln [OCl-]t which is a straight line with slope equals

to 11 (R2 = 099) suggesting that order with respect to hypochlorite at pH 90 is one

314 Effect of pH on the reaction rate

One important parameter that normally influences the reaction dynamics is pH To assess the

role of acid in the oxidation process the kinetics of the reaction as a function of pH was

investigated The effect of added acid on reaction was probed by the initial addition of varied

amounts of sulfuric acid solution maintaining the total ionic strength constant and the initial

pH values were simultaneously recorded The kinetic data obtained for different experiments

was analysed for k values using lsquoKinetAsystTM Fit Asystantrsquo The initial pH and k values

obtained after analysis for different runs are summarized in Table 312 Figure 316

illustrates the plot of the obtained k versus pH values A perusal of Figure 316 shows that

the increase in k values was small at low acid concentrations and the rise was bigger at

higher acid concentrations indicating the profound effect of pH on the reaction

Figure 316 Plot of k versus pH for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]eq (199x10-9- 7752 x 10-4 M)

0

01

02

03

04

05

06

07

08

09

1

3 4 5 6 7 8 9 10

k

pH

80

Table 312 Effect of pH on reaction rate for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M)

pH ks-1

989 0005

972 0011

945 0015

912 0021

881 0028

863 0039

815 0110

784 0199

755 0320

739 0398

693 0599

685 0638

650 0745

485 0847

420 0854

365 0865

344 0875

317 0878

315 0897


Further to establish the order with respect to acid the ln k versus ln [H+] values were plotted

(Figure 317) which gave a slope of 027 (R2 = 096) The observed partial reaction order

with respect to acid clearly suggests that the reaction mechanism is intricate and acid is

directly involved in the rate-limiting step

81

Figure 317 Plot of ln k versus ln [H+] for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M)

The observed partial order with respect to H+ can be viewed in terms of its role in speciation

of hypochlorite by protonation to hypochlorous acid and the existing equilibrium between

the two species ie OCl- + H+ HOCl With pKa = 74 for protonation of OCl- the addition

of acid will shift the equilibrium to the right Thus the oxidation of dye possibly occurs

simultaneously through its reaction with OCl- and HOCl species185

The observed increase in k values with increasing acid concentration suggests that the rate of

oxidation by HOCl is faster than with OCl- It can also be predictable based on the

oxidation potentials of the two species Of the chlorine-containing disinfecting agents

hypochlorous acid has the higher oxidation potential (Eo =144 V) compared to 139 V for

Cl2 and 112 V for OCl- ion The kinetic data obtained for acid variation studies was

scrutinized again for the likelihood of the occurrence of two competitive reactions Based on

that assumption the kinetic curves were analysed using fit for the two competitive first-order

y = 02711x + 37842Rsup2 = 09618

‐12

‐1

‐08

‐06

‐04

‐02

0

‐20 ‐15 ‐10 ‐5 0

ln k

acute

ln [H+]

82

reactions ie by using the equation y = -A exp (-R1 x) + -A exp (-R2 x) + C The

simulated curve fitted quite well with negligible residuals Typical curves are illustrated of

the Figures 318 and 319 and the obtained k1 and k2 values were summarised in Table

313

Figure 318 KinetAsystTM single-exponential equation fit of two curves and residuals (lower sketch) using the first-order equation for the reaction of [AM-]0 (70 x 10-5 M) with [OClˉ]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (012 M)

Figure 318 illustrates the typical KinetAsystTM fit of the two curves and the residual (lower

part of Figure 318) for the reaction of OCl- with amaranth using the first-order rate equation

Eqn y = -A exp (-k x) + C displaying the residuals where as Figure 319 illustrates the

same curve with fit obtained employing Eqn y = -A exp (-R1 x) + -A exp (-R2 x) + C

83

The residual (lower part) for the reaction of OCl- with later fit were much smaller suggesting

later is a better fit

Figure 319 KinetAsystTM double-exponential equation fit of two curves and residuals (lower sketch) for the two competitive first-order reactions for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (012 M)

The absorbance versus time data for different acidic conditions were analysed on the basis of

the occurrence of two simultaneous reactions and the corresponding pseudo first-order rate

constants obtained are summarized in Table 313 together with the estimated initial

concentrations of H+ OCl- and HOCl in equilibrium corresponding to different pH values

While k1 represents the pseudo first-order rate constant for the OCl- initiated oxidation k2

represents the corresponding value for the reaction by HOCl Further k1 and k2 are the

84

calculated second-order reaction constants for the competitive reactions by OCl- and HOCl

respectively

Table 313 Effect of acid on the speciation of hypochlorite and observed reaction rates

pH H+ [OCl-]eq [HOCl]eq k1s-1 k2s

-1 k1M-1s-1 k2M

-1s-1

863 234 x 10-9 340 x 10-3 194 x 10-3 80 x 10-2 0039 234 1990

815 706 x 10-9 307 x 10-3 530 x 10-3 71 x 10-2 0110 232 2077

784 144 x 10-8 266 x 10-3 938 x 10-3 65 x 10-2 0199 247 2132

755 281 x 10-8 213 x 10-3 147 x 10-2 52 x 10-2 0320 245 2183

739 406 x 10-8 180 x 10-3 179 x 10-2 47 x 10-2 0398 261 2219

693 117 x 10-7 930 x 10-4 267 x 10-2 25 x 10-2 0599 273 2244

685 141 x 10-7 810 x 10-4 279 x 10-2 17 x 10-2 0638 216 2288

650 315 x 10-7 410 x 10-4 319 x 10-2 80 x 10-3 0745 199 2338

485 141 x 10-5 100 x 10-5 359 x 10-2 20 x 10-5 0847 176 2360

420 630 x 10-5 234 x 10-5 360 x 10-2 39 x 10-5 0854 168 2375

365 224 x 10-5 659 x 10-6 360 x 10-2 10 x 10-5 0864 159 2402

344 363 x 10-5 406 x 10-6 360 x 10-2 57 x 10-6 0875 143 2431

317 675 x 10-5 218 x 10-6 360 x 10-2 26 x 10-6 0878 123 2439

315 707 x 10-5 208 x 10-6 360 x 10-2 25 x 10-6 0897 122 2493

314 723 x 10-5 204 x 10-6 360 x 10-2 24 x 10-6 0912 119 2535

289 1287 x 10-5 114 x 10-6 360 x 10-2 11 x 10-6 0958 102 2661 Mean k1 and k2 with standard deviation 19

plusmn 06 232

plusmn 18


where k1 and k2 pseudo first-order rate constants with respect to OCl- and HOCl

where k1= k1 [OCl-]eq and k2 = k2 [HOCl]eq where k1 and k2 represents the second order

reaction rates for OCl- and HOCl competitive reactions

85

The equilibrium concentrations of acid the OCl- and HOCl were calculated based on the

initial pH values and the protonation constant of hypochlorite An examination of the data in

the table shows that with increasing initial acid concentration a decreasing trend is registered

for k1 values while the k2 values showed an increasing trend The ln-ln plots of k1 and

[OCl-]eq and k2 and [HOCl]eq gave straight lines which are shown in Figures 3110 and

3111

Figure 3110 Plot of ln k versus ln [OCl-]eq for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at [H+]eq (397 x 10-6 - 775 x 10-3 M) [OCl-]eq (114 x 10-3 ndash 153 x 10-6 M)

Figure 3111 Plot of ln k versus ln [HOCl]eq for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at [H+]eq (199x10-9- 998 x 10-7 M) [OCl-]eq (276 x 10-2 ndash 33 x 10-6 M)

In Figure 3110 the values of [OCl-]eq at very low pH were not considered as [OCl-]eq was

small and hence pseudo first-order conditions will not be obeyed under those conditions The

y = 10717x + 11753Rsup2 = 09996

‐16

‐14

‐12

‐10

‐8

‐6

‐4

‐2

0

‐15 ‐10 ‐5 0

ln k

acute

ln [OCl‐]eq

y = 09297x + 28534Rsup2 = 09958

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4 ‐3

ln k

ln [HOCl]eq

86

mean values (19 plusmn 06) M-1 s-1 (232 plusmn 18) M-1 s-1 shown in Table 313 represent the k1 and

k2 values respectively which are the second-order coefficients for the OCl- and HOCl

initiated oxidations respectively The obtained results confirm that acid is not directly

involved in the rate limiting reaction as suggested earlier (page 79) but it influences the

equilibrium of OCl- to HOCl Increase in HOCl concentration results in a higher rate constant

indicating an increase in the rate of oxidation of the dye This explains the partial order

observed with respect to acid The observed decrease in reaction order with increasing [H+]

confirms that the observed reaction rate is a resultant effect of the reactions of AM- with

hypochlorite and hypochlorous acid but with a minor contribution of hypochlorite at lower

pH Interestingly the increase in acid concentration at pH lt 3 does not enhance the rate

constant significantly (Table 313) Under these conditions all the hypochlorite exists in

HOCl form thus the increase in [H+] will have no further applicable effect on the reaction

rate

315 Primary salt effect

The kinetic salt effect provides insight into the nature of the reacting species involved in the

rate-limiting step To identify the probable species involved in the rate limiting step the

reaction between hypochlorite and AM- was investigated as a function of varying ionic

strength (I) between 001 and 004 M with fixed initial concentrations of hypochlorite and

amaranth supplemented by sodium sulfate At pH 90 15 of total hypochlorite exists in the

form of HOCl Hence the curves were analysed for two consecutive reactions in the same

manner as it was done previously and results obtained are summarised in Table 314 For the

reaction between amaranth and hypochlorite the plot of log k versus I12 gave a linear curve

with a positive slope = 1216 and R2 = 098 (Figure 3112) The positive salt effect indicates

87

that the rate-limiting step involves species of like charges possibly AM- and OCl- ions The

reaction between AM- and HOCl slope was of fractional value (0793) (Figure 3112)

Table 314 Effect of ionic strength on the reaction rate [OCl-]t (145 x 10-3 M) [AM-]0 (70 x 10-5 M) pH = 90

Ionic strengthM k1s-1 k2s

-1

00092 0043 0047

00167 0050 0048

00242 0052 0048

00317 0054 0050

00392 0059 0051


Figure 3112 Plot of log k1 versusradic I (ionic strength) for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t

(145 x 10-3 M)) at pH 900 ionic strength (I = 0009-0039 M)

y = 12169x ‐ 14689Rsup2 = 09833

y = 07935x ‐ 31338Rsup2 = 09402

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

005 01 015 02

ln k

radicI

88

316 Kinetic salt effect at acidic pH

Under acidic conditions as 99 of the oxidant will be in the form of HOCl a neutral

species the kinetic salt effect should theoretically be nil Considering the reaction is between

cationic dye and a strongly polar HOCl a linear relationship is anticipated between rate

constant and ionic strength species and so the expected salt effect should be between the

protonated dye and HOCl The rate constant should therefore have linear dependence on ionic

strength Table 315 and Figure 3113 summaries the results of k values obtained as

function of ionic strength at low acid conditions

Table 315 Effect of ionic strength on the reaction rate for the reaction of [AM-]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) pH = 310

Ionic strengthM ks-1 00092 0047

00167 0048

00242 0048

00317 0050

00392 0051


Figure 3113 Plot of k versus radicI (ionic strength) for the reaction of [AM-]0 (7 x 10-4 M) with [OCl-]t (145 x 10-3 M) at varying ionic strength I(0009-0039 M) at fixed acid [H+]0 (45 x 10-3 M) and pH 40

y = 01333x + 00459Rsup2 = 09544

004650047

004750048

004850049

00495005

005050051

00515

0 001 002 003 004 005

k

IM

89

The k versus respective I values were plotted and shown in Figure 3113 A good linear

curve with R2 = 095 confirms such anticipated relationship The fractional slope indicates

that the rate limiting step does not involve two charged species under acidic pH Thus

possibly the rate limiting reaction involves one charged species AM- and a neutral species

HOCl as anticipated

317 Effect of chloride on the reaction rate

The influence of the added chloride was also studied In reality effluents from textile and

dyeing industries would contain a high concentration of salts which may affect the removal of

dye186 Considering chloride is one of the species associated with hypochlorite generation and

product of the oxidation reaction the effect of chloride on the reaction was investigated

Although initial chloride concentrations in the reaction mixture are less than 2 x 10-3 M the

effect of higher amounts of initial chloride is studied and results obtained are summarised in

Table 316

Table 316 Effect of addition of chloride ions for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [Cl-] (1 x 10-1 M)

[Cl-]M ks-1 0100 0107 0148 0109 0298 0107 0447 0104 0597 0104 0725 0104


A perusal of the results in Table 316 suggests that presence of chloride ion has marginal

effect on the reaction rate

90

318 Activation parameters

The activation parameters of the chemical reaction provide valuable information about the

nature of the transition state and the reaction mechanism A huge enthalpy of activation

(ΔHǂ) indicates that a large amount of stretching or breaking of chemical bonds is necessary

for the formation of the transition state The entropy of activation gives a measure of the

inherent probability of the transition state apart from energetic considerations187188 If ΔSǂ

is large and negative the formation of the transition state requires the reacting molecules to

orient into conformations and approach each other at a precise configuration189

The energy parameters for the dye with HOCl and OCl- reactions were studied by measuring

the rate constants over the range of 15 to 35o C temperature by using the Arrhenius and

Eyringrsquos equations190

Table 317 Varied temperature and observed rate constants for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M)

Temp K k1s-1 kM-2 s-1 k2s

-1 kM-2 s-1

283 0015 130 0033 287

288 0016 139 0052 452

293 0017 139 0060 522

298 0025 217 0072 626

303 0031 269 0091 791


where k = k[OCl-] [H+]

91

The Arrhenius plot was used to determine the Ea the activation energy of the reaction The

data were fitted by linear regression using the following equation ln k = -EaRT + ln A

(Figure 3114)

Figure 3114 Plot of ln k versus 1T for the reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at different temperatures (TK= 283-303)

Table 318 summarises the calculated values of four energy parameters namely the energies

of activation enthalpy and entropy for both the reactions

Table 318 Energy parameters

Reaction pathway Enthalpy of reaction

Hǂk J mol-1

Entropy of activation

SǂJ K-1 mol-1

Energy of activation

Eak J mol-1

AM- with OCl- 312 -1906 3365 plusmn 009

AM- with HOCl 243 -2228 2687 plusmn 009

The enthalpy of activation ΔHǂ for the reaction was calculated using the equation

y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

92

ΔHǂ = (Ea - mRT) The letters m R and T represent respectively the total-order of reaction

gas constant and temperature The ΔHǂ value at 25 ordmC was found to be 312 kJ mol-1 for the

OCl- ion initiated reaction and 243 kJ mol-1 for the reaction with HOCl Theoretically HOCl

reaction needed slightly lower energy of activation (2687 plusmn 009 kJ mol-1) compared to

(3365 plusmn 009 kJ mol-1) for the OCl- ion initiated reaction Both the reactions had large

negative entropies of activation suggesting the formation of a compact activated complex

319 Product identification and characterization

The reaction products from the aqueous reaction mixtures were extracted with diethyl ether

and the organic extract was further used for product separation and identification as explained

in the experimental section The main oxidation product separated using column

chromatography which was found to be 34-dihydroxy naphthalene-27-disulfonic sodium

salt (product P1 Table 319) The 1H NMR and 13C NMR are provided in (Appendix 1

Figure 113 and Figure 114) The 1H NMR showed the resonances that could be attributed

to the structure of Product P1 in particular four proton carbons can be seen in 1H NMR and

13C spectra showed the resonances between δ120 and δ145 that could be attributed to

aromatic portion of the P1 The resonance at δ 166 could be carbonyl group and the

resonance at δ106 could be due to the carbon atoms at the juncture between the two rings

The same extract was again analysed using the GC-MS The gas chromatograph (GC) of the

oxidation products (extract) showed two major peaks and no amaranth was present

GC-MS spectrum of product P2 (dichloro-1 4-naphthoquione Table 319) had molecular ion

peak at 274 which corresponds to the molecular formula of C10H6Cl2O2 The mz value 226

could be due to the loss of one chlorine atom and mz 191 corresponds to the loss of the

93

remaining chlorine atom The mass spectrum of the product P3 identified to be naphtha (2 3)

oxirene-2 3-dione (P3 Table 319) based on NIST library exhibited mz at 174 and the loss

of two oxygen atoms lead to mz 164 Further loss of the oxygen atom peak could be seen at

mz 130(M-2)

Both the products matched well (95) with the known compounds from the NIST library

database The GC-MS spectra are provided in (Appendix 1 Figure 111 and Figure 112)

Table 319 Plausible oxidation products

O

NaO3S

NaO3S

OH

Na+

(P1)

34-dihydroxy naphthalene-27-disulfonic

sodium salt

OO

Cl Cl

(P2)

dichloro-14-naphthoquione

OO

O

(P3)

naphtha (23) oxirene-23-dione

94

Literature reports show that little is known with certainty about effect of hypochlorite on azo

dyes and involved reaction mechanisms especially in alkaline media191192 In particular

about the certainty of the reactions with three oxidant species HOCl OCl- and Cl2 as they

coexist in equilibrium in aqueous solution Omura et al suggested that upon oxidation of azo

dyes isolation of products at low pH revealed the formation of naphthalene and 12-

naphthoquinone193 Elodie et al studied the oxidation of azo dyes such as azo-benzene

methyl orange and p-methyl red using electro-fenton process in acidic medium They

demonstrated that the degradation mechanism begins with azo bond cleavage and is followed

by the hydroxylation of aromatic rings The identified products were hydroquinone 14-

benzo-quinone pyrocatechol nitrocatechol 135-trihydroxynitrobenzene p-nitrophenol194

As reported in number of articles in literature the isolation and characterization of reaction

products of dyes is complicated by limitations in extraction and separation of products and

itrsquos a major challenge as the reaction intermediates are tend to further react or the dye

concentrations are too low with the hypochlorite195 Oakes et al studied the oxidation of azo

dyes by a range of oxidants196 and they investigated the reactive species responsible for

initiating oxidation in alkaline media and the effect of substituentrsquos on both dye and oxidant

using hypochlorite It was demonstrated that the relevant equilibrium has been shown that

HOCl is the active species towards the dye common anion in neutral to alkaline media197198

However they concluded that in acid medium equilibrium results in formation of aqueous

chlorine a powerful electrophile and acid solutions of hypochlorite generates chlorine and

thereby forming chlorinated organic molecules199

Oakes etal also studied the oxidation of azo dye methyl orange I and benzene is reported to

be one of the main reaction product with peroxo sulfate which was found to be benzene by

95

GC-MS analysis They suggested that the formation of benzene is probable by hydrogen atom

abstraction by phenyl radicals formed from decomposition of a diazene intermediate 200

3110 Stoichiometric equation

All the stoichiometry experiments were carried out using stock hypochlorite concentration of

00015 M The stoichiometry of the reaction was established with 11 and 15 ratios of

amaranth and hypochlorite respectively and the amount of dye and hypochlorite reacted were

estimated from the initial and residual amounts The stoichiometry was found to be

approximately 13 (plusmn 10) of AM- and HOCl Thus considering the major products identified

stoichiometric equation for the overall reaction can be written as

AM- + 3HOCl + 2H2O rarr P1 + P2 P3 + SO32-

+ Na+ + N2 + H3O+ + 3HCl (31)

where P1 (34-dihydroxy naphthalene-27-disulfonic sodium salt) P2 (dichloro-14

naphthoquione) and P3 (naphtha (23) oxirene-23-dione) products

3111 Reaction scheme

Based on the identified oxidation products and estimated stoichiometry of reactants the

probable mechanistic scheme is illustrated in the Figure 3115

When hypochlorite or HOCl reacts with amaranth hydroxy proton on the aromatic ring is

lost leaving negatively charged oxygen which delocalises onto the aromatic ring and

ultimately the nitrogen atom of the azo bond linking the two aromatic rings together This

molecule with negative charge acts as a nucleophile and attacks the oxygen atom of the HOCl

resulting in intermediate (I1) This in turn reacts with H+ to form another intermediate (I2)

96

A water molecule then attacks the electrophilic carbon of the (I2) resulting in the elimination

of water from the nitrogen atom of the azo bond producing (I3) Cleavage of the C-N bond

then occurs yielding (I4) with the other negatively charged species picking up proton to yield

P1 A further nucleophilic attack by water on the electrophilic carbon to which the sulfite

group is attached results in loss of a proton and replacement of the sulfite group by a

hydroxy group (I5) The nucleophilic attack of the hypochlorite ion on intermediate (I5) leads

to the formation of another intermediate (I6) and the release of N2 The electron

rearrangement further yields the quinone intermediate (I7) and loss of hydrogen chloride The

electrophilic attack of chlorine or HOCl on (I7) respectively produces either P2 or P3

97

N

ONaSO3

NaO3S

H

N SO3Na N

NaO3S

NaO3S

N SO3Na

OHO Cl

I1

N

NaO3S

NaO3S

N SO3Na

OO

H

HOCl

H+O

HH

ONaO3S

NaO3S

N

O H

SO3NaN

I3

I2

O

NaO3S

NaO3S

OH

P1

+ SO3NaNN

O

HH

I4

NN O H

H

Cl O

H

I5

HOCl

-N2Cl O O H

I6

OO

I7

HOCl OO

O

Cl2OO

Cl Cl P3P2

H+-

N

ONaO3S

N SO3Na

OHH

NaO3S

Figure 3115 Mechanistic scheme for the oxidation of amaranth with hypochlorite

98

3112 Proposed mechanism

Based on reaction stoichiometry estimated and the major products identified in agreement

with probable reaction scheme for the reaction of amaranth with hypochlorite the reaction

mechanism can be expressed in the following steps

H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2

AM- + HOCl rarr I1 + Cl-

I1 + H+ rarr I2+

I2+ + H2O rarr I3 + H3O

+

I3 + H2O + H+ rarr P1 + I4+

I4+ + H2O rarr I5

+ + Na+ + SO32- + H+

I5+ + HOCl rarr I6 + N2 + H+

I6 rarr I7 + HCl

I7 + Cl2 rarr P2

I7 + HOCl rarr P3 + HCl

R1

R2

R3

R4

R5

R6

R7

R8

R9

The overall reaction with HOCl is proposed as


+ Na+ + N2 + 3HCl (32)

3113 Rate law

The rate law expresses the relationship of the reaction rate and the concentrations of the

reactions raised to the same power ie the order of the reaction with respect to the respective

reactants or products The kinetic salt effect indicates the possible species involved in the

slowest step of the reaction scheme Thus the proposed reaction scheme should agree with the

99

experimentally observed reaction orders with respect to the reactants The first-order

dependence of the reaction rate on the reactants and the observed salt effect at pH 90

suggests that the rate limiting step involves one each of AM- and OCl- ions Thus the major

pathways of the reaction involve HOCl or OCl- forming possibly an activated complex

which undergoes decomposition to form the intermediates and products The intermediates

further undergo oxidation to give stable products

The reactions were studied under pseudo first-order conditions Thus the reaction involves

two pathways involving HOCl (fast and major pathway) and OCl-(slow and minor pathway)

Based on this assumption the rate law may be proposed as

Where the pseudo first-order const equals to

(33)

(34)

where and were the pseudo first-order rate constants corresponding to

hypochlorite and hypochlorous acid reactions of the dye Thus

(35)

3114 Simulations

The simulations were done to establish the probability of the reaction mechanism and to

prove that it is the more plausible one The Simkine 2 was used to simulate the curves using

the proposed mechanism and the experimental kinetic data generated in the current studies

The estimated rate constants were optimised to match the simulated curves with the

experimental curves The rate constants were adjusted to manually to test the sensitivity and

100

importance of the elementary reactions Table 3110 summarises the elementary steps and

rate coefficients finally used for the simulations Rate constants determined in the present

studies employed for C3 and C4 Literature values were used for reactions C1 and C2201202

and values C5 to C10 represent the optimised rate constants

Table 3110 Forward and reverse rate constants obtained from literature and simulations

Reaction Reaction Mechanism Forward rate Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1s-1 11 s-1

C3 AM- + HOCl rarr I1 + Cl- 23 x 101 M-1s-1 --

C4 AM- + OCl- rarr I1- + Cl- 188 x 101 M-1s-1 --

C5 I1+ H+ rarr I2+ 430 x 109 M-1s-1 --

C6 I1- + 2H+ rarr I2

+ 415 x 109 M-2s-1 --

C7 I2+ rarr P1 + I5

+ + Na+ + SO32- + H+ 301 x108 s-1 --

C8 I5+ + HOCl rarr I7 + N2 + H+ 649 x 109 M-1s-1 --

C9 I7 + Cl2 rarr P2 435 x 108 M-1s-1 --

C10 I 7 + HOCl rarr P3 + HCl 317 x 108 M-1s-1 --

The speciation of OCl- in presence of acid is shown by the equation C1 The rate limiting step

of the oxidation mechanism involves the steps initiated by OCl- or HOCl on AM- leading to

the formation of the reactive intermediate (Reactions C3 and C4 are the rate-determining

steps for amaranth oxidation) Reactions C5 to C10 show the consecutive steps for further

oxidation of the reactive intermediates by different species and C7 C9 and C10 representing

the reactions leading to different probable products

101

Figure 3116 Experimental curves versus simulated curves for reaction of [AM-]0 (70 x 10-5 M) with [OCl-]t (145x10-3 M)

Figure 3117 Intermediates and product formation for the reaction of amaranth with hypochlorite

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 20 40 60 80 100 120 140

ConcentrationM

Times

E1 S1

E2 S2

E3 S3

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 5 10 15 20 25 30

Concentration M

Times

Products(P1P2 and P3)

Experimental amp Simulated Curves(E1 S1)

Intermediates(I)

Experimental curves (E1 E2 and E3)

Simulated curves (S1S2 and S3)

102

Figure 3117 (conditions similar to curves in Figure 3116) curves E1 and S1 shows the

experimental and simulated curves for the reaction of AM- with OCl- P1 P2 and P3 show the

product formation and I indicate the intermediates formed during the process A fair

agreement between the experimental and corresponding simulated curves (Figure 3116)

strongly support the proposed reaction scheme as most probable to explain the intricate

reaction mechanism between amaranth and hypochlorite The simulations also support the

assumption that under low pH conditions HOCl is the crucial reactive intermediate to drive

the rapid kinetics rather than OCl- The concentration versus time data for all the reactants

and products and selected reaction intermediates for the experimental and simulated curves

tabulated (Appendix 1 Table 11 and Table 12)

103

32 Reaction between brilliant blue and hypochlorite

321 Order with respect to brilliant blue-R

The kinetic measurements for the consumption of brilliant blue-R (BB+) were conducted with

low concentrations of dye and excess of all other reagents and the progress of depletion was

monitored at 555 nm the maximum absorption corresponding to dye using stopped flow

technique At the absorption maxima no interference from products or intermediates was

observed Figure 321 shows the typical depletion curve of brilliant blue Perusal of the curve

shows that a typical reaction is completed in 80 seconds

Figure 321 Typical kinetic curve - absorbance versus time plot for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t

(15 x 10-3) at pH = 90 and 555 nm

The kinetic data acquired at single wavelength was analysed by employing the KinetAsystTM

software using the first-order rate equation to estimate the pseudo first-order rate constants


A KinetAsystTM fit for the first-order reaction using the rate equation was run and the

generated curve fits quite well along with the experimental curve Figure 322 illustrates

0

01

02

03

04

05

06

07

0 20 40 60 80 100

Absorban

ce

Times

104

both experimental and generated curves and the absorbance versus time data While the upper

curve shows the fit between the theoretical and experimental curves the lower plot indicates

the residuals illustrating good agreement between the two curves

Figure 322 KinetAsystTM single -exponential equation fit (green) and the experimental curve (red) with residuals shown in the (lower curve) and the rate parameters in the adjacent box for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M)

The fit results for the above curve shows that the rate constant obtained using first-order rate

equation is (0082 plusmn 90 x 10-5) s-1 illustrates that the reaction follows pseudo first-order

kinetics and the order with respect to dye is unity


To establish the order with respect to oxidant experiments were done using different initial

concentrations of hypochlorite at constant ionic strength (pH 90) As the initial concentration

of hypochlorite increased the rate of depletion of dye also increased significantly Figure

323 represents the typical curves of depletion of BB+ as function of time monitored at

105

555 nm for different initial concentrations of hypochlorite The absorbance versus time plots

is illustrated in Figure 323

Figure 323 Depletion of brilliant blue with various hypochlorite concentrations for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t x 10-3M (a = 073 b = 145 c = 218 d = 290 and e = 435) at pH 90

Different concentrations of hypochlorite reactions with the substrate with their theoretical

curves and residues are shown in Figure 324 a perusal of the curves from a to e in Figure

324 indicates that experimental and theoretical curves match well with small residues and

the k values were obtained by analysing the respective kinetic curves are also summarised

0

01

02

03

04

05

06

07

08

0 50 100 150 200 250 300

Absorban

ce

Time s

(a)

(b)

(c)

(d)(e)

106

(a) (b)

(c) (d)

(e)

Figure 324 Fits using KinetAsystTM single-exponential equation and rate equation 1 Exp + C y = -A exp (-k x) + C (where ks-1 a = 012 b= 0030 c = 0037 d = 0046 and e = 0086)

107

Table 321 shows the corresponding pseudo first-order rate coefficients k for different

hypochlorite concentrations

Table 321 The reaction between brilliant blue and hypochlorite at constant ionic [BB+]0 (70 x 10-5 M) [OCl-]t (0725 x 10-3 ndash 435 x 10-3 M) pH = 90 (I = 0128 M)

[OCl-]t 10-3 M ks-1 073 0012 145 0030 218 0037 290 0046 435 0086


A perusal of the data in table 321 shows that the first-order rate increased proportionately to

the increase in hypochlorite concentration To establish the order with respect to the

hypochlorite ln [OCl-]t versus ln k values obtained were plotted in Figure 325 which

resulted in a straight-line with slope 103 (R2 = 097) suggesting that order with respect to

hypochlorite at pH 90 is one

Figure 325 Plot of ln [OCl-]t versus ln k for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (0725 x 10-3 ndash 435 x 10-3 M) at pH = 90 and I = 0128 M

y = 10323x ‐ 0408Rsup2 = 09746

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐5 ‐4 ‐3 ‐2 ‐1 0

ln k

ln [OCl‐]t

108


The pH has significant influence on the relative formation of OCl- and HOCl species The

shift in the equilibrium is greatly influenced by acid concentration To assess the role of acid

in the oxidation process the kinetics of the reaction as function of pH was investigated

Figure 326 illustrates the plot of the k versus corresponding pH values

Figure 326 Plot of k versus pH for the reaction of [BB+]0 (70 x10-5 M) with [OCl-]t

(145 x 10-3 M) with [H+]e (199 x 10-9- 7752 x 10-4 M)

A perusal of the Figure 326 shows that the increase in k values was small at low acid

concentrations and while the increase was higher at higher acid concentrations pH below 70

onwards indicating the profound effect of pH on the reaction

The pseudo first-order rate constants obtained for different pH values were shown in Table

322

0

01

02

03

04

05

06

07

08

2 4 6 8 10

k

pH

109

Table 322 Effect of pH on the reaction rate

pH ks-1

900 00347

870 00345

835 00411

800 00491

770 00574

745 00640

720 00780

700 01018

675 01226

650 01425

600 02027

540 03160

370 05900

331 06704

329 06955

322 07093

311 07309



(Figure 327) which gave a slope 024 (R2 = 098) The observed partial reaction order with

respect to acid clearly suggests that reaction mechanism is intricate and acid is indirectly

involved in the rate limiting step

110

Figure 327 Plot of ln k versus ln [H+] for the reaction of [OCl-]t (145 x 10-3 M) with [BB+]0 (70 x 10-5 M) at [H+]eq (199 x 10-9- 7752 x 10-3 M)

From Figure 327 the observed order with respect to H+ is small suggesting that the reaction

rate observed is the resultant effect of the acid in the concentrations of hypochlorite and

hypochlorous acid The kinetic data was further analysed to estimate the pseudo first-order

rate constants for the two competitive reactions that are facilitated by hypochlorite ion and

hypochlorous acid respectively using two simultaneous first-order reactions using

KinetAsystTM analysis

y = 02414x + 15266Rsup2 = 09858

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐25 ‐20 ‐15 ‐10 ‐5 0

ln k

ln [H+]

111


(lower sketch) for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (013 M)

For comparison the theoretical fits for occurrence of single first-order reaction and two

simultaneous first-order reactions are shown in Figure 328 and Figure 329 respectively An

examination of the curves shows that Figure 329 has lower residuals compared to Figure

328 confirming the occurrence of two simultaneous reactions

112

Figure 329 KinetAsystTM double-exponential equation fit of two curves and residuals for two competitive first-order reactions (lower sketch) for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (012 M)

The calculated equilibrium concentrations for H+ OCl- and HOCl and the pseudo first-order

rate constants for hypochlorite k1 and hypochlorous acid k2 at different pH values are

summerised in Table 323

A perusal of Table 323 shows that k1 is much smaller in magnitude than k2 While k1

values had a decreasing trend k2 recorded an increasing trend This is predictable

considering the changes ie decrease in [OCl-] and increase in [HOCl] with increasing acid

concentration The mean values of second order rate constants 12 plusmn 02 M-1 s-1 220 plusmn 12

M-1 s-1 shown in Table 323 represent the k1 and k2 values respectively which are the

respective second-order coefficients for the OCl- and HOCl initiated oxidations

113

Table 323 Effect of acid on the speciation of hypochlorite and reaction rate

pH [H+] [OCl-]eq [HOCl]eq k1s-1 k2s

-1 k1M-1s-1 k2M

-1s-1

870 199 x 10-9 276 x 10-2 134 x 10-3 00390 00270 141 2008

835 445 x 10-9 261 x 10-2 285 x 10-3 00360 00610 137 2143

800 997 x 10-9 233 x 10-2 568 x 10-3 00303 01400 129 2464

770 199 x 10-8 195 x 10-2 949 x 10-3 00250 02050 128 2161

745 354 x 10-8 155 x 10-2 134 x 10-2 00190 02799 122 2081

720 629 x 10-8 114 x 10-2 176 x 10-2 00135 03670 118 2088

700 997 x 10-8 843 x 10-3 206 x 10-2 00094 04275 112 2079

675 177 x 10-7 543 x 10-3 236 x 10-2 00060 04930 110 2092

650 315 x 10-7 332 x 10-3 257 x 10-2 00035 05390 105 2100

600 998 x 10-7 114 x 10-3 279 x 10-2 00011 05880 100 2111

540 397 x 10-6 294 x 10-4 287 x 10-2 00002 06459 084 2250

370 199 x 10-4 595 x 10-6 290 x 10-2 -- 06582 -- 2270

331 489 x 10-4 242 x 10-6 290 x 10-2 -- 06652 -- 2294

329 512 x 10-4 232 x 10-6 290 x 10-2 -- 06725 -- 2319

322 602 x 10-4 197 x 10-6 290 x 10-2 -- 06842 -- 2359

311 775 x 10-4 153 x 10-6 290 x 10-2 -- 06910 -- 2383

Mean and standard deviation 12 plusmn 02 220plusmn 12



respectively k1= k1[OCl-]eq and k2 = k2[HOCl]eq where k1 and k2 represents the second-

order reaction rates for OCl- and HOCl competitive reactions

At pH below 3 no significant increase in rate constant was observed with increase in acid

concentration which anticipated at that pH as all OCl- will be in the form of HOCl a further

increase in the acid concentration does not increase the HOCl concentration Figure 3210

114

and Figure 3211 represents the order with respect to OCl- and HOCl in the pH range from

30 to 90

Figure 3210 Plot of ln k versus ln [OCl-]eq for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at [H+]eq (397 x 10-6 - 775 x 10-3 M)

[OClˉ]eq (114 x 10-3 ndash 153 x 10-6 M)

The ln-ln plot of k1 versus [OCl-]eq a fair straight line with gradient equal to 11 (Figure

3210) suggests that order with respect to hypochlorite is one At low pH the concentration

of hypochlorite reduces to small values where the pseudo first-order conditions with respect

to dye are no more valid Hence for such conditions k1 values were not estimated or that data

was not taken into consideration

Figure 3211 Plot of ln k versus ln [HOCl]eq for the reaction of [BB+]0 (70 x 10-5 M) with

[OCl-]t (145 x 10-3 M) at [H+]eq (199 x 10-9- 998 x 10-7 M) [HOClˉ]eq (276 x 10-2 ndash 33 x 10-6 M)

y = 1101x + 09865Rsup2 = 09135

‐01

6E‐16

01

02

03

04

05

06

‐5 ‐45 ‐4 ‐35 ‐3

ln k

`

ln [OCl‐]eq

y = 1034x + 32194Rsup2 = 09979

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐7 ‐6 ‐5 ‐4 ‐3 ‐2

ln k

`

ln [HOCl]eq

115

Figure 3211 a plot of ln [HOCl]eq versus ln k gave a linear curve with slope 1034

suggesting that reaction is predominantly between the HOCl and dye and the reaction has

first-order dependence on HOCl concentration

Although at alkaline pH the reaction order with respect to OCl- is one an observation of

Figure 3211 indicates that at neutral pH the change in rate constant is negligible due to low

concentration of OCl- at that pH Thus its contribution to overall reaction remains small

The obtained results confirm that acid is not directly involved in the rate limiting reaction for

the oxidation of brilliant blue but it influences the speciation and equilibrium of OCl- to

HOCl The observed decrease in reaction order with increasing [H+] confirms that observed

reaction rate is resultant effect of the reactions of BB+ with hypochlorite and hypochlorous

acid but with minor contribution of hypochlorite at lower pH


The influence of added salt on the reaction was studied and the results are summerised in

Table 324 An observation of results show an increasing ionic strength had negative salt

effect on both OCl- and HOCl initiated reactions The plot of log k versus I12 of the data

obtained gave a linear curve (A) with negative slope = 103 and R2 = 099 (Figure 3212)

Suggesting a negative salt effect with reacting species of opposite charges possibly BB+ and

OCl- ions The slope corresponds to linear curve B (0745 R2 = 099) corresponds to that of

the reaction between HOCl and BB+

116

Table 324 Effect of ionic strength on the reaction rate [OCl-]t (145 x 10-3 M) [BB+]0 (70 x 10-5 M) pH = 90


-1

00099 0035 00452

00188 0035 00459

00225 0037 00471

00263 0038 00485

00338 0040 00499


Figure 3212 Plot of log k versus ionic strength for the reaction of [OCl-]t (145 x 10-3 M)

with [BB+]0 (70 x 10-5 M) at pH = 9 ionic strength (I = 001-003 M) (A- OCl initiated B- HOCl initiated reaction)


Experiments were conducted to investigate the salt effect under acidic conditions At pH 31

with negligible amount of hypochlorite main reaction is anticipated between the protonated

y = ‐10346x ‐ 11666Rsup2 = 09931

y = ‐07456x ‐ 11354Rsup2 = 09937

‐148

‐146

‐144

‐142

‐14

‐138

‐136

‐134

‐132

‐13

‐128

022 023 024 025 026 027 028

log k

radicI

A

B

117

dye and HOCl if it is true salt effect will be less pronounced The k values obtained are

shown in Table 325

Table 325 Effect of Ionic Strength on the reaction rate for the reaction of [BB+]0 (70 x 10-5 M) [OCl-]t

(145 x 10-3 M) pH = 31

Ionic strengthM ks-1

00510 161

00547 157

00585 155

00622 153

00697 150


If the reaction is between neutral species (HOCl) and BB+ there should be linear relationship

between log k and I but plot of log k versus radicI from Table 325 did not give a good

straight line as anticipated and the obtained slope is -077 therefore the k versus respective

ionic strength values were plotted which is a linear curve suggesting that the rate limiting

step possible involves a neutral species (Figure 3213)

Figure 3213 Plot of k versus I (Ionic strength) for the reaction of [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at varying ionic strength I (0051-0069 M) at fixed acid [H+] (45 x 10-3 M) at pH 40

y = 57679x + 12139Rsup2 = 09752

148

15

152

154

156

158

16

162

164

003 004 005 006 007 008

k

IM

118

327 Effect of chloride on reaction rate

To investigate the effect of chloride on the reaction rates were measured with different

amounts of initially added chloride in the reaction while other conditions maintained the

same The observed rate constants suggest that chloride is not involved in any possible

reaction

Table 326 Effect of addition of chloride ions on the reaction [BB+]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) [Cl-] (1x10-1 M)

[Cl-]M ks-1 0000 0125 0148 0126 0298 0126 0447 0126 0597 0127 0725 0127





The energy parameters for the reactions of dye with HOCl and OCl- were estimated by

measuring the rate constants over the temperature range of 15 ordmC to 35 ordmC Table 327

summarises the calculated values of four energy parameters namely the energies of

activation enthalpy and entropy for both the reactions (Table 328) A typical Arrhenius plot

shown in Figure 3214 suggests that effect of temperature on the two reactions was not the

same

119

Table 327 Rate constants for the BB+ oxidation as function of temperature for the reaction of [BB+]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) at pH 90


-1 kM-2 s-1

283 0014 121 0041 356

288 0019 165 0058 504

293 0028 165 0064 556

298 0033 286 0079 686

303 0037 321 0098 852


and k = k[OCl-] [H+]

Figure 3214 Plot of ln k versus 1T for the reaction of with [BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) at varying temperature conditions (A-OCl initiated B-HOCl initiated reaction)

y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

120



HǂkJ mol-1


SǂJK-1 mol-1


EakJ mol-1

BB+ with OCl- 3305 -19193 3553 plusmn 009

BB+ with HOCl 2680 -20457 2928 plusmn 009

The ΔHǂ values are found to be 3305 kJ mol-1 and 2680 kJ mol-1 for the OCl- and HOCl

initiated reactions respectively The HOCl initiated reaction had slightly lower energy of

activation (2928 plusmn 009 kJ mol-1) compared to (3553 plusmn 009 kJ mol-1) the OCl- initiated

reaction The observed entropy of activation Sǂ -19193 for OCl ion initiated reaction and -

20457 for HOCl initiated reaction suggest that the formed activated complex is relatively of

compact nature


BB-OCl reaction product obtained after dichloromethane extraction (064 g) was

chromatographed using silica gel (Merck 9385) as the stationary phase on a 4 cm diameter

column The mobile phase consisted of hexane dichloromethane step gradient (100 hexane

(fractions 1-10) 10 dichloromethane in hexane (fractions 11-20) 30 dichloromethane in

hexane (fractions 21- 38) 50 dichloromethane in hexane (fraction 40-57) and 80

dichloromethane (fraction 58-64) Fractions of 10 mL were collected in each step From

these fractions total of four major compounds were separated namely products (P1 = 4-

ethoxy-phenylamine P2 = 3-ethylaminomethyl-benzenesulfonic acid P3 = 3- ethylamino

chloro methyl-benzene sulfonic acid and P4 = 4-[bis-(4-hydroxy-phenyl)-methylene]-

cyclohexa-25-hydroxide) The products P2 P3 and P4 were identified in the current study

Plausible oxidation products are shown Table 329

121

Proton NMR of product P2 (3-ethylaminomethyl-benzenesulfonicacid) showed appearance of

aromatic protons between 750 and 801 which integrates to the three protons of the

aromatic ring and methyl and methylene protons at 383 and 412 respectively

(Appendix 1 Figure 115) In the 13C spectrum the aromatic peaks are found in between

116 -168 The aromatic carbons in the 13C spectra can be seen between 130 and 150 The

ethyl group can be seen at 215 and triplet methyl at 09 (Appendix 1 Figure 116)

From GC-MS spectrum corresponding molecular ion peak with retention time 1399 min

could be found at mz 216 (M+1) representing the molecular formula of C9H13NO3S

(Appendix 1 Figure 117) From the product loss of sulfonyl and ethyl group leads to the

fragment with a molecular mass of mz 107 which accounts to the molecular formula

(C7H9N)

Proton NMR of the identified product P3 revealed that appearance of triplet and quartet for

methyl and methylene group at lower 092 and higher 229 respectively The protons of

the methylene group which serves as bridge between phenyl ring and tertiary nitrogen is seen

at higher 381 due to deshielding effect of substitutions All aromatic protons are seen

between 70-765 (Appendix 1 Figure 118) The 13C-NMR exhibited appearance of

methyl and methylene carbons at 1371 and 3737 respectively Higher 647 value for

methylene carbon is observed due to deshielding effect between phenyl and tertiary nitrogen

Aromatic carbons are observed between 13096 ndash 14463 (Appendix 1 Figure 119) The

GC-MS of product P3 showed mz at 249 (M+1) at 142 min which is in good agreement with

molecular formula of the identified product P3 (C9H12NO3ClS) The other significant peaks at

mz = 215 corresponds to loss of chlorine from product Molecular mass of mz 1072

122

corresponds to the loss of ethyl and sulfonyl groups which accounts to the molecular formula

(C7H9N) (Appendix 1 Figure 1110)

The proton NMR spectra of product P4 exhibits the resonances at 74 - 804 can be assigned

to the ortho-coupled protons of the two aromatic rings The integration is twice that of other

pair of the doublets because of the symmetry in the molecule The other pair of doublets can

be seen at 67 and 745 and can be assigned to the double bonds in the remaining ring

(Appendix 1 Figure 1111) The aromatic carbons in the 13C spectra can be found in the

range of 110 - 1403 (Appendix 1 Figure 1112) The GC-MS of product P4 revealed the

molecular mass of 292 (M+) at retention time 1519 min (Appendix 1 Figure 1113) which

is in good agreement with molecular formula C19H16O3 Loss of para hydroxy phenyl group

from product P4 led to the formation of the fragment with molecular mass 200 (C13H12O2)

followed by loss of the hydroxy group from the fragment to arrive at another fragment with

molecular mass 1851 (M+1) C13H12O


NH2

O

(P1)

4-ethoxy-phenylamine

N

SO3H

H

(P2)

3-ethylamino methyl-benzene sulfonic acid

123

NSO3H

Cl

(P3)

3-ethylamino chloro methylbenzene sulfonic

acid

OH OH

OH

(P4)

4-[bis-(4-hydroxy-phenyl)-methylene]-

cyclohexa-25-hydroxide


The stoichiometry of the reaction between brilliant blue and hypochlorite was established

with 11 and 110 ratio of the oxidant and the substrate The amount of brilliant blue-R

reacted was calculated from the initial and residual amounts The stoichiometry was found to

be approximately 14 (plusmn 10) The stoichiometry for the reaction can be expressed as

BB+ + 4HOCl + 3H2O rarr P1 + P2 + P3 + P4+

+ 3HCl + OH- + H+ (36)


Brilliant blue upon treatment with HOCl results in the formation of an intermediate I1 with

the loss of para ethoxy aniline as product P1 The intermediate I1 is attacked by OCl- ion to

form intermediate I2 which looses meta substituted benzyl ethyl amine as product P2 and

forms I3 Intermediate I3 is further attacked by HOCl ending up with the formation of product

124

P3 and intermediate I4 The latter is further attacked by three hydroxy ions and leads to the

formation of P4

NSO3

-

NN

O

SO3-

H

HOCl

NSO3H

NN

O

SO3H

HH

-OCl

NSO3H

N

SO3H

ClO

NH2

O

HOCl

-OCl

NSO3H

ClO OCl

N

SO3H

H

ClO OCl

NSO3H

ClO

OCl-

HO Cl

ClO OCl

OCl

NSO3H

Cl

H+OH-

OH OH

OH

+

SO3H

NSO3H

NClO H

P1I1

I2I3

P2

I5

P4

P3

I4

Figure 3215 Mechanistic scheme for the oxidation of brilliant blue-R with hypochlorite

125

3212 Proposed reaction mechanism

The probable reaction mechanism is proposed based on the known chemistry of hypochlorite

decomposition as discussed The reaction mechanism is represented as

H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2

BB+ + HOCl rarr I1+ + P1 R1

I1+ + HOCl rarr I1

2+ + OCl- R2

I22+ + OCl- rarr I3

+ + P2 R3

I3+ + HOCl rarr I4 + H+ R4

I4 + HOCl rarr I3+ + OH- + P3 R5

I3+ + 3H2O rarr P4

+ + 3HCl R6

The overall reaction mechanism is proposed as


+ 3HCl + OH- + H+

(37)

3213 Rate law

Based on the first-order dependence of the reaction rate on the reactants and observed

negative salt effect the rate law may be proposed as

(38)

Where and represents the rate constants

Where the pseudo first-order constant k equals to

(39)

126

(310)

and where (311)

(312)

3214 Simulations

Based on the comprehensive scheme (Figure 3215) and the subsequent proposed reaction

mechanism the reaction scheme in the product analysis detailed the structures of the probable

intermediates For the simulations only steps involving the formation of intermediates which

undergo consecutive reactions with other intermediates or reactive species are considered In

each elementary step while the overall charge and mass balances are strictly accounted for

the concentration of water which is the solvent is not simulated

The Table 3210 summarises the elementary steps and rate coefficients used for the

simulations Estimated rate coefficients were used for the remainder of the reactions Rate

constants determined in the present studies were employed for C3 and C4 Estimated rate

coefficients were adjusted such that the simulated curves agreed with the experimental

curves203


Reaction

No

Reaction Mechanism Forward rate

Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-2 s-1 11 s-1

C3 BB+ + HOCl rarr I1+ + P1 22x 101 M-1 s-1 --

127

Table 3210 contd

Reaction

No


Reverse rate

C5 BB+ + OCl- rarr I1 122 M-1 s-1 --

C6 I1 + H+ rarr I1+ + P1 330 x 109 M-1 s-1 --

C7 I1+ + HOCl rarr I1

2+ + OCl- 230 x 109 M-1 s-1 --

C8 I22+ + OCl- rarr I3

+ + P2 430 x 109 M-1 s-1 --

C9 I3+ + HOCl rarr I4 + H+ 341 x 109 M-1 s-1 --

C10 I4 + HOCl rarr I3+ + OH- + P3 301 x 108 M-1 s-1 --

C11 I3+ rarr P4

+ + 3HCl 417 x 108 s-1 --

The speciation of OCl- in the presence of acid is shown by the equation C1 The rate limiting

step of the oxidation mechanism involves steps initiated by OCl- or HOCl on BB+ leading to

the formation of the reactive intermediates Reactions C3 and C4 are the rate-determining

steps for brilliant blue-R oxidation Reactions C5-C8 shows the consecutive steps for further

oxidation of the reactive intermediates leading to different probable products

Three experimental curves were analyzed using Simkine 2 software and the generated

simulated curves are shown in Figure 3216

128

Figure 3216 Experimental curves versus simulated curves for reaction of [BB+]0 (70 x10-5 M) with [OCl-]t (145 x 10-3 M)

From Figure 3216 the experimental E1 E2 and E3 and corresponding simulated curves S1

S2 and S3 (dotted) are in agreement with each other confirming that the proposed reaction

scheme as most reasonable and estimated rate constants are fairly acceptable

0

000001

000002

000003

000004

000005

000006

000007

0 50 100 150 200 250

ConcentrationM

Times

E1S1

E2S2

E3S3


Simulated curves (S1 S2 and S3)

129

Figure 3217 Intermediates and product formation for the reaction of brilliant blue with hypochlorite

By maintaining the similar reaction conditions in Figure 3217 curves E1 and S1 indicates

the experimental and simulated curves for the reaction P1 P2 P3 and P4 show the product

formation and I is the intermediate formed during the process and also indicates that the dye

is completely transformed in to the products The data of the simulated versus experimental

curves and the concentrations of the other reactants intermediates and products are compiled

in (Appendix 1 Table 13 and Table 14)

0

000001

000002

000003

000004

000005

000006

000007

0 10 20 30 40 50 60 70

ConcentrationM

Times

Products (P1 P2P3P4)

Intermediates (I)

Experimental and Simulated curves (E1 S1)

130

33 Reaction of hypochlorite with safranine-O

331 Order with respect to safranine-O

To elucidate the mechanism of the reaction between this anthraquinone dye with

hypochlorite the kinetics of the reaction was studied under varied reaction conditions The

dye had absorption maximum at 519 nm with no peak shift due to pH variation In all the

cases the kinetic runs were conducted with excess concentrations of all the reagents except

safranine-O (SO+) which was taken at low concentration The reaction was monitored at

519 nm where interferences were observed during the reaction All the experiments were

carried out at (25 plusmn 01) ordmC Figure 331 shows the typical kinetic trace of [SO+]

Figure 331 Typical kinetic curve- absorbance versus time plot for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (15 x 10-3 M) at pH = 90 wavelength 519 nm


The kinetic data acquired at single wavelength measurements was analysed using the kinetic

software and the first-order rate equation as described earlier Figure 332 represents the

typical experimental curve with the fitted curve and the residuals A fair agreement between

the curves with small residuals suggests that reaction follows pseudo first-order kinetics for

the chosen conditions and order with respect to the dye is one

0

01

02

03

04

05

06

0 50 100 150

Absorban

ce

Times

131

Figure 332 KinetAsystTM single-exponential equation fit (green) and the experimental curve (red) with residuals shown in the (lower curve) and the rate parameters box for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t

(15 x 10-3 M)

Perusal of Figure 332 indicates that by employing first-order equation a good agreement

between experimental and theoretical curve is observed The kinetic data analysis results for

the curve displayed in the box shows that the rate constant obtained is (0019 plusmn 6 4 x 10-5) s-1

with small standard deviation and the reaction follows first-order kinetics with safranine-O




strength using sodium sulfate as a neutral salt Typical curves showing depletion of SO+ as

function of time at different initial concentrations of hypochlorite are shown in Figure 333

132

Figure 333 Depletion of safranine-O with various hypochlorite concentrations for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t x 10-3 M (a = 085 b = 170 c = 255 d = 340 and e = 510) at pH = 90

With increasing initial concentration of hypochlorite from (085-510) x 10-3 M the rate of

depletion of dye is increased proportionately The representative absorbances versus time

plots are shown in Figure 333 The pseudo first-order rate coefficients k for different

hypochlorite concentrations are shown in Table 331

The thumbnail impressions given in Figure 334 illustrates the depletion of the dye and

respective kinetic traces with residuals for the chosen conditions

‐01

6E‐16

01

02

03

04

05

06

07

0 50 100 150 200 250 300

Absorban

ce

Time s

(b)(c)(d)(e)

(a)

133

(a) (b)

(c) (d)

(e)

Figure 334 Fits using KinetAsystTM single-exponential equation and rate equation 1 Exp + C y = -A exp (-k x) + C where k s-1 (a= 00100 b = 00271 c = 00346 d = 00439 and e = 00520)

The observed ks-1 values are shown in Table 331 for different initial concentrations of total

hypochlorite for the curves analysed in Figure 334 and Figure 335 illustrates the ln k

versus ln [OCl-] for the same

134

Table 331 The reaction between safranine-O and hypochlorite at constant ionic strength [SO+]0 (30 x 10-5 M) [OCl-]t (085 x 10-4 ndash 51 x 10-3 M) pH = 90 (I = 0128 M)

[OCl-]t 10-3 M ks-1

0085 0010

170 0026

255 0034

340 0043

510 0052


Figure 335 Plot of ln [OCl-]t versus ln k for the reaction of [OCl-]t (085 x 10-4 - 51 x 10-3 M) with [SO+]0 (30 x 10-5 M) at pH = 900 and I = 0128 M

While the pseudo first-order rate constants increased proportionately with the increase in the

initial concentration of hypochlorite from Figure 335 the plot of ln k versus ln [OCl-] gave

good straight line with slope = 091 suggesting that the order with respect to oxidant is one

334 Effect of acid concentration on the reaction rate

To establish the role of acid in the reaction dynamics kinetic experiments were repeated with

fixed excess concentration of oxidant and low amount of dye and varied initial pH conditions

y = 09193x + 20384Rsup2 = 09533

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐8 ‐7 ‐6 ‐5 ‐4

ln k´

ln [OCl‐]t

135

from basic to acidic pH The obtained k values are summarized in Table 322 and Figure

336 illustrates the plot of pseudo first-order rate constant as function of pH With increase in

pH the change had different impact on the rate depending on the pH range The increase in

rate constant was small at neutral pH range while steep increase in the lower pH ranges

Figure 336 Plot of k versus pH for the reaction of [SO+]0 (30 x 10-5 M) with [OClˉ]t (145 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M)

Table 332 Effect of pH on reaction rate for the reaction of [SO+]0 (30 x 10-5 M) [OCl-]t (145 x 10-3 M)

pH ks-1

873 008

826 012

786 023

754 044

722 054

710 082

668 125

664 221

450 1975

‐45

05

55

105

155

205

255

305

355

405

275 375 475 575 675 775 875

k

pH

136

Table 332 contd

pH ks-1

390 2827

351 3256

361 3347

315 3571

313 3699

295 3964

285 4087


The increase in k values with increasing acid concentration suggests that oxidation with

formed HOCl is faster than with OCl- This can be possibly explained taking into

consideration the occurrences of simultaneous reactions initiated by OCl- and HOCl

Further to assess the order with respect to acid the ln k versus ln [H+] values were plotted

(Figure 337)

Figure 337 Plot of ln k versus ln [H+] for the reaction of [SO+]0 (3 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M)

y = 04715x + 7247Rsup2 = 09727

‐3

‐2

‐1

0

1

2

3

4

5

‐20 ‐15 ‐10 ‐5

ln k

ln[H+]

137

The plot of ln k versus ln [H+] gave a plot with positive slope = 0471 and R2 = 097 and two

distinct ranges observable one slow increase in k at high pH and another fast increase at low

pH The observed partial order with respect to H+ can be anticipated in view of the

conversion of hypochlorite to hypochlorous acid influenced by the acid concentrations

through protonation The rate of the oxidation of the substrate will depend on the reactivityrsquos

of hypochlorite and hypochlorous acid towards the dye The competitive oxidation of dye

occurs with OCl- and HOCl species and can be further established by re-analysing the curves

with two competitive reactions equations in the same manner as was done previously

Hence the kinetic data obtained with varied initial amounts of added acid was analysed

carefully to estimate the rate coefficient values for the occurrence of two competitive

reactions Assuming the incidence of two competitive reactions the kinetic data in the pH

range 60 to 20 was processed using the fit for two competitive first-order reactions The

generated and experimental curves fitted quite well with minimum residuals

Figure 338 and 339 respectively show the fitting of theoretical curves and residuals with

assumption of occurrence of either one pseudo first-order reaction or two pseudo first-order

reactions simultaneously

138

Figure 338 KinetAsystTM single-exponential equation fit of two curves and residuals (lower sketch) for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3M) [H+] (996 x 10-9 M) and I (0128 M)

Figure 339 KinetAsystTM double-exponential equation fit of two curves and residuals (lower part) for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) [H+] (996 x 10-9 M) and I (0128M)

The values of the two pseudo first-order rate constants obtained from the analysis are

summarized together with the initial equilibrium concentrations of acid hypochlorite and

hypochlorous acid indicated as [H+]eq [OCl-]eq and [HOCl]eq at different pH values

139

(Table 333) k1 represents the pseudo first-order rate constant for the OCl- initiated

oxidation and k2 represents the corresponding value for the reaction by HOCl Further k1 and

k2 are the calculated second-order rate constants for OCl- and HOCl facilitated reactions

respectively The ln-ln plots of k1 and [OCl-]eq and k2 and [HOCl]eq are illustrated in Figures

3310 and 3311 which were straight lines with decreasing order at different pH ranges

Figure 3310 Plot of ln k versus ln [HOCl]eq for the reaction [SO+]0 (7 x 10-5 M) with [OCl-]t (145 x 10-3 M) at [H+]eq (186 x 10-9 - 141 x 10-5 M)

Figure 3311 Plot of ln k versus ln [OCl-]eq for the reaction of [SO+]0 (30 x 10-5 M) with [OClˉ]t (145 x 10-3 M) at [H+]eq (186x 10-9- 141 x 10-5 M)

y = 1013x + 33473Rsup2 = 09936

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐6 ‐55 ‐5 ‐45 ‐4 ‐35 ‐3

ln k

ln[HOCl]eq

y = 05112x ‐ 2502Rsup2 = 09709

‐25

‐15

‐05

05

15

25

35

‐13 ‐11 ‐9 ‐7 ‐5 ‐3 ‐1

ln k

ln[OCl]eq

140

Table 333 Effect of acid on the speciation of hypochlorite and reaction rates

pH H+ [HOCl]eq [OCl-]eq k1s-1 k2s

-1 k1M-1 s-1 k2M

-1 s-1

873 186 x 10-9 156 x 10-3 340 x 10-2 0064 0093 195 2922

826 548 x 10-9 440 x 10-3 310 x 10-2 0066 0127 209 2999

786 138 x 10-8 921 x 10-3 260 x 10-2 0058 0276 217 3048

754 288 x 10-8 150 x 10-2 210 x 10-2 0053 0458 254 3087

722 601 x 10-8 215 x 10-2 140 x 10-2 0040 0676 279 3157

710 792 x 10-8 239 x 10-2 120 x 10-2 0035 0761 291 3209

668 208 x 10-8 301 x 10-2 590 x 10-2 0018 0985 318 3274

664 228 x 10-8 306 x 10-2 545 x 10-2 -- 107 -- 3528

405 890 x 10-5 360 x 10-2 164 x 10-5 -- 129 -- 3596

390 126 x 10-4 360 x 10-2 120 x 10-5 -- 130 -- 3624

351 309 x 10-4 360 x 10-2 455 x 10-6 -- 133 -- 3713

361 245 x 10-4 360 x 10-2 589 x 10-6 -- 136 -- 3780

315 707 x 10-4 360 x 10-2 203 x 10-6 -- 138 -- 3831

313 740 x 10-4 360 x 10-2 198 x 10-6 -- 141 -- 3922

295 112 x 10-3 360 x 10-2 134 x 10-6 -- 143 -- 3974

285 141 x 10-3 360 x 10-2 107 x 10-6 -- 144 -- 4005

Mean k1 and k2 with standard deviation 30 plusmn 05 348 plusmn 28


k1 = k1[OCl-]eq and k2 = k2[HOCl]eq where k1 and k2 represents the second-order reaction

rates for OCl- and HOCl competitive reactions The equilibrium concentrations of acid OCl-

and HOCl were calculated based on the measured initial pH values and the protonation

constant of hypochlorite From Table 333 the mean second-order rate coefficients for the

OCl- and HOCl initiated oxidations respectively are k1 (30 plusmn 05) M-1 s-1 and k2 (348 plusmn 28)

M-1 s-1 An examination of the data in Table 333 shows that with increasing initial acid

concentration the k2 values increased a decreasing trend is registered for k1 values

141

Interestingly at pH below 40 the overall rate constants observed tend to increase where there

is no further increase in [HOCl] is possible This suggests that unlike the other dyes

investigated possibly the protonated substrate gets oxidized much faster than the

unprotonated species In such a case the HOCl oxidizes the unprotonated and protonated

safranine-O at different rates

Considering the complexity of the reaction dynamics of oxidation of safranine-O under

varied pH conditions a generalized rate law accommodating the oxidation of SO+ by OCl-

and HOCl in competitive reactions at high and medium pH (gt 4) and the simultaneous

oxidation of unprotonated and protonated safranine-O at lower pH by HOCl can be expressed

as follows

(313)

At pH conditions above 4 where no protonated SOH2+ possibly exists the third term in the

above eqn [311] disappears and rate can be expressed as

(314)

Thus

where the pseudo first-order constant k equals to (315)

(316)

and were analyzed using

KinetAsyst specfit analysis and and are the second order

rate constants estimated from ΄ and ΄

(317)

142

Under pH conditions below 40 where all the hypochlorite is in the form of HOCl or the

concentration of [OCl-]eq is negligible it is expected the further increase in acid concentration

should result in no enhancement in k values At low pH interestingly the observed increase

in the overall pseudo first-order rate constant with an increase in acid concentration suggests

that acid has a diverse role to play in this mechanism This can only be explained based on

the possible protonation of the dye which in turn may get oxidised more easily than the

unprotonated species With further increase in the pH evidently with no peak shift from 520

nm absorption maximum is observed Thus obviously both the unprotonated and protonated

dye absorb at the same wavelength but possibly get oxidized by HOCl at different rates

Under these conditions the direct estimation of the pseudo first-order constants for these

reactions is not feasible due to lack of appropriate equations with software The assumption

can only be verified indirectly

As such at pH conditions below pH 4 where protonated SO+ may exist the first term in the

above equation 311 (ie may be neglected and rate may expressed as

(318)

(319)

(320)

and

If the assumption is correct and the rate equation holds good the plot of the overall rate

constant k in the pH range (90 to 60) versus [H+]eq should be a straight line with slope

143

equivalent to k3 and intercept equivalent to k2 k3 can be estimated knowing the value of K

the protonation constant for the dye The estimation of k3 value is limited due to the lack of

information on the protonation constant of safranine-O

Figure 3312 Plot of k versus [H+]eq below pH = 60

The fair agreements of the intercept value 3112 (Figure 3312) with the estimated value of

k2 = 3479 (Table 333) supports the approximation reasonable


At pH 90 HOCl exists in equilibrium to 15 together with OCl- so the curves were analysed

for two consecutive reactions in the same manner as it was done previously The results

obtained are summarized in Table 334

y = 71649x + 31127Rsup2 = 09658

32

33

34

35

36

37

38

39

40

41

00002 00004 00006 00008 0001 00012 00014

k

[H+]eq

144

Table 334 Effect of ionic strength on the reaction rate [SO+]0 = (3x 10-5 M) [OCl-]t (145 x 10-3 M) pH =9


-1 00092 0047 063

00167 0042 062

00242 0039 060

00317 0037 056

00392 0034 054


Figure 3313 Plot of log k1 and log k2 versus radicI for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t

(145 x 10-3M) at pH = 9 Ionic Strength (I = 0009 to 0039 M)

The plot of log k versus I12 of the data obtained gave a linear plot (A) with negative slope =

128 and R2 = 099 (Figure 3313) The negative salt effect indicates that the rate-limiting

step involves species of opposite charges possibly SO+ and OCl- ions The slope = 072 less

than unity represented by plot B Figure 3313 corresponds to the reaction between HOCl

and SO+

y = ‐12866x ‐ 1202Rsup2 = 09955

y = ‐07248x ‐ 01187Rsup2 = 09181

‐16

‐14

‐12

‐1

‐08

‐06

‐04

‐02

0

008 01 012 014 016 018 02

log kacute

radicI

B

A

145


The effect of added chloride was investigated to establish the rate constants and its

dependence on the ionic strength The k versus respective I values were plotted and are

shown in Figure 3314 Table 335 summarises the k values obtained as function of ionic

strength at low acid conditions The log k versus radicI did not show such dependence hence the

values of k versus I were plotted directly

Table 335 Effect of ionic strength on the reaction rate [SO+]0 (30 x 10-5 M) with [OCl-]t t (145 x 10-3M) pH = 40


00167 062

00242 060

00317 056

00392 054


Figure 3314 Plot of k versus I (Ionic strength) for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) at varying ionic strength I (00092 - 00392 M) at fixed acid [H+] (45 x 10-3 M)

y = ‐34x + 06745Rsup2 = 09635

052

054

056

058

06

062

064

066

0005 001 0015 002 0025 003 0035 004

k

IM

146

Figure 3314 shows the good linear curve which indicates the linear dependence on the ionic

strength with R2 values equals to 096 confirming that the reaction is between the cationic dye

and the hypochlorous acid which is neutral species


Considering chloride is one of the species associated with hypochlorite generation and

product of reaction the effect of chloride on the reaction was investigated by adding varying

amounts of chloride The increase in added chloride registered a negligible effect on the k

value (Table 336)

Table 336 Effect of addition of chloride ions for the reaction of [SO+]0 (30 x 10-5 M)with [OCl-]t (145 x 10-3 M)

[Cl-]M ks-1 0000 0901 0148 0901 0298 0902 0447 0902 0597 0902 0725 0903



Table 337 summarises the pseudo first-order and overall second order rate coefficients of

the hypochlorite and hypochlorous acid initiated oxidation of safranine-O at pH 90

investigated at five different temperatures unless otherwise identical conditions Using the

Eyringrsquos equation and the kinetic data as a function of temperature energy parameters

namely energy of activation enthalpy and entropies of activation were estimated

147

(Table 338) Figure 3315 shows the plot of ln rate coefficient versus reciprocal temperature

plots which were straight lines

Table 337 Varied temperature and observed rate constants for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M)

TempK k1s-1 kM-2 s-1 k2s

-1 kM-2 s-1

283 0019 172 0049 426

288 0022 200 0062 539

293 0037 336 0075 652

298 0041 372 0082 713

303 0051 463 0098 852


Figure 3315 Plot of ln k versus 1T for the reaction of [SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) at different temperatures (TK = 283-303) (A = OCl- reaction and B = HOCl reaction)

y = ‐44611x + 16295Rsup2 = 09509

y = ‐28627x + 11599Rsup2 = 09829

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

148


Enthalpy of reaction

HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

SO+ with OCl- 346 -18353 3709 plusmn 009

SO+ with HOCl 213 -22262 2304 plusmn 009

From the gradient value of Figure 3315 the energy of activation enthalpy and entropies of

activation for the reactions were estimated The enthalpy values were found to be 346 kJ

mol-1 for OCl- and 213 kJ mol-1 for the HOCl initiated reactions The HOCl initiated

oxidation which is relatively a fast reaction had lower energy of activation of (2304 plusmn 009

kJ mol-1) compared to (3709 plusmn 009 kJ mol-1) for the OCl- reaction Large negative entropies

of activation values -18353 with OCl- and -22262 with HOCl initiated reactions observed

experimentally reflect the possible formation of compact activated complex


The product obtained from SO-OCl reaction (05g) was separated by column

chromatography using silica gel (Merck 9385) as the stationary phase on 4 cm diameter

column The mobile phase consisted of a hexane dichloromethane ethyl acetate with step

gradient (100 hexane (fractions 1-10) increased by 10 dichloromethane (fractions 11-18)

20 dichloromethane (fractions 19-29) 40 dichloromethane (fractions 30-38) and 60

dichloromethane (fractions 39-47) Fractions of 10 mL were collected in each step Two

compounds were obtained from this dye they were from fractions 12-16 and 52-60 The

plausible products from the above fractions are P1 (4-amino-5-methylbenzene-12-dichloride)

and P2 (4-amino-6-(2-chloro-6-hydroxyphenyl amino) 3-methyl-cyclohexa-24-dienone

oxime) Product P2 is identified in the current study Plausible oxidation products were shown

in Table 339

149


H3C

H2N

OCl

OCl

(P1)

4-amino-5-methylbenzene-12-dichloride

N

N CH3

NH2

OH

ClOH

(P2)

4-amino-6-(2-chloro-6-hydroxy-

phenylimino)-3-methyl-cyclohexa-24-

dienone oxime

3310 Stoichiometry equation

Stoichiometry of the safranine oxidation with hypochlorite was carried out using stock

hypochlorite concentration of 00015 M The stoichiometry of the reaction was established

with 11 and 15 ratios of Safranine-O and hypochlorite respectively using Beer-Lamberts

law the ratio of dye consumed to the oxidant was determined The stoichiometry was found to

be approximately 14 (plusmn 10) of SO+ and HOCl Thus the stoichiometric equation for the

overall reaction can be written as

SO+ + 4HOCl rarr P1 + P2 + 2H+ + Cl- (321)

where P1 is (4-amino-5-methyl-benzene-12-dichloride) and P2 is (4-amino-6-(2-chloro-6-

hydroxy-phenylimino)-3-methyl-cyclohexa-24-dienone oxime)

150


When the dye molecule reacts with the oxidant the hypochlorite ion attacks on the

quaternary carbon adjacent to quaternary nitrogen which bears a bulky phenyl ring and the

proton is transferred on to the other tertiary nitrogen The OCl- ion attaches to the carbon and

will result in cleavage of the bond between quaternary carbon and quaternary nitrogen which

forms an intermediate I1 The intermediate I1 further gets attacked by the OCl- or HOCl at

quaternary carbon which is connected to quaternary nitrogen which results in the formation

of intermediate I2 and product P1 The intermediate I2 is further attacked by HOCl and

hydroxyl ion is transferred on to the secondary nitrogen on the ring system That leads the

nitrogen to its quaternary state resulting in the formation of I3

The OCl- abstracts a proton from quaternary nitrogen of intermediate I3 to form HOCl which

in turn further oxidises the intermediate I3 and leads to the formation of product P2 The

formation of product P2 is confirmed with 1H NMR 13C NMR and mass spectrum The

proton NMR spectra revealed that the singlet peak at 213 for methyl protons the primary

amino group is seen at 527 and three aromatic protons are found at the range of 64 to

76 (Appendix 1 Figure 1114) In 13C NMR the alkyl carbon is observed at 1412

Aromatic carbons are found at 124-129 The carbons which bear substituted nitrogenrsquos can

be seen at higher 179 and 182 values (Appendix 1 Figure 1115) From the GC-MS

spectrum the molecular ion peak M+ is found at 277 which is observed at retention time 2064

min and corresponds to the molecular formula (C13H12N3O2Cl) of the product P2 (Appendix

1 Figure 1116)

The plausible oxidation products can be explained by the mechanistic scheme illustrated in

Figure 3316

151

N

N CH3

NH2H2N

H3C

OCl-N

N CH3

NH2H2N

H3C

OCl

H

N

N CH3

NH2

H

N

N CH3

NH2

OH

ClOH

H3C

H2N

OCl

OCl

OCl

N

N CH3

NH2

OH

H

I1

P1

I2

I3

P2

H+

HO Cl

HOCl

Cl- +

+ H+

Figure 3316 Possible reaction pathway for the oxidation of safranine-O


The reaction mechanism for the oxidation of safranine-O can be proposed as

H+ + OCl- HOCl HOCl + Cl- + H+ Cl2 SO+ + HOCl rarr I1

+ R1

I1+ + HOCl rarrI2 + P1 + H+ R2

I2 + HOCl rarr I3 + Cl- R3

I3 + HOCl rarr P2 + H+ R4

152



where P1 is (4-amino-5-methyl-benzene-12dichloride) and P2 is (4-amino-6-(2-chloro-6-

hydroxy-phenylimino)-3-methyl-cyclohexa-24-dienone oxime) products

3313 Rate law

The rate law expresses the order of reaction with respect to the respective reactants The

observed first-order dependence of the reactants and the observed salt effect suggests that the

rate limiting step involves one ion each of SO+ and OCl- Thus the major pathway of the

reaction may involve both HOCl and OCl- to give an activated complex which decomposes

completely to form the intermediates and products

The reaction fulfils pseudo first-order conditions based on this assumption the rate law may

be proposed as

(323)

3314 Simulations

Simulation studies were conducted based on the proposed mechanistic scheme (Figure

3116) The reaction scheme detailed the structures of the probable intermediates and the

products identified The proposed mechanism and the mechanism used for the simulations

represent the steps involving the formation of intermediates which undergo consecutive

reactions with other intermediates or the reactive species The estimated rate constants were

adjusted automatically with Simkine 2 software Table 3310 summarises the elementary

steps and rate coefficients used for the simulations and estimated rate coefficients Rate

153

constants obtained from the experiments in the present studies were employed for C3 and C4

Estimated rate coefficients were adjusted such that the simulated curves agreed with the

experimental curves (C5- C8)


Reaction

No

Reaction Mechanism

Forward rate

Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x 10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1 s-1 11 s-1

C3 SO+ + HOCl rarr I1+ 347 x 102 M-1 s-1 --

C4 SO+ + OCl- rarr I1 302 M-1 s-1 --

C5 I1 + H + rarr I1+ 23x 109 M-1 s-1 --

C6 I1+ + HOCl rarrI2 + P1 + H+ 475 x 106 M-1 s-1 --

C7 I2 + HOCl rarr I3 + Cl- 603 x 109 M-1 s-1 --

C8 I3 + HOCl rarr P2 + H+ 578 x 109 M-2 s-1 --

The rate limiting step of the oxidation mechanism involves steps initiated by OCl- or HOCl

on SO+ leading to the formation of the reactive intermediates (Reactions C3 and C4 are the

rate-determining steps for safranine oxidation) Consecutive steps for further oxidation of the

reactive intermediates were shown from C5-C8 C6 and C8 representing the reactions leading

to different probable products

154

Figure 3317 Experimental curves versus simulated curves for reaction of [SO+]0 (30 x 10-5M) with [OCl-]t (145 x 10-3 M)

A fair agreement between the experimental and corresponding simulated curves

(Figure 3317) strongly supports that the proposed reaction scheme is most probable The

estimated rate constants are fairly acceptable and also substantiate that HOCl is the crucial

species that drives the rapid reaction kinetics under low pH conditions

0

0000005

000001

0000015

000002

0000025

0 50 100 150 200

ConcentrationM

Times



E2S2

E3S3

E1 S1

155

Figure 3318 Product and intermediate formation for the reaction of safranine-O with hypochlorite

A typical curve is analysed for product and intermediates formation and the analysis isshown

in Figure 3318 (conditions similar to curves in Figure 3317) Curves E1 and S1 shows the

experimental and simulated curves for the reaction P1 and P2 represent the product formation

while the substrate depletion (E1) and I represent the intermediates formed during the

process The compiled data of simulated versus experimental curves and the concentrations

of the other reactants intermediate and products are presented (Appendix 1 Table 15 and

16)

000E+00

500E‐06

100E‐05

150E‐05

200E‐05

250E‐05

0 20 40 60 80 100

Concentration M

Time s

Products (P1P2)


Intermediates (I)

156

CHAPTER 4


Chlorine dioxide is a strong oxidising agent with capability to oxidise both organic and

inorganic pollutants and biotical properties for disinfection of water Over 95 of the chlorine

dioxide produced in the world today is made from sodium chlorite Chlorine dioxide (ClO2)

has become the most significant bleaching agent in the pulp and paper industry and is

currently accepted as most prominent technology for water treatment In this chapter the

results of detailed kinetic and spectroscopic investigations carried out on the reactions of three

selected dyes ie amaranth brilliant blue-R and safranine-O with chlorine dioxide solution as

a function of pH are elaborated The interpretations from the kinetic studies were further

supported by measuring the energy parameters for the reactions product characterisation and

simulations Plausible mechanisms for all three reactions were proposed

41 Oxidation of amaranth and chlorine dioxide


The kinetics of reaction between amaranth and chlorine dioxide were studied under varied

reaction conditions with large excess concentration of chlorine dioxide relative to the dye All

the experiments were carried out at 25 ordmC (plusmn 01) except the runs for estimation of the energy

parameters Figure 411 shows a typical curve with 00115 M initial concentration of ClO2

and (7 x 10-5 M) of dye at pH 90 A perusal of Figure 411 shows that the reaction had an

exponential decay and reaction was completed in less than two seconds indicating that the

reaction is very fast under alkaline conditions

157

Figure 411 Typical kinetic curve absorbance versus time plot for the reaction of [AM]0 (7x 10-5 M) with [ClO2]t (115 x 10-3 M) at pH = 90


The kinetic data was analysed using the KinetAsystTM Fit Asystant and the first-order equation

as described in detail earlier Figure 412 represents the typical experimental curve with the

fitted curve

Figure 412 KinetAsystTM single-exponential equation fit of two curves and residuals (lower sketch) for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x

10-3 M) using the first-order equation 1 Exp + C y = -A exp (-k x ) + C

005

015

025

035

045

055

065

075

0 05 1 15 2

Absorban

ce

Times

158

An observation of Figure 412 shows that the software fit results for the above curve is a fair

agreement that occurs between the experimental and computed curves with small residuals

and the rate constant obtained using first-order rate equation shows that the pseudo first-order

rate constant is 434 plusmn 001 s-1 and further indicates that for the chosen conditions the reaction

follows first-order kinetics with respect to the dye

413 Order with respect to chlorine dioxide

To establish the reaction order with respect to oxidant the experiments were carried out at

various initial concentrations of chlorine dioxide to monitor the rate of reaction The reaction

was fast and all the reactions exhibited exponential decay characteristics The reaction rate

increased with the increase in the initial concentration of chlorine dioxide and reaction was

almost completed in less than two seconds (Figure 413)

Figure 413 Depletion of amaranth with various chlorine dioxide concentrations for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t

10-3 M (a = 252 b = 379 c = 505 d = 631 and e = 757) at pH = 90

0

01

02

03

04

05

06

07

08

09

0 05 1 15 2

Absorban

ce

Times

a

b

cd

e

159

The absorbance versus time plots and the corresponding k (s-1) values are illustrated in Figure

413 corresponding fitted curves are shown in Figure 414 The k values were obtained by

analysing the respective kinetic curves

(a) (b)

(c) (d)

(e)

Figure 414 Fits using KinetAsystTM single-exponential equation and rate equation 1 Exp + C y = -A exp (-k x) + C for the reaction for amaranth with chlorine dioxide where k s-1 (a = 332 b = 374 c = 399 d = 422 and e = 480)

160

Table 411 summarises the values of pseudo first-order rate coefficients k obtained for

different chlorine dioxide initial concentrations at fixed ionic strength and Figure 415

illustrates the ln [ClO2] versus ln k plot

Table 411 Reaction between amaranth and chlorine dioxide at constant ionic strength [ClO2]t

(25 x 10-3 ndash 75 x10-3 M) with [AM]0 (70 x 10-5 M) pH = 90 and ionic strength (I = 0128)

[ClO2] 10-3 M ks-1

252 3320

379 3740

505 3990

631 4340

757 4800


Figure 415 Plot of ln [ClO2]t versus ln k for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (25x 10-3 ndash 75 x 10-3 M) at pH = 90 and I = 0128 M

y = 10719x ‐ 07905Rsup2 = 09967

04

06

08

1

12

14

16

18

125 145 165 185 205 225

ln [ClO2] t

ln kacute

161

The plot of ln [ClO2] versus ln k (Figure 415) gave a linear curve with a slope (107) and

correction coefficient (099) suggesting that the reaction rate has first-order dependence on

[ClO2]0

414 Effect of pH on reaction rate and reaction order with respect to OH- ion

The literature survey of the chlorine dioxide chemistry shows that predominant oxidation

reaction mechanism for chlorine dioxide proceeds through a process known as free radical

electrophilic abstraction rather than by oxidative substitution or addition (as in chlorinating

agents such as chlorine or hypochlorite) Chlorine dioxide functions as a highly selective

oxidant due to its unique one-electron abstraction mechanism whereby it is reduced to

chlorite (ClO2-) Unlike the oxidants Cl2 and HOCl which are more effective under acidic

conditions chlorine dioxide is more reactive at higher pH 203

Chlorine dioxide is relatively inert and stable under acidic pH and it becomes unstable with

increasing pH204 Hence the influence of pH on the oxidation rate of the substrate by

chlorine dioxide was investigated under wide range of pH conditions The pseudo first-order

rate constants obtained at different pH conditions were plotted The plot of k versus pH

(Figure 416) suggests that the rate of oxidation of substrate increased with increasing pH

from 60 to 90

162

Figure 416 Plot of k versus pH for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M)

Table 412 Effect of pH on reaction rate for the reaction

pH ks-1

60 0409

64 0411

66 0411

68 0480

70 0490

72 0946

74 1552

76 1928

78 2250

80 2500

04

09

14

19

24

29

34

6 65 7 75 8 85 9

k

pH

163

Table 412 contdhellip

82 2790

84 2910

86 3150

88 3290

90 3310


To establish the role of hydroxide ion in the reaction mechanism the order with respect to

hydroxide ion was estimated by plotting the ln k versus ln [OH-] (Figure 417) The slope of

the plot was equal to 083 suggesting that reaction rate is close to first-order dependence on

the hydroxide concentration

Figure 417 Plot of ln [OH-] versus ln k for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)[OH-]eq (1 x 10-8 ndash 195 x 10 -7 M)

The [OH-] variation experiments were repeated with increased number of runs in each of the

pH ranges the log k versus log [OH-] were plotted in three different pH ranges (Figure 418)

The reaction order with respect to [OH-] is observed to decrease with increasing pH

y = 08321x + 12573Rsup2 = 08844

‐4

‐3

‐2

‐1

0

1

2

‐185 ‐175 ‐165 ‐155 ‐145 ‐135 ‐125

ln k

ln(OH‐)

164

Figure 418 Plot of log [OH-] versus log k at different pH conditions

The observed order with respect to hydroxide ion under near neutral conditions was near unity

and its decrease with increasing pH (Figure 418) can be possibly explained in terms of the

likely occurrence of competitive reactions involving chlorine dioxide with and without the

involvement of hydroxide ion The probable rate of reaction contributed by the two

competitive reactions may be expressed as

r = k1 [ClO2] [AM-] + kOH- [ClO2] [OH-] [AM-]

= k1 + kOH- [OH-][ClO2] [AM-] = k [ClO2] [AM-] = k [AM-]

(41)

Where k is the observed pseudo first-order rate constant in the presence of excess

concentration of chlorine dioxide The second-order rate constant k is equal to k[ClO2] and

for fixed [ClO2] it can be expressed as k = k[ClO2] = k1 + kOH- [OH-] where k1 is the

second-order rate constant for the reaction between chlorine dioxide and dye and kOH- is the

third-order rate constant for the reaction between chlorine dioxide and dye which is catalysed

by [OH-] If the assumption is valid then in presence of [OH-] conditions the plot of k[ClO2]

y = 10825x + 72892Rsup2 = 09915

y = 06802x + 45703Rsup2 = 08898

y = 01227x + 11484Rsup2 = 09362

‐2

‐15

‐1

‐05

0

05

1

15

2

‐8 ‐6 ‐4 ‐2 0

log k

log[OH‐]

165

versus [OH-] should give a straight line Such a linear curve should have intercept equal to k1

and slope equal to kOH- Most likely such a linear relationship may not be observed at high

concentrations of hydroxide when it reaches stoichiometric proportions of the reductant The

plot of second order rate constant k versus [OH-] is illustrated in Figure419 Table 413

summarises the calculated values of the second-order rate constant

Table 413 Calculated [OH-]eq values and corresponding second order constants for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

[OH-]eqM ks-1 k 102M-1s-1

794 x 10-9 008 03

158 x 10-8 012 05

251 x 10-8 015 10

631 x 10-8 017 18

178 x 10-7 049 33

631 x 10-7 130 63

316 x 10-6 430 104

794 x 10-6 580 129


166

Figure 419 Plot of [OH-] versus k[ClO2] for the reaction [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) [OH-]eq (10 x 10-8- 631 x 10-7 M)

An observation of the Figure 419 shows that y-intercept value (k1) is of very small value

suggesting that in the absence of hydroxide ion the reaction is very slow and almost nil

which can be predicted from the reported inert behavior of chlorine dioxide at acidic pH From

the plot (Figure 419) the catalytic constant for the hydroxide catalysed reaction was

estimated to be 40 x 109 M-2 s-1 in the pH range of 60 - 75

Although a number of literature reports describe the increased decomposition of chlorine

dioxide at higher pH conditions very few studies explain the chemistry involved in the

increased oxidative activity of chlorine dioxide With many reactants the reaction of chlorine

dioxide undergoing one electron reduction forming chlorite ion is fast (ClO2(aq) + e- ClO2-

Edeg = 0954 V)205206 during such reactions chlorite is reported as the reaction product At

alkaline pH conditions even in the absence of reducing substrates the chlorine dioxide is

known to disproportionate forming chlorite and chlorate ions various reactions leading to

y = 4E+09xRsup2 = 09711

0

200

400

600

800

1000

1200

1400

1600

‐1E‐07 358E‐20 1E‐07 2E‐07 3E‐07 4E‐07 5E‐07

kM

‐2s‐1

[OH‐]M

167

disproportionation of chlorine dioxide under alkaline conditions result only in formation of

less reactive species such as chlorite and chlorate207

ClO2 + AM- rarr ClO2- + AM (42)

2ClO2 + 2OH- rarr ClO2-+ ClO3

-+ H2O (43)

Under alkaline conditions relative to ClO2 both chlorite and chlorate ions are less reactive

species The reactions of chlorite ion are relatively slow under acidic conditions and much

slower with alkaline pH Chlorate is almost inert under alkaline conditions The species that

possibly could attack the substrates at a significant rate are HClO2 Cl2O4 HOCl and peroxide

ion Their concentrations under alkaline pH play a significant role in estimating their

contribution towards higher reactivity The concentrations of reactive species such as HClO2

and HOCl under alkaline conditions will be very small contributing negligibility towards the

oxidation of the substrate The formation of a dimer of ClO2 ie Cl2O4 is not pH dependent

Hydroxide ion with two molecules of ClO2 could lead to the formation of peroxide ion but in

small concentrations208209

ClO2 + OH- (OClOOH)- (44)

(OClOOH)- + ClO2 OClOOH + ClO2- (45)

OClOOH + OH- HOClO + HOO- (46)

HOO- + 2ClO2 + OH- 2ClO2- + H2O (47)

Thus the increased reactivity under alkaline pH is certainly not due to such less reactive

species Hence higher reaction rates with increasing hydroxide concentration observed need to

168

be explained from a different point of view This probably happens through OH- ion facilitated

generation of much reactive species Possibly such species could form a transient complex

involving OH- ion ClO2 and substrate Considering the almost first-order dependence of the

reaction rate on hydroxide ion near neutral conditions its direct role in the rate limiting step

through probable formation of a reactive intermediate involving oxidant reductant and

hydroxide can be envisaged

ClO2 + AM + OH- rarr [ClO2 AM OH-] (48)

Margerum et al210 in their studies on the oxidation of nitrogen dioxide with chlorine dioxide

under alkaline conditions suggested the role of hydroxide ion with a preferential binding to

NO2 yielding ClO2- and NO3

- as products If the nucleophile associated with ClO2 instead as

was reported previously ClO2- and ClO3

- would be the products Margerum et al indicated

in the mechanism that NO3- is formed preferentially over ClO3

- with small amounts of chlorate

415 Effect on pH on the order with respect to chlorine dioxide

To assess the role of pH on the reaction order with respect to chlorine dioxide experiments

were conducted with varied initial concentrations of chlorine dioxide at three pH values (70

80 and 90) The values of first-order rate coefficients k for different [ClO2] are shown in

Table 414 at different pH values

169

Table 414 Observed rate constants at pH 70 80 and 90 regions for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x10-3 M)

pH = 70

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 049 1944 194 x 108

277 078 2058 206 x 108

303 093 1841 184 x 108

328 130 2060 206 x 108

353 150 1981 198 x 108

Mean k2 with stddev 198 plusmn 09

pH = 80

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 250 9920 99 x 107

277 260 9386 94 x 107

303 290 9570 96 x 107

328 320 9756 98 x 107

353 350 9915 99 x 107


pH = 90

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 332 13174 13 x 107

278 374 13453 13 x 107

303 399 13168 13 x 107

328 422 12865 13 x 107

353 480 13597 14 x 107


where k2 = k [ClO2ˉ] k = k [ClO2][OH-] four replicate experiments with RSD lt 4

170

Figure 4110 Plot of ln k versus ln [ClO2] for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) a (pH = 90) b (pH = 80) c (pH = 70)

Figure 4110 shows the linear plots of ln k versus ln [ClO2] at pH 70 80 and 90 with slopes

equal to 101 104 and 101 respectively The experimental results confirm that the change in

pH doesnrsquot have influence on the order with respect to ClO2 or the overall reaction

mechanism


From the pH studies it is evident that the reaction pathway involves [OH-] at both neutral and

alkaline conditions To confirm this assumption the kinetic salt effect on the reaction was

investigated by measuring the reaction rates at varied ionic strengths and fixed concentrations

of amaranth and chlorine dioxide A perusal of Table 415 indicates that the increase in I

resulted in increase in k values resulting in positive salt effect The log k versus square root

of ionic strength is plotted in Figure 4111

y = 10131x + 30233Rsup2 = 09891

y = 10371x + 47055Rsup2 = 09724

y = 10193x + 49541Rsup2 = 09759

‐1

‐05

0

05

1

15

2

25

‐39 ‐37 ‐35 ‐33 ‐31 ‐29 ‐27 ‐25

ln k

ln [ClO2]

a

b

c

171

Table 415 Effect of ionic strength on the reaction rate [AM]0 (70 x 10-5M) with [ClO2]t (115 x 10-3 M) pH = 80

Ionic Strength IM ks-1

00096 311

00174 341

00262 357

00354 375

00397 395


Figure 4111 Plot of log k versus radicI for the reaction of [AM]0 (7 x 10-5 M) with [ClO2]t

(115 x 10-3 M) at varying ionic strength I (00096 - 003)

The positive slope obtained (094) with correlation coefficient R2 = 098 (Figure 4111)

indicates the rate-limiting step involves similar like charged species possibly ie [OHˉ] and

AM-

y = 09499x + 04017Rsup2 = 09814

048

05

052

054

056

058

06

008 01 012 014 016 018 02

log k

radicI

172


The reaction rate can be affected by the presence of other species The presence of the other

ions may interfere with the reaction being investigated The effect of chloride taken at varied

concentrations was investigated by adding small amounts of sodium chloride salt

Table 416 Varied chloride concentration and observed rate constants for the reaction of [AM]0 (70 x 10-5 M) with [ClO2]t (115x 10-3 M)

[Cl-]M ks-1

0148 0486

0298 0496

0447 0502

0597 0512

0725 0530


From Table 416 the added chloride shows a small increase in rate of oxidation Unfortunately

the literature survey did not provide any adequate explanation of such behavior Some

chloride and other species might have formed a weak oxidant hypochlorite that may have

contributed towards the increase in the rate


The enthalpy and entropy of activation of a chemical reaction provide valuable information

about the nature of the transition state and hence about the reaction mechanism The

temperature dependence of the rate constant k was studied by performing experiments at

different temperature ranges 10 ordmC to 30 ordmC A typical Eyringrsquos plot is shown in Figure 4112

Assuming that the main path way of oxidation is OH- facilitated and taking the reaction order

173

with respect to OH- as unity the overall third order reaction coefficients calculated in Table

417

Table 417 Varied temperature in presence of chlorine dioxide and observed rate constant for the reaction of[AM-]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

TK ks-1 k3 M-2 s-1

283 0050 333 x 106

288 0090 600 x 106

293 0120 800 x 106

298 0170 110 x 107

303 0210 140 x 107


Figure 4112 Plot of ln k versus 1T for the reaction of amaranth with ClO2 at different temperatures

From Figure 4112 the value of the slope obtained is equals to -EaR and the calculated

energy of activation for this reaction is found to be 5006 kJ mol-1

y = ‐60224x + 3641Rsup2 = 09739

148

15

152

154

156

158

16

162

164

166

168

000325 00033 000335 00034 000345 00035 000355

ln k

1T

174


Reaction Enthalpy of reaction

HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

AM- with ClO2 4758 -65873 5006

The enthalpy of activation ΔHǂ for the reaction was found to be 4758 kJ mol-1 while the

entropy of activation was equal to -65873 J K-1 mol-1 suggesting that entropy of activated

complex was much lower than that of reactants (Table 418) of large and negative and

suggests that the formation of the transition state requires the reacting molecules to orient into

small conformations and approach each other at a precise angle

419 Products identification and characterization

AM-ClO2 crude product (054 g) was chromatographed using silica gel as the stationary phase

on a 4 cm diameter column The mobile phase consisted of hexane ethyl acetate step gradient

100 hexane (fractions 1-20) 10 dichloromethane in hexane (fractions 20-30) 30

dichloromethane in hexane (fractions 30- 40) Fractions of 10 mL were collected in each step

(fractions 20-30) Elution with 40 ethyl acetate afforded compound 2 (5 mg) The plausible

products identified as (P1 = 12 dioxy-3-hyposufite-8-sodiumsufite P2 = 14 napthalenedione)

(Table 419) Product P2 is identified in this study

175

Table 419 Possible major oxidation products


Using 15 x 10-3 M ClO2 the stoichiometry of the reaction mixture was maintained with 11

and 15 ratios of amaranth and chlorine dioxide respectively After a 30 min reaction the

residual reacted was determined and the amounts reacted were estimated The stoichiometry

was found to be approximately 14 (plusmn 10) of AM- and ClO2 Thus the stoichiometric

equation for the overall reaction can be written as

AM- + 4ClO2 + OH- + H2O rarr P1 + P2 + 4ClO2- +3H+ + N2 + SO3

2- + Na+ (49)

Stoichiometry and reaction products varied with longer reaction times

HO3S

NaO3S

O

O

(P1)

12 dioxy-3-hyposulfite-8-sodium sulfite

O O

(P2)

14-napthalenedione or 14-napthaqunione

176


One electron abstraction by ClO2 molecule from nitrogen atom will result in intermediate I1

I1 resonates between the two structures Loss of a hydroxyl proton with subsequent attack by a

hydroxyl ion on the carbon atom bearing the nitrogen results in I2 Three further electron

abstractions from I2 (two electrons from nitrogen yielding N+ and one electron from the carbon

atom in between the two rings) results in I3 Loss of a proton and rearrangement of the

electrons results in product (P1) and the ring bearing the nitrogen is further attacked by two

hydroxyl ions resulting in I4 which undergoes oxidation to the product napthaquinone (P2)

The structure of the napthaquionone was verified by the GC-MS and 1H and 13C NMR

spectroscopy (Appendix 2 Figure 211 and Figure 212) The singlet peak at δ 69 are due to

the olefinic proton and the resonances at δ 77 - δ 82 are due to the protons on the aromatic

ring In the 13C NMR spectrum the carbonyl carbon is seen at δ 185 and the olefinic carbon

is seen at δ 126 The aromatic carbons are seen at δ 131 δ 133 and δ 138 The GC-MS shows

a molecular ion peak at 158 (product P2) at retention time 1265 min The loss of the carbonyl

group shows a peak at 130 (which is intermediate) and the loss of the double bond can be seen

at peak 104 (Appendix 2 Figure 213)

These identified oxidation products can be explained by the mechanistic scheme illustrated in

Figure 4113

177

N N SO3Na

OHNaO3S

NaO3S

ClO2 N N SO3Na

OH-O3S

NaO3S

N N SO3Na

OHO3S

NaO3S

I1

N

HO3S

NaO3S

N SO3Na

O

-OH

-OH

HO3S

NaO3S

O

N N SO3Na

OH ClO23

HO3S

NaO3S

O

N

O

N SO3Na

H

HO3S

NaO3S

O

O

SO3NaNN

-OH-OH

SO3NaOH

OHOH

-OH

H

I2I3

P1

P2

-OH

H+ +

I4

O O

Figure 4113 Plausablie mechanistic scheme for the oxidation of amaranth with chlorine dioxide

178


Based on the reaction scheme provided (Figure 4113) and the stoichiometric results obtained

the mechanism can be proposed as follows

ClO2 + AM- rarr ClO2

- + AM (very slow)

AM- + ClO2 + OH- rarr HO AM ClO2

2- (slow and rate limiting step)

HO AM ClO2

2- rarr ClO2- + HO AM- (fast)

AM- + ClO2 + OH-rarr I1 -+ ClO2

- R1

I1- + ClO2 rarr I2 + ClO2

- R2

I2 + ClO2rarr I3+

+ ClO2- R3

I3+ + ClO2rarr I4

2+ + ClO2- R4

I42+ rarr P1 + I5

+ + H+ + N2 R5

I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ R6

The overall reaction can be expressed as

AM- + 4ClO2 + OH- + H2O rarrP1 + P2 + 4ClO2- +3H+ + N2 +

SO32-

+ Na+

(410)

179

4113 Rate law

While the overall order was three on chlorine dioxide reductant and hydroxide ion all the

three reactants registered order of one each Further the observed positive salt effect on the

reaction rate suggests that the rate limiting step involves one each ie AM- and OH- Thus the

rate limiting step may involves both AM- OH- and ClO2 to form the activated complex The

activated complex further undergoes fast consecutive steps

k1 ClO2 AM- k2 ClO2 [OH-] AM- (411)

As the reaction conditions fulfill pseudo first-order conditions the rate law may be proposed

as

k1 ClO2 AM- kOH‐ ClO2 [OH-] AM- (412)

where kOH-k2

[OH-]

r k1 kOH‐ [OH-] ClO2 AM- (413)

when [ClO2] is in large excess then

k AM-

where the pseudo first-order constant k equals

k = k1 + kOH- [OH-][ClO2] (414)

180

4114 Simulations

The computer simulations were done using the proposed mechanism using simkine software

The estimated rate constants were adjusted using the software until better fitting was obtained

The rate coefficients used for final simulations were optimized and matching of the

computed curves with experimental profiles under varied reaction conditions obtained are

shown in Figure 4114 and Table 4110 C1 is experimentally determined values in the

current study Coefficients used for reactions C3 ndash C6 are the estimated rate constants The

simulated curves exhibit the behavior of the experimental curves The graphs showing the

simulated and experimental curves are illustrated in Figure 4114


Reaction No Reaction Forward rate

C1 AM- + ClO2 + OH-rarr I1 -+ ClO2 10 x 10-7 M-2s-1

C2 I1- + ClO2 rarr I2 + ClO2

- 40 x 109 M-1s-1

C3 I2 + ClO2rarr I3+

+ ClO2- 534 x 109 M-1 s-1

C4 I3

+ + ClO2rarr I42+ + ClO2

-

4 97 x 109 M-1s-1

C5 I42+ rarr P1 + I5

+ + H+ + N2 4 54 x 109 s-1

C6 I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ 517 x 109 M-1s-1

181

Figure 4114 Experimental curves versus simulated curves for reaction of [AM-]0 (70 x 10-5 M) with [ClO2]t (115x10-3 M)

From Figure 4114 the generated simulated curves which were indicated by dashed lines

matched with experimental curves fair agreement between the experimental and

corresponding simulated curves strongly support that proposed reaction scheme as most

probable and estimated rate constants are fairly acceptable

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Time s

E1 S1 E2 S2

E3 S3



182

Figure 4115 Intermediates and product formation for the reaction of amaranth with chlorine dioxide


experimental and simulated curves for the reaction The kinetic profiles of P1 P2 show their

formation and I is the intermediate formed during the process The data of simulated versus

experimental curves and the concentrations of the other reactants intermediates and products

are compiled and provided (Appendix 2 Table 21 Table 22)

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Times

Expermental and Simulated curves (E1 and S1)

Intermediates(I)

Products (P1 and P2)

183

42 Reaction of brilliant blue and chlorine dioxide


Using low concentrations of dye and about hundred-fold excess of other reactants the kinetics

of oxidation of brilliant blue by chlorine dioxide was studied as a function of oxidant

concentration pH ionic strength and temperature The reaction progress was monitored by

measuring the change in concentration of the dye at 555 nm which is its absorption

maximum At pH 90 the depletion of dye was fast and the reaction completed in less than

four seconds with [BB+]0 70 x 10-5 M and with [ClO2]t 115 x 10-3 M (Figure 421)

Figure 421 Typical kinetic curve absorbance versus time plot for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) at pH = 90

0

01

02

03

04

05

06

07

08

0 2 4 6 8 10

Absorban

ce

Time (sec)

184


The analysis of the kinetic data was accomplished using the KinetAsystTM Fit software as

described earlier All kinetic profiles fitted well with the single exponential equation

confirming the reaction follows first-order kinetics and the order with respect to the dye is

one Figure 422 represents the typical experimental curve with the fitted curve

Figure 422 KinetAsystTM single-exponential equation fit of two curves and residuals (lower sketch) for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) using the first-order equation

An observation of Figure 422 shows that software fit results for the above curve shows a fair

agreement between the experimental and computed curves with small residuals and the

pseudo first-order rate constant obtained is 1715 s-1 with standard deviation of 0073

185


The reaction order with respect to oxidant was investigated by measuring the reaction rates

with different initial concentrations of oxidant at constant initial ionic strength and pH

Typical kinetic traces obtained for different initial concentrations of chlorine dioxide are


Figure 423 Depletion of brilliant blue-R with various chlorine dioxide concentrations for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t 10-3 M at pH = 900 I (0128 M) with [ClO2]t 10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)

Figure 424 shows curves illustrated together with fitted curves and corresponding residuals

using a first-order expression

‐01

6E‐16

01

02

03

04

05

06

07

0 1 2 3 4 5

Absorban

ce

Time ( Sec)

c

b

d

e

186

(a) (b)

(c) (d)

(e)

Figure 424 Fits using Kinet Asyst TM single-exponential equation and rate equation y = - A exp (-k x) + C for the reaction of [BB+]0 (70 x 10-5 M) where k s (a = 332 b = 374 c= 399 d = 422 and e = 467)

187

The values of the pseudo first-order rate coefficients k increased with increasing initial

chlorine dioxide concentration and results obtained from the above depicted curves are listed

in the Table 421

Table 421 Reaction between brilliant blue and chlorine dioxide at constant ionic strength [ClO2]t (25 x 10- 3ndash 35 x10-3 M) with [BB+]0 (70 x 10-5 M) pH = 90 and Ionic Strength (I = 0128)

[ClO2]t 10-3 M ks-1 252 332 278 374 303 399 328 422

353 467


The ln [ClO2]t versus ln k plot of the data summarised in Table 421 is shown in Figure

425 which had slope value equal to 103 (R2 = 098) A linear relation with gradient equal to

unity confirms reaction has first-order dependence on the oxidant concentration

Figure 425 Plot of ln [ClO2]t versus ln k for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t

(25 x 10-3 ndash 35 x10-3 M) at pH = 90 and I = 0128 M

y = 10308x ‐ 49235Rsup2 = 09865

‐37

‐365

‐36

‐355

‐35

‐345

‐34

‐335

‐33

119 129 139 149

ln[ClO

2] t

ln k

188

424 Effect of pH on reaction rate and reaction order with respect to hydroxide ion

The dependence of the rate constant on pH was examined under wide range of pH conditions

The values of observed pseudo first-order rate constants at different pH conditions are

summarised in Table 422

Table 422 Effect of pH on reaction rate for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (25 x 10- 3ndash 35 x10-3 M)

pH ks-1

60 029

63 032

67 038

69 047

72 082

74 096

79 134

81 160

82 169

84 171

86 179

88 175

90 186


Figure 426 shows the plot of k versus pH Although chlorine dioxide is known to have a fast

reaction at alkaline pH a perusal of Figure 426 shows that the rate of oxidation of substrate

increases with increasing pH but the increases registered were not uniform

189

Figure 426 Plot of k versus pH for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 775 x 10-4 M)

Therefore to further establish the role of hydroxide ion in the reaction mechanism the order

with respect to it ln k values were plotted against their corresponding ln [OH-] values in the

pH range 80 - 90 (Figure 427) The slope of the plot was equal to 080 and suggests that

reaction rate has approximately first-order dependence on the hydroxide ion concentration

02

04

06

08

1

12

14

16

18

2

6 65 7 75 8 85 9

k

pH

190

Figure 427 Plot of ln [OH-] versus ln k [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

Figure 427 illustrates the figure depicting the ln [OH-] versus ln k graph over the pH range

50-90 is not a linear curve Representative linear curves obtained the three different pH

ranges were shown in Figure 428 and suggests that the observed reaction order with respect

to [OH-] is decreased with decreasing pH


y = 08011x + 11389Rsup2 = 09487

04

06

08

1

12

14

‐135 ‐13 ‐125 ‐12

ln k

ln(OH‐)

y = 02213x + 12206Rsup2 = 09432

y = 04638x + 29978Rsup2 = 09704

y = 08011x + 49463Rsup2 = 09487

‐08

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐8 ‐75 ‐7 ‐65 ‐6 ‐55 ‐5

log k

log [OH‐]

191

While the order with respect to hydroxide ion was close to one at neutral conditions it tends

to decrease with decreasing pH This could be due to likely occurrence of oxidation through

two competitive pathways ie one by direct reaction of chlorine dioxide with the cationic dye

and the other involving chlorine dioxide dye and hydroxyl ions at the same given time At

high pH with excess concentration of OH- the later reaction which is fast will be predominant

and at very low hydroxyl ion concentration only the former slow reaction will occur Thus

the probable rate of reaction contributed by the two competitive reactions may be expressed as

r = k1 [ClO2] [BB+] + KOH- [ClO2] [OH-] [BB+] (415)

= k1 + KOH- [OH-][ClO2] [BB+] = k [ClO2] [BB+] (416)

where k is the observed pseudo first-order rate constant in presence of excess of chlorine

dioxide The second-order constant k is equal to k[ClO2] and for fixed [ClO2] it can be

expressed as k = k1 + kOH- [OH-] where k1 is the second-order rate constant for the reaction

between chlorine dioxide and dye while kOH- is the third-order rate constant for the OH-

catalysed reaction between chlorine dioxide and dye

If the assumption is valid then with varied initial [OH-] conditions a plot of k[ClO2] against

[OH-] should give a straight line That linear curve should have an intercept equal to k1 and

gradient equal to kOH- Such linear relationship may not be observed at high concentrations of

hydroxide when it reaches stoichiometric proportions with the reductant The calculated

values of k at varied hydroxide concentrations are listed in Table 423 and the plot of second-

order constant k versus [OH-] is illustrated in Figure 429

192

Table 423 Calculated [OH]eq values and corresponding second-order constants for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

[OH-]0M ks-1 k 102 M-1s-1

100 x 10-8 029 193

200 x 10-8 032 213

257 x 10-8 035 237

501 x 10-8 038 253

794 x 10-8 047 314

132 x 10-7 062 413

195 x 10-7 082 546


An observation of the Figure 429 shows that y-intercept value k1 is small value suggesting

that in the absence of hydroxide ion the reaction is about 193 which can be anticipated

based on the known inert behavior of chlorine dioxide under acidic pH From the plot (Figure

429) the catalytic constant for the hydroxide catalysed reaction in the pH range of 60-75

was estimated to be 20 x 109 M-2 s-1

193

Figure 429 Plot of [OH-] versus k[ClO2] for the reaction [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) [OH-]eq(10 x 10-8 M - 195 x 10-7 M)

As discussed in detail for the reaction of ClO2 with amaranth considering almost first-order

dependence of the reaction rate on hydroxide ion near neutral conditions a rate limiting step

involving chlorine dioxide BB+ and hydroxide may be proposed with formation an activated

complex as intermediate which decomposes in a fast reaction to form the intermediates or

products

ClO2 + BB+ + OH- rarr [ClO2 BB+

OH-] (417)

425 Effect of pH on the order with respect to chlorine dioxide

Rates of reaction of chlorine dioxide at three different pH conditions of oxidation of brilliant

blue-R was studied The values of first-order rate coefficients k and the calculated second-

order rate constants k2 for different [ClO2] under varied pH conditions and third-order rate

constants k3 are summarised in Table 424

y = 2E+09x + 17235Rsup2 = 09947

100

150

200

250

300

350

400

450

500

550

600

‐5E‐08 18E‐21 5E‐08 1E‐07 15E‐07 2E‐07

kM

‐2s‐1

[OH‐]

194

Table 424 Observed rate constants at pH 70 80 and 90 regions for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

pH = 70

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 029 1150 115 x 108

277 044 1160 116 x 108

303 059 1168 117 x 108

328 075 1188 119 x 108

353 091 1202 120 x 108


pH = 80

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 108 4285 430 x 107

277 115 4151 420 x 107

303 124 4092 410 x 107

328 138 4207 420 x 107

353 141 3994 400 x 107


pH = 90

[ClO2]x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 298 11825 118 x 107

278 324 11510 115 x 107

303 352 11551 115 x 107

328 381 11585 115 x 107

353 425 11898 118 x 107


where k2 = k [ClO2] k = k [ClO2][OH-]


195

Figure 4210 Plot of ln k versus ln [ClO2] for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) A (pH = 90) B (pH = 80) C (pH = 70)

Figure 4210 illustrates the plots of ln k versus ln [ClO2] at pH 70 80 and 90 obtained were

linear with the slopes equal to 104 084 103 respectively The reaction order unity with

respect to ClO2 under different pH conditions confirms that the change in pH doesnrsquot have

influence on the order with respect to ClO2 or on the overall reaction mechanism


The effect of added salt on the reaction of the dye with the oxidant were investigated by

adding different concentrations of neutral salt and by measuring the reaction rates with fixed

concentrations of brilliant blue and chlorine dioxide The obtained k values are summarised in

Table 425

y = 1039x + 25823Rsup2 = 09999

y = 08489x + 3195Rsup2 = 09763

y = 1016x + 48161Rsup2 = 09881

‐15

‐1

‐05

0

05

1

15

2

25

3

‐4 ‐35 ‐3 ‐25 ‐2

ln k

ln [ClO2]

A

B

C

196

Table 425 Effect of ionic strength on the reaction rate [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) pH = 90

Ionic strength IM ks-1

00096 0091

00174 0095

00262 0105

00354 0109

00397 0111


The log k versus square root of ionic strength values are plotted in Figure 4211 which

indicates a good straight line with positive slope value with R2 = 097

Figure 4211 Plot of log k versus radicI for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) at varying ionic strength I (00050 - 0056)

From Figure 4211 the observed positive slope indicates the positive salt effect confirming the

rate-limiting step involves oppositely charged species ie possibly [OHˉ] and BB+ ions

y = 09016x ‐ 11324Rsup2 = 0974

‐106

‐104

‐102

‐1

‐098

‐096

‐094

009 011 013 015 017 019

logk

radicI

197


The activity of the reaction rate can be affected by the presence of other species The presence

of the other ions may interfere with the reaction being investigated The effect of chloride

taken at varied concentrations was investigated by adding small amounts of sodium chloride

salt

Table 426 Varied chloride concentration and observed rate constants for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

[Cl-]M ks-1

0148 0720

0298 0730

0447 0710

0597 0710

0725 0720


From Table 426 the added chloride indicate a littleno change in the rate of the reaction nor

its participation in any important reaction

428 Effect of temperature on rate of reaction

In order to study the effect of reaction temperature on the degradation of brilliant blue-R a

series of experiments were conducted at different temperature ranges 10 ordmC to 30 ordmC The

third-order rate constants at different temperatures were obtained from the kinetic curves The

results are tabulated in Table 427

198

Table 427 Varied temperature in presence of chlorine dioxide and observed rate constant for the reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

TK ks-1 k3 M-2s-1

283 0100 70 x 106

288 0136 90 x 106

293 0172 11 x 107

298 0260 17 x 107

303 0329 22 x 107


The ln k2 values were plotted against the corresponding reciprocal temperature values and the

linear plot is illustrated in the Figure 4212 From the plot the activation energy Ea and the

other energy parameters were estimated (Table 428)

Figure 4212 Plot of ln k versus 1T for the reaction of brilliant blue with ClO2 at different temperatures

y = ‐51842x + 34016Rsup2 = 0992

156

158

16

162

164

166

168

17

000325 00033 000335 00034 000345 00035 000355

ln k

1T

199


Reaction Enthalpy of activation

HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

BB+ with ClO2 4758 -67636 5006

The enthalpy of activation ΔHǂ for the reaction was calculated using the equation ΔHǂ = (Ea

ndash mRT) where m is the total order of reaction and R and T are the gas constant and

temperature respectively The activation energy obtained were (Ea = 5006 kJ mol-1) ΔHǂ

value at 25ordm C was found to be 4758 kJ mol-1 and the reaction had large negative entropy of

activation (-67636 J K-1 mol-1) suggesting the formation of an tightly packed activated

complex resulting in decrease in entropy


The extraction of the oxidation product of brilliant blue with chlorine dioxide was done as

explained in the experimental chapter (Section 217 page no 69) Separation of BB-ClO2 (44

mg) afforded two compounds compound 1 (8 mg) and compound 2 (5 mg) These were from

fraction 41-46 eluted with 50 dichloromethane in hexane compound 1 was from fraction

54-56 eluted by 70 dichloromethane The fraction 57-64 yielded compound 2 when eluted

with 80 dichloromethane The identified products were (P1 = 4-(4-ethoxy-phenylamino)-

benzoic acid and P2 = N-(4-ethoxy-phenyl)-hydroxylamine) (Table 429)

The proton NMR spectrum of the product (P1) exhibited triplet for methyl protons at 083

and 146 quartet for methylene proton at 412 and eight aromatic protons are in the range of

200

620 - 740 (Appendix 2 Figure 214) 13C NMR reveals that carbonyl carbon is observed

at 16972 and aromatic carbons are in the range of 11618 - 14947 The alkyl carbons are

observed at 6037 and 1408 for -CH2 and -CH3 respectively (Appendix 2 Figure 215)

The GC-MS of product P1 showed molecular ion peak at mz 257 (M+) this corresponds to

molecular formula of C15H15NO3 The observed prominent peak at mz 229 (M+) was due to

loss of ethyl group and the mz 110 (M+1) corresponds to loss of p-aminophenol

(Appendix 2 Figure 216)

The 1H-NMR spectrum of product P2 displayed ethyl protons at 149 and 417 - 419 as

triplet and quartet for methyl and methylene protons respectively Methylene protons are

observed at 529 and aromatic protons are observed as multiplet in the range of 671 -

808 (Appendix 2 Figure 217) The 13C NMR spectrum exhibited two alkyl carbon at lower

112 and 6037 for -CH3 and -CH2 respectively The methylene carbon is observed at

higher 6383 due to deshielding effect from aromatic ring Aromatic carbons are observed at

11880 -14947 and two aromatic carbons are observed at higher 14032 and 14947 due

to more deshielding effect from the substituentrsquos on the carbon (Appendix 2 Figure 218)

Mass spectrum of P2 exhibited molecular ion peak at 578 (M+) which was in agreement with

molecular mass of P2 Another significant peak was observed at 249 (M-1) due to the loss of

two moles of meta-substituted benzyl group (Appendix 2 Figure 219)

201

Table 429 Plausible major oxidation products

N

O

H

COOH

(P1)

4-(4-ethoxy-phenylamino)-benzoic acid

N

SO3

NSO3

(P2)

N-(4-ethoxy-phenyl)-hydroxylamine


The stoichiometry experiments were carried out using 00015 M chlorine dioxide

concentration The stoichiometry is established with 11 and 15 ratios of the dye and

oxidant Residual amounts of dye and chlorine dioxide reacted were estimated from the

initial and final concentrations The stoichiometry was found to be roughly 12 (plusmn 10) of

BB+ and ClO2 Thus the stoichiometric equation for the overall reaction can be represented as

BB+ + 2 ClO2 + 3OH- rarr P1 + P2 + 2 ClO2- + H2O (418)

where P1-(4-Ethoxy-phenylamino)-benzoic Acid and P2N-(4-Ethoxy-phenyl)-

hydroxylamine

202


When brilliant blue is made to contact with the oxidant chlorine dioxide the hydroxy radical

attacks the carbon radical and forms a hydroxyl intermediate I1 The intermediate I1 is again

attacked by hydroxyl ion and forms ether type of intermediate I2 and the it gets oxidized by

hydroxyl ion which to yield product substituted biphenyl analog P1 and substituted biphenyl

amine analog P2

The identified oxidation products can be explained by the mechanistic scheme shown in

Figure 4213

203

NSO3

N

O

H

N

SO3

ClO2

N

O

H

N

SO3

NSO3

OH

N

O

H

N

SO3

NSO3

N

O

H

N

SO3

NSO3

O

H

OH

N

O

H

N

SO3

O

NSO3

HO-N

O

H

COOH

N

SO3

NSO3

I1

I2

P1 P2

ClO2

Figure 4213 Mechanistic scheme for oxidation of brilliant blue-R with chlorine dioxide


The reaction mechanism and the rate law can be proposed based on the known chemistry of

chlorine dioxide decomposition as discussed

ClO2 + BB+ rarr ClO2

- + BB2+ Very slow (419)

BB+ + ClO2 + OH- rarr HO BB ClO2 rarr ClO2

- + HO BB+

Rate limiting step

(420)

204

HO BB+ + H2O rarr BB2+ + OH- fast (421)

BB+ + ClO2 + OH-rarr I1+ + ClO2

- R1

I1+ + OH- rarr I2 + H2O

R2

I2 + ClO2 + OH- rarr P1 +P2 + ClO2- R3

Overall equation can be represented as

BB+ + 2ClO2 + 3OH- rarr P1 + P2 + 2ClO2- + H2O (422)

4213 Rate law

The rate law for the oxidation of brilliant blue has been thoroughly examined The first-order

dependence of the reaction rate on the reactants and the observed salt effect suggests that the

rate limiting step involves one each of like charges possibly the BB+ and hydroxide ions and

ClO2 Thus the major pathway of the reaction may involve both chlorine dioxide and [OH-]

ion to give an activated complex which decomposes to form the intermediates and products

k1[ClO2][BB+ ] + k2 [ClO2][OH-] [BB+

] (423)


as

k1[ClO2][BB+] + kOH- [ClO2][OH-][BB+] (424)

205

where kOH-k2

[OH-]

r k1 + kOH- [OH-][ClO2] [BB+] (425)


k [BB+] (426)

where the pseudo first-order const k equals

k = k1 + kOH- [OH-] ClO2 (427)

4214 Simulations

Simulations were done to validate the proposed mechanisms and prove that it is the more

probable one The estimated rate constant were optimized and adjusted until the simulated

curves matched well with the experimental curves (Table 4210) The simulated curves

exhibit the behavior of the experimental curves The graphs showing the simulated and

experimental curves are illustrated in Figure 4214



C1 BB+ + ClO2 + OH-rarr I1+ + ClO2

- 172 x 102 M-1 s-1

C2 I1+ + OH- rarr I2 + H2O

200 x 109 M-2 s-1

C3 I2 + ClO2 + OH- rarr P1 +P2 + ClO2- 321 x 109 M-2 s-1

206

Figure 4214 Experimental curves versus simulated curves for reaction of [BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M)

The simulations were based on the proposed comprehensive mechanism The reaction scheme

in the product analysis gives details for the intermediate structures The simulated curves

matched with experimental curves confirming the suggested mechanism to be probable Rate

constants from C1 and C2 are experimental values and C3 is the estimated rate constant

0

000001

000002

000003

000004

000005

000006

000007

000008

0 5 10 15 20 25

Concentration M

Times

E1S1

E2S2

E3S3

Experimental curves (E1E2 and E3 )Simulated curves (S1 S2 and S3)

207

Figure 4215 Intermediates and product formation for selected typical kinetic curves (E2 S2)

Figure 4215 illustrates reaction conditions similar to curves in Figure 4214 Curves E2 and

S2 shows the experimental and simulated curves for the reaction The curves P1 P2 and P3

show the products formation and I is the intermediate formed during the process

A fair agreement between the experimental and corresponding simulated curves strongly

support that the proposed reaction scheme as most probable and estimated rate constants are

fairly acceptable The data of simulated versus experimental curves and the concentrations of

the other reactants intermediates and products are compiled (Appendix 2 Table 23 Table

24)

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

0 2 4 6 8 10 12

Concentration M

Time s

Products (P1P2 P3)

Experimental and Simulated curves (E2S2)

Intermediates (I)

208

43 Oxidation of safranine-O with chlorine dioxide

431 Reaction of safranine-O and chlorine dioxide

The reaction of safranine-O with chlorine dioxide was studied by kinetic approach The

reaction rate was measured by monitoring the change in absorbance at its λmax (519 nm) as a

function of time Figure 431 illustrates the absorbance versus time plot for the reaction of

safranine-O (30 x 10-5 M) with [ClO2]t = 115 x 10-3 M at pH 900 The depletion of safranine

was completed in less than ten seconds indicating that the reaction is fast (Figure 431)

Figure 431 Typical absorbance versus time plot for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) at pH = 900


The obtained curve from Figure 432 represents the experimental curve and matching this

curve generated by asystant software using a first-order rate equation

0

01

02

03

04

05

06

07

08

09

0 2 4 6 8 10 12

Absorban

ce

Time (sec)

209

Figure 432 KinetAsystTM single-exponential equation fit of two curves and residuals (lower sketch) for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x

10-3 M) using the first-order equation

An observation of Figure 432 shows fair agreement between the experimental (red) and

computed (green) curves with small residue (bottom blue curve) The estimated pseudo first-

order rate constant had a value of 06609 s-1 with standard deviation of 00051 indicating that

for the chosen conditions the reaction follows the first-order kinetics with respect to the dye


To establish the reaction order with respect to the oxidant kinetic runs were carried out by

varying initial concentrations of chlorine dioxide at constant pH and ionic strength All the

reactions exhibited exponential decay and the reaction rate increased with the increase in the

initial concentration of chlorine dioxide

210

Figure 433 Depletion of safranine-O with various chlorine dioxide concentrations for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t

10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)

Figure 433 illustrates the kinetic runs for different initial concentrations of chlorine

dioxideand the software fit analysis and corresponding estimated pseudo first-order rate

constants are shown in Figure 434 (curves a to e)

0

01

02

03

04

05

06

07

08

0 1 2 3 4 5

Absorban

ce

Time s

ecb

a

d

211

(a) (b)

(c) (d)

(e)

Figure 434 Experimental and computed fits using KinetAsystTM single- exponential equation for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t

10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)

The values of the estimated pseudo first-order rate coefficients k for different initial chlorine

dioxide concentrations are listed in the Table 431

212

Table 431 Reaction between safranine-O and chlorine dioxide at constant ionic strength [SO+]0 (30 x 10-5 M) with [ClO2]t (25 x 10-3 ndash 75 x10-3 M) pH = 90 and Ionic Strength (I = 0128)

[ClO2]t 10-3 M ks-1

252 2100

278 2310

303 2610

328 2820

353 3010


Further the plot of ln k versus ln [ClO2] gave a linear curve with a slope 109 and correction

coefficient 099 (Figure 435) suggesting that the reaction rate has first-order dependence on

[ClO2]0

Figure 435 Plot of ln [ClO2]t versus ln k for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (25 x 10-3 ndash 75 x10-3 M) at pH = 900 and I = 0128 M

y = 1097x + 4779Rsup2 = 0994

06

07

08

09

1

11

12

13

14

15

16

‐37 ‐36 ‐35 ‐34 ‐33

ln k

ln [ClO2]t

213

434 Effect of pH

The effect of variation of initial pH on the oxidation of safraninendashO was studied using fixed

concentration of substrate and oxidant and by adding various initial concentrations of acid

Table 432 represents the obtained pseudo first-order rate constants

Table 432 Effect of pH on reaction rate

pH ks-1

60 0405

63 041

66 0421

68 0475

70 0499

72 0956

74 1752

76 1828

78 211

80 245

82 269

84 281

86 325

88 349

90 361


The plot of k versus pH is illustrated in (Figure 436) A perusal of the curve suggests that

the rate of oxidation of substrate increased with increasing pH and increase was significant at

higher pH range

214

Figure 436 Plot of k versus pH for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M)

Between the pH range 60 and 70 there is very marginal increase in the rate constants This

could be explained due to the slow reactivity of chlorine dioxide under acidic conditions and

the latter increase is due to the high reactivity of chlorine dioxide at alkaline pH range

To have a close look at the role of OH- ions in the reaction the kinetic data for the pH range

(60 ndash 90) in Table 432 was plotted as ln k versus ln [OH-] plot (Figure 437) which gave a

straight line with slope = 081 an gradient R2 = 095 It shows that in the alkaline pH range

reaction order with respect to hydroxyl ion is about unity

0

05

1

15

2

25

3

35

4

45

5

6 65 7 75 8 85 9

ks

‐1

pH

215

Figure 437 Plot of ln [OH-] versus ln k for the reaction of [SO+]0 (30 x 10-5M) with [ClO2]t (115 x 10-3 M)

When all the kinetic data over the pH range 30 to 90 was plotted (Figure 437) the slope of

curve registered a continuous decrease with decrease in pH The data can be approximately

divided into three ranges where somewhat linear relationship can be established The slope of

those curves clearly shows the order with respect to hydroxyl ion decrease from 081 (in the

pH range 90 - 80) to 0019 (in the pH range 70 - 30)


y = 081x + 11269Rsup2 = 0953

0

05

1

15

2

25

‐135 ‐13 ‐125 ‐12 ‐115 ‐11

ln k

ln(OH‐)

y = 01651x + 08533Rsup2 = 09089

y = 01944x + 13006Rsup2 = 09979

y = 0809x + 48942Rsup2 = 0953

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐75 ‐65 ‐55 ‐45

log k

log [OH‐]

216

Initially the observed order with respect to hydroxide ion under near neutral conditions is less

than one and further decreased to 016 at pH 60 This observed decrease in order with

respect to hydroxide ion could possibly be explained by assuming the two competitive

reactions contributing toward the overall oxidation of substrate namely reaction one the

direct reaction between substrate and chlorine dioxide and the other involving substrate ClO2

and hydroxide ion The rate law for competitive oxidation of substrate can be written as

r = k1 [ClO2] [SO+] + KOH- [ClO2] [OH-] [SO+] (428)

= k1 +KkOH- [OH-][ClO2] [SO+] (429)

= k [ClO2] [SO+] (430)

= krsquo [SO+] (431)

where k represents the observed pseudo first-order rate constant in presence of excess

concentration of chlorine dioxide For fixed excess concentration of ClO2 k = k1 + kOH-

[OH-] where the second-order constant k will be equal to ln k[ClO2] and k1 and kOH-

respectively represent the second-order rate constant for the reaction between chlorine dioxide

and dye and the third-order rate constant for the reaction between chlorine dioxide and dye

involving OH- ion For this assumption to be correct a plot of k[ClO2] versus [OH-] should

give a straight line That linear curve should have intercept = k1 and slope = kOH- Possibly at

high concentrations of hydroxide such linear relationship may not be observed due to

stoichiometric magnitude of the dye

Table 433 summarises the values of equilibrium concentrations of hydroxide ion for the

given pH its corresponding k and calculated k values

217

Table 433 Calculated [OH-]eq values and corresponding second-order constants for their reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M)

[OH-]eq k k 102M-1s-1

182 x 10-8 0369 246

251 x 10-8 0411 274

398 x 10-8 0411 274

631 x 10-8 0480 320

100 x 10-7 0490 326

158 x 10-7 0946 630

251 x 10-7 1052 701


Figure 439 illustrates the plot of k versus [OH-] (data from Table 432)

Figure 439 Plot of [OH-] versus k[ClO2] for the reaction [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) [OH-]eq (18 x 10-8 - 251 x 10-7 M)

y = 2E+09x + 19826Rsup2 = 0915

0

100

200

300

400

500

600

700

800

0 5E‐08 00000001 15E‐07 00000002 25E‐07 00000003

kM

‐2s‐1

[OH‐] M

218

An observation of Figure 439 indicates that k1 value (y-intercept) is small that suggests that

in the absence of hydroxide ion the reaction rate is small which can be predicted from the

reported inert behavior of chlorine dioxide at acidic pH From the plot (Figure 439) the

catalytic constant for the hydroxide catalysed reaction was estimated to be 20 x 109 M-2 s-1 in

the pH range of 60 ndash 75 Considering almost first-order dependence of the reaction rate on

hydroxide ion near neutral conditions a rate limiting step involving chlorine dioxide SO+ and

hydroxide is proposed in section 4312


The kinetic runs further carried out to determine the effect of pH on reaction order with

respect to oxidant Experiments were conducted in three different pH range (70 80 and 90)

with varied initial concentrations of chlorine dioxide The values of first-order rate

coefficients k and corresponding calculated second-order rate constants k2 are shown in the

Table 434

Table 434 Observed rate constants at pH 70 80 and 90 regions for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x10-3 M)

pH = 70

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 049 1944 194 x 108

278 059 2122 212 x 108

303 065 2145 215 x 108

328 069 2104 21 0x 108

353 074 2096 21 0x 108


219

Table 434 contd

pH = 80

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 115 4563 456 x 108

278 135 4856 486 x 108

303 145 4785 479 x 108

328 160 4878 488 x 108

353 175 4972 497 x 108


pH = 90

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 190 7540 754 x 108

278 208 7482 748 x 108

303 222 7327 733 x 108

328 250 7622 762 x 108

353 280 7932 793 x 108




Figure 4310 Plot of ln k versus ln [ClO2] for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) a (pH=90) b (pH=80) c (pH=70)

y = 11338x + 47969Rsup2 = 09766

y = 12126x + 4618Rsup2 = 09907

y = 1181x + 36698Rsup2 = 09632 ‐1

‐05

0

05

1

15

‐37 ‐36 ‐35 ‐34 ‐33 ‐32

ln k

ln[ClO2]

220

The reaction orders with respect to oxidant at pH 7080 and 90 were 121 115 and 118

respectively and all the values were of approximately of unity The reaction orders obtained

confirm that the change in pH does not have any influence on the order with respect to ClO2

implying that reaction pathway remains unchanged


Experiments were conducted to establish the reacting species involved in the rate limiting

step by measuring the rate coefficients for the same reaction conditions at varied initial ionic

strengths Sodium sulfate was used as neutral salt to adjust the ionic strength The obtained

results summarised in Table 435 indicate that the k values tend to decrease with increasing

ionic strength

Table 435 Effect of ionic strength on the reaction rate [SO+]0 (30 x 10-5 M) [ClO2]t (115 x 10-3 M) at pH = 80


00096 0126

00174 0109

00262 0105

00354 0096

00397 0093


221

Figure 4311 Plot of log k versus radicI for the reaction of [SO+]0 (30 x 10-5 M) with [ClO2]t (115 x 10-3 M) at varying ionic strength I (0009 - 004 M)

Figure 4311 shows the plot of log k versus square root of ionic strength and the observed

slope = -126 with negative primary salt effect suggests that reactive species in the rate-

determining step are of opposite nature and possibly the OHˉ and SO+ ions

437 Effect of chloride on rate of reaction

Similar to the studies with other substrates the impact of chloride on the reaction was

examined The results in Table 436 show that addition of initial chloride ion caused some

increase in the rate constant No explanation was found in the literature but this increase may

be due to the possible formation of other weak reactive oxidising species such as HOCl

y = ‐12368x ‐ 07853Rsup2 = 09731

‐104

‐102

‐1

‐098

‐096

‐094

‐092

‐09

‐088

009 011 013 015 017 019

log k

radicI

222

Table 436 Varied chloride concentration and observed rate constants for the reaction of [SO+]0 (30 x10-5 M) with [ClO2]t (115x 10-3 M)

IM ks-1

0060 0153

0061 0155

0062 0160

0063 0175

0064 0176


438 Effect of temperature

The temperature dependence of the rate constant k was studied by performing experiments at

different temperatures ranges from 10 oC to 30 oC From the values of k third order rate

constants with respect to OH- were calculated and summrised in Table 437 A typical

Eyringrsquos plot is shown in Figure 4312

Table 437 Varied temperature in presence of chlorine dioxide and observed rate constant for the reaction of [ClO2]t (115x 10-3 M) with [SO+]0 (30 x10-5 M) at

pH 90

TK ks-1 k3 M-2s-1

283 125 83 x 107

288 152 10 x 108

293 179 12 x 108

298 193 13 x 108

303 205 14 x 108 Mean of four replicate experiments with relative standard deviation lt 4

223

Figure 4312 Plot of ln k versus 1T for the reaction of [SO+]0 (3 x 10-5 M) with [ClO2]t (115 x 10-3 M)



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

SO+ with ClO2 1508 -74836 1755

Using the slope and intercept of Figure 4312 the calculated activation energy obtained

(Table 438) were (Ea = 1755 kJ mol-1) Hǂ value at 25 ordmC was found to be 1508 kJ mol-1

and the reaction had large negative entropy of activation (-74836 J K-1 mol-1) suggesting the

formation of an activated complex resulting in a decrease in entropy

y = ‐21128x + 2575Rsup2 = 09501

182

183

184

185

186

187

188

189

000325 00033 000335 00034 000345 00035 000355

ln k

1T

224


The product extracted from the reaction of SO-ClO2 (035 g) was separated by column


column The mobile phase consisted of a hexane dichloromethane ethyl acetate step gradient

100 hexane (fractions 1-15) increasing by 10 dichloromethane (fraction 15-18) 20

dichloromethane (fraction 19-29) 40 dichloromethane (fraction 30-38) Fractions of 10 mL

were collected in each step Two compounds were obtained from this dye they were from

fractions 12-16 and 52-60 Product P1(phenol) and P2 (37-dimethyl-phenazine-2-8-diol)

(Table 439) Product P2 is identified in the current study

The proton NMR spectrum of product P2 exhibits olefinic methyl groups at lower 21

aromatic protons in the range of 657 to 67 (Appendix 2 Figure 2110) due to symmetry

in the molecule one half of the product can be seen The 13C NMR spectrum revealed the

appearance of aromatic carbons that were observed in the rage of 116 to 149 Two methyl

groups corresponds to the 2968 and 1695 (Appendix 2 Figure 2111) The mass

spectrum of the product P2 showed molecular ion peak at mz 2391 (M-) at retention time

1397 min that accounts to the molecular formula of C14H14N2O2 (Appendix 2 Figure 2112)

The observed peak at mz212 (M+) may be due the loss of two methyl groups from the

product P2

225

Table 439 Major oxidation products

OH

(P1)

phenol

N

N CH3H3C

OHOH

(P2)

37-dimethyl-phenazine-2-8-diol


The stoichiometry experiments were conducted in a similar manner as it was described

earlier The stoichiometry was found to be approximately 15 (plusmn 10) of SO+ to ClO2 The


SO+ + 4 ClO2 + 5OH- rarr P1 + P2 + 4ClO2- + 2NH2OH (432)

where (P1 = phenol) and (P2 =37-dimethyl-phenazine-2-8-diol)


When chlorine dioxide comes in contact with the dye safranine-O the hydroxyl ion attacks the

quarternary carbon of phenyl group which is a substituent on nitrogen atom forming an

226

intermediate I1 together with possible product phenol (P1) The intermediate I1 further

undergoes oxidation with chlorine dioxide to yield product P2 which is confirmed by NMR

and GC-MS spectrum

N

N CH3

NH2H2N

H3C

ClO2

H3C

H2N N NH2

CH3N

OH

N

N CH3

N

H3C

H

HH2N

OH

OHI1

P1ClO2

N

N CH3

N

H3C

H

H

OHH2N

HO

N

N CH3H3C

OHH2N

I2

I3

N

N CH3

OH N

H3C

H

H

OH

N

N CH3H3C

OHN

H

H

OH

ClO2

OH-

ClO2

OH-

OH

N

N CH3H3C

OHOH

I4

P2

Figure 4313 Mechanistic scheme for the oxidation of safrainine-O with chlorine dioxide

227


The overall reaction scheme for safranine oxidation with chlorine dioxide can be proposed as

ClO2 + SO+ rarr ClO2- + SO2+ Very slow (433)

SO+ + ClO2 + OH- rarr HO SO ClO2 rarr ClO2- + HO SO+ Rate

limiting

(434)

HO SO+ + H2O rarr SO2+ + OH- fast

SO+ + ClO2 + OH- rarr P1 + I1

+ + ClO2

- R1

I1+ + ClO2 + OH-

rarr I2+ + ClO2

- R2

I2+ + OH- rarr I3

+ NH2OH R3

I3 + ClO2 + OH-

rarr I4 + ClO2- R4

I4 + ClO2 + OH- rarr P2 + NH2OH+ ClO2

- R5

The overall equation can be represented as


228

4313 Rate law

The first-order dependence of the reaction rate on the reactants and from the salt effect

experiments the major pathway of the reaction may involve both chlorine dioxide and [OH-]


Under such circumstances the rate law can be proposed as

k1 [ClO2][SO+] + k2 [ClO2][OH-] [SO+] (436)


as

k1 ClO2 SO+ ‐ ClO2 [OH-] SO+ (437)

where kOH-k2

[OH-]

r k1 kOH‐ [OH-] ClO2 SO+ (438)


k SO+ (439)


k k1 kOH‐ [OH-] ClO2 (440)

229

4314 Simulations

The reaction scheme from product analysis gives insight for the intermediate structures To

support the mechanism is probable one the simulations were done based on the

comprehensive mechanism explained in Figure 4313 The rate constants obtained from

experimental data were employed and for the other steps estimated rate constants were

calculated and provided for simulation programme (Table 4310) Rate constants from C1

and C2 are experimental values C3- C5 are the estimated rate constants



C1 SO+ + ClO2 + OH- rarr P1 + I1

+ + ClO2

- 198 x 102 M-1 s-1

C2 I1+ + ClO2 + OH-

rarr I2+ + ClO2

- 200 x 109 M-2s-1

C3 I2+ + OH- rarr I3

+ NH2OH 456 x 109 M-2s-1

C4 I3 + ClO2 + OH-

rarr I4 + ClO2- 590 x 109 M-2s-1

C5 I4 + ClO2 + OH- rarr P2 + NH2OH+ ClO2

- 675 x 109 M-2s-1

Figure 4314 Experimental curves versus simulated curves for reaction of [SO+]0 (70 x 10-5 M) with [ClO2]t (145 x 10-3 M) intermediates and product formation

0

000001

000002

000003

000004

000005

000006

000007

000008

0 05 1 15 2 25 3 35 4

ConcentrationM

Times

E1 S1

E2 S2

E3 S3

Experimental curves (E1E2 and E3)simulated curves (S1 S2 and S3)

230

The graphs showing the simulated and experimental curves are illustrated in Figure 4314

The estimated rate constants are optimized to obtain the better fits using the Simkine 2

programme The simulated curves matched with experimental curves confirming the

suggested mechanism to be probable

Figure 4315 Product and intermediate formation for the reaction of safranine-O with chlorine dioxide

Figure 4315 for the similar experimental conditions E1 and S1 represents experimental

and simulated curves for the reaction P1 P2 P3 show the product formation and I is the

intermediates formed during the process The data of simulated versus experimental curves

and the concentrations of the other reactants intermediates and products are compiled in

(Appendix 2 Table 25 and Table 26)

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 1 2 3 4 5 6

Concentration M

Times

Products (P1P2P3)


Intermediates (I)

231

CHAPTER 5

CONCLUSIONS

51 Reactions with hypochlorite

The oxidation reaction mechanisms of three water soluble textile dyes amaranth (azo dye)

brilliant blue-R (triaryl dye) and safranine-O (azine dye) with hypochlorite were investigated

by kinetic approach The kinetics of all the reactions were studied under low dye

concentration conditions and with excess concentrations of all the other reagents Under those

conditions all the reactions followed pseudo first-order kinetics confirming the first-order

dependence of the reaction rate on the organic substrate concentration Although reaction

rates had first-order dependence on the oxidising agent for the three reactions pH played an

important role With increasing acid concentration the reaction order with respect to acid

decreased from unity to fractional value For all the three reactions it was found that acid

was not directly involved in the rate limiting step but it influenced the equilibrium

concentrations of hypochlorite and hypochlorous acid The oxidation of all the three organic

substrates occurred through competitive pathways one facilitated by hypochlorite ion and the

other by hypochlorous acid The oxidation by hypochlorous acid reaction was found to be the

faster and major pathway The major oxidation products were identified and the

stoichiometric ratios for all the reactions were established Based on the major oxidation

products and the partial orders with respect to the reactants probable reaction mechanisms

were elucidated The proposed mechanisms were validated by the simulation of the kinetic

profiles The energy parameters inclusive of Arrhenius factor enthalpy entropy and energy

of activations for both pathways of the three reactions were estimated

232

For the amaranth oxidation reaction the second-order rate constants for OCl- and HOCl

facilitated oxidations were (k1 = 19 plusmn 06) M-1 s-1 and (k2 = 232 plusmn 18) M-1 s-1 respectively

The rate limiting steps involved reaction between AM- and OCl- ions and AM- and HOCl

which was confirmed by the positive salt effect (log k versus I12) for the former reaction and a

linear relation between k and the ionic strength in the latter At high pH conditions reaction

was slow and reached a plateau with increasing acid concentrations The energy parameters

namely the energy and entropy of activations were (3365 kJ mol-1 and -1906 J K-1 mol-1) for

OCl- initiated reaction and (2687 k J mol-1 and -2228 J K-1 mol-1) for the reaction with HOCl

The main plausible oxidation products were 34-dihydroxy naphthalene-27 disulfonic sodium

salt dichloro-14-naphthoquione and naphtha (23) oxirene-23-dione The stoichiometric

ratio of dye to hypochlorite was found to be 13

For the brilliant blue oxidation reaction the second-order rate constants for OCl- and HOCl

initiated oxidations were (k1 = 12 plusmn 02) M-1 s-1 and (k2 = 220 plusmn 12) M-1 s-1 respectively

The species that are involved in the rate determining steps for the two paths were BB+ and

OCl- ions and BB+ and HOCl This was supported by the observed negative salt effect (log k

versus I12) for the hypochlorite driven reaction and the linear relation between k and I in the

later case At high pH reaction was slow and reached a maximum at increased [H+] The

values of energy and entropy of activations were (3553 kJ mol-1 and -19193 J K-1 mol-1) for

OCl- initiated reaction and (2928 kJ mol-1 and -20457 J K-1 mol-1) for the reaction with

HOCl The main oxidation products were 4-ethoxy-phenylamine 3-ethylaminomethyl-

benzenesulfonicacid anion 3- ethylamino chloro methyl-benzene sulfonic acid anion and 4-

[bis-(4-hydroxy-phenyl)-methylene]-cyclohexa-25-hydroxide For the safranine-O oxidation

reaction the second-order rate constants for OCl- and HOCl driven oxidations were (k1 = 30

plusmn 05) M-1 s-1 and (k2 = 348 plusmn 28) M-1 s-1 respectively The rate limiting steps involved

233

reactions between SO+ and OCl- ions and SO+ and HOCl which again were supported by the

observed negative salt effect (log k versus I12) for the former reaction and a linear relation

between k and I for the SO+HOCl as it involved reaction between charged species SO+ and

neutral polar species HOCl At alkaline pH the reaction was slow and the reaction rate

recorded continued rise with increasing acid concentration This suggests that at low pH

possibly the protonated substrate gets oxidized faster than the unprotonated entity The

energy parameters namely energy and entropy of activations (3709 kJ mol-1 and -18353

J K-1 mol-1) for the OCl- initiated reaction and (2304 kJ mol-1 and -22262 J K-1 mol-1) for the

reaction with HOCl The main oxidation products were 4-amino-5-methyl-benzene-1 2

dichloride and amino-6-(2-chloro-6-hydroxy-phenylimino)-3-methyl-cyclohexa-24-dienone

oxime

A comparison of the rate constants suggests that the oxidation of the two textile dyes

amaranth and brilliant blue-R had second-order rate constants of similar magnitude for both

the hypochlorite and HOCl initiated oxidations but the rate constant for safranine-O was

observed to much higher than the other two dyes

While the amaranthhypochlorite reaction needed three moles of HOCl (six electron

oxidation) brilliant blue-R consumed four moles of HOCl (eight electron oxidation) and

safranine-O oxidations consumed four moles of HOCl A longer exposure of the dyes to

oxidants resulted in increased consumption of the reactant resulting in further oxidation of

the reaction products A comparison of energy parameters reveals that the safranine-O

required slightly higher activation energy to that of amaranth and brilliant blue-R The

entropy values obtained indicates that amaranth and brilliant blue-R had same activation

energies where as safranine-O recorded slightly lower values with hypochlorite initiated

234

reactions and safranine-O and amaranth recorded similar entropy values compared to

brilliant blue-R which had slightly lower values

52 Reactions with chlorine dioxide

The kinetics and mechanisms of the of oxidation of three water soluble textile dyes amaranth

(azo dye) brilliant blue-R (triaryl dye) and safranine-O (azine dye) with chlorine dioxide

were investigated in detail The decolorisation kinetics of the dyes was studied with excess

concentrations of all the other reagents except the dye which was taken at low concentration

Under the chosen conditions all the reactions followed pseudo first-order kinetics with

respect to organic substrate Under all conditions the reaction rate had first-order dependence

on the chlorine dioxide concentration while the concentration of hydroxide ion played an

important role as catalyst hence the pseudo first-order rate constants registered an increasing

trend with increase in [OH-] The reaction rate had first-order dependence on hydroxide ion

when its concentration was low but order with respect to [OH-] decreased when [OH-] was in

stoichiometric proportion to reactants The experimental data suggested that the predominant

oxidation reaction mechanism for chlorine dioxide proceeds through free radical electrophilic

(ie electron-attracting) abstraction rather than by oxidative substitution or addition (as in

chlorinating agents such as chlorine or hypochlorite) The rate limiting step involved the

formation of an activated complex involving one each of ClO2 dye and OH- ions That

complex possibly had both chlorine dioxide and hydroxide ion directly attached to organic

substrate

For the amaranth oxidation by chlorine dioxide the second-order rate constants are k2 = (198

plusmn 09) M-1 s-1 at pH 70 (971 plusmn 23) M-1 s-1 pH 80 and pH 90 (1325 plusmn 28) M-1 s-1

respectively The elementary rate limiting step involved reaction between similar charged

235

ions AM- and [OH-] which was confirmed by the positive salt effect (log k versus I12) The

catalytic constant for hydroxyl ion was estimated to be 40 x 109 M-2 s-1 in the pH range of

60-75 The energy parameters namely energy and entropy of activations were 5006 kJ mol-

1 and -65873 J K-1 mol-1 respectively The main oxidation products were 12-dioxy-3

hyposulfite- 8 sodium sulfite and 14-napthalenedione

For the chlorine dioxide-brilliant blue-R reaction the second-order rate constants were

k2 = (117 plusmn 02 M-1 s-1) at pH 70 (414 plusmn 11 M-1 s-1) at pH 80 and (1167 plusmn 17 M-1 s-1) at

pH 90 The rate limiting step involved reaction between BB+ and OH- ions in addition to

ClO2 The involvement of oppositely charged species was validated by the positive salt effect

(log k versus I12) observed The catalytic constant for [OH-] catalysed reaction was estimated

to be 20 x 109 M-2 s-1 in the pH range 60 -75 The values of energy and entropy of

activations were 5006 kJ mol-1 and -67636 J K-1 mol-1 respectively The main oxidation

products were identified as 4-(4-ethoxy-phenylamino)-benzoic acid N-(4-ethoxy-phenyl)-

hydroxylamine

For the safranine-O oxidation with chlorine dioxide values of the second-order rate constants

k2 were (208 plusmn 08 M-1 s-1) (481 plusmn 15 M-1 s-1) and (7580 plusmn 22 M-1 s-1) at pH 70 80 and

pH 90 respectively The rate limiting steps involved reactions between SO+ and OH- ions

which are supported by the exerted negative kinetic salt effect The energy and entropy of

activation values were 1755 kJ mol-1 and -74836 J K-1 mol-1 respectively The main

oxidation products identified were phenol 37-dimethyl-phenazine-28-diol (P2) as identified

in the current study

236

In relative terms under identical conditions comparing the values at pH 70 amaranth and

safranin-O had pseudo first-order rate constants of similar magnitudes while brilliant blue-R

had a lower value At pH 90 high k values were observed for Amaranth reaction followed by

brilliant blue-R and safranine-O reactions had lower rate coefficient values

Amaranth-chlorine dioxide reaction had a 14 stoichiometric ratio showing a four electron

abstraction where as brilliant blue consumed two moles of chlorine dioxide with two electron

abstraction and safranine-O consumed four moles of chlorine dioxide suggesting four

electron abstraction

Scope for future work

This work has potential for further investigations to evaluate the effect of longer exposure of

dyes to oxidants and the scope of various recyclable heterogeneous catalyst materials to

achieve complete mineralization of the organic substrates with better efficiencies and in

shorter durations

237

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186 N Zaghbani A Hafiane and M Dhahbi Desalination 2008 222 348-356

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198 J Oakes Coloration Technology 2002 32(1) 63-79

199 J March in Advances in Organic Chemistry 6th Edition John Wiley and Sons 2007

1703-1731



202 L K Adam IFabian K Suzuki and G Gordon Inorg Chem 1992 31 3534-3541

203 V Csorda B Bubnis Istvaacuten Faacutebiaacuten and G Gordon Inorg Chem 2001 40

1833-1836

204 B R Deshwal and H Lee Ind Eng Chem 2004 10(4) 667-673

205 HDR Engineering Inc Hand book of public water systems 2nd Edition John Wiley amp

Sons 2001 p526-528

206 L M Babcock T Pentecost and W H Koppeno1 J Phys Chem 1983 93

8126-8127

207 E M Aieta and J D Berg J Am Water Works Assoc 1986 78 62-70

247

208 I N Odeh J S Francisco and DW Margerum Inorg Chem 2002 41

6500-6506

209 J Hoigne H Bader Water Res 1994 28 45-55

210 RH Becker JS Nicoson and DW Margerum Inorg Chem 2003 42 7938-7944

248

APPENDIX 1-CHAPTER 3

11 Amaranth oxidation products with hypochlorite

Figure 111 GC-MS spectrum of amaranth oxidation product P2 dichloro-14-naphthoquione (mz = 228) with hypochlorite

249

Figure 112 GC-MS spectrum of amaranth oxidation product P3 naphtha (2 3) Oxirene-27- dione (mz = 174) with hypochlorite

250

Figure 113 1H NMR spectrum of amaranth product P1 (34-dihydroxy naphthalene-27 di sulphonic sodium salt) with hypochlorite

251

Figure 114 13C NMR spectrum of amaranth oxidation product P1 (34-dihydroxy naphthalene- 27 di sulphonic sodium salt) with hypochlorite

252

Table 11 Amaranth - hypochlorite experimental and simulated curves-compiled data

Time E1 Time S1 Time E2 Time S2 Time E3 Time S3

02 700E-05 1757 646E-05 0 700E-05 063 612E-05 0 700E-05 0254 596E-05

04 696E-05 1991 640E-05 02 681E-05 073 601E-05 02 610E-05 0293 580E-05

06 692E-05 2225 635E-05 04 663E-05 083 592E-05 0293 573E-05 0332 564E-05

08 687E-05 246 630E-05 06 645E-05 093 582E-05 0332 557E-05 0371 549E-05

1 683E-05 2694 625E-05 0732 633E-05 102 573E-05 0371 543E-05 041 533E-05

12 679E-05 2929 620E-05 083 625E-05 112 563E-05 041 528E-05 0449 519E-05

14 675E-05 3163 615E-05 0927 617E-05 122 554E-05 0449 514E-05 0488 505E-05

16 671E-05 3397 611E-05 1025 608E-05 132 546E-05 0488 500E-05 0527 492E-05

176 667E-05 3632 605E-05 1123 600E-05 142 537E-05 0527 487E-05 0566 478E-05

196 663E-05 3866 6E-05 122 592E-05 151 529E-05 0566 474E-05 0605 465E-05

199 659E-05 41 596E-05 1318 585E-05 161 521E-05 0605 462E-05 0644 453E-05

269 645E-05 5507 570E-05 1904 539E-05 22 475E-05 084 393E-05 0879 386E-05

313 640E-05 621 558E-05 2197 518E-05 249 454E-05 0957 362E-05 0996 356E-05

316 636E-05 6444 554E-05 2294 511E-05 259 447E-05 0996 353E-05 1035 347E-05

336 635E-05 6679 550E-05 2392 504E-05 269 440E-05 1035 343E-05 1074 338E-05

34 632E-05 6913 546E-05 249 498E-05 278 434E-05 1074 334E-05 1113 329E-05

387 623E-05 7851 530E-05 288 472E-05 317 41E-05 123 300E-05 1269 297E-05

407 622E-05 8085 526E-05 2978 466E-05 327 404E-05 1269 292E-05 1308 289E-05

41 618E-05 8319 523E-05 3076 459E-05 337 398E-05 1308 285E-05 1347 282E-05

43 618E-05 8554 519E-05 3173 453E-05 347 392E-05 1347 277E-05 1387 274E-05

48 605E-05 9726 501E-05 3662 424E-05 395 365E-05 1543 242E-05 1582 241E-05

5 604E-05 996 497E-05 3759 418E-05 405 360E-05 1582 236E-05 1621 235E-05

504 601E-05 1019 494E-05 3857 413E-05 415 355E-05 1621 230E-05 166 230E-05

524 600E-05 1043 490E-05 3955 407E-05 425 351E-05 166 223E-05 1699 224E-05

527 596E-05 1066 486E-05 4052 402E-05 435 346E-05 1699 218E-05 1738 218E-05

574 588E-05 116 473E-05 4443 381E-05 474 327E-05 1855 195E-05 1894 197E-05

594 587E-05 1184 469E-05 454 376E-05 483 322E-05 1894 190E-05 1933 192E-05

598 584E-05 1207 466E-05 4638 371E-05 493 318E-05 1933 185E-05 1972 187E-05

618 583E-05 123 463E-05 4736 366E-05 503 314E-05 1972 180E-05 2012 183E-05

621 580E-05 1254 46E-05 4833 361E-05 513 310E-05 2012 176E-05 2051 178E-05

641 579E-05 1277 456E-05 4931 356E-05 522 306E-05 2051 171E-05 209 174E-05

688 571E-05 1371 444E-05 5322 338E-05 561 290E-05 2207 153E-05 2246 157E-05

691 567E-05 1394 441E-05 5419 333E-05 571 285E-05 2246 149E-05 2285 154E-05

738 559E-05 1488 429E-05 581 316E-05 61 271E-05 2402 134E-05 2441 139E-05

758 559E-05 1512 426E-05 5908 312E-05 62 267E-05 2441 131E-05 248 136E-05

762 555E-05 1535 423E-05 6005 307E-05 63 264E-05 248 127E-05 2519 132E-05

782 555E-05 1559 420E-05 6103 303E-05 64 260E-05 2519 124E-05 2558 129E-05

785 551E-05 1582 417E-05 6201 299E-05 649 257E-05 2558 121E-05 2597 126E-05

253

805 551E-05 1605 414E-05 6298 295E-05 659 254E-05 2597 117E-05 2636 123E-05

902 532E-05 1816 390E-05 7177 262E-05 747 226E-05 2949 922E-06 2988 989E-06

996 517E-05 2004 369E-05 7958 235E-05 825 203E-05 3261 744E-06 3301 818E-06

102 516E-05 2027 367E-05 8056 232E-05 835 201E-05 3301 725E-06 334 798E-06

102 513E-05 2051 364E-05 8154 229E-05 845 198E-05 334 705E-06 3379 778E-06

104 513E-05 2074 362E-05 8251 226E-05 854 196E-05 3379 687E-06 3418 761E-06

104 509E-05 2098 359E-05 8349 223E-05 864 193E-05 3418 669E-06 3457 743E-06

106 509E-05 2121 357E-05 8447 220E-05 874 191E-05 3457 651E-06 3496 726E-06

107 506E-05 2144 355E-05 8544 217E-05 884 188E-05 3496 634E-06 3535 708E-06

109 505E-05 2168 352E-05 8642 214E-05 893 186E-05 3535 617E-06 3574 691E-06

109 502E-05 2191 35E-05 874 211E-05 903 184E-05 3574 601E-06 3613 675E-06

118 488E-05 2379 331E-05 9521 190E-05 981 166E-05 3886 485E-06 3926 56E-06

12 488E-05 2402 329E-05 9618 187E-05 991 164E-05 3926 472E-06 3965 548E-06

121 485E-05 2426 327E-05 9716 185E-05 10 162E-05 3965 459E-06 4004 535E-06

123 484E-05 2449 325E-05 9814 182E-05 101 160E-05 4004 447E-06 4043 524E-06

123 481E-05 2473 323E-05 9911 180E-05 102 158E-05 4043 435E-06 4082 512E-06

125 481E-05 2496 321E-05 1001 178E-05 103 156E-05 4082 424E-06 4121 500E-06

13 474E-05 259 313E-05 104 168E-05 107 149E-05 4238 381E-06 4277 457E-06

13 471E-05 2613 311E-05 105 166E-05 108 147E-05 4277 371E-06 4316 446E-06

132 470E-05 2637 309E-05 106 164E-05 109 145E-05 4316 361E-06 4355 437E-06

137 461E-05 2754 299E-05 1108 153E-05 114 136E-05 4511 316E-06 455 390E-06

148 447E-05 2965 282E-05 1196 136E-05 123 122E-05 4863 248E-06 4902 320E-06

149 445E-05 2988 281E-05 1206 134E-05 124 121E-05 4902 242E-06 4941 314E-06

151 444E-05 3012 279E-05 1216 132E-05 125 119E-05 4941 235E-06 498 307E-06

151 442E-05 3035 277E-05 1226 131E-05 125 118E-05 498 229E-06 5019 301E-06

153 441E-05 3059 275E-05 1235 129E-05 126 116E-05 5019 223E-06 5058 295E-06

158 432E-05 3176 267E-05 1284 121E-05 131 109E-05 5215 195E-06 5254 265E-06

16 432E-05 3199 265E-05 1294 119E-05 132 108E-05 5254 190E-06 5293 259E-06

161 429E-05 3223 264E-05 1304 117E-05 133 107E-05 5293 185E-06 5332 253E-06

163 429E-05 3246 262E-05 1313 116E-05 134 106E-05 5332 180E-06 5371 249E-06

163 426E-05 327 260E-05 1323 114E-05 135 104E-05 5371 175E-06 541 243E-06

168 420E-05 3363 254E-05 1362 108E-05 139 996E-06 5527 157E-06 5566 225E-06

17 420E-05 3387 253E-05 1372 107E-05 14 984E-06 5566 153E-06 5605 219E-06

17 417E-05 341 251E-05 1382 105E-05 141 973E-06 5605 149E-06 5644 216E-06

177 408E-05 3551 242E-05 144 973E-06 147 906E-06 584 127E-06 5879 191E-06

179 408E-05 3574 241E-05 145 960E-06 148 894E-06 5879 124E-06 5918 187E-06

179 405E-05 3598 239E-05 146 948E-06 149 884E-06 5918 120E-06 5957 184E-06

181 405E-05 3621 237E-05 147 935E-06 15 872E-06 5957 117E-06 5996 181E-06

188 396E-05 3762 229E-05 1528 863E-06 156 815E-06 6191 998E-07 623 163E-06

189 394E-05 3785 228E-05 1538 851E-06 157 804E-06 623 972E-07 6269 159E-06

191 393E-05 3809 227E-05 1548 840E-06 158 794E-06 6269 946E-07 6308 156E-06

254

191 391E-05 3832 225E-05 1558 829E-06 159 784E-06 6308 921E-07 6347 153E-06

198 385E-05 3949 218E-05 1606 775E-06 164 742E-06 6504 806E-07 6543 138E-06

198 383E-05 3973 217E-05 1616 765E-06 165 733E-06 6543 784E-07 6582 135E-06

20 382E-05 3996 216E-05 1626 755E-06 166 723E-06 6582 764E-07 6621 133E-06

20 380E-05 402 214E-05 1636 745E-06 166 716E-06 6621 743E-07 666 130E-06

207 372E-05 416 207E-05 1694 688E-06 172 666E-06 6855 633E-07 6894 118E-06

209 372E-05 4184 206E-05 1704 678E-06 173 658E-06 6894 616E-07 6933 116E-06

21 369E-05 4207 205E-05 1714 669E-06 174 650E-06 6933 600E-07 6972 115E-06

212 369E-05 423 203E-05 1724 660E-06 175 642E-06 6972 584E-07 7011 112E-06

212 367E-05 4254 202E-05 1733 652E-06 176 635E-06 7011 569E-07 705 111E-06

27 309E-05 5402 153E-05 2212 338E-06 224 369E-06 8925 153E-07 8964 605E-07

271 307E-05 5426 152E-05 2222 334E-06 225 364E-06 8964 149E-07 9003 605E-07

277 302E-05 5543 148E-05 227 312E-06 23 344E-06 916 130E-07 9199 574E-07

278 300E-05 5566 148E-05 228 308E-06 231 341E-06 9199 127E-07 9238 566E-07

28 300E-05 559 147E-05 229 304E-06 232 337E-06 9238 124E-07 9277 570E-07

28 298E-05 5613 146E-05 23 300E-06 233 333E-06 9277 120E-07 9316 565E-07

282 298E-05 5637 145E-05 231 296E-06 234 329E-06 9316 117E-07 9355 563E-07

313 271E-05 6246 126E-05 2563 209E-06 259 250E-06 1033 584E-08 1037 467E-07

322 264E-05 6434 121E-05 2642 188E-06 267 229E-06 1064 471E-08 1068 454E-07

327 258E-05 6551 118E-05 269 176E-06 272 217E-06 1084 412E-08 1088 437E-07

329 258E-05 6574 117E-05 27 173E-06 273 215E-06 1088 401E-08 1092 450E-07

329 257E-05 6598 117E-05 271 171E-06 274 213E-06 1092 391E-08 1096 446E-07

331 256E-05 6621 116E-05 272 169E-06 275 211E-06 1096 380E-08 11 442E-07

332 255E-05 6645 115E-05 2729 167E-06 276 209E-06 11 370E-08 1104 430E-07

339 249E-05 6785 112E-05 2788 154E-06 282 196E-06 1123 315E-08 1127 442E-07

346 244E-05 6926 109E-05 2847 142E-06 288 185E-06 1146 269E-08 115 426E-07

348 244E-05 6949 108E-05 2856 140E-06 289 185E-06 115 262E-08 1154 423E-07

348 242E-05 6973 107E-05 2866 138E-06 29 182E-06 1154 255E-08 1158 422E-07

35 242E-05 6996 107E-05 2876 136E-06 291 180E-06 1158 248E-08 1162 412E-07

36 234E-05 7207 102E-05 2964 121E-06 299 166E-06 1193 195E-08 1197 419E-07

362 234E-05 7231 102E-05 2974 119E-06 30 164E-06 1197 190E-08 1201 404E-07

362 232E-05 7254 101E-05 2983 118E-06 301 161E-06 1201 185E-08 1205 410E-07

364 232E-05 7277 101E-05 2993 116E-06 302 160E-06 1205 180E-08 1209 415E-07

369 229E-05 7371 985E-06 3032 110E-06 306 153E-06 1221 162E-08 1225 408E-07

369 227E-05 7395 981E-06 3042 109E-06 307 150E-06 1225 157E-08 1229 395E-07

378 222E-05 7559 947E-06 311 989E-07 314 139E-06 1252 130E-08 1256 401E-07

379 221E-05 7582 943E-06 312 976E-07 315 138E-06 1256 127E-08 126 394E-07

381 221E-05 7606 937E-06 313 963E-07 316 136E-06 126 124E-08 1264 397E-07

386 216E-05 7723 915E-06 3179 901E-07 321 131E-06 1279 108E-08 1283 393E-07

388 216E-05 7746 909E-06 3188 889E-07 322 13E-06 1283 105E-08 1287 395E-07

388 215E-05 777 905E-06 3198 877E-07 323 129E-06 1287 102E-08 1291 391E-07

255

39 214E-05 7793 900E-06 3208 866E-07 324 127E-06 1291 997E-09 1295 382E-07

39 213E-05 7816 895E-06 3218 854E-07 325 127E-06 1295 970E-09 1299 379E-07

399 208E-05 7981 866E-06 3286 778E-07 332 120E-06 1322 805E-09 1326 384E-07

40 207E-05 8004 862E-06 3296 768E-07 333 118E-06 1326 784E-09 133 381E-07

402 207E-05 8027 858E-06 3306 757E-07 333 117E-06 133 763E-09 1334 387E-07

432 188E-05 866 752E-06 3569 528E-07 36 903E-07 1436 370E-09 1439 359E-07

451 178E-05 9012 697E-06 3716 432E-07 375 811E-07 1494 248E-09 1498 368E-07

451 177E-05 9035 694E-06 3725 426E-07 375 811E-07 1498 241E-09 1502 365E-07

458 173E-05 9176 673E-06 3784 393E-07 381 775E-07 1521 205E-09 1525 365E-07

46 173E-05 9199 670E-06 3794 388E-07 382 758E-07 1525 200E-09 1529 362E-07

461 172E-05 9223 666E-06 3804 383E-07 383 757E-07 1529 195E-09 1533 365E-07

463 172E-05 9246 665E-06 3813 378E-07 384 752E-07 1533 190E-09 1537 356E-07

47 167E-05 941 642E-06 3882 344E-07 391 715E-07 1561 157E-09 1564 356E-07

472 167E-05 9434 639E-06 3891 340E-07 392 711E-07 1564 153E-09 1568 349E-07

481 162E-05 9621 618E-06 397 305E-07 40 663E-07 1596 124E-09 16 358E-07

495 156E-05 9902 582E-06 4087 260E-07 412 615E-07 1643 895E-10 1646 347E-07

496 155E-05 9926 579E-06 4097 256E-07 413 613E-07 1646 872E-10 165 346E-07

498 155E-05 9949 577E-06 4106 253E-07 414 610E-07 165 849E-10 1654 341E-07

498 154E-05 9973 575E-06 4116 250E-07 415 599E-07 1654 826E-10 1658 353E-07

50 153E-05 9996 572E-06 4126 246E-07 416 590E-07 1658 805E-10 1662 341E-07

50 153E-05 1002 569E-06 4136 243E-07 416 590E-07 1662 783E-10 1666 352E-07

502 152E-05 1004 567E-06 4145 240E-07 417 593E-07 1666 763E-10 167 351E-07

503 151E-05 1007 565E-06 4155 237E-07 418 585E-07 167 742E-10 1674 352E-07

51 148E-05 1021 549E-06 4214 218E-07 424 565E-07 1693 632E-10 1697 349E-07

54 136E-05 1079 489E-06 4458 156E-07 449 483E-07 1791 324E-10 1795 330E-07

549 132E-05 1098 472E-06 4536 141E-07 457 468E-07 1822 261E-10 1826 340E-07

55 131E-05 110 470E-06 4546 139E-07 458 467E-07 1826 254E-10 183 333E-07

552 131E-05 1103 469E-06 4556 137E-07 458 457E-07 183 248E-10 1834 342E-07

552 130E-05 1105 466E-06 4565 135E-07 459 458E-07 1834 241E-10 1838 334E-07

561 127E-05 1122 451E-06 4634 123E-07 466 433E-07 1861 200E-10 1865 339E-07

568 124E-05 1138 437E-06 4702 112E-07 473 427E-07 1889 166E-10 1893 330E-07

57 124E-05 114 435E-06 4712 110E-07 474 431E-07 1893 161E-10 1896 331E-07

571 123E-05 1143 433E-06 4722 109E-07 475 419E-07 1896 157E-10 19 330E-07

573 123E-05 1145 432E-06 4731 108E-07 476 424E-07 19 153E-10 1904 338E-07

573 122E-05 1147 43E-06 4741 106E-07 477 423E-07 1904 149E-10 1908 328E-07

58 120E-05 1159 421E-06 479 993E-08 482 407E-07 1924 130E-10 1928 330E-07

58 120E-05 1161 419E-06 48 979E-08 483 410E-07 1928 127E-10 1932 326E-07

589 116E-05 118 404E-06 4878 880E-08 491 398E-07 1959 102E-10 1963 328E-07

591 116E-05 1182 403E-06 4888 868E-08 492 398E-07 1963 997E-11 1967 326E-07

598 114E-05 1197 392E-06 4946 801E-08 498 369E-07 1986 849E-11 199 318E-07

599 113E-05 1199 390E-06 4956 791E-08 499 373E-07 199 826E-11 1994 321E-07

256

Table 12 Amaranth -hypochlorite intermediate and product formation-compiled data

TIME AM- I7 P1 P2 P3

041 528E-05 276E-07 172E-05 170E-05 170E-05

049 500E-05 164E-07 200E-05 198E-05 198E-05

053 487E-05 136E-07 213E-05 212E-05 212E-05

057 474E-05 116E-07 226E-05 225E-05 225E-05

061 461E-05 101E-07 239E-05 238E-05 238E-05

064 449E-05 891E-08 251E-05 250E-05 250E-05

068 437E-05 795E-08 263E-05 262E-05 262E-05

072 426E-05 717E-08 274E-05 274E-05 274E-05

076 414E-05 651E-08 286E-05 285E-05 285E-05

08 403E-05 595E-08 297E-05 296E-05 296E-05

084 393E-05 547E-08 307E-05 307E-05 307E-05

088 382E-05 505E-08 318E-05 317E-05 317E-05

092 372E-05 468E-08 328E-05 327E-05 327E-05

096 362E-05 436E-08 338E-05 337E-05 337E-05

1 353E-05 407E-08 347E-05 347E-05 347E-05

103 344E-05 381E-08 356E-05 356E-05 356E-05

107 334E-05 357E-08 366E-05 365E-05 365E-05

111 326E-05 336E-08 374E-05 374E-05 374E-05

115 317E-05 317E-08 383E-05 383E-05 383E-05

119 309E-05 299E-08 391E-05 391E-05 391E-05

123 301E-05 283E-08 399E-05 399E-05 399E-05

127 293E-05 268E-08 407E-05 407E-05 407E-05

186 196E-05 135E-08 504E-05 504E-05 504E-05

189 191E-05 130E-08 509E-05 509E-05 509E-05

193 186E-05 125E-08 514E-05 514E-05 514E-05

197 181E-05 120E-08 519E-05 519E-05 519E-05

201 176E-05 116E-08 524E-05 524E-05 524E-05

205 171E-05 111E-08 529E-05 528E-05 528E-05

209 167E-05 107E-08 533E-05 533E-05 533E-05

213 163E-05 103E-08 537E-05 537E-05 537E-05

248 128E-05 752E-09 572E-05 572E-05 572E-05

252 124E-05 727E-09 576E-05 575E-05 575E-05

256 121E-05 703E-09 579E-05 579E-05 579E-05

26 118E-05 680E-09 582E-05 582E-05 582E-05

264 115E-05 658E-09 585E-05 585E-05 585E-05

268 112E-05 636E-09 588E-05 588E-05 588E-05

271 109E-05 616E-09 591E-05 591E-05 591E-05

275 106E-05 596E-09 594E-05 594E-05 594E-05

279 103E-05 577E-09 597E-05 597E-05 597E-05

283 101E-05 559E-09 599E-05 599E-05 599E-05

287 979E-06 541E-09 602E-05 602E-05 602E-05

303 880E-06 477E-09 612E-05 612E-05 612E-05

307 857E-06 462E-09 614E-05 614E-05 614E-05

311 835E-06 448E-09 617E-05 616E-05 616E-05

314 813E-06 434E-09 619E-05 619E-05 619E-05

318 791E-06 421E-09 621E-05 621E-05 621E-05

322 771E-06 408E-09 623E-05 623E-05 623E-05

326 750E-06 396E-09 625E-05 625E-05 625E-05

33 731E-06 384E-09 627E-05 627E-05 627E-05

353 623E-06 321E-09 638E-05 638E-05 638E-05

357 606E-06 311E-09 639E-05 639E-05 639E-05

361 590E-06 302E-09 641E-05 641E-05 641E-05

365 575E-06 293E-09 643E-05 642E-05 642E-05

369 560E-06 285E-09 644E-05 644E-05 644E-05

373 545E-06 277E-09 645E-05 645E-05 645E-05

377 531E-06 269E-09 647E-05 647E-05 647E-05

381 517E-06 261E-09 648E-05 648E-05 648E-05

385 503E-06 253E-09 650E-05 650E-05 650E-05

389 490E-06 246E-09 651E-05 651E-05 651E-05

393 477E-06 239E-09 652E-05 652E-05 652E-05

396 465E-06 232E-09 654E-05 654E-05 654E-05

4 452E-06 226E-09 655E-05 655E-05 655E-05

428 375E-06 185E-09 662E-05 662E-05 662E-05

432 366E-06 180E-09 663E-05 663E-05 663E-05

436 356E-06 175E-09 664E-05 664E-05 664E-05

439 347E-06 170E-09 665E-05 665E-05 665E-05

443 338E-06 165E-09 666E-05 666E-05 666E-05

447 329E-06 160E-09 667E-05 667E-05 667E-05

451 320E-06 156E-09 668E-05 668E-05 668E-05

486 252E-06 121E-09 675E-05 675E-05 675E-05

49 245E-06 118E-09 675E-05 675E-05 675E-05

494 239E-06 115E-09 676E-05 676E-05 676E-05

498 233E-06 112E-09 677E-05 677E-05 677E-05

502 226E-06 108E-09 677E-05 677E-05 677E-05

506 221E-06 106E-09 678E-05 678E-05 678E-05

51 215E-06 103E-09 679E-05 679E-05 679E-05

514 209E-06 998E-10 679E-05 679E-05 679E-05

257

518 204E-06 971E-10 680E-05 680E-05 680E-05

521 198E-06 945E-10 680E-05 680E-05 680E-05

561 152E-06 718E-10 685E-05 685E-05 685E-05

564 148E-06 699E-10 685E-05 685E-05 685E-05

568 144E-06 680E-10 686E-05 686E-05 686E-05

572 140E-06 662E-10 686E-05 686E-05 686E-05

576 137E-06 644E-10 686E-05 686E-05 686E-05

588 126E-06 594E-10 687E-05 687E-05 687E-05

592 123E-06 578E-10 688E-05 688E-05 688E-05

596 120E-06 562E-10 688E-05 688E-05 688E-05

6 116E-06 547E-10 688E-05 688E-05 688E-05

603 113E-06 532E-10 689E-05 689E-05 689E-05

607 110E-06 518E-10 689E-05 689E-05 689E-05

611 108E-06 504E-10 689E-05 689E-05 689E-05

682 666E-07 310E-10 693E-05 693E-05 693E-05

686 649E-07 302E-10 694E-05 694E-05 694E-05

689 632E-07 294E-10 694E-05 694E-05 694E-05

693 615E-07 286E-10 694E-05 694E-05 694E-05

697 599E-07 279E-10 694E-05 694E-05 694E-05

701 583E-07 271E-10 694E-05 694E-05 694E-05

705 568E-07 264E-10 694E-05 694E-05 694E-05

744 435E-07 202E-10 696E-05 696E-05 696E-05

752 413E-07 191E-10 696E-05 696E-05 696E-05

787 325E-07 150E-10 697E-05 697E-05 697E-05

791 316E-07 146E-10 697E-05 697E-05 697E-05

795 308E-07 143E-10 697E-05 697E-05 697E-05

799 300E-07 139E-10 697E-05 697E-05 697E-05

803 292E-07 135E-10 697E-05 697E-05 697E-05

807 284E-07 132E-10 697E-05 697E-05 697E-05

811 277E-07 128E-10 697E-05 697E-05 697E-05

877 176E-07 814E-11 698E-05 698E-05 698E-05

908 142E-07 657E-11 699E-05 699E-05 699E-05

912 139E-07 640E-11 699E-05 699E-05 699E-05

971 931E-08 429E-11 699E-05 699E-05 699E-05

975 906E-08 418E-11 699E-05 699E-05 699E-05

978 882E-08 407E-11 699E-05 699E-05 699E-05

982 859E-08 396E-11 699E-05 699E-05 699E-05

986 837E-08 386E-11 699E-05 699E-05 699E-05

99 815E-08 376E-11 699E-05 699E-05 699E-05

994 793E-08 366E-11 699E-05 699E-05 699E-05

998 772E-08 356E-11 699E-05 699E-05 699E-05

10 752E-08 347E-11 699E-05 699E-05 699E-05

107 466E-08 215E-11 700E-05 700E-05 700E-05

133 806E-09 371E-12 700E-05 700E-05 700E-05

133 784E-09 361E-12 700E-05 700E-05 700E-05

141 473E-09 218E-12 700E-05 700E-05 700E-05

141 461E-09 212E-12 700E-05 700E-05 700E-05

142 449E-09 207E-12 700E-05 700E-05 700E-05

142 437E-09 201E-12 700E-05 700E-05 700E-05

142 425E-09 196E-12 700E-05 700E-05 700E-05

15 257E-09 118E-12 700E-05 700E-05 700E-05

15 250E-09 115E-12 700E-05 700E-05 700E-05

151 243E-09 112E-12 700E-05 700E-05 700E-05

153 202E-09 931E-13 700E-05 700E-05 700E-05

154 197E-09 906E-13 700E-05 700E-05 700E-05

154 192E-09 883E-13 700E-05 700E-05 700E-05

155 182E-09 836E-13 700E-05 700E-05 700E-05

155 177E-09 814E-13 700E-05 700E-05 700E-05

156 172E-09 793E-13 700E-05 700E-05 700E-05

156 168E-09 772E-13 700E-05 700E-05 700E-05

156 163E-09 752E-13 700E-05 700E-05 700E-05

157 159E-09 732E-13 700E-05 700E-05 700E-05

157 155E-09 713E-13 700E-05 700E-05 700E-05

158 151E-09 695E-13 700E-05 700E-05 700E-05

158 147E-09 676E-13 700E-05 700E-05 700E-05

16 129E-09 592E-13 700E-05 700E-05 700E-05

16 125E-09 577E-13 700E-05 700E-05 700E-05

161 122E-09 561E-13 700E-05 700E-05 700E-05

161 119E-09 547E-13 700E-05 700E-05 700E-05

162 116E-09 532E-13 700E-05 700E-05 700E-05

162 113E-09 518E-13 700E-05 700E-05 700E-05

162 110E-09 505E-13 700E-05 700E-05 700E-05

163 107E-09 491E-13 700E-05 700E-05 700E-05

171 611E-10 281E-13 700E-05 700E-05 700E-05

18 331E-10 152E-13 700E-05 700E-05 700E-05

18 322E-10 148E-13 700E-05 700E-05 700E-05

181 314E-10 145E-13 700E-05 700E-05 700E-05

181 298E-10 137E-13 700E-05 700E-05 700E-05

196 114E-10 526E-14 700E-05 700E-05 700E-05

196 111E-10 513E-14 700E-05 700E-05 700E-05

199 899E-11 414E-14 700E-05 700E-05 700E-05

199 876E-11 403E-14 700E-05 700E-05 700E-05

258

12 Brilliant blue-R oxidation products with hypochlorite

Figure 115 1H NMR spectrum for brilliant blue-R major oxidation product P2 (3- ethyl amino methyl benzene sulphonic acid) with hypochlorite

259

Figure 116 13C NMR spectrum for brilliant blue-R major oxidation product P2 (3- ethyl amino methyl benzene sulphonic acid) with hypochlorite

260

Figure 117 GC-MS spectrum for brilliant blue-R major oxidation product P2 (3- ethyl amino methyl benzene sulphonic acid) with hypochlorite

261

Figure 118 1H NMR spectrum for brilliant blue-R major oxidation product P3 (3- ethyl amino methyl-benzene sulphonic acid) with hypochlorite

262

Figure 119 13C NMR spectrum for brilliant blue-R major oxidation product P3 (3-ethyl amino methyl-benzene sulphonic acid) with hypochlorite

263

Figure 1110 GC-MS spectrum for brilliant blue-R major oxidation product P3 (3-ethyl amino methyl benzene sulphonic acid) with hypochlorite

264

Figure 1111 1H NMR spectrum of brilliant blue-R major oxidation product P4 (4-[bis-(4-hydroxy-phenyl)-methylene]-cyclohexa-25-hydroxide) with hypochlorite

265

Figure 1112 13C NMR spectrum of brilliant blue-R major oxidation product P4 (4-[bis-(4-hydroxy-phenyl)-methylene]-cyclohexa-25-hydroxide) with hypochlorite

266

Figure 1113 GC-MS spectrum of brilliant blue-R major oxidation product P4 (4-[bis-(4-hydroxy-phenyl)-methylene]-cyclohexa-25-hydroxide) with hypochlorite

267

Table 13 Brilliant Blue - hypochlorite experimental and simulated curves-compiled data

Time E1 S1 Time E2 S2 Time E3 S3

023193 526E-05 586E-05 011597 445E-05 558E-05 0057982 271E-05 561E-05

070068 627E-05 580E-05 035035 614E-05 544E-05 017517 483E-05 548E-05

11694 601E-05 565E-05 058473 617E-05 531E-05 029235 567E-05 537E-05

16382 576E-05 551E-05 08191 601E-05 52E-05 040953 584E-05 526E-05

21069 554E-05 537E-05 10535 584E-05 509E-05 052672 576E-05 516E-05

25757 533E-05 524E-05 12879 567E-05 498E-05 06439 562E-05 506E-05

30444 514E-05 511E-05 15222 552E-05 489E-05 076109 547E-05 496E-05

35132 495E-05 498E-05 17566 538E-05 479E-05 087827 532E-05 487E-05

39819 479E-05 486E-05 1991 524E-05 47E-05 099545 517E-05 477E-05

44507 462E-05 474E-05 22254 511E-05 461E-05 11126 504E-05 468E-05

49194 447E-05 462E-05 24598 499E-05 452E-05 12298 491E-05 459E-05

53881 433E-05 450E-05 26941 486E-05 444E-05 1347 478E-05 451E-05

58569 419E-05 439E-05 29285 475E-05 436E-05 14642 466E-05 442E-05

63256 406E-05 428E-05 31629 464E-05 428E-05 15814 454E-05 434E-05

67944 393E-05 418E-05 33973 453E-05 42E-05 16986 444E-05 426E-05

72631 382E-05 408E-05 36316 443E-05 412E-05 18157 433E-05 418E-05

77319 37E-05 398E-05 3866 434E-05 405E-05 19329 423E-05 410E-05

82006 36E-05 388E-05 41004 424E-05 397E-05 20501 413E-05 403E-05

86694 35E-05 378E-05 43348 415E-05 39E-05 21673 404E-05 395E-05

14294 255E-05 282E-05 71473 326E-05 315E-05 35735 312E-05 319E-05

14763 249E-05 275E-05 73817 319E-05 309E-05 36907 306E-05 313E-05

15232 243E-05 268E-05 76161 314E-05 304E-05 38079 3E-05 308E-05

15701 237E-05 262E-05 78505 308E-05 298E-05 39251 294E-05 302E-05

16169 232E-05 256E-05 80848 302E-05 293E-05 40422 288E-05 297E-05

16638 226E-05 250E-05 83192 296E-05 288E-05 41594 283E-05 292E-05

17107 221E-05 244E-05 85536 292E-05 283E-05 42766 277E-05 287E-05

17576 216E-05 238E-05 8788 286E-05 278E-05 43938 272E-05 282E-05

18044 211E-05 232E-05 90224 281E-05 273E-05 4511 267E-05 277E-05

18513 207E-05 227E-05 92567 276E-05 268E-05 46282 262E-05 272E-05

18982 202E-05 221E-05 94911 271E-05 264E-05 47453 257E-05 268E-05

19451 198E-05 216E-05 97255 267E-05 259E-05 48625 252E-05 263E-05

19919 194E-05 211E-05 99599 262E-05 255E-05 49797 248E-05 259E-05

20388 19E-05 206E-05 10194 257E-05 25E-05 50969 243E-05 255E-05

20857 186E-05 201E-05 10429 253E-05 246E-05 52141 239E-05 250E-05

21326 182E-05 196E-05 10663 249E-05 242E-05 53313 234E-05 246E-05

21794 179E-05 192E-05 10897 244E-05 237E-05 54484 23E-05 242E-05

22263 176E-05 187E-05 11132 24E-05 233E-05 55656 226E-05 238E-05

22732 172E-05 183E-05 11366 236E-05 229E-05 56828 222E-05 234E-05

268

27888 142E-05 141E-05 13944 198E-05 189E-05 69718 183E-05 195E-05

28357 14E-05 137E-05 14179 195E-05 186E-05 7089 18E-05 192E-05

28825 138E-05 134E-05 14413 192E-05 183E-05 72062 177E-05 189E-05

29294 135E-05 131E-05 14647 189E-05 18E-05 73234 175E-05 186E-05

29763 133E-05 128E-05 14882 186E-05 177E-05 74406 172E-05 183E-05

30232 131E-05 125E-05 15116 183E-05 174E-05 75578 169E-05 180E-05

307 13E-05 122E-05 15351 181E-05 171E-05 76749 166E-05 177E-05

31169 128E-05 119E-05 15585 178E-05 168E-05 77921 163E-05 174E-05

31638 126E-05 116E-05 15819 175E-05 165E-05 79093 161E-05 171E-05

32107 124E-05 114E-05 16054 173E-05 162E-05 80265 158E-05 169E-05

32575 122E-05 111E-05 16288 171E-05 159E-05 81437 156E-05 166E-05

48982 785E-06 490E-06 24491 111E-05 877E-06 12245 949E-06 959E-06

4945 776E-06 478E-06 24726 11E-05 862E-06 12362 936E-06 944E-06

49919 767E-06 467E-06 2496 109E-05 848E-06 12479 919E-06 930E-06

50388 76E-06 457E-06 25194 107E-05 833E-06 12597 907E-06 916E-06

50857 748E-06 446E-06 25429 106E-05 819E-06 12714 896E-06 902E-06

51325 74E-06 436E-06 25663 105E-05 805E-06 12831 884E-06 888E-06

56482 652E-06 338E-06 28241 946E-06 669E-06 1412 771E-06 752E-06

5695 645E-06 330E-06 28476 934E-06 658E-06 14237 761E-06 740E-06

72888 458E-06 150E-06 36445 67E-06 371E-06 18222 515E-06 445E-06

77575 417E-06 119E-06 38788 611E-06 314E-06 19393 464E-06 384E-06

78044 414E-06 117E-06 39023 606E-06 308E-06 19511 459E-06 379E-06

78513 412E-06 114E-06 39257 601E-06 303E-06 19628 454E-06 373E-06

99606 299E-06 404E-07 49804 411E-06 143E-06 24901 313E-06 193E-06

10007 295E-06 395E-07 50039 409E-06 14E-06 25018 311E-06 190E-06

10054 295E-06 386E-07 50273 406E-06 138E-06 25135 309E-06 188E-06

10101 294E-06 377E-07 50507 402E-06 136E-06 25253 306E-06 185E-06

10148 293E-06 368E-07 50742 399E-06 134E-06 2537 303E-06 182E-06

10195 29E-06 360E-07 50976 398E-06 131E-06 25487 302E-06 180E-06

10242 288E-06 352E-07 51211 392E-06 129E-06 25604 299E-06 177E-06

10289 287E-06 344E-07 51445 393E-06 127E-06 25721 298E-06 174E-06

10336 284E-06 336E-07 51679 387E-06 125E-06 25838 296E-06 172E-06

12914 231E-06 946E-08 6457 278E-06 499E-07 32284 227E-06 775E-07

12961 23E-06 924E-08 64804 276E-06 491E-07 32401 225E-06 764E-07

13007 23E-06 904E-08 65039 277E-06 483E-07 32518 225E-06 753E-07

13054 229E-06 883E-08 65273 275E-06 475E-07 32635 224E-06 742E-07

13101 228E-06 863E-08 65508 274E-06 467E-07 32752 224E-06 732E-07

13148 227E-06 843E-08 65742 273E-06 459E-07 3287 222E-06 721E-07

13523 223E-06 701E-08 67617 264E-06 402E-07 33807 218E-06 643E-07

15117 206E-06 321E-08 75586 231E-06 228E-07 37791 197E-06 394E-07

15164 205E-06 313E-08 7582 231E-06 224E-07 37908 196E-06 388E-07

269

15211 205E-06 306E-08 76055 23E-06 22E-07 38026 197E-06 383E-07

16429 194E-06 168E-08 82149 215E-06 143E-07 41072 181E-06 263E-07

16476 194E-06 164E-08 82383 214E-06 141E-07 4119 181E-06 260E-07

16523 193E-06 161E-08 82617 215E-06 138E-07 41307 18E-06 256E-07

1657 192E-06 157E-08 82852 214E-06 136E-07 41424 181E-06 252E-07

16617 193E-06 153E-08 83086 214E-06 134E-07 41541 179E-06 249E-07

16664 192E-06 150E-08 8332 213E-06 132E-07 41658 179E-06 245E-07

16711 192E-06 147E-08 83555 212E-06 129E-07 41775 18E-06 241E-07

18539 179E-06 597E-09 92696 193E-06 675E-08 46346 164E-06 138E-07

18586 178E-06 583E-09 9293 193E-06 664E-08 46463 165E-06 136E-07

18632 178E-06 570E-09 93164 192E-06 653E-08 4658 163E-06 134E-07

18679 18E-06 557E-09 93399 192E-06 642E-08 46697 164E-06 132E-07

18726 178E-06 545E-09 93633 191E-06 632E-08 46814 163E-06 130E-07

18773 177E-06 532E-09 93867 192E-06 621E-08 46932 163E-06 128E-07

1882 178E-06 520E-09 94102 189E-06 611E-08 47049 162E-06 126E-07

18867 175E-06 508E-09 94336 19E-06 601E-08 47166 163E-06 125E-07

18914 177E-06 497E-09 94571 189E-06 591E-08 47283 162E-06 123E-07

18961 178E-06 485E-09 94805 189E-06 581E-08 474 162E-06 121E-07

19007 176E-06 474E-09 95039 188E-06 572E-08 47518 162E-06 119E-07

19054 177E-06 464E-09 95274 188E-06 562E-08 47635 162E-06 118E-07

19101 176E-06 453E-09 95508 187E-06 553E-08 47752 161E-06 116E-07

19148 175E-06 443E-09 95742 188E-06 544E-08 47869 16E-06 114E-07

19195 175E-06 433E-09 95977 187E-06 535E-08 47986 16E-06 113E-07

19242 175E-06 423E-09 96211 186E-06 526E-08 48103 16E-06 111E-07

19289 175E-06 413E-09 96446 186E-06 517E-08 48221 161E-06 110E-07

19336 175E-06 404E-09 9668 185E-06 509E-08 48338 16E-06 108E-07

19382 174E-06 395E-09 96914 184E-06 5E-08 48455 159E-06 106E-07

19429 174E-06 386E-09 97149 185E-06 492E-08 48572 16E-06 105E-07

19476 174E-06 377E-09 97383 185E-06 484E-08 48689 158E-06 103E-07

19523 173E-06 368E-09 97617 182E-06 476E-08 48807 157E-06 102E-07

1957 174E-06 360E-09 97852 185E-06 468E-08 48924 159E-06 101E-07

19617 173E-06 352E-09 98086 183E-06 46E-08 49041 159E-06 991E-08

19664 173E-06 344E-09 98321 182E-06 453E-08 49158 157E-06 977E-08

19711 172E-06 336E-09 98555 182E-06 445E-08 49275 158E-06 963E-08

19757 172E-06 328E-09 98789 183E-06 438E-08 49392 157E-06 949E-08

23695 154E-06 474E-10 11848 158E-06 108E-08 59236 136E-06 284E-08

23836 155E-06 443E-10 11918 157E-06 103E-08 59587 135E-06 272E-08

23882 155E-06 433E-10 11941 157E-06 101E-08 59705 135E-06 268E-08

23929 156E-06 423E-10 11965 157E-06 994E-09 59822 135E-06 264E-08

270

Table 14 Brilliant blue - hypochlorite intermediate and product formation -compiled data TIME P4 HOCl P1 BB+ P2 I1 P3

017517 170E-05 104E-03 385E-06 561E-05 385E-06 486E-07 337E-06

029235 198E-05 108E-03 515E-06 548E-05 515E-06 348E-07 480E-06

040953 212E-05 109E-03 630E-06 537E-05 630E-06 308E-07 599E-06

052672 225E-05 109E-03 738E-06 526E-05 738E-06 290E-07 709E-06

06439 238E-05 109E-03 841E-06 516E-05 841E-06 279E-07 813E-06

076109 250E-05 109E-03 942E-06 506E-05 942E-06 271E-07 915E-06

087827 262E-05 109E-03 104E-05 496E-05 104E-05 264E-07 101E-05

22845 274E-05 108E-03 205E-05 395E-05 205E-05 201E-07 203E-05

24017 285E-05 108E-03 212E-05 388E-05 212E-05 196E-07 210E-05

25188 296E-05 108E-03 219E-05 381E-05 219E-05 192E-07 217E-05

2636 307E-05 108E-03 226E-05 374E-05 226E-05 188E-07 224E-05

27532 317E-05 108E-03 232E-05 368E-05 232E-05 184E-07 231E-05

28704 327E-05 108E-03 239E-05 361E-05 239E-05 180E-07 237E-05

29876 337E-05 108E-03 245E-05 355E-05 245E-05 176E-07 244E-05

31048 347E-05 107E-03 252E-05 348E-05 252E-05 173E-07 250E-05

32219 356E-05 107E-03 258E-05 342E-05 258E-05 169E-07 256E-05

33391 365E-05 107E-03 264E-05 336E-05 264E-05 166E-07 262E-05

34563 374E-05 107E-03 270E-05 330E-05 270E-05 162E-07 268E-05

35735 383E-05 107E-03 276E-05 324E-05 276E-05 159E-07 274E-05

36907 391E-05 107E-03 281E-05 319E-05 281E-05 156E-07 280E-05

38079 399E-05 107E-03 287E-05 313E-05 287E-05 153E-07 285E-05

39251 407E-05 107E-03 292E-05 308E-05 292E-05 150E-07 291E-05

61515 504E-05 106E-03 377E-05 223E-05 377E-05 104E-07 376E-05

66203 524E-05 106E-03 392E-05 208E-05 392E-05 962E-08 391E-05

67375 528E-05 106E-03 395E-05 205E-05 395E-05 945E-08 394E-05

68547 533E-05 106E-03 398E-05 202E-05 398E-05 928E-08 398E-05

69718 537E-05 106E-03 402E-05 198E-05 402E-05 911E-08 401E-05

7089 572E-05 106E-03 405E-05 195E-05 405E-05 895E-08 404E-05

72062 575E-05 106E-03 408E-05 192E-05 408E-05 879E-08 407E-05

73234 579E-05 106E-03 411E-05 189E-05 411E-05 863E-08 410E-05

74406 582E-05 106E-03 414E-05 186E-05 414E-05 848E-08 413E-05

75578 585E-05 106E-03 417E-05 183E-05 417E-05 833E-08 416E-05

76749 588E-05 106E-03 420E-05 180E-05 420E-05 818E-08 419E-05

77921 591E-05 106E-03 423E-05 177E-05 423E-05 804E-08 422E-05

79093 594E-05 106E-03 426E-05 174E-05 426E-05 790E-08 425E-05

80265 597E-05 106E-03 429E-05 171E-05 429E-05 776E-08 428E-05

81437 599E-05 106E-03 431E-05 169E-05 431E-05 762E-08 431E-05

82609 602E-05 106E-03 434E-05 166E-05 434E-05 749E-08 433E-05

271

8378 612E-05 106E-03 437E-05 163E-05 437E-05 736E-08 436E-05

84952 614E-05 106E-03 439E-05 161E-05 439E-05 723E-08 439E-05

86124 616E-05 106E-03 442E-05 158E-05 442E-05 711E-08 441E-05

87296 619E-05 106E-03 444E-05 156E-05 444E-05 699E-08 444E-05

88468 621E-05 106E-03 447E-05 153E-05 447E-05 687E-08 446E-05

8964 623E-05 106E-03 449E-05 151E-05 449E-05 675E-08 449E-05

90811 625E-05 105E-03 452E-05 148E-05 452E-05 663E-08 451E-05

91983 627E-05 105E-03 454E-05 146E-05 454E-05 652E-08 453E-05

12831 645E-05 105E-03 510E-05 902E-06 510E-05 390E-08 509E-05

12948 647E-05 105E-03 511E-05 888E-06 511E-05 384E-08 511E-05

13065 648E-05 105E-03 513E-05 875E-06 513E-05 378E-08 512E-05

13183 650E-05 105E-03 514E-05 861E-06 514E-05 372E-08 513E-05

133 651E-05 105E-03 515E-05 848E-06 515E-05 366E-08 515E-05

13417 652E-05 105E-03 516E-05 836E-06 516E-05 360E-08 516E-05

13534 654E-05 105E-03 518E-05 823E-06 518E-05 355E-08 517E-05

13651 655E-05 105E-03 519E-05 811E-06 519E-05 349E-08 519E-05

15878 662E-05 105E-03 539E-05 609E-06 539E-05 259E-08 539E-05

15995 663E-05 105E-03 540E-05 600E-06 540E-05 255E-08 540E-05

16112 664E-05 105E-03 541E-05 591E-06 541E-05 251E-08 541E-05

16698 665E-05 105E-03 545E-05 548E-06 545E-05 232E-08 545E-05

16815 666E-05 105E-03 546E-05 540E-06 546E-05 229E-08 546E-05

16932 667E-05 105E-03 547E-05 532E-06 547E-05 225E-08 547E-05

1705 668E-05 105E-03 548E-05 524E-06 548E-05 222E-08 547E-05

17167 675E-05 105E-03 548E-05 517E-06 548E-05 219E-08 548E-05

17987 675E-05 104E-03 553E-05 466E-06 553E-05 196E-08 553E-05

20096 676E-05 104E-03 564E-05 357E-06 564E-05 150E-08 564E-05

21971 685E-05 104E-03 572E-05 282E-06 572E-05 118E-08 572E-05

25135 686E-05 104E-03 581E-05 190E-06 581E-05 789E-09 581E-05

25253 686E-05 104E-03 581E-05 188E-06 581E-05 778E-09 581E-05

2537 686E-05 104E-03 582E-05 185E-06 582E-05 766E-09 581E-05

25487 687E-05 104E-03 582E-05 182E-06 582E-05 755E-09 582E-05

25604 688E-05 104E-03 582E-05 180E-06 582E-05 744E-09 582E-05

25721 688E-05 104E-03 582E-05 177E-06 582E-05 733E-09 582E-05

25838 688E-05 104E-03 583E-05 174E-06 583E-05 723E-09 582E-05

25956 689E-05 104E-03 583E-05 172E-06 583E-05 712E-09 583E-05

26073 689E-05 104E-03 583E-05 169E-06 583E-05 702E-09 583E-05

2619 689E-05 104E-03 583E-05 167E-06 583E-05 691E-09 583E-05

26307 693E-05 104E-03 584E-05 165E-06 584E-05 681E-09 583E-05

26424 694E-05 104E-03 584E-05 162E-06 584E-05 672E-09 584E-05

28182 694E-05 104E-03 587E-05 130E-06 587E-05 539E-09 587E-05

29706 694E-05 104E-03 589E-05 108E-06 589E-05 446E-09 589E-05

272

29823 694E-05 104E-03 589E-05 107E-06 589E-05 440E-09 589E-05

2994 694E-05 104E-03 589E-05 105E-06 589E-05 433E-09 589E-05

30057 694E-05 104E-03 590E-05 104E-06 590E-05 427E-09 590E-05

30174 696E-05 104E-03 590E-05 102E-06 590E-05 421E-09 590E-05

34627 697E-05 104E-03 594E-05 590E-07 594E-05 243E-09 594E-05

4119 698E-05 104E-03 597E-05 263E-07 597E-05 108E-09 597E-05

41307 698E-05 104E-03 597E-05 260E-07 597E-05 107E-09 597E-05

41424 698E-05 104E-03 597E-05 256E-07 597E-05 105E-09 597E-05

41541 699E-05 104E-03 597E-05 252E-07 597E-05 104E-09 597E-05

41658 699E-05 104E-03 598E-05 249E-07 598E-05 102E-09 598E-05

41775 699E-05 104E-03 598E-05 245E-07 598E-05 101E-09 598E-05

41893 699E-05 104E-03 598E-05 241E-07 598E-05 991E-10 598E-05

4201 699E-05 104E-03 598E-05 238E-07 598E-05 977E-10 598E-05

42947 699E-05 104E-03 598E-05 212E-07 598E-05 871E-10 598E-05

43533 699E-05 104E-03 598E-05 197E-07 598E-05 811E-10 598E-05

4365 699E-05 104E-03 598E-05 195E-07 598E-05 799E-10 598E-05

43768 699E-05 104E-03 598E-05 192E-07 598E-05 787E-10 598E-05

4576 699E-05 104E-03 598E-05 150E-07 598E-05 617E-10 598E-05

45877 699E-05 104E-03 599E-05 148E-07 599E-05 608E-10 599E-05

45994 700E-05 104E-03 599E-05 146E-07 599E-05 599E-10 599E-05

46111 700E-05 104E-03 599E-05 144E-07 599E-05 591E-10 599E-05

48103 700E-05 104E-03 599E-05 113E-07 599E-05 463E-10 599E-05

54783 700E-05 104E-03 600E-05 497E-08 600E-05 204E-10 600E-05

549 700E-05 104E-03 600E-05 490E-08 600E-05 201E-10 600E-05

55017 700E-05 104E-03 600E-05 483E-08 600E-05 198E-10 600E-05

55134 700E-05 104E-03 600E-05 476E-08 600E-05 195E-10 600E-05

56189 700E-05 104E-03 600E-05 419E-08 600E-05 172E-10 600E-05

56306 700E-05 104E-03 600E-05 413E-08 600E-05 169E-10 600E-05

56423 700E-05 104E-03 600E-05 407E-08 600E-05 167E-10 600E-05

5865 700E-05 104E-03 600E-05 310E-08 600E-05 127E-10 600E-05

58767 700E-05 104E-03 600E-05 305E-08 600E-05 125E-10 600E-05

58884 700E-05 104E-03 600E-05 301E-08 600E-05 123E-10 600E-05

59002 700E-05 104E-03 600E-05 297E-08 600E-05 122E-10 600E-05

59939 700E-05 104E-03 600E-05 264E-08 600E-05 108E-10 600E-05

60439 700E-05 104E-03 600E-05 249E-08 600E-05 102E-10 600E-05

273

13 Safranine-O oxidation products with hypochlorite

Figure 1114 1H NMR spectrum of safranine-O major oxidation product P2 (4-amino-6-(-2- chloro-6-hydroxy-phenylimini)-3-methyl cyclohexa-24-dienone oxide) with hypochlorite

274

Figure 1115 13C NMR spectrum of safranine-O major oxidation product P2 (4-amino-6-(-2- chloro-6-hydroxy-phenylimini)-3-methyl cyclohexa-24-dienone oxide) with hypochlorite

275

Figure 1116 GC-MS spectrum of safranine-O major oxidation product P2 (4-amino-6-(-2- chloro-6-hydroxy-phenylimini)-3-methyl cyclohexa-24-dienone oxide) with hypochlorite

276

Table 15 Safranine-O - hypochlorite experimental and simulated curves-compiled data


02899 192E-05 0 000002 017395 168E-05 0 000002 0087 126E-05 0 000002

08759 199E-05 02 199E-05 052551 194E-05 02 198E-05 02628 182E-05 02 198E-05

14618 195E-05 04 198E-05 087708 189E-05 04 197E-05 04385 191E-05 02628 197E-05

20477 192E-05 06 198E-05 12286 184E-05 05255 196E-05 06143 189E-05 04385 195E-05

26337 188E-05 08 197E-05 15802 18E-05 07255 194E-05 07901 185E-05 06143 193E-05

32196 186E-05 0876 197E-05 19318 177E-05 08771 193E-05 09659 182E-05 07901 191E-05

38056 183E-05 1076 196E-05 22833 173E-05 10771 192E-05 11416 179E-05 09659 189E-05

43915 18E-05 1276 195E-05 26349 171E-05 12286 191E-05 13174 176E-05 11416 187E-05

49774 177E-05 1462 194E-05 29865 168E-05 14286 189E-05 14932 173E-05 13174 185E-05

55634 175E-05 1662 193E-05 3338 165E-05 15802 188E-05 1669 171E-05 14932 183E-05

61493 172E-05 1862 193E-05 36896 163E-05 17802 187E-05 18447 169E-05 1669 181E-05

67353 17E-05 2048 192E-05 40411 161E-05 19318 185E-05 20205 167E-05 18447 179E-05

73212 167E-05 2248 191E-05 43927 158E-05 21318 184E-05 21963 165E-05 20205 177E-05

79072 165E-05 2448 19E-05 47443 156E-05 22833 183E-05 23721 163E-05 21963 176E-05

84931 163E-05 2634 19E-05 50958 154E-05 24833 182E-05 25478 161E-05 23721 174E-05

9079 161E-05 2834 189E-05 54474 152E-05 26349 18E-05 27236 159E-05 25478 172E-05

9665 158E-05 3034 188E-05 5799 15E-05 28349 179E-05 28994 157E-05 27236 17E-05

10251 156E-05 322 187E-05 61505 148E-05 29865 178E-05 30752 156E-05 28994 168E-05

10837 154E-05 342 187E-05 65021 146E-05 31865 177E-05 32509 154E-05 30752 167E-05

11423 152E-05 362 186E-05 68536 144E-05 3338 176E-05 34267 153E-05 32509 165E-05

12009 15E-05 3806 185E-05 72052 142E-05 3538 174E-05 36025 151E-05 34267 163E-05

12595 148E-05 4006 184E-05 75568 14E-05 36896 173E-05 37783 149E-05 36025 161E-05

13181 146E-05 4206 184E-05 79083 138E-05 38896 172E-05 3954 148E-05 37783 16E-05

13767 145E-05 4392 183E-05 82599 137E-05 40411 171E-05 41298 147E-05 3954 158E-05

14353 143E-05 4592 182E-05 86115 135E-05 42411 17E-05 43056 145E-05 41298 157E-05

14938 141E-05 4792 182E-05 8963 133E-05 43927 169E-05 44814 143E-05 43056 155E-05

15524 139E-05 4977 181E-05 93146 132E-05 45927 167E-05 46571 142E-05 44814 153E-05

1611 138E-05 5177 18E-05 96661 13E-05 47443 166E-05 48329 141E-05 46571 152E-05

16696 136E-05 5377 179E-05 10018 128E-05 49443 165E-05 50087 139E-05 48329 15E-05

17282 134E-05 5563 179E-05 10369 127E-05 50958 164E-05 51845 138E-05 50087 149E-05

17868 133E-05 5763 178E-05 10721 125E-05 52958 163E-05 53603 137E-05 51845 147E-05

18454 131E-05 5963 177E-05 11072 124E-05 54474 162E-05 5536 135E-05 53603 146E-05

1904 13E-05 6149 177E-05 11424 122E-05 56474 161E-05 57118 134E-05 5536 144E-05

23728 118E-05 7721 171E-05 14236 111E-05 70536 152E-05 7118 124E-05 69422 132E-05

24314 117E-05 7907 17E-05 14588 11E-05 72052 151E-05 72938 123E-05 7118 131E-05

24899 116E-05 8107 17E-05 1494 108E-05 74052 15E-05 74696 122E-05 72938 13E-05

25485 114E-05 8307 169E-05 15291 107E-05 75568 149E-05 76453 121E-05 74696 128E-05

26071 113E-05 8493 168E-05 15643 106E-05 77568 148E-05 78211 12E-05 76453 127E-05

277

26657 112E-05 8693 168E-05 15994 104E-05 79083 147E-05 79969 119E-05 78211 126E-05

30173 105E-05 9865 164E-05 18104 972E-06 8963 141E-05 90515 112E-05 88758 118E-05

30759 104E-05 1007 163E-05 18455 96E-06 9163 14E-05 92273 111E-05 90515 117E-05

31345 103E-05 1025 162E-05 18807 95E-06 93146 139E-05 94031 11E-05 92273 116E-05

31931 102E-05 1045 162E-05 19158 938E-06 95146 138E-05 95789 109E-05 94031 114E-05

44236 816E-06 1455 149E-05 26541 737E-06 13182 12E-05 1327 904E-06 13094 92E-06

44821 808E-06 1475 148E-05 26893 729E-06 13382 119E-05 13446 896E-06 1327 91E-06

45407 8E-06 1494 148E-05 27244 721E-06 13533 118E-05 13622 889E-06 13446 901E-06

45993 792E-06 1514 147E-05 27596 712E-06 13733 117E-05 13798 88E-06 13622 892E-06

50095 738E-06 1651 143E-05 30057 657E-06 1494 112E-05 15028 827E-06 14852 829E-06

50681 731E-06 167 143E-05 30408 651E-06 1514 111E-05 15204 82E-06 15028 82E-06

51267 724E-06 169 142E-05 3076 643E-06 15291 11E-05 15379 813E-06 15204 812E-06

72947 508E-06 2413 123E-05 43768 428E-06 21819 858E-06 21883 589E-06 21707 552E-06

73533 503E-06 2431 122E-05 44119 424E-06 21971 853E-06 22059 584E-06 21883 547E-06

78806 462E-06 2607 118E-05 47283 384E-06 23577 801E-06 23641 541E-06 23465 498E-06

79392 458E-06 2627 117E-05 47635 38E-06 23729 796E-06 23817 536E-06 23641 493E-06

79978 454E-06 2647 117E-05 47986 376E-06 23929 79E-06 23993 531E-06 23817 488E-06

80564 45E-06 2666 117E-05 48338 371E-06 2408 786E-06 24168 527E-06 23993 483E-06

8115 446E-06 2686 116E-05 4869 367E-06 2428 78E-06 24344 523E-06 24168 478E-06

81736 441E-06 2706 116E-05 49041 363E-06 24432 775E-06 2452 518E-06 24344 473E-06

82322 438E-06 2724 115E-05 49393 36E-06 24632 769E-06 24696 514E-06 2452 468E-06

82908 433E-06 2744 115E-05 49744 356E-06 24783 765E-06 24871 51E-06 24696 463E-06

90525 384E-06 2999 109E-05 54315 31E-06 27093 699E-06 27156 456E-06 26981 404E-06

91111 381E-06 3017 109E-05 54666 307E-06 27244 695E-06 27332 453E-06 27156 4E-06

91697 378E-06 3037 108E-05 55018 303E-06 27444 69E-06 27508 449E-06 27332 396E-06

95212 358E-06 3155 106E-05 57127 284E-06 28499 662E-06 28563 427E-06 28387 372E-06

95798 354E-06 3175 105E-05 57479 282E-06 28651 659E-06 28738 423E-06 28563 368E-06

96384 351E-06 3193 105E-05 5783 279E-06 28851 653E-06 28914 42E-06 28738 364E-06

9697 348E-06 3213 104E-05 58182 276E-06 29002 65E-06 2909 417E-06 28914 361E-06

10752 297E-06 3565 972E-06 6451 228E-06 32166 575E-06 32254 358E-06 32078 299E-06

1081 294E-06 3585 968E-06 64861 226E-06 32366 571E-06 3243 355E-06 32254 296E-06

10869 292E-06 3603 964E-06 65213 223E-06 32518 567E-06 32606 352E-06 3243 293E-06

10928 289E-06 3623 96E-06 65565 221E-06 32718 563E-06 32781 349E-06 32606 29E-06

10986 287E-06 3643 956E-06 65916 219E-06 32869 56E-06 32957 346E-06 32781 287E-06

11045 284E-06 3662 953E-06 66268 217E-06 33069 555E-06 33133 343E-06 32957 284E-06

11103 281E-06 3682 949E-06 66619 214E-06 33221 552E-06 33309 34E-06 33133 281E-06

11162 279E-06 3702 945E-06 66971 212E-06 33421 548E-06 33484 338E-06 33309 278E-06

1122 277E-06 372 941E-06 67322 21E-06 33572 545E-06 3366 335E-06 33484 275E-06

11279 274E-06 374 938E-06 67674 208E-06 33772 54E-06 33836 333E-06 3366 272E-06

11338 272E-06 376 934E-06 68026 206E-06 33924 537E-06 34012 33E-06 33836 27E-06

11396 269E-06 3779 93E-06 68377 203E-06 34124 533E-06 34188 327E-06 34012 267E-06

278

13857 187E-06 4599 788E-06 83143 131E-06 41507 401E-06 4157 232E-06 41394 172E-06

13916 186E-06 4619 785E-06 83494 13E-06 41658 399E-06 41746 23E-06 4157 171E-06

13974 184E-06 4639 782E-06 83846 129E-06 41858 396E-06 41922 228E-06 41746 169E-06

14033 183E-06 4658 779E-06 84197 128E-06 4201 393E-06 42097 227E-06 41922 167E-06

14092 182E-06 4678 776E-06 84549 126E-06 4221 39E-06 42273 225E-06 42097 165E-06

1415 18E-06 4698 773E-06 84901 125E-06 42361 388E-06 42449 223E-06 42273 164E-06

14209 178E-06 4717 77E-06 85252 124E-06 42561 385E-06 42625 221E-06 42449 162E-06

14267 177E-06 4737 767E-06 85604 122E-06 42713 383E-06 42801 219E-06 42625 16E-06

14736 164E-06 4892 743E-06 88416 113E-06 44119 363E-06 44207 205E-06 44031 148E-06

14795 163E-06 4912 74E-06 88768 112E-06 44319 36E-06 44383 203E-06 44207 146E-06

14853 162E-06 4932 737E-06 89119 111E-06 44471 358E-06 44558 202E-06 44383 144E-06

14912 16E-06 4951 734E-06 89471 11E-06 44671 355E-06 44734 201E-06 44558 143E-06

1626 133E-06 5401 671E-06 97557 866E-07 4869 304E-06 48777 166E-06 48601 113E-06

16318 132E-06 542 668E-06 97908 862E-07 4889 302E-06 48953 165E-06 48777 111E-06

16377 131E-06 544 666E-06 9826 855E-07 49041 3E-06 49128 164E-06 48953 11E-06

16435 13E-06 546 663E-06 98611 847E-07 49241 298E-06 49304 162E-06 49128 109E-06

16494 129E-06 5478 66E-06 98963 837E-07 49393 296E-06 4948 161E-06 49304 108E-06

16553 127E-06 5498 658E-06 99315 829E-07 49593 294E-06 49656 16E-06 4948 107E-06

16611 127E-06 5518 655E-06 99666 82E-07 49744 292E-06 49832 158E-06 49656 106E-06

1667 126E-06 5537 653E-06 10002 814E-07 49944 29E-06 50007 157E-06 49832 105E-06

16728 124E-06 5557 65E-06 10037 806E-07 50096 288E-06 50183 156E-06 50007 104E-06

17373 114E-06 5771 623E-06 10424 721E-07 52054 267E-06 52117 143E-06 51941 924E-07

1831 101E-06 6084 585E-06 10986 623E-07 54866 24E-06 54929 126E-06 54753 783E-07

18838 934E-07 626 564E-06 11303 574E-07 56424 226E-06 56511 117E-06 56335 713E-07

18896 928E-07 628 562E-06 11338 568E-07 56624 224E-06 56687 117E-06 56511 705E-07

19951 812E-07 6632 524E-06 11971 481E-07 59788 198E-06 59851 102E-06 59675 585E-07

2001 804E-07 665 522E-06 12006 474E-07 5994 197E-06 60027 101E-06 59851 579E-07

20068 799E-07 667 519E-06 12041 472E-07 6014 196E-06 60202 995E-07 60027 573E-07

20127 792E-07 669 517E-06 12076 466E-07 60291 195E-06 60378 989E-07 60202 567E-07

20537 755E-07 6826 503E-06 12322 441E-07 61546 185E-06 61609 942E-07 61433 527E-07

20596 747E-07 6846 501E-06 12357 435E-07 61697 184E-06 61784 935E-07 61609 522E-07

20654 743E-07 6866 499E-06 12392 43E-07 61897 183E-06 6196 926E-07 61784 516E-07

20713 74E-07 6885 498E-06 12428 427E-07 62049 182E-06 62136 921E-07 6196 511E-07

20771 731E-07 6905 496E-06 12463 423E-07 62249 18E-06 62312 911E-07 62136 506E-07

2083 727E-07 6925 494E-06 12498 422E-07 62401 179E-06 62487 904E-07 62312 501E-07

20889 718E-07 6943 492E-06 12533 417E-07 62601 178E-06 62663 899E-07 62487 495E-07

20947 714E-07 6963 49E-06 12568 415E-07 62752 177E-06 62839 89E-07 62663 49E-07

21006 707E-07 6983 488E-06 12603 41E-07 62952 176E-06 63015 885E-07 62839 485E-07

21064 699E-07 7002 486E-06 12638 406E-07 63104 175E-06 63191 882E-07 63015 48E-07

21123 695E-07 7022 484E-06 12674 403E-07 63304 173E-06 63366 877E-07 63191 475E-07

22705 575E-07 7549 435E-06 13623 318E-07 68026 144E-06 68112 714E-07 67937 359E-07

279

22764 57E-07 7569 433E-06 13658 316E-07 68226 143E-06 68288 707E-07 68112 355E-07

22822 57E-07 7588 432E-06 13693 313E-07 68377 143E-06 68464 702E-07 68288 352E-07

22881 565E-07 7608 43E-06 13728 311E-07 68577 141E-06 6864 695E-07 68464 348E-07

22939 562E-07 7628 428E-06 13763 311E-07 68729 141E-06 68815 693E-07 6864 344E-07

22998 557E-07 7646 427E-06 13799 306E-07 68929 14E-06 68991 686E-07 68815 341E-07

23056 554E-07 7666 425E-06 13834 303E-07 6908 139E-06 69167 681E-07 68991 337E-07

23115 547E-07 7686 423E-06 13869 304E-07 6928 138E-06 69343 68E-07 69167 334E-07

23994 494E-07 7979 399E-06 14396 267E-07 71893 125E-06 71979 607E-07 71804 286E-07

24053 489E-07 7998 398E-06 14431 264E-07 72093 124E-06 72155 606E-07 71979 283E-07

24697 45E-07 8214 381E-06 14818 239E-07 74002 115E-06 74089 562E-07 73913 252E-07

25342 417E-07 8428 365E-06 15205 22E-07 7596 106E-06 76022 513E-07 75846 225E-07

254 416E-07 8448 363E-06 1524 217E-07 76111 106E-06 76198 512E-07 76022 223E-07

25459 412E-07 8467 362E-06 15275 217E-07 76311 105E-06 76374 507E-07 76198 22E-07

25517 408E-07 8487 36E-06 1531 216E-07 76463 104E-06 7655 504E-07 76374 218E-07

26865 355E-07 8935 329E-06 16119 186E-07 8053 893E-07 80592 431E-07 80417 172E-07

26924 35E-07 8955 328E-06 16154 181E-07 80682 888E-07 80768 425E-07 80592 17E-07

26982 351E-07 8975 327E-06 16189 182E-07 80882 881E-07 80944 424E-07 80768 168E-07

27041 35E-07 8994 325E-06 16224 183E-07 81033 876E-07 8112 42E-07 80944 166E-07

27099 346E-07 9014 324E-06 1626 178E-07 81233 869E-07 81295 419E-07 8112 165E-07

2792 318E-07 9287 307E-06 16752 163E-07 83694 791E-07 83756 375E-07 83581 142E-07

27978 319E-07 9307 306E-06 16787 16E-07 83846 786E-07 83932 376E-07 83756 141E-07

28037 316E-07 9327 304E-06 16822 16E-07 84046 78E-07 84108 378E-07 83932 139E-07

29092 283E-07 9678 284E-06 17455 143E-07 8721 691E-07 87272 331E-07 87096 116E-07

2915 281E-07 9697 283E-06 1749 145E-07 87361 687E-07 87448 335E-07 87272 114E-07

29267 276E-07 9737 28E-06 1756 141E-07 87713 678E-07 87799 331E-07 87623 112E-07

29326 275E-07 9756 279E-06 17596 136E-07 87913 673E-07 87975 324E-07 87799 111E-07

29385 272E-07 9776 278E-06 17631 138E-07 88065 669E-07 88151 321E-07 87975 11E-07

29443 276E-07 9796 277E-06 17666 14E-07 88265 663E-07 88327 321E-07 88151 109E-07

29795 267E-07 9913 271E-06 17877 133E-07 89319 637E-07 89381 312E-07 89205 102E-07

29853 265E-07 9931 27E-06 17912 132E-07 89471 633E-07 89557 31E-07 89381 101E-07

29912 262E-07 9951 269E-06 17947 133E-07 89671 629E-07 89733 302E-07 89557 1E-07

29971 262E-07 9971 267E-06 17982 133E-07 89822 625E-07 89909 301E-07 89733 99E-08

280

Table 16 Safranine-O - hypochlorite intermediate and product formation- compiled data TIME SO P1 I P2

200E-05 000E+00 000E+00 000E+00

02 198E-05 235E-07 910E-09 226E-07

026275 197E-05 308E-07 907E-09 299E-07

043852 195E-05 513E-07 898E-09 504E-07

06143 193E-05 715E-07 888E-09 706E-07

079008 191E-05 916E-07 879E-09 907E-07

096585 189E-05 111E-06 870E-09 111E-06

11416 187E-05 131E-06 861E-09 130E-06

13174 185E-05 150E-06 852E-09 150E-06

14932 183E-05 170E-06 843E-09 169E-06

1669 181E-05 189E-06 834E-09 188E-06

62391 138E-05 619E-06 636E-09 618E-06

64149 137E-05 633E-06 630E-09 633E-06

65907 135E-05 647E-06 623E-09 647E-06

67665 134E-05 661E-06 617E-09 661E-06

69422 132E-05 675E-06 610E-09 675E-06

7118 131E-05 689E-06 604E-09 688E-06

72938 130E-05 703E-06 598E-09 702E-06

74696 128E-05 716E-06 592E-09 715E-06

76453 127E-05 729E-06 586E-09 729E-06

78211 126E-05 743E-06 580E-09 742E-06

79969 124E-05 756E-06 574E-09 755E-06

81727 123E-05 768E-06 568E-09 768E-06

83484 122E-05 781E-06 562E-09 781E-06

14852 829E-06 117E-05 382E-09 117E-05

15028 820E-06 118E-05 378E-09 118E-05

15204 812E-06 119E-05 374E-09 119E-05

15379 804E-06 120E-05 370E-09 120E-05

15555 795E-06 120E-05 367E-09 120E-05

15731 787E-06 121E-05 363E-09 121E-05

15907 779E-06 122E-05 359E-09 122E-05

16083 771E-06 123E-05 355E-09 123E-05

16258 763E-06 124E-05 352E-09 124E-05

16434 755E-06 125E-05 348E-09 124E-05

1661 747E-06 125E-05 344E-09 125E-05

23465 498E-06 150E-05 230E-09 150E-05

23641 493E-06 151E-05 227E-09 151E-05

26453 417E-06 158E-05 192E-09 158E-05

26629 413E-06 159E-05 190E-09 159E-05

26805 409E-06 159E-05 188E-09 159E-05

26981 404E-06 160E-05 186E-09 160E-05

27156 400E-06 160E-05 185E-09 160E-05

27332 396E-06 160E-05 183E-09 160E-05

27508 392E-06 161E-05 181E-09 161E-05

27684 388E-06 161E-05 179E-09 161E-05

2786 384E-06 162E-05 177E-09 162E-05

28035 380E-06 162E-05 175E-09 162E-05

32957 284E-06 172E-05 131E-09 172E-05

33133 281E-06 172E-05 130E-09 172E-05

33309 278E-06 172E-05 128E-09 172E-05

33484 275E-06 172E-05 127E-09 172E-05

3366 272E-06 173E-05 126E-09 173E-05

33836 270E-06 173E-05 124E-09 173E-05

34012 267E-06 173E-05 123E-09 173E-05

34188 264E-06 174E-05 122E-09 174E-05

34363 261E-06 174E-05 121E-09 174E-05

34539 259E-06 174E-05 119E-09 174E-05

34715 256E-06 174E-05 118E-09 174E-05

34891 253E-06 175E-05 117E-09 175E-05

35066 251E-06 175E-05 116E-09 175E-05

38055 210E-06 179E-05 969E-10 179E-05

3823 208E-06 179E-05 959E-10 179E-05

38406 206E-06 179E-05 949E-10 179E-05

38582 204E-06 180E-05 939E-10 180E-05

38758 201E-06 180E-05 929E-10 180E-05

38933 199E-06 180E-05 920E-10 180E-05

44734 142E-06 186E-05 653E-10 186E-05

4491 140E-06 186E-05 646E-10 186E-05

45086 139E-06 186E-05 639E-10 186E-05

45261 137E-06 186E-05 633E-10 186E-05

45437 136E-06 186E-05 626E-10 186E-05

45613 134E-06 187E-05 620E-10 187E-05

45789 133E-06 187E-05 613E-10 187E-05

45965 132E-06 187E-05 607E-10 187E-05

4614 130E-06 187E-05 601E-10 187E-05

46316 129E-06 187E-05 595E-10 187E-05

46492 128E-06 187E-05 588E-10 187E-05

281

46668 126E-06 187E-05 582E-10 187E-05

46843 125E-06 188E-05 576E-10 188E-05

47019 124E-06 188E-05 570E-10 188E-05

47195 122E-06 188E-05 564E-10 188E-05

47371 121E-06 188E-05 559E-10 188E-05

52292 905E-07 191E-05 418E-10 191E-05

52468 896E-07 191E-05 413E-10 191E-05

52644 886E-07 191E-05 409E-10 191E-05

5282 877E-07 191E-05 405E-10 191E-05

52996 868E-07 191E-05 401E-10 191E-05

53171 859E-07 191E-05 396E-10 191E-05

53347 850E-07 191E-05 392E-10 191E-05

5616 720E-07 193E-05 332E-10 193E-05

56335 713E-07 193E-05 329E-10 193E-05

56511 705E-07 193E-05 325E-10 193E-05

56687 698E-07 193E-05 322E-10 193E-05

56863 691E-07 193E-05 319E-10 193E-05

57038 684E-07 193E-05 315E-10 193E-05

57214 677E-07 193E-05 312E-10 193E-05

5739 670E-07 193E-05 309E-10 193E-05

57566 663E-07 193E-05 306E-10 193E-05

57742 656E-07 193E-05 303E-10 193E-05

57917 649E-07 194E-05 299E-10 194E-05

58093 642E-07 194E-05 296E-10 194E-05

58269 636E-07 194E-05 293E-10 194E-05

58445 629E-07 194E-05 290E-10 194E-05

5862 623E-07 194E-05 287E-10 194E-05

58796 616E-07 194E-05 284E-10 194E-05

61784 516E-07 195E-05 238E-10 195E-05

6196 511E-07 195E-05 236E-10 195E-05

62136 506E-07 195E-05 233E-10 195E-05

62312 501E-07 195E-05 231E-10 195E-05

62487 495E-07 195E-05 229E-10 195E-05

62663 490E-07 195E-05 226E-10 195E-05

62839 485E-07 195E-05 224E-10 195E-05

63015 480E-07 195E-05 222E-10 195E-05

63191 475E-07 195E-05 219E-10 195E-05

63366 470E-07 195E-05 217E-10 195E-05

63542 465E-07 195E-05 215E-10 195E-05

63718 461E-07 195E-05 213E-10 195E-05

63894 456E-07 195E-05 210E-10 195E-05

64069 451E-07 195E-05 208E-10 195E-05

64245 446E-07 196E-05 206E-10 196E-05

64421 442E-07 196E-05 204E-10 196E-05

64597 437E-07 196E-05 202E-10 196E-05

70749 304E-07 197E-05 140E-10 197E-05

70925 301E-07 197E-05 139E-10 197E-05

711 298E-07 197E-05 137E-10 197E-05

73913 252E-07 197E-05 116E-10 197E-05

80065 175E-07 198E-05 809E-11 198E-05

80241 173E-07 198E-05 800E-11 198E-05

80417 172E-07 198E-05 792E-11 198E-05

80592 170E-07 198E-05 784E-11 198E-05

80768 168E-07 198E-05 776E-11 198E-05

80944 166E-07 198E-05 768E-11 198E-05

8112 165E-07 198E-05 760E-11 198E-05

81295 163E-07 198E-05 752E-11 198E-05

81471 161E-07 198E-05 744E-11 198E-05

81647 160E-07 198E-05 736E-11 198E-05

81823 158E-07 198E-05 729E-11 198E-05

81999 156E-07 198E-05 721E-11 198E-05

82174 155E-07 198E-05 714E-11 198E-05

8235 153E-07 198E-05 706E-11 198E-05

82526 152E-07 198E-05 699E-11 198E-05

82702 150E-07 199E-05 692E-11 198E-05

82877 148E-07 199E-05 685E-11 199E-05

83053 147E-07 199E-05 678E-11 199E-05

83229 145E-07 199E-05 671E-11 199E-05

86393 121E-07 199E-05 556E-11 199E-05

86569 119E-07 199E-05 551E-11 199E-05

86745 118E-07 199E-05 545E-11 199E-05

282

APPENDIX 2 ndash CHAPTER 4

21 Amaranth oxidation products with chlorine dioxide

Figure 211 1H NMR spectrum of amaranth oxidation product P2 (14 napthalenedione) with chlorine dioxide

283

Figure 212 13C NMR spectrum of amaranth oxidation product product P2 (14 napthalenedione) with chlorine dioxide

284

Figure 213 GC-MS spectrum of amaranth oxidation product P2 (14 napthalenedione) with chlorine dioxide

285

Table 21 Amaranth - chlorine dioxide experimental and simulated curves-compiled data

TIME E1 Time E2 Time E3 TIME S1 Time S2 Time S3

0 700E-05 00019 621E-05 0002 596E-05 0 700E-05 00146 670E-05 0005 713E-05

0018 633E-05 00215 578E-05 0021 495E-05 00136 612E-05 00635 587E-05 0054 605E-05

0021 619E-05 00254 568E-05 0025 478E-05 00175 589E-05 00732 572E-05 0063 59E-05

0025 606E-05 00293 558E-05 0029 462E-05 00215 568E-05 0083 559E-05 0073 575E-05

0029 594E-05 00332 548E-05 0033 446E-05 00254 548E-05 00928 546E-05 0083 561E-05

0033 582E-05 00371 538E-05 0037 431E-05 00293 529E-05 01025 533E-05 0093 548E-05

0037 570E-05 0041 529E-05 0041 417E-05 00332 511E-05 01123 521E-05 0103 537E-05

0041 559E-05 00449 52E-05 0045 404E-05 00371 494E-05 01221 510E-05 0112 525E-05

0045 548E-05 00488 51E-05 0049 391E-05 0041 477E-05 01319 499E-05 0122 514E-05

0049 537E-05 00527 501E-05 0053 379E-05 00449 461E-05 01416 489E-05 0132 503E-05

0053 527E-05 00566 492E-05 0057 367E-05 00488 446E-05 01514 479E-05 0142 493E-05

0057 517E-05 00605 484E-05 006 355E-05 00527 432E-05 01612 469E-05 0151 484E-05

006 508E-05 00644 477E-05 0064 345E-05 00566 418E-05 01709 460E-05 0161 474E-05

0092 441E-05 00956 419E-05 0096 272E-05 00878 326E-05 02491 397E-05 0239 411E-05

0096 433E-05 00995 412E-05 01 264E-05 00917 317E-05 02589 390E-05 0249 404E-05

01 426E-05 01034 406E-05 0103 256E-05 00956 307E-05 02686 383E-05 0259 397E-05

0103 419E-05 01073 4E-05 0107 249E-05 00995 299E-05 02784 377E-05 0269 391E-05

0107 412E-05 01112 393E-05 0111 242E-05 01034 290E-05 02882 371E-05 0278 384E-05

0228 265E-05 02323 252E-05 0232 111E-05 02245 127E-05 05911 244E-05 0581 248E-05

0232 262E-05 02362 249E-05 0236 108E-05 02284 124E-05 06009 242E-05 0591 245E-05

0236 259E-05 02401 246E-05 024 106E-05 02323 121E-05 06106 239E-05 0601 242E-05

024 256E-05 0244 243E-05 0244 104E-05 02362 118E-05 06204 236E-05 0611 24E-05

0244 253E-05 02479 239E-05 0248 101E-05 02401 115E-05 06302 234E-05 062 237E-05

0248 249E-05 02518 236E-05 0252 992E-06 0244 113E-05 06399 231E-05 063 234E-05

0252 246E-05 02557 233E-05 0256 971E-06 02479 110E-05 06497 229E-05 064 231E-05

0256 243E-05 02596 23E-05 026 950E-06 02518 107E-05 06595 226E-05 065 228E-05

026 241E-05 02635 227E-05 0264 929E-06 02557 105E-05 06692 224E-05 0659 226E-05

0264 238E-05 02674 224E-05 0267 91E-06 02596 102E-05 0679 222E-05 0669 223E-05

0267 235E-05 02713 221E-05 0271 891E-06 02635 997E-06 06888 219E-05 0679 22E-05

0271 232E-05 02752 218E-05 0275 870E-06 02674 973E-06 06986 217E-05 0689 218E-05

0275 229E-05 02791 216E-05 0279 853E-06 02713 950E-06 07083 215E-05 0699 215E-05

0279 227E-05 0283 213E-05 0283 836E-06 02752 927E-06 07181 213E-05 0708 213E-05

0435 148E-05 04392 13E-05 0439 403E-06 04314 367E-06 11089 150E-05 1099 14E-05

0439 146E-05 04431 129E-05 0443 396E-06 04353 359E-06 11187 149E-05 1109 139E-05

0611 975E-06 06149 794E-06 0615 232E-06 06071 135E-06 15486 110E-05 1539 956E-06

0701 802E-06 07047 633E-06 0705 193E-06 06968 814E-07 17733 960E-06 1764 81E-06

0705 795E-06 07086 626E-06 0709 192E-06 07008 796E-07 17831 955E-06 1773 805E-06

0752 720E-06 07554 559E-06 0755 177E-06 07476 613E-07 19003 894E-06 1891 742E-06

286

0755 715E-06 07593 555E-06 0759 177E-06 07515 600E-07 19101 889E-06 19 738E-06

0759 709E-06 07632 55E-06 0763 176E-06 07554 587E-07 19199 884E-06 191 734E-06

0763 703E-06 07671 545E-06 0767 176E-06 07593 574E-07 19297 879E-06 192 729E-06

0841 600E-06 08452 456E-06 0845 161E-06 08374 371E-07 21251 793E-06 2115 644E-06

0845 595E-06 08491 453E-06 0849 162E-06 08413 363E-07 21348 789E-06 2125 641E-06

0935 498E-06 09389 377E-06 0939 150E-06 09311 221E-07 23596 705E-06 235 564E-06

0939 494E-06 09428 375E-06 0943 151E-06 0935 216E-07 23693 702E-06 236 56E-06

1103 362E-06 11068 282E-06 1107 140E-06 1099 869E-08 27797 582E-06 277 458E-06

1107 359E-06 11107 279E-06 1111 141E-06 11029 850E-08 27895 579E-06 278 455E-06

1111 357E-06 11146 277E-06 1115 140E-06 11068 832E-08 27992 577E-06 279 455E-06

1716 121E-06 17197 16E-06 172 132E-06 17119 294E-09 43137 325E-06 4304 3E-06

172 121E-06 17236 161E-06 1724 134E-06 17158 288E-09 43235 324E-06 4314 299E-06

1724 120E-06 17275 16E-06 1728 132E-06 17197 281E-09 43332 323E-06 4324 299E-06

1728 119E-06 17314 159E-06 1731 134E-06 17236 275E-09 4343 322E-06 4333 3E-06

1731 118E-06 17353 159E-06 1735 133E-06 17275 270E-09 43528 321E-06 4343 297E-06

1888 904E-07 18915 152E-06 1892 133E-06 18837 114E-09 47436 282E-06 4734 284E-06

1892 898E-07 18954 151E-06 1895 132E-06 18876 112E-09 47534 281E-06 4744 283E-06

1931 840E-07 19344 148E-06 1934 132E-06 19266 900E-10 48511 273E-06 4841 28E-06

1934 835E-07 19383 148E-06 1938 133E-06 19305 881E-10 48609 272E-06 4851 28E-06

1938 829E-07 19422 148E-06 1942 133E-06 19344 862E-10 48706 271E-06 4861 279E-06

1942 824E-07 19461 149E-06 1946 132E-06 19383 844E-10 48804 270E-06 4871 28E-06

1946 818E-07 195 148E-06 195 132E-06 19422 826E-10 48902 269E-06 488 279E-06

1981 771E-07 19852 148E-06 1985 131E-06 19774 680E-10 49781 262E-06 4968 276E-06

287

Table 22 Amaranth -chlorine dioxide intermediate and product formation-compiled data

TIME AM- P1 I1 P2

0 700E-05 413E-13 237E-11 242E-11

577E-08 700E-05 238E-06 675E-10 238E-06

584E-03 676E-05 389E-06 658E-10 389E-06

974E-03 661E-05 534E-06 643E-10 534E-06

0013644 647E-05 674E-06 628E-10 674E-06

0017548 633E-05 809E-06 614E-10 809E-06

0021452 619E-05 939E-06 600E-10 939E-06

0025356 606E-05 106E-05 587E-10 106E-05

002926 594E-05 118E-05 574E-10 118E-05

0033164 582E-05 130E-05 562E-10 130E-05

0037068 570E-05 141E-05 551E-10 141E-05

0040972 559E-05 152E-05 539E-10 152E-05

0044876 548E-05 163E-05 528E-10 163E-05

004878 537E-05 173E-05 518E-10 173E-05

0052684 527E-05 183E-05 507E-10 183E-05

0056588 517E-05 192E-05 498E-10 192E-05

0060492 508E-05 202E-05 488E-10 202E-05

0064396 498E-05 211E-05 479E-10 211E-05

00683 489E-05 219E-05 470E-10 219E-05

0072204 481E-05 228E-05 461E-10 228E-05

0076108 472E-05 236E-05 453E-10 236E-05

0080012 464E-05 244E-05 444E-10 244E-05

0083916 456E-05 252E-05 437E-10 252E-05

008782 448E-05 259E-05 429E-10 259E-05

0091724 441E-05 267E-05 421E-10 267E-05

0095628 433E-05 274E-05 414E-10 274E-05

0099532 426E-05 281E-05 407E-10 281E-05

010344 419E-05 288E-05 400E-10 288E-05

010734 412E-05 294E-05 394E-10 294E-05

011124 406E-05 301E-05 387E-10 301E-05

011515 399E-05 307E-05 381E-10 307E-05

011905 393E-05 313E-05 375E-10 313E-05

012296 387E-05 319E-05 369E-10 319E-05

012686 381E-05 325E-05 363E-10 325E-05

013076 375E-05 330E-05 357E-10 330E-05

013467 370E-05 336E-05 351E-10 336E-05

0162 333E-05 371E-05 316E-10 371E-05

021275 279E-05 424E-05 264E-10 424E-05

021665 276E-05 428E-05 260E-10 428E-05

022056 272E-05 431E-05 257E-10 431E-05

022446 269E-05 435E-05 253E-10 434E-05

022836 265E-05 438E-05 250E-10 438E-05

023227 262E-05 441E-05 247E-10 441E-05

023617 259E-05 444E-05 244E-10 444E-05

024008 256E-05 447E-05 241E-10 447E-05

024398 253E-05 451E-05 238E-10 451E-05

038452 168E-05 533E-05 157E-10 533E-05

038843 167E-05 535E-05 156E-10 535E-05

039233 165E-05 537E-05 154E-10 537E-05

039624 163E-05 538E-05 152E-10 538E-05

040014 162E-05 540E-05 151E-10 540E-05

040404 160E-05 542E-05 149E-10 542E-05

040795 158E-05 543E-05 148E-10 543E-05

041185 157E-05 545E-05 146E-10 545E-05

041576 155E-05 546E-05 145E-10 546E-05

061486 966E-06 604E-05 896E-11 604E-05

061876 958E-06 605E-05 888E-11 605E-05

062267 950E-06 606E-05 880E-11 606E-05

062657 941E-06 607E-05 872E-11 607E-05

063048 933E-06 607E-05 865E-11 607E-05

063438 925E-06 608E-05 857E-11 608E-05

080616 644E-06 636E-05 594E-11 636E-05

081006 639E-06 637E-05 590E-11 637E-05

081396 634E-06 637E-05 585E-11 637E-05

081787 629E-06 638E-05 580E-11 638E-05

082177 624E-06 638E-05 576E-11 638E-05

082568 619E-06 639E-05 571E-11 639E-05

082958 614E-06 639E-05 567E-11 639E-05

083348 609E-06 640E-05 562E-11 640E-05

083739 604E-06 640E-05 558E-11 640E-05

084129 600E-06 640E-05 553E-11 640E-05

08452 595E-06 641E-05 549E-11 641E-05

08491 590E-06 641E-05 545E-11 641E-05

0853 586E-06 642E-05 540E-11 642E-05

098574 452E-06 655E-05 416E-11 655E-05

098964 448E-06 656E-05 413E-11 655E-05

099355 445E-06 656E-05 410E-11 656E-05

288

12161 294E-06 671E-05 269E-11 671E-05

122 291E-06 671E-05 268E-11 671E-05

12239 289E-06 671E-05 266E-11 671E-05

12278 287E-06 671E-05 264E-11 671E-05

12317 285E-06 672E-05 262E-11 672E-05

12356 283E-06 672E-05 260E-11 672E-05

12395 281E-06 672E-05 258E-11 672E-05

12434 279E-06 672E-05 256E-11 672E-05

12473 277E-06 672E-05 254E-11 672E-05

12512 275E-06 673E-05 253E-11 673E-05

12551 273E-06 673E-05 251E-11 673E-05

1259 271E-06 673E-05 249E-11 673E-05

12903 257E-06 675E-05 235E-11 675E-05

12942 255E-06 675E-05 234E-11 675E-05

12981 253E-06 675E-05 232E-11 675E-05

1302 251E-06 675E-05 230E-11 675E-05

13059 249E-06 675E-05 229E-11 675E-05

13098 248E-06 675E-05 227E-11 675E-05

13137 246E-06 676E-05 226E-11 676E-05

13176 244E-06 676E-05 224E-11 676E-05

13215 243E-06 676E-05 222E-11 676E-05

1665 132E-06 687E-05 121E-11 687E-05

16689 132E-06 687E-05 120E-11 687E-05

16728 131E-06 687E-05 120E-11 687E-05

16767 130E-06 687E-05 119E-11 687E-05

16807 129E-06 687E-05 118E-11 687E-05

17002 125E-06 688E-05 114E-11 688E-05

17041 124E-06 688E-05 113E-11 688E-05

17861 108E-06 689E-05 982E-12 689E-05

179 107E-06 689E-05 976E-12 689E-05

17939 106E-06 689E-05 969E-12 689E-05

19774 776E-07 692E-05 708E-12 692E-05

19813 771E-07 692E-05 703E-12 692E-05

19852 766E-07 692E-05 699E-12 692E-05

19891 761E-07 692E-05 694E-12 692E-05

1993 756E-07 692E-05 690E-12 692E-05

289

22 Brilliant blue-R oxidation products with chlorine dioxide

Figure 214 1H NMR spectrum of brilliant blue-R major oxidation product P1 (4-(4- ethoxy-phenyl amino)-benzoic acid) with chlorine oxide

290

Figure 215 13C NMR spectrum of brilliant blue-R major oxidation product P1 4-(4- ethoxy-phenyl amino)-benzoic acid ) with chlorine oxide

291

Figure 216 GC-MS spectrum of brilliant blue-R major oxidation product P1 4-(4-ethoxy-phenylamino)-benzoic acid) with chlorine oxide

292

Figure 217 1H NMR spectrum of brilliant blue-R major oxidation product P2 (N-(4- ethoxy-phenyl-hydroxyl amine) with chlorine oxide

293

Figure 218 13C NMR spectrum of brilliant blue-R major oxidation product P2 (N-(4- ethoxy-phenyl-hydroxyl amine) with chlorine oxide

294

Figure 219 GC-MS spectrum of brilliant blue-R major oxidation product P2 (N-(4- ethoxy-phenyl-hydroxyl amine) with chlorine oxide

295

Table 23 Brilliant blue-R chlorine dioxide experimental and simulated curves- compiled data


0004834 495E-05 486E-05 0009664 617E-05 681777E-05 0019327 477357E-05 682E-05

0014605 476E-05 476E-05 0029194 52E-05 518738E-05 0058389 463358E-05 519E-05

0024376 457E-05 467E-05 0048725 496E-05 473146E-05 009745 450185E-05 473E-05

0034146 447E-05 459E-05 0068256 496E-05 455748E-05 013651 437765E-05 456E-05

0043917 44E-05 450E-05 0087786 496E-05 442709E-05 017557 426036E-05 443E-05

0053688 433E-05 442E-05 010732 489E-05 430699E-05 021463 414937E-05 431E-05

0063458 427E-05 434E-05 012685 478E-05 419942E-05 02537 404425E-05 42E-05

0073229 422E-05 427E-05 014638 465E-05 410301E-05 029276 394451E-05 41E-05

0083 417E-05 419E-05 016591 456E-05 00000401 033182 384973E-05 401E-05

009277 41E-05 412E-05 018544 446E-05 392408E-05 037088 375956E-05 392E-05

010254 405E-05 405E-05 020497 435E-05 383981E-05 040994 367367E-05 384E-05

026864 328E-05 312E-05 053699 288E-05 262757E-05 1074 265557E-05 263E-05

027841 323E-05 308E-05 055652 28E-05 256845E-05 1113 261337E-05 257E-05

036635 287E-05 273E-05 07323 231E-05 21068E-05 14646 228778E-05 211E-05

037612 283E-05 270E-05 075183 227E-05 206311E-05 15037 22567E-05 206E-05

038589 279E-05 266E-05 077136 223E-05 202184E-05 15427 222639E-05 202E-05

039566 275E-05 263E-05 079089 219E-05 198641E-05 15818 219698E-05 199E-05

040543 271E-05 260E-05 081042 215E-05 195068E-05 16208 216827E-05 195E-05

04152 267E-05 256E-05 082995 211E-05 191573E-05 16599 214032E-05 192E-05

042497 263E-05 253E-05 084948 208E-05 188126E-05 1699 211316E-05 188E-05

043474 26E-05 250E-05 086901 205E-05 00000185 1738 208662E-05 185E-05

044451 256E-05 247E-05 088854 201E-05 182233E-05 17771 206082E-05 182E-05

045429 253E-05 244E-05 090807 198E-05 179369E-05 18161 203559E-05 179E-05

046406 249E-05 241E-05 09276 195E-05 176583E-05 18552 201098E-05 177E-05

047383 245E-05 239E-05 094714 192E-05 173689E-05 18943 198702E-05 174E-05

04836 242E-05 236E-05 096667 189E-05 171087E-05 19333 196357E-05 171E-05

049337 238E-05 233E-05 09862 186E-05 168544E-05 19724 194068E-05 169E-05

06497 192E-05 195E-05 12987 152E-05 137592E-05 25974 163591E-05 138E-05

065947 19E-05 193E-05 13182 151E-05 136291E-05 26364 161998E-05 136E-05

075718 169E-05 175E-05 15135 137E-05 123689E-05 3027 147607E-05 124E-05

076695 167E-05 173E-05 15331 136E-05 122854E-05 30661 146303E-05 123E-05

077672 166E-05 171E-05 15526 135E-05 121641E-05 31052 145025E-05 122E-05

078649 164E-05 170E-05 15721 134E-05 120544E-05 31442 143764E-05 121E-05

079626 163E-05 168E-05 15916 133E-05 119485E-05 31833 142525E-05 119E-05

080603 161E-05 166E-05 16112 132E-05 118612E-05 32224 141309E-05 119E-05

10112 133E-05 137E-05 20213 115E-05 103592E-05 40426 119668E-05 104E-05

1021 132E-05 136E-05 20409 114E-05 103184E-05 40817 118793E-05 103E-05

10308 131E-05 135E-05 20604 113E-05 102689E-05 41208 117931E-05 103E-05

296

10405 129E-05 134E-05 20799 113E-05 102165E-05 41598 117079E-05 102E-05

10503 128E-05 132E-05 20994 112E-05 101563E-05 41989 116239E-05 102E-05

10601 128E-05 131E-05 2119 112E-05 101272E-05 4238 115412E-05 101E-05

10698 126E-05 130E-05 21385 111E-05 100835E-05 4277 114593E-05 101E-05

10796 126E-05 129E-05 2158 11E-05 100204E-05 43161 113788E-05 1E-05

10894 125E-05 128E-05 21776 11E-05 998155E-06 43551 11299E-05 998E-06

10991 124E-05 127E-05 21971 109E-05 994369E-06 43942 112203E-05 994E-06

11089 123E-05 126E-05 22166 108E-05 00000099 44333 111428E-05 99E-06

11187 122E-05 125E-05 22362 108E-05 983883E-06 44723 110661E-05 984E-06

11285 121E-05 124E-05 22557 107E-05 97932E-06 45114 109905E-05 979E-06

14216 101E-05 974E-06 28416 916E-06 871214E-06 56832 908951E-06 871E-06

14314 998E-06 967E-06 28611 909E-06 869524E-06 57223 903641E-06 87E-06

15584 937E-06 878E-06 3115 854E-06 82734E-06 62301 839142E-06 827E-06

15681 934E-06 871E-06 31346 852E-06 823903E-06 62691 834507E-06 824E-06

17245 875E-06 777E-06 34471 787E-06 781398E-06 68941 765966E-06 781E-06

17342 874E-06 772E-06 34666 784E-06 779631E-06 69332 762007E-06 78E-06

1744 87E-06 766E-06 34861 779E-06 777728E-06 69722 758072E-06 778E-06

17538 867E-06 761E-06 35057 776E-06 775835E-06 70113 754171E-06 776E-06

18613 833E-06 705E-06 37205 737E-06 746932E-06 7441 713428E-06 747E-06

1871 83E-06 700E-06 374 733E-06 746184E-06 748 709902E-06 746E-06

18808 828E-06 696E-06 37596 731E-06 74301E-06 75191 706404E-06 743E-06

20176 791E-06 634E-06 4033 684E-06 708932E-06 8066 660314E-06 709E-06

20274 789E-06 629E-06 40525 68E-06 707864E-06 8105 657207E-06 708E-06

20371 786E-06 625E-06 4072 677E-06 706194E-06 81441 654132E-06 706E-06

20469 786E-06 621E-06 40916 675E-06 702583E-06 81831 651072E-06 703E-06

20567 784E-06 617E-06 41111 672E-06 699786E-06 82222 648036E-06 7E-06

20664 78E-06 613E-06 41306 668E-06 699029E-06 82613 645029E-06 699E-06

20762 778E-06 609E-06 41502 665E-06 696427E-06 83003 642038E-06 696E-06

2086 777E-06 605E-06 41697 664E-06 694243E-06 83394 639069E-06 694E-06

20958 775E-06 601E-06 41892 662E-06 692194E-06 83785 63613E-06 692E-06

21055 771E-06 597E-06 42088 657E-06 689592E-06 84175 633205E-06 69E-06

21153 77E-06 593E-06 42283 655E-06 688728E-06 84566 630308E-06 689E-06

21251 767E-06 590E-06 42478 653E-06 686583E-06 84956 627426E-06 687E-06

21348 765E-06 586E-06 42673 651E-06 683583E-06 85347 624565E-06 684E-06

21446 762E-06 582E-06 42869 647E-06 680806E-06 85738 621732E-06 681E-06

21544 759E-06 578E-06 43064 645E-06 67965E-06 86128 618912E-06 68E-06

21642 758E-06 575E-06 43259 641E-06 678641E-06 86519 61612E-06 679E-06

23498 715E-06 510E-06 4697 586E-06 635291E-06 9394 566574E-06 635E-06

23596 716E-06 506E-06 47166 584E-06 63368E-06 94331 564139E-06 634E-06

2467 692E-06 473E-06 49314 559E-06 612437E-06 98628 538433E-06 612E-06

24768 691E-06 470E-06 49509 554E-06 611058E-06 99018 536184E-06 611E-06

297

24866 688E-06 467E-06 49705 553E-06 606748E-06 99409 533949E-06 607E-06

24964 688E-06 465E-06 499 551E-06 605126E-06 998 531735E-06 605E-06

25061 688E-06 462E-06 50095 547E-06 602544E-06 10019 529535E-06 603E-06

25159 686E-06 459E-06 5029 544E-06 599796E-06 10058 527349E-06 6E-06

25257 682E-06 456E-06 50486 544E-06 598806E-06 10097 525176E-06 599E-06

25354 681E-06 453E-06 50681 541E-06 597971E-06 10136 523018E-06 598E-06

28188 631E-06 382E-06 56345 479E-06 549631E-06 11269 465777E-06 55E-06

28286 627E-06 379E-06 5654 476E-06 545534E-06 11308 463978E-06 546E-06

28383 627E-06 377E-06 56736 475E-06 544553E-06 11347 46219E-06 545E-06

28481 627E-06 375E-06 56931 473E-06 542951E-06 11386 460412E-06 543E-06

37177 49E-06 229E-06 74313 327E-06 418437E-06 14863 334824E-06 418E-06

37275 491E-06 227E-06 74508 325E-06 418573E-06 14902 333709E-06 419E-06

3874 472E-06 210E-06 77438 304E-06 39634E-06 15488 317572E-06 396E-06

38838 471E-06 209E-06 77633 304E-06 395951E-06 15527 316537E-06 396E-06

3962 461E-06 200E-06 79196 292E-06 388699E-06 15839 308422E-06 389E-06

39717 459E-06 199E-06 79391 29E-06 385291E-06 15878 307429E-06 385E-06

39815 458E-06 198E-06 79586 29E-06 383272E-06 15917 306439E-06 383E-06

39913 458E-06 197E-06 79782 289E-06 381495E-06 15956 305454E-06 381E-06

4001 458E-06 196E-06 79977 287E-06 380689E-06 15995 304473E-06 381E-06

40108 456E-06 195E-06 80172 286E-06 381107E-06 16034 303472E-06 381E-06

41671 437E-06 179E-06 83297 265E-06 363777E-06 16659 288398E-06 364E-06

41769 434E-06 179E-06 83493 265E-06 362039E-06 16699 287492E-06 362E-06

41867 436E-06 178E-06 83688 265E-06 363845E-06 16738 286589E-06 364E-06

41965 435E-06 177E-06 83883 262E-06 360757E-06 16777 285691E-06 361E-06

42062 433E-06 176E-06 84079 261E-06 360291E-06 16816 284796E-06 36E-06

4558 393E-06 146E-06 9111 225E-06 322903E-06 18222 254927E-06 323E-06

45677 392E-06 145E-06 91305 224E-06 322165E-06 18261 25416E-06 322E-06

45775 389E-06 145E-06 915 221E-06 322165E-06 183 253396E-06 322E-06

48315 364E-06 127E-06 96578 194E-06 29535E-06 19316 234527E-06 295E-06

48413 364E-06 126E-06 96773 193E-06 293796E-06 19355 233841E-06 294E-06

48511 362E-06 126E-06 96969 192E-06 293524E-06 19394 233157E-06 294E-06

48609 362E-06 125E-06 97164 193E-06 292427E-06 19433 232476E-06 292E-06

48706 361E-06 124E-06 97359 19E-06 290796E-06 19472 231797E-06 291E-06

48804 361E-06 124E-06 97555 188E-06 290136E-06 19511 231121E-06 29E-06

48902 36E-06 123E-06 9775 188E-06 289602E-06 1955 230447E-06 29E-06

48999 358E-06 123E-06 97945 187E-06 288282E-06 19589 229776E-06 288E-06

49097 357E-06 122E-06 98141 186E-06 286951E-06 19628 229108E-06 287E-06

49781 351E-06 118E-06 99508 18E-06 280621E-06 19902 224484E-06 281E-06

49879 349E-06 117E-06 99703 179E-06 278709E-06 19941 223836E-06 279E-06

49976 348E-06 911E-07 99898 178E-06 278019E-06 1998 215738E-06 278E-06

298

Table 24 Brilliant blue-R-chlorine dioxide Intermediate and product formation -compiled data

TIME OH- P1 P2

0029194 527E-05 230E-06 230E-06

0048725 513E-05 373E-06 373E-06

0068256 499E-05 507E-06 507E-06

0087786 487E-05 634E-06 634E-06

010732 475E-05 754E-06 754E-06

012685 463E-05 867E-06 867E-06

014638 452E-05 975E-06 975E-06

016591 442E-05 108E-05 108E-05

018544 433E-05 117E-05 117E-05

020497 423E-05 127E-05 127E-05

02245 414E-05 136E-05 136E-05

024403 406E-05 144E-05 144E-05

026356 398E-05 152E-05 152E-05

077136 269E-05 160E-05 281E-05

079089 266E-05 167E-05 284E-05

081042 263E-05 174E-05 287E-05

082995 260E-05 181E-05 290E-05

090807 249E-05 205E-05 301E-05

09276 246E-05 211E-05 304E-05

094714 244E-05 216E-05 306E-05

096667 241E-05 221E-05 309E-05

09862 239E-05 226E-05 311E-05

10057 236E-05 231E-05 314E-05

10253 234E-05 236E-05 316E-05

10448 232E-05 240E-05 318E-05

10643 230E-05 245E-05 320E-05

10839 228E-05 249E-05 322E-05

11034 226E-05 253E-05 324E-05

11229 224E-05 257E-05 326E-05

11424 222E-05 261E-05 328E-05

1162 220E-05 264E-05 330E-05

11815 218E-05 268E-05 332E-05

1201 216E-05 271E-05 334E-05

12206 214E-05 275E-05 336E-05

12401 212E-05 278E-05 338E-05

12596 210E-05 281E-05 340E-05

12792 209E-05 284E-05 341E-05

12987 207E-05 287E-05 343E-05

13182 205E-05 290E-05 345E-05

13377 204E-05 293E-05 346E-05

14745 193E-05 311E-05 357E-05

1494 192E-05 314E-05 358E-05

15135 191E-05 316E-05 359E-05

15331 189E-05 318E-05 361E-05

15526 188E-05 320E-05 362E-05

15721 187E-05 322E-05 363E-05

15916 185E-05 324E-05 364E-05

16112 184E-05 326E-05 366E-05

16307 183E-05 328E-05 367E-05

16502 182E-05 330E-05 368E-05

16698 181E-05 332E-05 369E-05

16893 180E-05 334E-05 370E-05

17088 178E-05 336E-05 372E-05

17284 177E-05 338E-05 373E-05

17479 176E-05 340E-05 374E-05

299

22166 154E-05 341E-05 396E-05

23924 148E-05 355E-05 402E-05

24119 147E-05 357E-05 403E-05

24315 146E-05 358E-05 404E-05

2451 146E-05 359E-05 404E-05

27049 138E-05 361E-05 412E-05

27244 137E-05 362E-05 413E-05

44822 104E-05 372E-05 446E-05

45017 104E-05 373E-05 446E-05

45212 104E-05 374E-05 446E-05

45408 104E-05 375E-05 446E-05

47361 101E-05 385E-05 449E-05

55759 929E-06 386E-05 457E-05

55954 928E-06 387E-05 457E-05

5615 926E-06 388E-05 457E-05

57517 915E-06 393E-05 458E-05

57712 913E-06 394E-05 459E-05

57907 911E-06 395E-05 459E-05

58103 910E-06 396E-05 459E-05

58298 908E-06 397E-05 459E-05

58493 907E-06 397E-05 459E-05

58689 905E-06 398E-05 459E-05

58884 904E-06 399E-05 459E-05

59079 902E-06 399E-05 460E-05

59275 901E-06 400E-05 460E-05

5947 899E-06 401E-05 460E-05

59665 898E-06 402E-05 460E-05

5986 896E-06 402E-05 460E-05

60056 895E-06 403E-05 460E-05

68845 836E-06 404E-05 466E-05

6904 835E-06 404E-05 466E-05

7236 816E-06 405E-05 468E-05

72555 815E-06 406E-05 468E-05

72751 814E-06 406E-05 468E-05

76071 797E-06 407E-05 470E-05

76266 796E-06 407E-05 470E-05

76462 795E-06 408E-05 470E-05

80368 777E-06 409E-05 472E-05

80563 776E-06 409E-05 472E-05

80954 774E-06 410E-05 472E-05

81149 773E-06 411E-05 472E-05

89742 739E-06 412E-05 476E-05

90133 738E-06 413E-05 476E-05

90914 735E-06 415E-05 476E-05

9111 734E-06 415E-05 476E-05

91305 733E-06 416E-05 476E-05

915 733E-06 416E-05 477E-05

98141 711E-06 419E-05 479E-05

98336 710E-06 419E-05 479E-05

98531 710E-06 420E-05 479E-05

98727 709E-06 420E-05 479E-05

98922 708E-06 421E-05 479E-05

99117 708E-06 421E-05 479E-05

99703 706E-06 423E-05 479E-05

99898 706E-06 423E-05 479E-05

104898 691E-06 423E-05 481E-05

300

23 Safranine-O oxidation products with chlorine dioxide

Figure 2110 1H NMR spectrum of safranine-O major oxidation product P2 (37-dimethyl-phenazine-28-diol) with chlorine dioxide

301

Figure 2111 13 CNMR spectrum of safranine-O major oxidation product P2 (37- dimethyl-phenazine-28-diol) with chlorine dioxide

302

Figure 2112 GC-MS spectrum of safranine-O major oxidation product P2 (37- dimethyl-phenazine-28-diol) with chlorine dioxide

303

Table 25 Safraninee -O chlorine dioxide simulation data experimental and simulated curves- compiled data

Time E1 Time E2 Time E3 Time S1 Time S2 Time S3

00048 73E-05 00029 738E-05 00029 729E-05 00048 000007 00029 000007 00029 000007

00146 72E-05 00088 735E-05 00088 727E-05 00146 678E-05 00088 683E-05 000875 67E-05

00244 7E-05 00146 723E-05 00146 713E-05 00244 664E-05 00146 671E-05 001461 65E-05

00341 68E-05 00205 71E-05 00205 697E-05 00341 651E-05 00205 661E-05 002047 63E-05

02784 39E-05 01669 537E-05 01669 438E-05 02784 392E-05 01669 467E-05 016687 35E-05

02882 38E-05 01727 531E-05 01727 431E-05 02882 384E-05 01727 461E-05 017272 35E-05

0298 38E-05 01786 524E-05 01786 424E-05 0298 376E-05 01786 455E-05 017858 34E-05

03077 37E-05 01844 518E-05 01844 417E-05 03077 369E-05 01844 45E-05 018443 33E-05

03175 36E-05 01903 513E-05 01903 41E-05 03175 362E-05 01903 445E-05 019029 33E-05

03273 35E-05 01962 507E-05 01962 404E-05 03273 355E-05 01962 44E-05 019615 32E-05

0337 35E-05 0202 501E-05 0202 396E-05 0337 348E-05 0202 435E-05 0202 32E-05

03468 34E-05 02079 495E-05 02079 39E-05 03468 342E-05 02079 43E-05 020786 31E-05

03566 34E-05 02137 489E-05 02137 384E-05 03566 335E-05 02137 425E-05 021371 31E-05

04738 27E-05 0284 428E-05 0284 318E-05 04738 267E-05 0284 374E-05 028399 25E-05

04836 26E-05 02898 424E-05 02898 314E-05 04836 262E-05 02898 37E-05 028984 25E-05

04934 26E-05 02957 419E-05 02957 309E-05 04934 258E-05 02957 366E-05 02957 25E-05

05031 26E-05 03016 414E-05 03016 304E-05 05031 253E-05 03016 363E-05 030155 24E-05

05129 25E-05 03074 41E-05 03074 3E-05 05129 248E-05 03074 359E-05 030741 24E-05

05227 25E-05 03133 406E-05 03133 296E-05 05227 244E-05 03133 356E-05 031327 24E-05

05325 24E-05 03191 401E-05 03191 291E-05 05325 239E-05 03191 352E-05 031912 23E-05

05422 24E-05 0325 396E-05 0325 287E-05 05422 235E-05 0325 349E-05 032498 23E-05

0552 23E-05 03308 392E-05 03308 283E-05 0552 231E-05 03308 346E-05 033083 23E-05

07474 17E-05 0448 322E-05 0448 212E-05 07474 163E-05 0448 289E-05 044795 18E-05

07572 17E-05 04538 318E-05 04538 21E-05 07572 16E-05 04538 286E-05 045381 17E-05

0767 16E-05 04597 315E-05 04597 207E-05 0767 158E-05 04597 284E-05 045967 17E-05

07767 16E-05 04655 312E-05 04655 204E-05 07767 155E-05 04655 282E-05 046552 17E-05

07865 16E-05 04714 309E-05 04714 201E-05 07865 153E-05 04714 279E-05 047138 17E-05

07963 16E-05 04772 306E-05 04772 198E-05 07963 15E-05 04772 277E-05 047723 17E-05

0806 15E-05 04831 303E-05 04831 196E-05 0806 148E-05 04831 275E-05 048309 17E-05

08158 15E-05 0489 3E-05 0489 193E-05 08158 145E-05 0489 273E-05 048895 16E-05

08256 15E-05 04948 298E-05 04948 191E-05 08256 143E-05 04948 271E-05 04948 16E-05

08353 15E-05 05007 295E-05 05007 188E-05 08353 141E-05 05007 268E-05 050066 16E-05

08451 15E-05 05065 292E-05 05065 185E-05 08451 138E-05 05065 266E-05 050651 16E-05

08549 14E-05 05124 289E-05 05124 183E-05 08549 136E-05 05124 264E-05 051237 16E-05

08647 14E-05 05182 287E-05 05182 181E-05 08647 134E-05 05182 262E-05 051823 15E-05

08744 14E-05 05241 284E-05 05241 178E-05 08744 132E-05 05241 26E-05 052408 15E-05

08842 14E-05 05299 282E-05 05299 176E-05 08842 13E-05 05299 258E-05 052994 15E-05

0894 14E-05 05358 279E-05 05358 174E-05 0894 128E-05 05358 256E-05 053579 15E-05

304

09037 13E-05 05417 276E-05 05417 171E-05 09037 126E-05 05417 254E-05 054165 15E-05

09135 13E-05 05475 274E-05 05475 169E-05 09135 124E-05 05475 252E-05 054751 15E-05

09233 13E-05 05534 272E-05 05534 167E-05 09233 122E-05 05534 25E-05 055336 15E-05

09331 13E-05 05592 269E-05 05592 165E-05 09331 12E-05 05592 248E-05 055922 14E-05

09428 13E-05 05651 267E-05 05651 163E-05 09428 118E-05 05651 246E-05 056507 14E-05

11187 98E-06 06705 228E-05 06705 13E-05 11187 9E-06 06705 217E-05 067048 12E-05

11285 97E-06 06763 226E-05 06763 129E-05 11285 887E-06 06763 215E-05 067634 12E-05

11382 96E-06 06822 225E-05 06822 127E-05 11382 874E-06 06822 214E-05 068219 12E-05

15291 61E-06 09164 165E-05 09164 819E-06 15291 509E-06 09164 166E-05 091643 83E-06

15388 6E-06 09223 164E-05 09223 809E-06 15388 503E-06 09223 165E-05 092229 83E-06

15486 59E-06 09282 163E-05 09282 803E-06 15486 497E-06 09282 164E-05 092815 82E-06

15584 58E-06 0934 161E-05 0934 797E-06 15584 49E-06 0934 163E-05 0934 82E-06

15681 58E-06 09399 16E-05 09399 787E-06 15681 484E-06 09399 162E-05 093986 81E-06

15779 57E-06 09457 159E-05 09457 78E-06 15779 478E-06 09457 161E-05 094571 8E-06

15877 57E-06 09516 158E-05 09516 774E-06 15877 473E-06 09516 16E-05 095157 8E-06

15975 56E-06 09574 157E-05 09574 765E-06 15975 467E-06 09574 16E-05 095743 79E-06

16072 56E-06 09633 156E-05 09633 758E-06 16072 461E-06 09633 159E-05 096328 78E-06

1617 55E-06 09691 155E-05 09691 75E-06 1617 456E-06 09691 158E-05 096914 78E-06

16268 55E-06 0975 154E-05 0975 743E-06 16268 45E-06 0975 157E-05 097499 77E-06

21251 37E-06 12736 112E-05 12736 487E-06 21251 255E-06 12736 12E-05 12736 54E-06

21348 36E-06 12795 111E-05 12795 482E-06 21348 252E-06 12795 12E-05 12795 54E-06

21446 36E-06 12854 111E-05 12854 479E-06 21446 249E-06 12854 119E-05 12854 53E-06

21544 36E-06 12912 11E-05 12912 477E-06 21544 247E-06 12912 118E-05 12912 53E-06

21642 36E-06 12971 109E-05 12971 473E-06 21642 244E-06 12971 118E-05 12971 52E-06

21739 36E-06 13029 109E-05 13029 469E-06 21739 242E-06 13029 117E-05 13029 52E-06

21837 35E-06 13088 109E-05 13088 466E-06 21837 239E-06 13088 117E-05 13088 52E-06

21935 35E-06 13146 108E-05 13146 463E-06 21935 237E-06 13146 116E-05 13146 51E-06

22032 35E-06 13205 107E-05 13205 459E-06 22032 235E-06 13205 116E-05 13205 51E-06

2213 35E-06 13264 107E-05 13264 457E-06 2213 232E-06 13264 115E-05 13264 51E-06

22228 35E-06 13322 106E-05 13322 455E-06 22228 23E-06 13322 115E-05 13322 5E-06

22325 34E-06 13381 105E-05 13381 449E-06 22325 228E-06 13381 114E-05 13381 5E-06

2555 29E-06 15313 894E-06 15313 372E-06 2555 167E-06 15313 981E-06 15313 41E-06

25647 29E-06 15372 888E-06 15372 369E-06 25647 165E-06 15372 977E-06 15372 41E-06

25745 29E-06 1543 884E-06 1543 368E-06 25745 164E-06 1543 973E-06 1543 4E-06

25843 29E-06 15489 882E-06 15489 368E-06 25843 162E-06 15489 968E-06 15489 4E-06

25941 29E-06 15547 878E-06 15547 365E-06 25941 161E-06 15547 964E-06 15547 4E-06

26038 29E-06 15606 872E-06 15606 363E-06 26038 16E-06 15606 96E-06 15606 4E-06

26136 28E-06 15664 869E-06 15664 361E-06 26136 158E-06 15664 956E-06 15664 39E-06

26234 29E-06 15723 865E-06 15723 36E-06 26234 157E-06 15723 952E-06 15723 39E-06

26331 28E-06 15782 861E-06 15782 359E-06 26331 155E-06 15782 947E-06 15782 39E-06

26429 28E-06 1584 858E-06 1584 357E-06 26429 154E-06 1584 943E-06 1584 39E-06

305

26527 28E-06 15899 855E-06 15899 357E-06 26527 153E-06 15899 939E-06 15899 38E-06

26625 28E-06 15957 85E-06 15957 355E-06 26625 151E-06 15957 935E-06 15957 38E-06

26722 28E-06 16016 845E-06 16016 352E-06 26722 15E-06 16016 931E-06 16016 38E-06

2682 28E-06 16074 844E-06 16074 352E-06 2682 149E-06 16074 927E-06 16074 38E-06

26918 28E-06 16133 84E-06 16133 351E-06 26918 147E-06 16133 923E-06 16133 38E-06

27015 28E-06 16192 835E-06 16192 348E-06 27015 146E-06 16192 919E-06 16192 37E-06

27113 28E-06 1625 832E-06 1625 346E-06 27113 145E-06 1625 916E-06 1625 37E-06

27211 27E-06 16309 829E-06 16309 345E-06 27211 144E-06 16309 912E-06 16309 37E-06

27309 28E-06 16367 823E-06 16367 344E-06 27309 142E-06 16367 908E-06 16367 37E-06

27406 27E-06 16426 82E-06 16426 341E-06 27406 141E-06 16426 904E-06 16426 36E-06

32096 24E-06 19237 686E-06 19237 288E-06 32096 963E-07 19237 744E-06 19237 28E-06

32194 24E-06 19295 683E-06 19295 29E-06 32194 956E-07 19295 741E-06 19295 28E-06

32292 24E-06 19354 681E-06 19354 288E-06 32292 949E-07 19354 739E-06 19354 27E-06

32389 24E-06 19412 679E-06 19412 284E-06 32389 942E-07 19412 736E-06 19412 27E-06

32487 24E-06 19471 677E-06 19471 285E-06 32487 935E-07 19471 733E-06 19471 27E-06

41574 22E-06 24917 53E-06 24917 243E-06 41574 506E-07 24917 523E-06 24917 17E-06

41671 22E-06 24976 528E-06 24976 241E-06 41671 503E-07 24976 522E-06 24976 17E-06

41769 22E-06 25034 527E-06 25034 241E-06 41769 5E-07 25034 52E-06 25034 17E-06

41867 22E-06 25093 526E-06 25093 242E-06 41867 497E-07 25093 518E-06 25093 17E-06

41965 22E-06 25151 525E-06 25151 24E-06 41965 494E-07 25151 516E-06 25151 16E-06

42062 22E-06 2521 523E-06 2521 241E-06 42062 491E-07 2521 515E-06 2521 16E-06

4216 22E-06 25268 524E-06 25268 242E-06 4216 488E-07 25268 513E-06 25268 16E-06

42258 22E-06 25327 52E-06 25327 241E-06 42258 486E-07 25327 511E-06 25327 16E-06

45287 21E-06 27142 488E-06 27142 237E-06 45287 408E-07 27142 461E-06 27142 14E-06

45384 21E-06 27201 486E-06 27201 236E-06 45384 406E-07 27201 46E-06 27201 14E-06

45482 21E-06 27259 488E-06 27259 237E-06 45482 404E-07 27259 458E-06 27259 14E-06

4558 21E-06 27318 486E-06 27318 236E-06 4558 401E-07 27318 457E-06 27318 14E-06

45677 21E-06 27376 486E-06 27376 235E-06 45677 399E-07 27376 455E-06 27376 14E-06

45775 21E-06 27435 485E-06 27435 234E-06 45775 397E-07 27435 454E-06 27435 14E-06

48804 21E-06 2925 463E-06 2925 231E-06 48804 338E-07 2925 411E-06 2925 12E-06

48902 21E-06 29309 462E-06 29309 23E-06 48902 336E-07 29309 409E-06 29309 12E-06

48999 21E-06 29368 46E-06 29368 229E-06 48999 335E-07 29368 408E-06 29368 12E-06

49097 21E-06 29426 46E-06 29426 229E-06 49097 333E-07 29426 407E-06 29426 12E-06

49195 21E-06 29485 46E-06 29485 229E-06 49195 331E-07 29485 406E-06 29485 12E-06

49293 21E-06 29543 458E-06 29543 23E-06 49293 33E-07 29543 404E-06 29543 12E-06

4939 21E-06 29602 459E-06 29602 229E-06 4939 328E-07 29602 403E-06 29602 11E-06

49586 21E-06 29719 458E-06 29719 23E-06 49586 325E-07 29719 4E-06 29719 11E-06

49683 21E-06 29777 455E-06 29777 229E-06 49683 323E-07 29777 399E-06 29777 11E-06

49781 21E-06 29836 456E-06 29836 228E-06 49781 322E-07 29836 398E-06 29836 11E-06

49879 21E-06 29895 455E-06 29895 23E-06 49879 32E-07 29895 397E-06 29895 11E-06

49976 21E-06 29953 451E-06 29953 229E-06 49976 318E-07 29953 395E-06 29953 11E-06

306

Table 26 Safranine-O -chlorine dioxide simulation data product and intermediate

formation- compiled data TIME CLO2- P1 I1 P2

0014605 216E-06 121E-09 215E-06 496E-09

0024376 356E-06 199E-09 355E-06 137E-08

0034146 493E-06 276E-09 490E-06 266E-08

0043917 628E-06 351E-09 623E-06 437E-08

0053688 759E-06 424E-09 752E-06 647E-08

0063458 887E-06 496E-09 878E-06 897E-08

0073229 101E-05 567E-09 100E-05 118E-07

0083 114E-05 635E-09 112E-05 151E-07

009277 126E-05 703E-09 124E-05 187E-07

010254 137E-05 768E-09 135E-05 226E-07

011231 149E-05 833E-09 146E-05 269E-07

012208 160E-05 896E-09 157E-05 315E-07

063993 503E-05 289E-08 448E-05 551E-06

06497 507E-05 291E-08 450E-05 564E-06

065947 510E-05 293E-08 452E-05 576E-06

066924 513E-05 295E-08 454E-05 588E-06

067901 516E-05 297E-08 456E-05 601E-06

068878 519E-05 299E-08 458E-05 613E-06

069855 523E-05 301E-08 460E-05 626E-06

070832 526E-05 303E-08 461E-05 638E-06

071809 528E-05 305E-08 463E-05 651E-06

072786 531E-05 307E-08 465E-05 663E-06

073763 534E-05 309E-08 466E-05 676E-06

074741 537E-05 310E-08 468E-05 688E-06

075718 540E-05 312E-08 469E-05 701E-06

076695 542E-05 314E-08 471E-05 713E-06

077672 545E-05 316E-08 472E-05 726E-06

078649 547E-05 317E-08 473E-05 738E-06

079626 550E-05 319E-08 474E-05 751E-06

080603 552E-05 320E-08 476E-05 763E-06

08158 555E-05 322E-08 477E-05 776E-06

082557 557E-05 324E-08 478E-05 789E-06

083534 559E-05 325E-08 479E-05 801E-06

10308 597E-05 350E-08 492E-05 105E-05

10405 599E-05 351E-08 492E-05 106E-05

10503 600E-05 352E-08 493E-05 107E-05

10601 602E-05 354E-08 493E-05 109E-05

10698 603E-05 355E-08 493E-05 110E-05

10796 605E-05 356E-08 493E-05 111E-05

15681 652E-05 390E-08 484E-05 167E-05

15779 652E-05 391E-08 484E-05 168E-05

15877 653E-05 391E-08 483E-05 169E-05

15975 653E-05 392E-08 483E-05 170E-05

16072 654E-05 392E-08 482E-05 171E-05

1617 654E-05 393E-08 482E-05 172E-05

16268 655E-05 393E-08 481E-05 173E-05

16365 656E-05 394E-08 481E-05 174E-05

16463 656E-05 394E-08 480E-05 175E-05

16561 657E-05 395E-08 480E-05 176E-05

16658 657E-05 395E-08 479E-05 177E-05

16756 658E-05 395E-08 479E-05 178E-05

16854 658E-05 396E-08 479E-05 179E-05

16952 659E-05 396E-08 478E-05 180E-05

17049 659E-05 397E-08 478E-05 181E-05

17147 660E-05 397E-08 477E-05 182E-05

17245 660E-05 397E-08 477E-05 183E-05

17342 661E-05 398E-08 476E-05 184E-05

1744 661E-05 398E-08 476E-05 185E-05

17538 661E-05 399E-08 475E-05 186E-05

17636 662E-05 399E-08 474E-05 187E-05

17733 662E-05 399E-08 474E-05 188E-05

17831 663E-05 400E-08 473E-05 189E-05

17929 663E-05 400E-08 473E-05 190E-05

18026 664E-05 400E-08 472E-05 191E-05

18124 664E-05 401E-08 472E-05 192E-05

18222 664E-05 401E-08 471E-05 193E-05

18319 665E-05 401E-08 471E-05 194E-05

18417 665E-05 402E-08 470E-05 195E-05

18515 666E-05 402E-08 470E-05 195E-05

18613 666E-05 402E-08 469E-05 196E-05

28676 687E-05 423E-08 412E-05 275E-05

28774 687E-05 423E-08 411E-05 276E-05

28872 688E-05 423E-08 411E-05 277E-05

2897 688E-05 423E-08 410E-05 277E-05

29067 688E-05 424E-08 410E-05 278E-05

307

29165 688E-05 424E-08 409E-05 278E-05

29263 688E-05 424E-08 408E-05 279E-05

2936 688E-05 424E-08 408E-05 280E-05

29458 688E-05 424E-08 407E-05 280E-05

29556 688E-05 424E-08 407E-05 281E-05

29653 688E-05 424E-08 406E-05 281E-05

29751 688E-05 424E-08 406E-05 282E-05

29849 689E-05 424E-08 405E-05 283E-05

29947 689E-05 425E-08 405E-05 283E-05

30044 689E-05 425E-08 404E-05 284E-05

30142 689E-05 425E-08 404E-05 284E-05

3024 689E-05 425E-08 403E-05 285E-05

31705 690E-05 426E-08 396E-05 294E-05

31803 690E-05 426E-08 395E-05 294E-05

31901 690E-05 426E-08 395E-05 295E-05

34246 692E-05 428E-08 384E-05 308E-05

34343 692E-05 428E-08 383E-05 308E-05

34441 692E-05 429E-08 383E-05 309E-05

34539 692E-05 429E-08 382E-05 309E-05

35027 692E-05 429E-08 380E-05 312E-05

35125 692E-05 429E-08 379E-05 312E-05

35223 692E-05 429E-08 379E-05 313E-05

3532 692E-05 429E-08 379E-05 313E-05

35418 693E-05 429E-08 378E-05 314E-05

35516 693E-05 429E-08 378E-05 314E-05

36786 693E-05 430E-08 372E-05 321E-05

36884 693E-05 430E-08 372E-05 321E-05

40597 695E-05 432E-08 356E-05 338E-05

40694 695E-05 432E-08 356E-05 339E-05

40792 695E-05 432E-08 355E-05 339E-05

4089 695E-05 432E-08 355E-05 339E-05

40987 695E-05 432E-08 355E-05 340E-05

41085 695E-05 432E-08 354E-05 340E-05

41183 695E-05 432E-08 354E-05 341E-05

41281 695E-05 433E-08 353E-05 341E-05

41378 695E-05 433E-08 353E-05 341E-05

41476 695E-05 433E-08 353E-05 342E-05

41574 695E-05 433E-08 352E-05 342E-05

41671 695E-05 433E-08 352E-05 343E-05

41769 695E-05 433E-08 352E-05 343E-05

41867 695E-05 433E-08 351E-05 343E-05

41965 695E-05 433E-08 351E-05 344E-05

42062 695E-05 433E-08 350E-05 344E-05

44016 696E-05 434E-08 343E-05 352E-05

44114 696E-05 434E-08 343E-05 352E-05

44212 696E-05 434E-08 342E-05 353E-05

44309 696E-05 434E-08 342E-05 353E-05

44407 696E-05 434E-08 342E-05 354E-05

44505 696E-05 434E-08 341E-05 354E-05

44603 696E-05 434E-08 341E-05 354E-05

447 696E-05 434E-08 341E-05 355E-05

44798 696E-05 434E-08 340E-05 355E-05

44896 696E-05 434E-08 340E-05 355E-05

44993 696E-05 434E-08 340E-05 356E-05

45091 696E-05 434E-08 339E-05 356E-05

45189 696E-05 434E-08 339E-05 357E-05

45287 696E-05 434E-08 339E-05 357E-05

45384 696E-05 434E-08 338E-05 357E-05

45482 696E-05 434E-08 338E-05 358E-05

4558 696E-05 434E-08 338E-05 358E-05

45677 696E-05 434E-08 337E-05 358E-05

48804 697E-05 435E-08 327E-05 369E-05

48902 697E-05 435E-08 327E-05 370E-05

48999 697E-05 435E-08 326E-05 370E-05

49097 697E-05 435E-08 326E-05 370E-05

49195 697E-05 435E-08 326E-05 371E-05

49293 697E-05 435E-08 325E-05 371E-05

4939 697E-05 435E-08 325E-05 371E-05

49488 697E-05 436E-08 325E-05 372E-05

49586 697E-05 436E-08 324E-05 372E-05

49683 697E-05 436E-08 324E-05 372E-05

49879 697E-05 436E-08 323E-05 373E-05

49976 697E-05 436E-08 323E-05 373E-05

Talanta 64 (2004) 18ndash22

Effluent treatment using electrochemically bleachedseawatermdashoxidative degradation of pollutants

SB Jonnalagaddalowast S Nadupalli

Department of Chemistry University of Durban-Westville P Bag X54001 Durban 4000 South Africa

Received 12 August 2003 received in revised form 24 November 2003 accepted 27 November 2003

Available online 19 May 2004

Abstract

Use of seawater electrolytically enriched with hypochlorite and the in situ generation of hypochlorite on the high seas stand a goodchance for disinfection and decrease of bio and non-biodegradable organics in effluent before discharged into estuaries and deep oceansEnriched seawater effectively decreased the biological oxygen demand measured over 5 days (BOD) and chemical oxygen demand (COD)levels of semi-treated wastewater The oxidative degradation of Brilliant Blue a triaryl industrial dye by hypochlorite and electrolyticallyenriched seawater are compared at pH 65 Both had similar magnitude second-order rate constants (21plusmn1 Mminus1 sminus1) and procedure is feasibleIncrease in acid concentration enhanced the reaction rate With 11 and 1100 molar ratios of dye to hypochlorite the COD= 140 mg Lminus1 of10 times 10minus3 M dye reduced to 100 and 30 mg Lminus1 respectivelycopy 2004 Elsevier BV All rights reserved

Keywords Seawater Hypochlorite Electrochemical generation Oxidative degradation Chemical pollutants Disinfection

1 Introduction

Urbanization has had significant impacts on the humanhealth through hydrology of the environment by controllingthe nature of runoff waters and the delivery of pollutants torivers streams lakes and ocean The striking feature of thedistribution of the worldrsquos population is the tendency for ur-banization near vast water sources Since the beginning ofthe Industrial Revolution urban development has influencedthe flow and storage of water as well as the quality of avail-able fresh water Many coastal cities dispose their munic-ipal wastewater to the sea through ocean outfall facilitieseither as raw sewage or after preliminary treatment The en-vironmental impacts of these discharges depend strongly onthe discharge location level of treatment if any and on thephysical chemical and biological nature of the water bodyDue to poor water quality resulting from highly polluted ef-fluent discharges many estuaries and sea beaches are healthhazards The impact of wastewater discharges on the marine

lowast Corresponding author Tel+27-31-204-4325fax +27-31-204-4000

E-mail addresses jonnapixieudwacza (SB Jonnalagadda) srini-vaspixieudwacza (S Nadupalli)

environment is likely to worsen in the future due to popu-lation growth urbanization and the increase in water supplyconnection and sewerage levels The growth will be mostsevere in developing countries while in industrialized coun-tries it might actually decrease as a result of water demandmanagement and the introduction of cleaner production andwater saving technologies[1]

Literature survey shows a number of oxidative methodsincluding advanced oxidation processes involving ozoneperoxide UV radiation and catalysts[2] Comminellis andPulgarin have investigated the anodic oxidation of organicson the electrode surface[3] Rodrigo et al have reportedimproved ways to treat wastewater electrochemically usingboron-duped diamond electrodes[4] while Ferro et alhave reported the efficient way generating chlorine us-ing boron-doped diamond electrodes Haenni et al havereported the scope for such system in disinfecting poolwater have been reported[56] Chlorination through useof gas chlorination or hypochlorination has become themost common type of wastewater and water disinfection[7] Hypochlorination of water is more economical in watertreatment Hypochlorite is a strong oxidizing agent biocidedefouling agent and deodorizer Normally the hypochlori-nation is achieved through a chemical feed pump to inject

0039-9140$ ndash see front matter copy 2004 Elsevier BV All rights reserveddoi101016jtalanta200311045

SB Jonnalagadda S Nadupalli Talanta 64 (2004) 18ndash22 19

a calcium or sodium hypochlorite solution The generationof hypochlorite using seawater as the chloride source hasgreat scope as it leads to insitu generation of hypochloriteunder verity of situations where seawater is accessible andabundant Another dimension the utility of bleached seawater is reported passivity in metals from corrosion throughdecreased dissolved oxygen levels The solubility of oxygenin water is dramatically reduces by increased hypochloritelevels

This manuscript covers the systematic studies showingthe effect electrochemically generated hypochlorite usingseawater and its scope in oxidation of organics and indisinfection to achieve hygienic aesthetic and sustainableenvironment through the improved effluent quality

2 Experimental

Natural Seawater composition of chloride ion Clminus isabout 195000 ppm or 195 g Lminus1 and Na+ ion is about107 g Lminus1 [8] Thus seawater with 053 mol Lminus1 of chlorideion works out to be a abundant source of chloride for elec-trochemical generation of chlorine and then hypochloritethrough itrsquos disproportionation reaction[9]

For the control experiments hypochlorite was gener-ated by bubbling chlorine gas through cold solution of5 sodium hydroxide The Baird and Tatlock ElectrolyticAnalysis apparatus was used for electrochemical generationof hypochlorite from seawater The equipment consists of asingle compact unit containing its own low voltage directcurrent supply unit capable of giving an output of 0ndash10 Aat up to 12 V Optimum and cost effective conditions forthe generation of hypochlorite from sea water were cov-ered vessel with volume 200 ml water electrolysis duration45 min temperature 20C pH 674 Under these condi-tions (122 plusmn 03) times 10minus2 M of hypochlorite was obtained[9] Arsenite method was used for the determination of thehypochlorite concentration in the sample[710]

The electrolysis chemistry is as follows

Anode 2Clminus(aq) rarr Cl2(g) + 2eminus

Cathode 2H2O(l) + 2eminus rarr H2(g) + 2OHminus(aq)

Overall 2H2O(l) + 2Clminus(aq) rarr H2(g) + Cl2(g)

+ 2OHminus(aq)

and

Cl2(g) + H2O(l) rarr 2H + (aq) + OClminus(aq) + Clminus(aq)

21 Bacterial sensitivity BOD and COD tests

These tests constitute a simple and reliable technique es-pecially applicable to routine bacteriological work It con-sists of concentrating disks with known concentrations of

hypochlorite placing them on plates of a culture mediumcontaining a bacterium and after incubation determining thedegree of sensitivity by measuring the easily visible areas ofinhibition of growth produced by the diffusion of hypochlo-rite from the disks into the surrounding medium biologi-cal oxygen demand measured over 5 days (BOD) chemicaloxygen demand (COD) total dissolved and total suspendedsolids were determined using standard procedures[9]

22 Kinetics

The kinetics of the reaction is studied using the HITECHSF-61 DX2 Micro volume double mixing stopped flow ap-paratus with thermostat control and software for data cap-ture and analysis The reaction kinetics was monitored at(250 plusmn 01)C

3 Results and discussion

31 Bacterial sensitivity

The bacterial sensitivity test using the medium nutrientagar coated on petri dishes and the bacteriumEscherichiacoli (E coli) showed that the hypochlorite solution generatedusing seawater sample is good anti bacterial and equally ef-ficient as the commercial bleach samples under comparableconditions in the bacterial growth inhibition after the 24 hincubation[9]

32 BOD5 and COD

The effect of the seawater sample containing hypochloriteon the BOD levels of wastewater is investigated by addingvarying amounts of seawater to fixed volumes of wastew-ater Wastewater samples were collected from the sewagetreatment works after the primary treatment but prior to thesecondary treatment The BOD level for the untreated sam-ples (200 ml) was reduced from 13 mg Lminus1 to 01 mg Lminus1

upon treatment with seawater sample (6 ml) The reductionof BOD levels is expected based on the diminished bacte-rial oxidation of organics mater due the anti bacterial actionof hypochlorite Sample from waste water works after sec-ondary treatment had almost zero BOD levels which had noeffect due to addition of bleached seawater[9] The chem-ical oxygen demand of primarily treated Sample (100 ml)was reduced from 440 mg Lminus1 to 160 mg Lminus1 upon mixingwith 50 ml to 40 mg Lminus1 with 100 ml of the bleached sea-water sample Obviously the powerful oxidizing capacity ofhypochlorite decreases the COD levels[9]

33 Oxidative degradation of organics

Further the oxidative degradation kinetics of the organ-ics normally present in the effluent is investigated in detailThe reaction of a selected representative dye Brilliant Blue

20 SB Jonnalagadda S Nadupalli Talanta 64 (2004) 18ndash22

which is used in textile and food industries with hypochlo-rite is studied under controlled conditions and using thebleached seawater

Brilliant Blue is a triarylmethane type of dye (disodium-(4-(N-ethyl-3-sulfonatobenzylamino) phenyl)--(4-N-ethyl-3-sulfonatobenzylamino cyclohexa-25-dienylidene)toluene-2-sulfonate) Brilliant Blue is water solublewith MAX at 555 nm and absorption coefficientε =215times 104 dm3 molminus1 cmminus1 Hence the kinetics was moni-tored at 555 nm

All the kinetic runs were conducted with excess hypochlo-rite and low dye concentrations Under such conditions ex-periments followed pseudo first-order kinetics indicatingreaction order with respect to the dye is one Further thepseudo first-order rate constantkprime increased proportionallywith the increase in the initial concentration of hypochloritesuggesting that reaction has first-order dependence on theconcentration of the oxidant and total order is two

All experiments were repeated with seawater contain-ing electrochemically generated hypochloriteFig 1 illus-trates the kinetic profiles of depletion of Brilliant Blue inpresence of seawater containing different initial amounts

Time sec

0 20 40 60

[BB

+ ] M

0

5e-6

1e-5

2e-5

2e-5

3e-5

3e-5

[Brilliant blue] = 70 x 10-5 M

[Hypochlorite] 10-2 M = a 038b 094 c 112 and d 150

a

d

Fig 1 Effect of Electrolyzed seawater on the depletion rate of Brilliant Bluendashabsorbance vs time plots

of hypochlorite The reaction of dye both with con-trol hypochlorite solution and enriched seawater too hadsecond-order and one each with respect to both the dye andhypochlorite Table 1 summarizes the pseudo first-orderconstants from the experiments and the estimated half re-action times and second-order rate constants for both thecontrol and seawater enriched experiments

Further the lnkprime versus ln [hypochlorite] for the controland seawater experiments gave straight lines with (y =11572x + 40049 R2 = 09954) and (y = 10891x +40049R2 = 09885) respectively A perusal of the slopesshows that under both the situations the reactions havefirst-order dependence on hypochlorite concentration Thesecond-order rate constants of the two sets of experimentsare of similar magnitude and most importantly the reactionsare fast This conclusively confirms the scope of hypochlo-rite enriched seawater in treatment of wastewaters and in-dustrial effluent

At very high pH where bulk of the hypochlorite is inthe hypochlorite form and with very low concentration ofHOCl reaction is very slow suggesting the rate constant forthe reaction between OClminus and the dye is small

As all the experiments were done at pH 65 the effect ofacid on the reaction between Brilliant Blue and hypochloriteis further investigated with added acid under both controland seawater enriched with hypochlorite conditions and re-sults were similar The kinetic data obtained with seawaterconditions is summarized inTable 2 With the increase in theconcentration of added acid the pseudo first-order rate con-stant increased To understand the reaction dynamics a closelook at the chemistry of hypochlorite is essential HOCl withpKa = 74 is a week acid and itrsquos dissociation constant is4times10minus8 indicating that even very low concentration of acidshifts the equilibrium towards formation of HOCl[11] The


Table 1Rate coefficients for the reaction between Brilliant Blue and (i) hypochlorite (control) and (ii) electrolytically bleached seawater

Hypochlorite (control)a Seawater enriched with hypochloritea

OCLminus (10minus3 M) kprime (10minus2 sminus1) t12 (s) k (Mminus1 sminus1) OClminus (10minus3 M) kprime (10minus2 sminus1) t12 (s) k (Mminus1 sminus1)

117 223 310 1909 375 790 88 2107234 513 135 2194 750 1595 43 2127351 739 94 2106 938 1929 36 2058468 1073 65 2294 1125 2411 29 2143585 1313 53 2244 150 3345 21 2230

Mean k = 2149plusmn 064 Meank = 2134plusmn 052

[BB+] = 75 times 10minus5 M pH = 65 and temperature= 25Ca Total hypochlorite concentration= [OClminus] + [HOCl]

preliminary experiments showed that at very high pH above9 when bulk of the hypochlorite is in the hypochlorite formand with very low concentration of HOCl the reaction wasvery slow suggesting the rate constant for the reaction be-tween OClminus and the dye is small At pH 74 the concentra-tions of hypochlorite and hypochlorous acid will be equalWith the increase in acid concentration the HOCl concen-tration increases and at pH 65 the percentage of hypochlor-ous acid in the mixture reaches about 71 suggesting themajor pathway for the reaction is through of oxidation byHOCl (Table 1)

With initial concentration of hypochlorite 15 times 10minus3 M(Table 2) to achieve pH 65 in the control experiment theadded acid concentration is about 168 times 104 M and theresultant hypochlorous acid concentration is 1166times 104 Min both cases

Table 2summarizes the added initial acid and the com-piled hypochlorous acid concentrations and the correspond-ing pseudo first order rate constants (kprime) obtained The plotof the lnkprime versus ln [HOCl] concentration gave a goodstraight line withR2 = 0987 suggesting the first-orderdependence of the reaction rate on the acid concentrationThe calculated second order rate constants for the overall second-order rate constants are also summarized inTable 2

To investigate the impact of the oxidation of BrilliantBlue using hypochlorite the BOD and COD for the reactionmixture was determined in duplicate experiments The BOD

Table 2Effect of acid on the reaction between Brilliant Blue and seawater enrichedwith hypochlorite

[H+] (10minus4 M) [HOCl] (10minus3 M) k (10minus2 sminus1) k (Mminus1 sminus1)a

0 1066 320 300210 1166 345 295920 1266 371 293130 1366 403 295140 1464 449 306650 1499 462 3082Mean= 2999plusmn 063

[BB+] = 75times 10minus5 M hypochlorite 15times 10minus3 M initial pH = 65 andtemperature= 25C

a k = kprime[HOCl]

values were very low with significant changes for prior toand after reaction of dye with the bleached seawater 10 times103 M Brilliant Blue (1 ml) had initial COD of 140 mg Lminus1

and upon addition bleached seawater in the 11 and 1100molar ratios the COD reduced to 100 and 30 mg Lminus1 respec-tively Even with 1100 molar ratio the residual COD showsthat the dye is oxidized but not completely mineralizedThe total oxidizable carbon (TOC) could not be determined

To estimate scope of the bleached seawater in oxidiz-ing the wastewater containing other dyes the kinetics ofnumber of dyes which are normally used in the textile andother industries or as stains with hypochlorite are studiedin presence of hypochlorite and bleached seawater from theunpublished data and from the literature are compiled andsummarized inTable 3

Table 3summarizes the second-order rate constants forthe reaction of hypochlorite at pH 65 for variety of dyesThe magnitude of the rate coefficients clearly demonstratethat most of the dyes are easily oxidized by the hypochlorieenriched seawater Ru(III) is observed to catalyze the oxida-tion by hypochlorite hence studies are in progress to exploresuitable heterogeneous catalyst to enhance the efficiency ofoxidation by hypochlorite under seawater pH conditions

Ocean outfalls can work efficiently and may be a satis-factory solution to effluent management Under the rightconditions properly treated effluent discharged into deepocean water with strong currents will have little or noenvironmental impacts

Table 3Second-order rate coefficients for different dyes with hypochlorite

Name of dye Category of dye k (Mminus1 sminus1)

Brilliant Bluea Triaryl dye 215plusmn 06Indigocarmine[12]b Indigo dye 180plusmn 01Amaranth[13]a Azo dye 262plusmn 05Safranine-O[13]a Phenazine dye 484plusmn 11Methylene Violet[14]b Phenazine dye 221plusmn 05Meldolarsquos Blue[15]b Phenoxazine dye 21plusmn 03Brilliant Cresyl Blue[15]b Phenoxazine dye 212plusmn 03Nile Blue [15]b Phenoxazine dye 1020plusmn 120

Temperature 25C pH = 65a Both controlled and enriched seawater experimentsb Controlled runs only


4 Conclusions

The bleached seawater can effectively oxidize the aro-matic dye Brilliant Blue in short duration but the residualCOD values after oxidation indicate that complete min-eralization does not occur for the studies conditions Theeffluent treatment using the hypochlorite enriched seawa-ter has potential to decrease the levels of toxins bacteriaBOD COD and organics to the acceptable levels beforedischarged into deep oceans rivers or estuaries to affordaesthetic hygienic and sustainable environment and safeseas for future generations

In addition to the effluent treatment the electrolytic gen-eration of hypochlorite in high seas has great scope in thedisinfection deodourising and defouling the deep sea plat-forms ship decks and the oceanariams The use of efficientcatalysts and improved electrolyzing systems such as boron-duped diamond electrodes could further enhance the eco-nomic and effective use of bleached sea water in treatmentof wastewaters

The solubility of oxygen in water is dramatically reducesby increased hypochlorite levels Thus bleached seawateralso provides an additional advantage as anti-corrosion agenttowards metals in the installations exposed to seawater

Acknowledgements

Authors thank the National Research Foundation Preto-ria and the University of Durban-Westville Durban for thefinancial support both research and participation in the con-ference

References

[1] W Viessman MJ Hammer Water supply and pollution controlfifth edition Harper Collins College publishers New York 1993p 860

[2] R Andreozzi V Caprio A Insola R Marotta Cataacutelisis Today 53(1999) 51

[3] Ch Comminellis S Pulgarin J Appl Electrochem 21 (1991)703

[4] MA Rodrigo PA Michaud I Duo G Cerisola Ch ComminellisJ Electrochem Soc 148 (2001) D60ndashD64

[5] S Ferro A De Battisti I Duo Ch Comninellis W Haenni APerret J Electrochem Soc 147 (2000) 2614

[6] W Haenni J Gobet A Perret L Pupunat Ph Rychen ChComninellis B Corea in Proceedings of the Electrochem SocMeeting San Francisco 2001 pp 1ndash8

[7] G Gordon WJ Cooper RG Rice GE Pacey Disinfectant Residualmeasurement Methods AWWA Research Report American WaterWorks Research Foundation Denver Colorado 1987 and referencestherein

[8] G Bearman Ocean Chemistry and deep-sea sediments PergamonSydney 1989

[9] V Chunilall M Govender SB Jonnalagadda J Environ Sci HealthA37 (2002) 1523 and references therein

[10] AI Vogel Textbook Of Quantitative Inorganic Chemistry third edLongmans Green and Co London 1966 p 365

[11] LC Adam I Fabian K Suzuki G Gordon Inorg Chem 31 (1992)3534

[12] A Hariram V Govender SB Jonnalagadda J Environ Sci Health38 (2003) 1055

[13] S Nadupalli SB Jonnlagadda unpublished work[14] LQ Qwabe Kinetic-Analytical determination of Ru(III) using Ox-

idation of Phenoxazine dyes MSc Thesis University of Durban-Westville 2002

[15] SB Jonnalagadda B Pare M Shezi Int J Chem Kinet WileyNew York 35 2003 21

Coverpagepdf

Table of Contents

LIST OF FIGURES

CHAPTER1AND2FINAL

CHAPTER3 AM-OCL COMBINED5

CHAPTER6_AM ClO2COMBINED

Conclusions

references

Appendix

PUBLICATION

Effluent treatment using electrochemically bleached seawater-oxidative degradation of pollutants

Introduction

Experimental

Bacterial sensitivity BOD and COD tests

Kinetics

Results and discussion

Bacterial sensitivity

BOD5 and COD

Oxidative degradation of organics

Conclusions

Acknowledgements

References

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HEB 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 HRV (Za stvaranje Adobe PDF dokumenata najpogodnijih za visokokvalitetni ispis prije tiskanja koristite ove postavke Stvoreni PDF dokumenti mogu se otvoriti Acrobat i Adobe Reader 50 i kasnijim verzijama) HUN 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 ITA 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 JPN ltFEFF9ad854c18cea306a30d730ea30d730ec30b951fa529b7528002000410064006f0062006500200050004400460020658766f8306e4f5c6210306b4f7f75283057307e305930023053306e8a2d5b9a30674f5c62103055308c305f0020005000440046002030d530a130a430eb306f3001004100630072006f0062006100740020304a30883073002000410064006f00620065002000520065006100640065007200200035002e003000204ee5964d3067958b304f30533068304c3067304d307e305930023053306e8a2d5b9a306b306f30d530a930f330c8306e57cb30818fbc307f304c5fc59808306730593002gt KOR ltFEFFc7740020c124c815c7440020c0acc6a9d558c5ec0020ace0d488c9c80020c2dcd5d80020c778c1c4c5d00020ac00c7a50020c801d569d55c002000410064006f0062006500200050004400460020bb38c11cb97c0020c791c131d569b2c8b2e4002e0020c774b807ac8c0020c791c131b41c00200050004400460020bb38c11cb2940020004100630072006f0062006100740020bc0f002000410064006f00620065002000520065006100640065007200200035002e00300020c774c0c1c5d0c11c0020c5f40020c2180020c788c2b5b2c8b2e4002egt LTH 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 LVI 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 NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken die zijn geoptimaliseerd voor prepress-afdrukken van hoge kwaliteit De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 50 en hoger) NOR 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 POL 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 PTB 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 RUM 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 RUS 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 SKY ltFEFF0054006900650074006f0020006e006100730074006100760065006e0069006100200070006f0075017e0069007400650020006e00610020007600790074007600e100720061006e0069006500200064006f006b0075006d0065006e0074006f0076002000410064006f006200650020005000440046002c0020006b0074006f007200e90020007300610020006e0061006a006c0065007001610069006500200068006f0064006900610020006e00610020006b00760061006c00690074006e00fa00200074006c0061010d00200061002000700072006500700072006500730073002e00200056007900740076006f00720065006e00e900200064006f006b0075006d0065006e007400790020005000440046002000620075006400650020006d006f017e006e00e90020006f00740076006f00720069016500200076002000700072006f006700720061006d006f006300680020004100630072006f00620061007400200061002000410064006f00620065002000520065006100640065007200200035002e0030002000610020006e006f0076016100ed00630068002egt SLV 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 SUO 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 SVE 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 TUR ltFEFF005900fc006b00730065006b0020006b0061006c006900740065006c0069002000f6006e002000790061007a006401310072006d00610020006200610073006b013100730131006e006100200065006e0020006900790069002000750079006100620069006c006500630065006b002000410064006f006200650020005000440046002000620065006c00670065006c0065007200690020006f006c0075015f007400750072006d0061006b0020006900e70069006e00200062007500200061007900610072006c0061007201310020006b0075006c006c0061006e0131006e002e00200020004f006c0075015f0074007500720075006c0061006e0020005000440046002000620065006c00670065006c0065007200690020004100630072006f006200610074002000760065002000410064006f00620065002000520065006100640065007200200035002e003000200076006500200073006f006e0072006100730131006e00640061006b00690020007300fc007200fc006d006c00650072006c00650020006100e70131006c006100620069006c00690072002egt UKR 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 ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing Created PDF documents can be opened with Acrobat and Adobe Reader 50 and later) gtgt Namespace [ (Adobe) (Common) (10) ] OtherNamespaces [ ltlt AsReaderSpreads false CropImagesToFrames true ErrorControl WarnAndContinue FlattenerIgnoreSpreadOverrides false IncludeGuidesGrids false IncludeNonPrinting false IncludeSlug false Namespace [ (Adobe) (InDesign) (40) ] OmitPlacedBitmaps false OmitPlacedEPS false OmitPlacedPDF false SimulateOverprint Legacy gtgt ltlt AddBleedMarks false AddColorBars false AddCropMarks false AddPageInfo false AddRegMarks false ConvertColors ConvertToCMYK DestinationProfileName () DestinationProfileSelector DocumentCMYK Downsample16BitImages true FlattenerPreset ltlt PresetSelector MediumResolution gtgt FormElements false GenerateStructure false IncludeBookmarks false IncludeHyperlinks false IncludeInteractive false IncludeLayers false IncludeProfiles false MultimediaHandling UseObjectSettings Namespace [ (Adobe) (CreativeSuite) (20) ] PDFXOutputIntentProfileSelector DocumentCMYK PreserveEditing true UntaggedCMYKHandling LeaveUntagged UntaggedRGBHandling UseDocumentProfile UseDocumentBleed false gtgt ]gtgt setdistillerparamsltlt HWResolution [2400 2400] PageSize [612000 792000]gtgt setpagedevice

ltlt ASCII85EncodePages false AllowTransparency false AutoPositionEPSFiles true AutoRotatePages None Binding Left CalGrayProfile (Dot Gain 20) CalRGBProfile (sRGB IEC61966-21) CalCMYKProfile (US Web Coated 050SWOP051 v2) sRGBProfile (sRGB IEC61966-21) CannotEmbedFontPolicy Error CompatibilityLevel 14 CompressObjects Tags CompressPages true ConvertImagesToIndexed true PassThroughJPEGImages true CreateJobTicket false DefaultRenderingIntent Default DetectBlends true DetectCurves 00000 ColorConversionStrategy CMYK DoThumbnails false EmbedAllFonts true EmbedOpenType false ParseICCProfilesInComments true EmbedJobOptions true DSCReportingLevel 0 EmitDSCWarnings false EndPage -1 ImageMemory 1048576 LockDistillerParams false MaxSubsetPct 100 Optimize true OPM 1 ParseDSCComments true ParseDSCCommentsForDocInfo true PreserveCopyPage true PreserveDICMYKValues true PreserveEPSInfo true PreserveFlatness true PreserveHalftoneInfo false PreserveOPIComments true PreserveOverprintSettings true StartPage 1 SubsetFonts true TransferFunctionInfo Apply UCRandBGInfo Preserve UsePrologue false ColorSettingsFile () AlwaysEmbed [ true ] NeverEmbed [ true ] AntiAliasColorImages false CropColorImages true ColorImageMinResolution 300 ColorImageMinResolutionPolicy OK DownsampleColorImages true ColorImageDownsampleType Bicubic ColorImageResolution 300 ColorImageDepth -1 ColorImageMinDownsampleDepth 1 ColorImageDownsampleThreshold 150000 EncodeColorImages true ColorImageFilter DCTEncode AutoFilterColorImages true ColorImageAutoFilterStrategy JPEG ColorACSImageDict ltlt QFactor 015 HSamples [1 1 1 1] VSamples [1 1 1 1] gtgt ColorImageDict ltlt QFactor 015 HSamples [1 1 1 1] VSamples [1 1 1 1] gtgt JPEG2000ColorACSImageDict ltlt TileWidth 256 TileHeight 256 Quality 30 gtgt JPEG2000ColorImageDict ltlt TileWidth 256 TileHeight 256 Quality 30 gtgt AntiAliasGrayImages false CropGrayImages true GrayImageMinResolution 300 GrayImageMinResolutionPolicy OK DownsampleGrayImages true GrayImageDownsampleType Bicubic GrayImageResolution 300 GrayImageDepth -1 GrayImageMinDownsampleDepth 2 GrayImageDownsampleThreshold 150000 EncodeGrayImages true GrayImageFilter DCTEncode AutoFilterGrayImages true GrayImageAutoFilterStrategy JPEG GrayACSImageDict ltlt QFactor 015 HSamples [1 1 1 1] VSamples [1 1 1 1] gtgt GrayImageDict ltlt QFactor 015 HSamples [1 1 1 1] VSamples [1 1 1 1] gtgt JPEG2000GrayACSImageDict ltlt TileWidth 256 TileHeight 256 Quality 30 gtgt JPEG2000GrayImageDict ltlt TileWidth 256 TileHeight 256 Quality 30 gtgt AntiAliasMonoImages false CropMonoImages true MonoImageMinResolution 1200 MonoImageMinResolutionPolicy OK DownsampleMonoImages true MonoImageDownsampleType Bicubic MonoImageResolution 1200 MonoImageDepth -1 MonoImageDownsampleThreshold 150000 EncodeMonoImages true MonoImageFilter CCITTFaxEncode MonoImageDict ltlt K -1 gtgt AllowPSXObjects false CheckCompliance [ None ] PDFX1aCheck false PDFX3Check false PDFXCompliantPDFOnly false PDFXNoTrimBoxError true PDFXTrimBoxToMediaBoxOffset [ 000000 000000 000000 000000 ] PDFXSetBleedBoxToMediaBox true PDFXBleedBoxToTrimBoxOffset [ 000000 000000 000000 000000 ] PDFXOutputIntentProfile () PDFXOutputConditionIdentifier () PDFXOutputCondition () PDFXRegistryName () PDFXTrapped False CreateJDFFile false Description ltlt ARA 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 BGR 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 CHS ltFEFF4f7f75288fd94e9b8bbe5b9a521b5efa7684002000410064006f006200650020005000440046002065876863900275284e8e9ad88d2891cf76845370524d53705237300260a853ef4ee54f7f75280020004100630072006f0062006100740020548c002000410064006f00620065002000520065006100640065007200200035002e003000204ee553ca66f49ad87248672c676562535f00521b5efa768400200050004400460020658768633002gt CHT ltFEFF4f7f752890194e9b8a2d7f6e5efa7acb7684002000410064006f006200650020005000440046002065874ef69069752865bc9ad854c18cea76845370524d5370523786557406300260a853ef4ee54f7f75280020004100630072006f0062006100740020548c002000410064006f00620065002000520065006100640065007200200035002e003000204ee553ca66f49ad87248672c4f86958b555f5df25efa7acb76840020005000440046002065874ef63002gt CZE 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 DAN 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 DEU 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 ESP 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 ETI 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 FRA 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 GRE ltFEFF03a703c103b703c303b903bc03bf03c003bf03b903ae03c303c403b5002003b103c503c403ad03c2002003c403b903c2002003c103c503b803bc03af03c303b503b903c2002003b303b903b1002003bd03b1002003b403b703bc03b903bf03c503c103b303ae03c303b503c403b5002003ad03b303b303c103b103c603b1002000410064006f006200650020005000440046002003c003bf03c5002003b503af03bd03b103b9002003ba03b103c42019002003b503be03bf03c703ae03bd002003ba03b103c403ac03bb03bb03b703bb03b1002003b303b903b1002003c003c103bf002d03b503ba03c403c503c003c903c403b903ba03ad03c2002003b503c103b303b103c303af03b503c2002003c503c803b703bb03ae03c2002003c003bf03b903cc03c403b703c403b103c2002e0020002003a403b10020005000440046002003ad03b303b303c103b103c603b1002003c003bf03c5002003ad03c703b503c403b5002003b403b703bc03b903bf03c503c103b303ae03c303b503b9002003bc03c003bf03c103bf03cd03bd002003bd03b1002003b103bd03bf03b903c703c403bf03cd03bd002003bc03b5002003c403bf0020004100630072006f006200610074002c002003c403bf002000410064006f00620065002000520065006100640065007200200035002e0030002003ba03b103b9002003bc03b503c403b103b303b503bd03ad03c303c403b503c103b503c2002003b503ba03b403cc03c303b503b903c2002egt HEB 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 HRV (Za stvaranje Adobe PDF dokumenata najpogodnijih za visokokvalitetni ispis prije tiskanja koristite ove postavke Stvoreni PDF dokumenti mogu se otvoriti Acrobat i Adobe Reader 50 i kasnijim verzijama) HUN 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 ITA 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 JPN ltFEFF9ad854c18cea306a30d730ea30d730ec30b951fa529b7528002000410064006f0062006500200050004400460020658766f8306e4f5c6210306b4f7f75283057307e305930023053306e8a2d5b9a30674f5c62103055308c305f0020005000440046002030d530a130a430eb306f3001004100630072006f0062006100740020304a30883073002000410064006f00620065002000520065006100640065007200200035002e003000204ee5964d3067958b304f30533068304c3067304d307e305930023053306e8a2d5b9a306b306f30d530a930f330c8306e57cb30818fbc307f304c5fc59808306730593002gt KOR ltFEFFc7740020c124c815c7440020c0acc6a9d558c5ec0020ace0d488c9c80020c2dcd5d80020c778c1c4c5d00020ac00c7a50020c801d569d55c002000410064006f0062006500200050004400460020bb38c11cb97c0020c791c131d569b2c8b2e4002e0020c774b807ac8c0020c791c131b41c00200050004400460020bb38c11cb2940020004100630072006f0062006100740020bc0f002000410064006f00620065002000520065006100640065007200200035002e00300020c774c0c1c5d0c11c0020c5f40020c2180020c788c2b5b2c8b2e4002egt LTH 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 LVI 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 NLD (Gebruik deze instellingen om Adobe PDF-documenten te maken die zijn geoptimaliseerd voor prepress-afdrukken van hoge kwaliteit De gemaakte PDF-documenten kunnen worden geopend met Acrobat en Adobe Reader 50 en hoger) NOR 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 POL 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 PTB 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 RUM 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 RUS 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 SKY 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 SLV 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 SUO 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 SVE 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 TUR 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 UKR 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 ENU (Use these settings to create Adobe PDF documents best suited for high-quality prepress printing Created PDF documents 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ii

DECLARATION

The experimental work described in this thesis was carried out in the School of Chemistry

University of KwaZulu-Natal Durban under the supervision of Professor SB Jonnalagadda and

co-supervisor Dr N Koorbanally

These studies represent original work by the author and have not otherwise been submitted in

any form for any degree or diploma to any tertiary institution Where use has been made of the

work of others it is duly acknowledged in the text

Signed ______________________ Name _____________________ Date ___________

As the candidatersquos supervisor I havehave not approved this thesisdissertation for submission

Signed ______________________ Name _____________________ Date ___________

iii











iv

ACKNOWLEDGEMENTS












encouragement


and help





social environment



v

PUBLICATIONS




Oral Presentations



Dioxiderdquo




Local





International



vi

TABLE OF CONTENTS

Abstract xiv


List of tables xxvi


CHAPTER 1

11 Introduction 1


121 Ozonation 5

122 Chlorination 6










171 Acid dyes 16

vii

172 Direct dyes 17


174 Sulfur dyes 18


176 Basic dyes 20

177 Vat dyes 20



181 Azo dyes 25


183 Azine dyes 26










viii








1141 Simulations 45






CHAPTER 2

21 Experimental 52






ix










CHAPTER 3











x





3113 Rate law 99















3213 Rate law 125

xi















3313 Rate law 152


CHAPTER 4




xii












4113 Rate law 179









xiii







4213 Rate law 204














xiv


4313 Rate law 228


CHAPTER 5

Conclusions 231

References 237

Appendix 248

xv

ABSTRACT





















xvi




















xvii

LIST OF FIGURES













[AM-]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 51


















(70 x 10-5 M) with [OCl-]t (15 x 10-3 M)) 75

xviii



b = 170 c = 255 d = 340 and e = 510) at pH = 90 76



c = 0145 d = 0175 and e = 0322)) 77




(145 x 10-3 M) [H+]eq (199x10-9- 7752 x 10-4 M) 79


[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 81




and I (012 M)) 82




[H+]0 (996 x 10-9 M) and I (012 M) 83



775 x 10-3 M) [OCl-]eq (114 x 10-3 -153 x 10-6 M) 85



[OCl-]eq (276 x 10-2 -33 x 10-6 M) 85



strength (I = 0009 - 0039 M) 87

xix








(70 x 10-5 M) with [OCl-]t (145x10-3 M) 101


hypochlorite 102






(70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 104



145 c = 218 d = 290 and e = 435) at pH 90 105



c = 0037 d = 0046 and e = 0086) 106









[OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (013 M) 111

xx




(996 x 10-9M) and I (012 M) 112



[OCl-]eq (114 x 10-3 -153 x 10-6M) 114



[HOClˉ]eq (276 x 10-2 -33 x 10-6 M) 114











hypochlorite 124


[BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 128





519 nm 130



xxi


[OCl-]t (15 x 10-3 M) 131



170 c = 255 d = 340 and e = 510) at pH = 90 132



0027 c = 0034 d = 0043 and e = 0052) 133




[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 135


[OCl-]t (145 x 10-3 M) [H+]eq (199x 10-9- 7752 x 10-4 M) 136



[OCl-]t (145 x 10- 3M) [H+] (996 x 10-9 M) and I (0128 M) 138



[OCl-]t (145 x 10-3 M) [H+] (996 x 10-9 M) and I (0128M) 138








0039 M) 144



fixed acid [H+] (45 x 10-3 M) 145

xxii






[SO+]0 (30 x10-5M) with [OCl-]t (145 x 10-3 M) 154


hypochlorite 155






C y = -A exp (-k x) + C) 157



379 c = 505 d = 631 and e = 757) at pH = 90 158




e = 480) 159




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 162





[ClO2]t (115 x 10-3 M) [OH-]eq (10 x 10-8- 631 x 10-7 M) 166

xxiii










(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 181











c = 303 d = 328 and e = 353) 185



k s (a = 332 b = 374 c = 399 d = 422 and e = 467) 186




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 189


(115 x 10-3 M) 190

xxiv













(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 206


(E2 S2) 207








(a = 252 b= 278 c= 303 d = 328 and e = 353) 210



(a = 252 b= 278 c = 303 d = 328 and e = 353) 211




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 214

xxv


with [ClO2]t (115 x 10-3 M) 214



[ClO2]t (115 x 10-3 M) [OH-]eq (18 x 10-8- 251 x 10-7 M) 217




[ClO2]t (115 x 10-3 M) at I (0009 - 004 M) 221


(115 x 10-3 M) 223


dioxide 226






xxvi

LIST OF TABLES






[OCl-]t (145 x 10-3 M) 81



[AM-]0 (70 x 10-5 M) pH = 90 87


[AM-]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) pH = 310 88


with [OCl-]t (145 x 10-3 M) [Cl-] = 1x10-1M 89


(70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 90



Simulations 107


[BB+]0 (70 x 10-5 M) [OCl-]t (0725 x 10-3 -435 x 10-3 M) pH = 90 107




[BB+]0 (70 x 10-5 M) pH = 90 116


[BB+]0 (70 x10-5 M) [OCl-]t (145 x 10-3 M) pH = 31 117


[OCl-]t (145 x 10-3 M) [Cl-] (1x10-1 M) 118




xxvii



simulations 126


strength 134


[OCl-]t (145 x 10-3) 135



[OCl-]t (145 x 10-3 M) pH =90 143


[OCl-]t (145 x 10-3M) pH = 40 145


(30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146


[SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146




simulations 153








[ClO2]t (115 x10-3 M) 169


[ClO2]t (115 x 10-3 M) pH = 80 171



xxviii



(115 x 10-3 M) 173







[ClO2]t (25 x 10- 3-35 x10-3 M) 188




[BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 194


[ClO2]t (115 x 10-3 M) pH = 90 196





[ClO2]t (115 x 10-3 M) 198




simulations 205





xxix




[SO+]0 (30 x 10-5 M) with [ClO2]t (115 x10-3 M) 218


[ClO2]t (115 x 10-3 M) pH = 80) 220






simulations 229

xxx




I ionic strength



AM- amaranth




ClO2- chlorite

ClO3- chlorate

cm centimetre

activation enthalpy

activation entropy

e- electron


Exp exponential

g gram

gL gram per litre



HOCl hypochlorite

K Kelvin






L litre


M-1 s-1 mol L sec

mg milligrams

mL millilitre


ng nano gram

nm nano metre

xxxi






s second

SO+ safranine-O dye

t time


TM trade mark

UV ultraviolet

V volt

z ionic charge


1

CHAPTER 1

11 Introduction





















2
























3























4
























5













121 Ozonation








harmful compounds31

6






















7

122 Chlorination























with chlorine gas44

8
















formed








9
















produced on-site








10











streams5960












11






















12






















13
























14























15
























16


















171 Acid dyes






17



NSO3

-

NN

O

SO3-

H


172 Direct dyes








OH

H2N

N

SO3Na

N NHCONH N N

OH

SO3NaNaO3S

NH2


18

173 Disperse dyes










Figure 11394

NaO3SSO3Na

N

NOH

N

CH3

NaO3S N

N

Cl

N

Cl


174 Sulfur dyes






19



NO-O

N

O-

O

OH


175 Reactive dyes









NaO3SOCH2CH2O2S

OCH3

N N

OH

SO3Na


20

176 Basic dyes











Figure 11697

N

N CH3

NH2H2N

H3C


177 Vat dyes







21



O

O HN

O

ONH

OO














22

























23























24























25



is given below


181 Azo dyes


















26














183 Azine dyes







27







3 OCl- = ClO3- + 2 Cl- (19)

OCl (110)




OCl- + ClO2- ClO3

- + Cl- (fast) (112)












28





stoichiometry128

2 HOCl + OCl- ClO3- + 2 H+ + 2 Cl- (114)


















29



visible light131132








In alkali

OCl- + H2O + 2e- Cl- + 2OH- (115)

In acid

OCl- + 2H+ + 2e- Cl- + H2O (116)







30


pH [OCl-] [HOCl]

20 045 9955

30 121 9879

40 323 9677

50 832 9168

60 1978 8022

70 4013 5987

80 6457 3543

90 8320 1680

100 9309 691













lights

31












ClO2 + 4H+ + 4e- rarr Cl- + 2H2O (118)




-144145


- 137


- + H2O (119)





- (036 to 097 mgL)


32


not contain ClO3-






- (121)
















33





















34

















rarr (124)



(125)


35


(126)


(127)


ln

(128)


129 to 130)

ln ln (129)

or

(130)








36

(131)




(132)

(133)




(134)


(135)


0 (136)


(137)


which implies that

(138)


37

(139)


(140)


(141)

which affords

(142)


ln ln (143)


ndash (kf + kb)



(144)


(145)



38






For the reaction

rarr

(146)


(147)




(148)









39


ndash ndash

(151)


x

ndash x ndash x

(152)


ln ndash

(153)

1ln (154)









conditions


=


(155)

40








(156)







(157)




(158)

and

(159)

41

At equilibrium

(160)


0 (161)

This implies that

(162)


as

(163)

Resulting in

(164)


(165)


(166)


(167)

Which results in

42

ln

(168)








rarr rarr

(169)


(170)

(171)

(172)


for has two terms


[A] [A]0 [B]0 = 0 [C]0 = 0 (173)

and at any time t

43

(174)


(175)


(176)



(176) yields

(177)




1

(178)






44















(181)







45







1131 Simulations









circumstances161







46
























47













constant








48



















49




















50













51





52

CHAPTER 2

21 Experimental















N N SO3-

O-

-O3S

-O3S


53













‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

54

NSO3

-

NN

O

SO3-

H









0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorabnce

Wavelength (nm)

55






N

N CH3

NH2H2N

H3C






‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

56
















57









air


Anode 2Cl- (aq) Cl2 (g) + 2e- (21)



58





















59















2 OCl- + As2O3 As2O5 + 2 Cl- (25)








60


















61
















mgmL ClO

A B N 1349

mL sample titrated

(26)

mgmL Cl

A B N 3545

mL sample titrated

(27)


mgL ClO

A B N 13490

mL sample

(28)

62

mgL Cl

A B N 35450

mL sample

(29)





















63











64


65


66


67


68























69























70
























71





x1 x2 x3 xn-1 xn


ā = x1 + x2 + x3 + + xn-1 + xn

n (210)



n ndash 1 (211)




n ndash 1


form

12

N1 N2 N3



i=1 j=1 k=1

N1 + N2 + N3 + - Ns

(212)



72

2110 Variance (s2)








CV = (s ā) x 100








73

CHAPTER 3





















74


(15 x 10-3 M) at pH = 90 and 520 nm












‐01

0

01

02

03

04

05

06

07

08

0 20 40 60 80 100 120 140

Absorban

ce

Times

75


(15 x 10-3 M)














76






‐01

0

01

02

03

04

05

06

0 20 40 60 80 100 120

Absorban

ce

Time s

a

b

c

de

77

(a) (b)

(c) (d)

(e)


78



and pH equals to 90


[OCl-]t 10-3 M ks-1

050 0041

170 0093

255 0145

340 0175

510 0322



y = 11072x + 46582Rsup2 = 09928

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4

lnk`

ln [OCl‐]t

79















0

01

02

03

04

05

06

07

08

09

1

3 4 5 6 7 8 9 10

k

pH

80


pH ks-1

989 0005

972 0011

945 0015

912 0021

881 0028

863 0039

815 0110

784 0199

755 0320

739 0398

693 0599

685 0638

650 0745

485 0847

420 0854

365 0865

344 0875

317 0878

315 0897






81














y = 02711x + 37842Rsup2 = 09618

‐12

‐1

‐08

‐06

‐04

‐02

0

‐20 ‐15 ‐10 ‐5 0

ln k

acute

ln [H+]

82




313






83










84


respectively



-1 k1M-1s-1 k2M

-1s-1

863 234 x 10-9 340 x 10-3 194 x 10-3 80 x 10-2 0039 234 1990

815 706 x 10-9 307 x 10-3 530 x 10-3 71 x 10-2 0110 232 2077

784 144 x 10-8 266 x 10-3 938 x 10-3 65 x 10-2 0199 247 2132

755 281 x 10-8 213 x 10-3 147 x 10-2 52 x 10-2 0320 245 2183

739 406 x 10-8 180 x 10-3 179 x 10-2 47 x 10-2 0398 261 2219

693 117 x 10-7 930 x 10-4 267 x 10-2 25 x 10-2 0599 273 2244

685 141 x 10-7 810 x 10-4 279 x 10-2 17 x 10-2 0638 216 2288

650 315 x 10-7 410 x 10-4 319 x 10-2 80 x 10-3 0745 199 2338

485 141 x 10-5 100 x 10-5 359 x 10-2 20 x 10-5 0847 176 2360

420 630 x 10-5 234 x 10-5 360 x 10-2 39 x 10-5 0854 168 2375

365 224 x 10-5 659 x 10-6 360 x 10-2 10 x 10-5 0864 159 2402

344 363 x 10-5 406 x 10-6 360 x 10-2 57 x 10-6 0875 143 2431

317 675 x 10-5 218 x 10-6 360 x 10-2 26 x 10-6 0878 123 2439

315 707 x 10-5 208 x 10-6 360 x 10-2 25 x 10-6 0897 122 2493

314 723 x 10-5 204 x 10-6 360 x 10-2 24 x 10-6 0912 119 2535


plusmn 06 232

plusmn 18





85






3111





y = 10717x + 11753Rsup2 = 09996

‐16

‐14

‐12

‐10

‐8

‐6

‐4

‐2

0

‐15 ‐10 ‐5 0

ln k

acute

ln [OCl‐]eq

y = 09297x + 28534Rsup2 = 09958

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4 ‐3

ln k

ln [HOCl]eq

86













rate











87





-1

00092 0043 0047

00167 0050 0048

00242 0052 0048

00317 0054 0050

00392 0059 0051




y = 12169x ‐ 14689Rsup2 = 09833

y = 07935x ‐ 31338Rsup2 = 09402

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

005 01 015 02

ln k

radicI

88











00167 0048

00242 0048

00317 0050

00392 0051



y = 01333x + 00459Rsup2 = 09544

004650047

004750048

004850049

00495005

005050051

00515

0 001 002 003 004 005

k

IM

89





HOCl as anticipated








Table 316


[Cl-]M ks-1 0100 0107 0148 0109 0298 0107 0447 0104 0597 0104 0725 0104




90














-1 kM-2 s-1

283 0015 130 0033 287

288 0016 139 0052 452

293 0017 139 0060 522

298 0025 217 0072 626

303 0031 269 0091 791



91



(Figure 3114)






Hǂk J mol-1


SǂJ K-1 mol-1


Eak J mol-1




y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

92























93




mz 130(M-2)




O

NaO3S

NaO3S

OH

Na+

(P1)


sodium salt

OO

Cl Cl

(P2)


OO

O

(P3)


94
























95











+ Na+ + N2 + H3O+ + 3HCl (31)











96










97

N

ONaSO3

NaO3S

H

N SO3Na N

NaO3S

NaO3S

N SO3Na

OHO Cl

I1

N

NaO3S

NaO3S

N SO3Na

OO

H

HOCl

H+O

HH

ONaO3S

NaO3S

N

O H

SO3NaN

I3

I2

O

NaO3S

NaO3S

OH

P1

+ SO3NaNN

O

HH

I4

NN O H

H

Cl O

H

I5

HOCl

-N2Cl O O H

I6

OO

I7

HOCl OO

O

Cl2OO

Cl Cl P3P2

H+-

N

ONaO3S

N SO3Na

OHH

NaO3S


98





H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2


I1 + H+ rarr I2+


+

I3 + H2O + H+ rarr P1 + I4+

I4+ + H2O rarr I5

+ + Na+ + SO32- + H+


I6 rarr I7 + HCl

I7 + Cl2 rarr P2


R1

R2

R3

R4

R5

R6

R7

R8

R9



+ Na+ + N2 + 3HCl (32)

3113 Rate law





99











(33)

(34)



(35)

3114 Simulations






100







C1 H+ + OCl- HOCl 397 x 10-4 M-1s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1s-1 11 s-1



C5 I1+ H+ rarr I2+ 430 x 109 M-1s-1 --


+ 415 x 109 M-2s-1 --

C7 I2+ rarr P1 + I5

+ + Na+ + SO32- + H+ 301 x108 s-1 --


C9 I7 + Cl2 rarr P2 435 x 108 M-1s-1 --








101



000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 20 40 60 80 100 120 140

ConcentrationM

Times

E1 S1

E2 S2

E3 S3

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 5 10 15 20 25 30

Concentration M

Times



Intermediates(I)



102











103










(15 x 10-3) at pH = 90 and 555 nm






0

01

02

03

04

05

06

07

0 20 40 60 80 100

Absorban

ce

Times

104













105








0

01

02

03

04

05

06

07

08

0 50 100 150 200 250 300

Absorban

ce

Time s

(a)

(b)

(c)

(d)(e)

106

(a) (b)

(c) (d)

(e)


107




[OCl-]t 10-3 M ks-1 073 0012 145 0030 218 0037 290 0046 435 0086








y = 10323x ‐ 0408Rsup2 = 09746

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐5 ‐4 ‐3 ‐2 ‐1 0

ln k

ln [OCl‐]t

108







(145 x 10-3 M) with [H+]e (199 x 10-9- 7752 x 10-4 M)





322

0

01

02

03

04

05

06

07

08

2 4 6 8 10

k

pH

109


pH ks-1

900 00347

870 00345

835 00411

800 00491

770 00574

745 00640

720 00780

700 01018

675 01226

650 01425

600 02027

540 03160

370 05900

331 06704

329 06955

322 07093

311 07309






110








y = 02414x + 15266Rsup2 = 09858

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐25 ‐20 ‐15 ‐10 ‐5 0

ln k

ln [H+]

111







112











113



-1 k1M-1s-1 k2M

-1s-1

870 199 x 10-9 276 x 10-2 134 x 10-3 00390 00270 141 2008

835 445 x 10-9 261 x 10-2 285 x 10-3 00360 00610 137 2143

800 997 x 10-9 233 x 10-2 568 x 10-3 00303 01400 129 2464

770 199 x 10-8 195 x 10-2 949 x 10-3 00250 02050 128 2161

745 354 x 10-8 155 x 10-2 134 x 10-2 00190 02799 122 2081

720 629 x 10-8 114 x 10-2 176 x 10-2 00135 03670 118 2088

700 997 x 10-8 843 x 10-3 206 x 10-2 00094 04275 112 2079

675 177 x 10-7 543 x 10-3 236 x 10-2 00060 04930 110 2092

650 315 x 10-7 332 x 10-3 257 x 10-2 00035 05390 105 2100

600 998 x 10-7 114 x 10-3 279 x 10-2 00011 05880 100 2111

540 397 x 10-6 294 x 10-4 287 x 10-2 00002 06459 084 2250

370 199 x 10-4 595 x 10-6 290 x 10-2 -- 06582 -- 2270

331 489 x 10-4 242 x 10-6 290 x 10-2 -- 06652 -- 2294

329 512 x 10-4 232 x 10-6 290 x 10-2 -- 06725 -- 2319

322 602 x 10-4 197 x 10-6 290 x 10-2 -- 06842 -- 2359

311 775 x 10-4 153 x 10-6 290 x 10-2 -- 06910 -- 2383









114


30 to 90


[OClˉ]eq (114 x 10-3 ndash 153 x 10-6 M)








y = 1101x + 09865Rsup2 = 09135

‐01

6E‐16

01

02

03

04

05

06

‐5 ‐45 ‐4 ‐35 ‐3

ln k

`

ln [OCl‐]eq

y = 1034x + 32194Rsup2 = 09979

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐7 ‐6 ‐5 ‐4 ‐3 ‐2

ln k

`

ln [HOCl]eq

115




















116



-1

00099 0035 00452

00188 0035 00459

00225 0037 00471

00263 0038 00485

00338 0040 00499







y = ‐10346x ‐ 11666Rsup2 = 09931

y = ‐07456x ‐ 11354Rsup2 = 09937

‐148

‐146

‐144

‐142

‐14

‐138

‐136

‐134

‐132

‐13

‐128

022 023 024 025 026 027 028

log k

radicI

A

B

117


shown in Table 325


(145 x 10-3 M) pH = 31


00510 161

00547 157

00585 155

00622 153

00697 150








y = 57679x + 12139Rsup2 = 09752

148

15

152

154

156

158

16

162

164

003 004 005 006 007 008

k

IM

118





reaction


[Cl-]M ks-1 0000 0125 0148 0126 0298 0126 0447 0126 0597 0127 0725 0127










same

119



-1 kM-2 s-1

283 0014 121 0041 356

288 0019 165 0058 504

293 0028 165 0064 556

298 0033 286 0079 686

303 0037 321 0098 852




y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

120



HǂkJ mol-1


SǂJK-1 mol-1


EakJ mol-1








compact nature













121











(C7H9N)












122















NH2

O

(P1)


N

SO3H

H

(P2)


123

NSO3H

Cl

(P3)


acid

OH OH

OH

(P4)









+ 3HCl + OH- + H+ (36)






124


formation of P4

NSO3

-

NN

O

SO3-

H

HOCl

NSO3H

NN

O

SO3H

HH

-OCl

NSO3H

N

SO3H

ClO

NH2

O

HOCl

-OCl

NSO3H

ClO OCl

N

SO3H

H

ClO OCl

NSO3H

ClO

OCl-

HO Cl

ClO OCl

OCl

NSO3H

Cl

H+OH-

OH OH

OH

+

SO3H

NSO3H

NClO H

P1I1

I2I3

P2

I5

P4

P3

I4


125




H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2


I1+ + HOCl rarr I1

2+ + OCl- R2

I22+ + OCl- rarr I3

+ + P2 R3



I3+ + 3H2O rarr P4

+ + 3HCl R6



+ 3HCl + OH- + H+

(37)

3213 Rate law



(38)



(39)

126

(310)

and where (311)

(312)

3214 Simulations











curves203


Reaction

No


Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-2 s-1 11 s-1


127

Table 3210 contd

Reaction

No


Reverse rate

C5 BB+ + OCl- rarr I1 122 M-1 s-1 --

C6 I1 + H+ rarr I1+ + P1 330 x 109 M-1 s-1 --


2+ + OCl- 230 x 109 M-1 s-1 --


+ + P2 430 x 109 M-1 s-1 --



C11 I3+ rarr P4

+ + 3HCl 417 x 108 s-1 --








128





0

000001

000002

000003

000004

000005

000006

000007

0 50 100 150 200 250

ConcentrationM

Times

E1S1

E2S2

E3S3



129








0

000001

000002

000003

000004

000005

000006

000007

0 10 20 30 40 50 60 70

ConcentrationM

Times


Intermediates (I)


130

















0

01

02

03

04

05

06

0 50 100 150

Absorban

ce

Times

131


(15 x 10-3 M)










132








‐01

6E‐16

01

02

03

04

05

06

07

0 50 100 150 200 250 300

Absorban

ce

Time s

(b)(c)(d)(e)

(a)

133

(a) (b)

(c) (d)

(e)





134


[OCl-]t 10-3 M ks-1

0085 0010

170 0026

255 0034

340 0043

510 0052









y = 09193x + 20384Rsup2 = 09533

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐8 ‐7 ‐6 ‐5 ‐4

ln k´

ln [OCl‐]t

135







pH ks-1

873 008

826 012

786 023

754 044

722 054

710 082

668 125

664 221

450 1975

‐45

05

55

105

155

205

255

305

355

405

275 375 475 575 675 775 875

k

pH

136

Table 332 contd

pH ks-1

390 2827

351 3256

361 3347

315 3571

313 3699

295 3964

285 4087






(Figure 337)


y = 04715x + 7247Rsup2 = 09727

‐3

‐2

‐1

0

1

2

3

4

5

‐20 ‐15 ‐10 ‐5

ln k

ln[H+]

137

















138






139








y = 1013x + 33473Rsup2 = 09936

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐6 ‐55 ‐5 ‐45 ‐4 ‐35 ‐3

ln k

ln[HOCl]eq

y = 05112x ‐ 2502Rsup2 = 09709

‐25

‐15

‐05

05

15

25

35

‐13 ‐11 ‐9 ‐7 ‐5 ‐3 ‐1

ln k

ln[OCl]eq

140



-1 k1M-1 s-1 k2M

-1 s-1

873 186 x 10-9 156 x 10-3 340 x 10-2 0064 0093 195 2922

826 548 x 10-9 440 x 10-3 310 x 10-2 0066 0127 209 2999

786 138 x 10-8 921 x 10-3 260 x 10-2 0058 0276 217 3048

754 288 x 10-8 150 x 10-2 210 x 10-2 0053 0458 254 3087

722 601 x 10-8 215 x 10-2 140 x 10-2 0040 0676 279 3157

710 792 x 10-8 239 x 10-2 120 x 10-2 0035 0761 291 3209

668 208 x 10-8 301 x 10-2 590 x 10-2 0018 0985 318 3274

664 228 x 10-8 306 x 10-2 545 x 10-2 -- 107 -- 3528

405 890 x 10-5 360 x 10-2 164 x 10-5 -- 129 -- 3596

390 126 x 10-4 360 x 10-2 120 x 10-5 -- 130 -- 3624

351 309 x 10-4 360 x 10-2 455 x 10-6 -- 133 -- 3713

361 245 x 10-4 360 x 10-2 589 x 10-6 -- 136 -- 3780

315 707 x 10-4 360 x 10-2 203 x 10-6 -- 138 -- 3831

313 740 x 10-4 360 x 10-2 198 x 10-6 -- 141 -- 3922

295 112 x 10-3 360 x 10-2 134 x 10-6 -- 143 -- 3974

285 141 x 10-3 360 x 10-2 107 x 10-6 -- 144 -- 4005










141










as follows

(313)



(314)

Thus


(316)




(317)

142















(318)

(319)

(320)

and



143











y = 71649x + 31127Rsup2 = 09658

32

33

34

35

36

37

38

39

40

41

00002 00004 00006 00008 0001 00012 00014

k

[H+]eq

144



-1 00092 0047 063

00167 0042 062

00242 0039 060

00317 0037 056

00392 0034 054








and SO+

y = ‐12866x ‐ 1202Rsup2 = 09955

y = ‐07248x ‐ 01187Rsup2 = 09181

‐16

‐14

‐12

‐1

‐08

‐06

‐04

‐02

0

008 01 012 014 016 018 02

log kacute

radicI

B

A

145









00167 062

00242 060

00317 056

00392 054



y = ‐34x + 06745Rsup2 = 09635

052

054

056

058

06

062

064

066

0005 001 0015 002 0025 003 0035 004

k

IM

146








value (Table 336)


[Cl-]M ks-1 0000 0901 0148 0901 0298 0902 0447 0902 0597 0902 0725 0903








147





-1 kM-2 s-1

283 0019 172 0049 426

288 0022 200 0062 539

293 0037 336 0075 652

298 0041 372 0082 713

303 0051 463 0098 852



y = ‐44611x + 16295Rsup2 = 09509

y = ‐28627x + 11599Rsup2 = 09829

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

148



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1





















in Table 339

149


H3C

H2N

OCl

OCl

(P1)


N

N CH3

NH2

OH

ClOH

(P2)



dienone oxime











150





















1 Figure 1116)


Figure 3316

151

N

N CH3

NH2H2N

H3C

OCl-N

N CH3

NH2H2N

H3C

OCl

H

N

N CH3

NH2

H

N

N CH3

NH2

OH

ClOH

H3C

H2N

OCl

OCl

OCl

N

N CH3

NH2

OH

H

I1

P1

I2

I3

P2

H+

HO Cl

HOCl

Cl- +

+ H+





+ R1




152





3313 Rate law







be proposed as

(323)

3314 Simulations








153





Reaction

No

Reaction Mechanism

Forward rate

Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x 10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1 s-1 11 s-1


C4 SO+ + OCl- rarr I1 302 M-1 s-1 --

C5 I1 + H + rarr I1+ 23x 109 M-1 s-1 --









154






0

0000005

000001

0000015

000002

0000025

0 50 100 150 200

ConcentrationM

Times



E2S2

E3S3

E1 S1

155








16)

000E+00

500E‐06

100E‐05

150E‐05

200E‐05

250E‐05

0 20 40 60 80 100

Concentration M

Time s

Products (P1P2)


Intermediates (I)

156

CHAPTER 4





















157





fitted curve



005

015

025

035

045

055

065

075

0 05 1 15 2

Absorban

ce

Times

158













10-3 M (a = 252 b = 379 c = 505 d = 631 and e = 757) at pH = 90

0

01

02

03

04

05

06

07

08

09

0 05 1 15 2

Absorban

ce

Times

a

b

cd

e

159




(a) (b)

(c) (d)

(e)


160






[ClO2] 10-3 M ks-1

252 3320

379 3740

505 3990

631 4340

757 4800



y = 10719x ‐ 07905Rsup2 = 09967

04

06

08

1

12

14

16

18

125 145 165 185 205 225

ln [ClO2] t

ln kacute

161



[ClO2]0














from 60 to 90

162



pH ks-1

60 0409

64 0411

66 0411

68 0480

70 0490

72 0946

74 1552

76 1928

78 2250

80 2500

04

09

14

19

24

29

34

6 65 7 75 8 85 9

k

pH

163


82 2790

84 2910

86 3150

88 3290

90 3310










y = 08321x + 12573Rsup2 = 08844

‐4

‐3

‐2

‐1

0

1

2

‐185 ‐175 ‐165 ‐155 ‐145 ‐135 ‐125

ln k

ln(OH‐)

164









(41)







y = 10825x + 72892Rsup2 = 09915

y = 06802x + 45703Rsup2 = 08898

y = 01227x + 11484Rsup2 = 09362

‐2

‐15

‐1

‐05

0

05

1

15

2

‐8 ‐6 ‐4 ‐2 0

log k

log[OH‐]

165








794 x 10-9 008 03

158 x 10-8 012 05

251 x 10-8 015 10

631 x 10-8 017 18

178 x 10-7 049 33

631 x 10-7 130 63

316 x 10-6 430 104

794 x 10-6 580 129


166














y = 4E+09xRsup2 = 09711

0

200

400

600

800

1000

1200

1400

1600

‐1E‐07 358E‐20 1E‐07 2E‐07 3E‐07 4E‐07 5E‐07

kM

‐2s‐1

[OH‐]M

167





-+ H2O (43)














HOO- + 2ClO2 + OH- 2ClO2- + H2O (47)



168





















169


pH = 70

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 049 1944 194 x 108

277 078 2058 206 x 108

303 093 1841 184 x 108

328 130 2060 206 x 108

353 150 1981 198 x 108


pH = 80

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 250 9920 99 x 107

277 260 9386 94 x 107

303 290 9570 96 x 107

328 320 9756 98 x 107

353 350 9915 99 x 107


pH = 90

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 332 13174 13 x 107

278 374 13453 13 x 107

303 399 13168 13 x 107

328 422 12865 13 x 107

353 480 13597 14 x 107



170





mechanism








y = 10131x + 30233Rsup2 = 09891

y = 10371x + 47055Rsup2 = 09724

y = 10193x + 49541Rsup2 = 09759

‐1

‐05

0

05

1

15

2

25

‐39 ‐37 ‐35 ‐33 ‐31 ‐29 ‐27 ‐25

ln k

ln [ClO2]

a

b

c

171



00096 311

00174 341

00262 357

00354 375

00397 395






AM-

y = 09499x + 04017Rsup2 = 09814

048

05

052

054

056

058

06

008 01 012 014 016 018 02

log k

radicI

172






[Cl-]M ks-1

0148 0486

0298 0496

0447 0502

0597 0512

0725 0530












173


417


TK ks-1 k3 M-2 s-1

283 0050 333 x 106

288 0090 600 x 106

293 0120 800 x 106

298 0170 110 x 107

303 0210 140 x 107





y = ‐60224x + 3641Rsup2 = 09739

148

15

152

154

156

158

16

162

164

166

168

000325 00033 000335 00034 000345 00035 000355

ln k

1T

174



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

AM- with ClO2 4758 -65873 5006














175









2- + Na+ (49)


HO3S

NaO3S

O

O

(P1)


O O

(P2)


176


















Figure 4113

177

N N SO3Na

OHNaO3S

NaO3S

ClO2 N N SO3Na

OH-O3S

NaO3S

N N SO3Na

OHO3S

NaO3S

I1

N

HO3S

NaO3S

N SO3Na

O

-OH

-OH

HO3S

NaO3S

O

N N SO3Na

OH ClO23

HO3S

NaO3S

O

N

O

N SO3Na

H

HO3S

NaO3S

O

O

SO3NaNN

-OH-OH

SO3NaOH

OHOH

-OH

H

I2I3

P1

P2

-OH

H+ +

I4

O O


178





- + AM (very slow)



HO AM ClO2



- R1


- R2

I2 + ClO2rarr I3+

+ ClO2- R3

I3+ + ClO2rarr I4

2+ + ClO2- R4

I42+ rarr P1 + I5

+ + H+ + N2 R5

I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ R6



SO32-

+ Na+

(410)

179

4113 Rate law








as


where kOH-k2

[OH-]



k AM-


k = k1 + kOH- [OH-][ClO2] (414)

180

4114 Simulations













- 40 x 109 M-1s-1


+ ClO2- 534 x 109 M-1 s-1

C4 I3


-

4 97 x 109 M-1s-1


+ + H+ + N2 4 54 x 109 s-1

C6 I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ 517 x 109 M-1s-1

181






000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Time s

E1 S1 E2 S2

E3 S3



182







000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Times


Intermediates(I)


183










0

01

02

03

04

05

06

07

08

0 2 4 6 8 10

Absorban

ce

Time (sec)

184










185









‐01

6E‐16

01

02

03

04

05

06

07

0 1 2 3 4 5

Absorban

ce

Time ( Sec)

c

b

d

e

186

(a) (b)

(c) (d)

(e)


187



in the Table 421


[ClO2]t 10-3 M ks-1 252 332 278 374 303 399 328 422

353 467







y = 10308x ‐ 49235Rsup2 = 09865

‐37

‐365

‐36

‐355

‐35

‐345

‐34

‐335

‐33

119 129 139 149

ln[ClO

2] t

ln k

188






pH ks-1

60 029

63 032

67 038

69 047

72 082

74 096

79 134

81 160

82 169

84 171

86 179

88 175

90 186





189






02

04

06

08

1

12

14

16

18

2

6 65 7 75 8 85 9

k

pH

190







y = 08011x + 11389Rsup2 = 09487

04

06

08

1

12

14

‐135 ‐13 ‐125 ‐12

ln k

ln(OH‐)

y = 02213x + 12206Rsup2 = 09432

y = 04638x + 29978Rsup2 = 09704

y = 08011x + 49463Rsup2 = 09487

‐08

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐8 ‐75 ‐7 ‐65 ‐6 ‐55 ‐5

log k

log [OH‐]

191





















192


[OH-]0M ks-1 k 102 M-1s-1

100 x 10-8 029 193

200 x 10-8 032 213

257 x 10-8 035 237

501 x 10-8 038 253

794 x 10-8 047 314

132 x 10-7 062 413

195 x 10-7 082 546







193






products


OH-] (417)






y = 2E+09x + 17235Rsup2 = 09947

100

150

200

250

300

350

400

450

500

550

600

‐5E‐08 18E‐21 5E‐08 1E‐07 15E‐07 2E‐07

kM

‐2s‐1

[OH‐]

194


pH = 70

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 029 1150 115 x 108

277 044 1160 116 x 108

303 059 1168 117 x 108

328 075 1188 119 x 108

353 091 1202 120 x 108


pH = 80

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 108 4285 430 x 107

277 115 4151 420 x 107

303 124 4092 410 x 107

328 138 4207 420 x 107

353 141 3994 400 x 107


pH = 90

[ClO2]x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 298 11825 118 x 107

278 324 11510 115 x 107

303 352 11551 115 x 107

328 381 11585 115 x 107

353 425 11898 118 x 107




195










Table 425

y = 1039x + 25823Rsup2 = 09999

y = 08489x + 3195Rsup2 = 09763

y = 1016x + 48161Rsup2 = 09881

‐15

‐1

‐05

0

05

1

15

2

25

3

‐4 ‐35 ‐3 ‐25 ‐2

ln k

ln [ClO2]

A

B

C

196



00096 0091

00174 0095

00262 0105

00354 0109

00397 0111







y = 09016x ‐ 11324Rsup2 = 0974

‐106

‐104

‐102

‐1

‐098

‐096

‐094

009 011 013 015 017 019

logk

radicI

197





salt


[Cl-]M ks-1

0148 0720

0298 0730

0447 0710

0597 0710

0725 0720









198


TK ks-1 k3 M-2s-1

283 0100 70 x 106

288 0136 90 x 106

293 0172 11 x 107

298 0260 17 x 107

303 0329 22 x 107






y = ‐51842x + 34016Rsup2 = 0992

156

158

16

162

164

166

168

17

000325 00033 000335 00034 000345 00035 000355

ln k

1T

199



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

BB+ with ClO2 4758 -67636 5006

















200



















201


N

O

H

COOH

(P1)


N

SO3

NSO3

(P2)










hydroxylamine

202






amine analog P2


Figure 4213

203

NSO3

N

O

H

N

SO3

ClO2

N

O

H

N

SO3

NSO3

OH

N

O

H

N

SO3

NSO3

N

O

H

N

SO3

NSO3

O

H

OH

N

O

H

N

SO3

O

NSO3

HO-N

O

H

COOH

N

SO3

NSO3

I1

I2

P1 P2

ClO2








- + HO BB+

Rate limiting step

(420)

204



- R1


R2




4213 Rate law






k1[ClO2][BB+ ] + k2 [ClO2][OH-] [BB+

] (423)


as


205

where kOH-k2

[OH-]

r k1 + kOH- [OH-][ClO2] [BB+] (425)


k [BB+] (426)


k = k1 + kOH- [OH-] ClO2 (427)

4214 Simulations









- 172 x 102 M-1 s-1


200 x 109 M-2 s-1


206






0

000001

000002

000003

000004

000005

000006

000007

000008

0 5 10 15 20 25

Concentration M

Times

E1S1

E2S2

E3S3


207









24)

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

0 2 4 6 8 10 12

Concentration M

Time s

Products (P1P2 P3)


Intermediates (I)

208












0

01

02

03

04

05

06

07

08

09

0 2 4 6 8 10 12

Absorban

ce

Time (sec)

209












210


10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)




0

01

02

03

04

05

06

07

08

0 1 2 3 4 5

Absorban

ce

Time s

ecb

a

d

211

(a) (b)

(c) (d)

(e)


10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)



212


[ClO2]t 10-3 M ks-1

252 2100

278 2310

303 2610

328 2820

353 3010




[ClO2]0


y = 1097x + 4779Rsup2 = 0994

06

07

08

09

1

11

12

13

14

15

16

‐37 ‐36 ‐35 ‐34 ‐33

ln k

ln [ClO2]t

213

434 Effect of pH





pH ks-1

60 0405

63 041

66 0421

68 0475

70 0499

72 0956

74 1752

76 1828

78 211

80 245

82 269

84 281

86 325

88 349

90 361




higher pH range

214









0

05

1

15

2

25

3

35

4

45

5

6 65 7 75 8 85 9

ks

‐1

pH

215








y = 081x + 11269Rsup2 = 0953

0

05

1

15

2

25

‐135 ‐13 ‐125 ‐12 ‐115 ‐11

ln k

ln(OH‐)

y = 01651x + 08533Rsup2 = 09089

y = 01944x + 13006Rsup2 = 09979

y = 0809x + 48942Rsup2 = 0953

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐75 ‐65 ‐55 ‐45

log k

log [OH‐]

216








= k1 +KkOH- [OH-][ClO2] [SO+] (429)

= k [ClO2] [SO+] (430)













217


[OH-]eq k k 102M-1s-1

182 x 10-8 0369 246

251 x 10-8 0411 274

398 x 10-8 0411 274

631 x 10-8 0480 320

100 x 10-7 0490 326

158 x 10-7 0946 630

251 x 10-7 1052 701




y = 2E+09x + 19826Rsup2 = 0915

0

100

200

300

400

500

600

700

800

0 5E‐08 00000001 15E‐07 00000002 25E‐07 00000003

kM

‐2s‐1

[OH‐] M

218













Table 434


pH = 70

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 049 1944 194 x 108

278 059 2122 212 x 108

303 065 2145 215 x 108

328 069 2104 21 0x 108

353 074 2096 21 0x 108


219

Table 434 contd

pH = 80

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 115 4563 456 x 108

278 135 4856 486 x 108

303 145 4785 479 x 108

328 160 4878 488 x 108

353 175 4972 497 x 108


pH = 90

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 190 7540 754 x 108

278 208 7482 748 x 108

303 222 7327 733 x 108

328 250 7622 762 x 108

353 280 7932 793 x 108





y = 11338x + 47969Rsup2 = 09766

y = 12126x + 4618Rsup2 = 09907

y = 1181x + 36698Rsup2 = 09632 ‐1

‐05

0

05

1

15

‐37 ‐36 ‐35 ‐34 ‐33 ‐32

ln k

ln[ClO2]

220










ionic strength



00096 0126

00174 0109

00262 0105

00354 0096

00397 0093


221










y = ‐12368x ‐ 07853Rsup2 = 09731

‐104

‐102

‐1

‐098

‐096

‐094

‐092

‐09

‐088

009 011 013 015 017 019

log k

radicI

222


IM ks-1

0060 0153

0061 0155

0062 0160

0063 0175

0064 0176








pH 90

TK ks-1 k3 M-2s-1

283 125 83 x 107

288 152 10 x 108

293 179 12 x 108

298 193 13 x 108


223




HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

SO+ with ClO2 1508 -74836 1755





y = ‐21128x + 2575Rsup2 = 09501

182

183

184

185

186

187

188

189

000325 00033 000335 00034 000345 00035 000355

ln k

1T

224


















product P2

225


OH

(P1)

phenol

N

N CH3H3C

OHOH

(P2)











226



and GC-MS spectrum

N

N CH3

NH2H2N

H3C

ClO2

H3C

H2N N NH2

CH3N

OH

N

N CH3

N

H3C

H

HH2N

OH

OHI1

P1ClO2

N

N CH3

N

H3C

H

H

OHH2N

HO

N

N CH3H3C

OHH2N

I2

I3

N

N CH3

OH N

H3C

H

H

OH

N

N CH3H3C

OHN

H

H

OH

ClO2

OH-

ClO2

OH-

OH

N

N CH3H3C

OHOH

I4

P2


227





limiting

(434)



+ + ClO2

- R1

I1+ + ClO2 + OH-

rarr I2+ + ClO2

- R2

I2+ + OH- rarr I3

+ NH2OH R3

I3 + ClO2 + OH-

rarr I4 + ClO2- R4


- R5



228

4313 Rate law





k1 [ClO2][SO+] + k2 [ClO2][OH-] [SO+] (436)


as

k1 ClO2 SO+ ‐ ClO2 [OH-] SO+ (437)

where kOH-k2

[OH-]



k SO+ (439)


k k1 kOH‐ [OH-] ClO2 (440)

229

4314 Simulations










+ + ClO2

- 198 x 102 M-1 s-1

C2 I1+ + ClO2 + OH-

rarr I2+ + ClO2

- 200 x 109 M-2s-1


+ NH2OH 456 x 109 M-2s-1

C4 I3 + ClO2 + OH-

rarr I4 + ClO2- 590 x 109 M-2s-1


- 675 x 109 M-2s-1


0

000001

000002

000003

000004

000005

000006

000007

000008

0 05 1 15 2 25 3 35 4

ConcentrationM

Times

E1 S1

E2 S2

E3 S3


230











000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 1 2 3 4 5 6

Concentration M

Times

Products (P1P2P3)


Intermediates (I)

231

CHAPTER 5

CONCLUSIONS





















232

























233











oxime













234




















substrate




235














hydroxylamine








236













shorter durations

237

REFERENCES












77 247-255




Mater 2009 161 974-981

















238



917-929




2008 194 275-285








44(1) 48-56







71-75




410




1(2) 203 -206




239
















3541







1389-1393






297-307


773


240


2002 9(1) 5-14




1992 92(6) 82-88





77 275-286





1972 p230-256



Denver CO AWWA 1996









105-114




Assoc 2008 58 647-656

241


2000 21(3) 241-248


160-165









1981 p 144


Science 2006 293 16-26



195


34(3) 227-241


173-179



2007 73 47-54








197-200

242


349-352


Chem Res 2000 39(9) 3241-3248


45(14) 4898-4904






1972 p 604




pigments 2004 62(2) 181-195





2006 27(1-3) 121-134


352


142-149






1663-1665



243


81-88
















1965 p245-267






p207-220


397





66(11) 703-706


943-957

244






69-77














2004 p140-144 268 -280











221-230



245









82-85


Educ 1982 12 885-886





VCH New York 1990 p1-22 57-68 177-180




Boston 1999 p365-385 598





1989 p340-359








Chemistry 2003 27 147-152

246




644-651







190 H Eyring Chem Rev 1935 17(1) 65-77





38-44






1703-1731





1833-1836



Sons 2001 p526-528


8126-8127


247


6500-6506



248




249


250


251


252



02 700E-05 1757 646E-05 0 700E-05 063 612E-05 0 700E-05 0254 596E-05

04 696E-05 1991 640E-05 02 681E-05 073 601E-05 02 610E-05 0293 580E-05

06 692E-05 2225 635E-05 04 663E-05 083 592E-05 0293 573E-05 0332 564E-05

08 687E-05 246 630E-05 06 645E-05 093 582E-05 0332 557E-05 0371 549E-05

1 683E-05 2694 625E-05 0732 633E-05 102 573E-05 0371 543E-05 041 533E-05

12 679E-05 2929 620E-05 083 625E-05 112 563E-05 041 528E-05 0449 519E-05

14 675E-05 3163 615E-05 0927 617E-05 122 554E-05 0449 514E-05 0488 505E-05

16 671E-05 3397 611E-05 1025 608E-05 132 546E-05 0488 500E-05 0527 492E-05

176 667E-05 3632 605E-05 1123 600E-05 142 537E-05 0527 487E-05 0566 478E-05

196 663E-05 3866 6E-05 122 592E-05 151 529E-05 0566 474E-05 0605 465E-05

199 659E-05 41 596E-05 1318 585E-05 161 521E-05 0605 462E-05 0644 453E-05

269 645E-05 5507 570E-05 1904 539E-05 22 475E-05 084 393E-05 0879 386E-05

313 640E-05 621 558E-05 2197 518E-05 249 454E-05 0957 362E-05 0996 356E-05

316 636E-05 6444 554E-05 2294 511E-05 259 447E-05 0996 353E-05 1035 347E-05

336 635E-05 6679 550E-05 2392 504E-05 269 440E-05 1035 343E-05 1074 338E-05

34 632E-05 6913 546E-05 249 498E-05 278 434E-05 1074 334E-05 1113 329E-05

387 623E-05 7851 530E-05 288 472E-05 317 41E-05 123 300E-05 1269 297E-05

407 622E-05 8085 526E-05 2978 466E-05 327 404E-05 1269 292E-05 1308 289E-05

41 618E-05 8319 523E-05 3076 459E-05 337 398E-05 1308 285E-05 1347 282E-05

43 618E-05 8554 519E-05 3173 453E-05 347 392E-05 1347 277E-05 1387 274E-05

48 605E-05 9726 501E-05 3662 424E-05 395 365E-05 1543 242E-05 1582 241E-05

5 604E-05 996 497E-05 3759 418E-05 405 360E-05 1582 236E-05 1621 235E-05

504 601E-05 1019 494E-05 3857 413E-05 415 355E-05 1621 230E-05 166 230E-05

524 600E-05 1043 490E-05 3955 407E-05 425 351E-05 166 223E-05 1699 224E-05

527 596E-05 1066 486E-05 4052 402E-05 435 346E-05 1699 218E-05 1738 218E-05

574 588E-05 116 473E-05 4443 381E-05 474 327E-05 1855 195E-05 1894 197E-05

594 587E-05 1184 469E-05 454 376E-05 483 322E-05 1894 190E-05 1933 192E-05

598 584E-05 1207 466E-05 4638 371E-05 493 318E-05 1933 185E-05 1972 187E-05

618 583E-05 123 463E-05 4736 366E-05 503 314E-05 1972 180E-05 2012 183E-05

621 580E-05 1254 46E-05 4833 361E-05 513 310E-05 2012 176E-05 2051 178E-05

641 579E-05 1277 456E-05 4931 356E-05 522 306E-05 2051 171E-05 209 174E-05

688 571E-05 1371 444E-05 5322 338E-05 561 290E-05 2207 153E-05 2246 157E-05

691 567E-05 1394 441E-05 5419 333E-05 571 285E-05 2246 149E-05 2285 154E-05

738 559E-05 1488 429E-05 581 316E-05 61 271E-05 2402 134E-05 2441 139E-05

758 559E-05 1512 426E-05 5908 312E-05 62 267E-05 2441 131E-05 248 136E-05

762 555E-05 1535 423E-05 6005 307E-05 63 264E-05 248 127E-05 2519 132E-05

782 555E-05 1559 420E-05 6103 303E-05 64 260E-05 2519 124E-05 2558 129E-05

785 551E-05 1582 417E-05 6201 299E-05 649 257E-05 2558 121E-05 2597 126E-05

253

805 551E-05 1605 414E-05 6298 295E-05 659 254E-05 2597 117E-05 2636 123E-05

902 532E-05 1816 390E-05 7177 262E-05 747 226E-05 2949 922E-06 2988 989E-06

996 517E-05 2004 369E-05 7958 235E-05 825 203E-05 3261 744E-06 3301 818E-06

102 516E-05 2027 367E-05 8056 232E-05 835 201E-05 3301 725E-06 334 798E-06

102 513E-05 2051 364E-05 8154 229E-05 845 198E-05 334 705E-06 3379 778E-06

104 513E-05 2074 362E-05 8251 226E-05 854 196E-05 3379 687E-06 3418 761E-06

104 509E-05 2098 359E-05 8349 223E-05 864 193E-05 3418 669E-06 3457 743E-06

106 509E-05 2121 357E-05 8447 220E-05 874 191E-05 3457 651E-06 3496 726E-06

107 506E-05 2144 355E-05 8544 217E-05 884 188E-05 3496 634E-06 3535 708E-06

109 505E-05 2168 352E-05 8642 214E-05 893 186E-05 3535 617E-06 3574 691E-06

109 502E-05 2191 35E-05 874 211E-05 903 184E-05 3574 601E-06 3613 675E-06

118 488E-05 2379 331E-05 9521 190E-05 981 166E-05 3886 485E-06 3926 56E-06

12 488E-05 2402 329E-05 9618 187E-05 991 164E-05 3926 472E-06 3965 548E-06

121 485E-05 2426 327E-05 9716 185E-05 10 162E-05 3965 459E-06 4004 535E-06

123 484E-05 2449 325E-05 9814 182E-05 101 160E-05 4004 447E-06 4043 524E-06

123 481E-05 2473 323E-05 9911 180E-05 102 158E-05 4043 435E-06 4082 512E-06

125 481E-05 2496 321E-05 1001 178E-05 103 156E-05 4082 424E-06 4121 500E-06

13 474E-05 259 313E-05 104 168E-05 107 149E-05 4238 381E-06 4277 457E-06

13 471E-05 2613 311E-05 105 166E-05 108 147E-05 4277 371E-06 4316 446E-06

132 470E-05 2637 309E-05 106 164E-05 109 145E-05 4316 361E-06 4355 437E-06

137 461E-05 2754 299E-05 1108 153E-05 114 136E-05 4511 316E-06 455 390E-06

148 447E-05 2965 282E-05 1196 136E-05 123 122E-05 4863 248E-06 4902 320E-06

149 445E-05 2988 281E-05 1206 134E-05 124 121E-05 4902 242E-06 4941 314E-06

151 444E-05 3012 279E-05 1216 132E-05 125 119E-05 4941 235E-06 498 307E-06

151 442E-05 3035 277E-05 1226 131E-05 125 118E-05 498 229E-06 5019 301E-06

153 441E-05 3059 275E-05 1235 129E-05 126 116E-05 5019 223E-06 5058 295E-06

158 432E-05 3176 267E-05 1284 121E-05 131 109E-05 5215 195E-06 5254 265E-06

16 432E-05 3199 265E-05 1294 119E-05 132 108E-05 5254 190E-06 5293 259E-06

161 429E-05 3223 264E-05 1304 117E-05 133 107E-05 5293 185E-06 5332 253E-06

163 429E-05 3246 262E-05 1313 116E-05 134 106E-05 5332 180E-06 5371 249E-06

163 426E-05 327 260E-05 1323 114E-05 135 104E-05 5371 175E-06 541 243E-06

168 420E-05 3363 254E-05 1362 108E-05 139 996E-06 5527 157E-06 5566 225E-06

17 420E-05 3387 253E-05 1372 107E-05 14 984E-06 5566 153E-06 5605 219E-06

17 417E-05 341 251E-05 1382 105E-05 141 973E-06 5605 149E-06 5644 216E-06

177 408E-05 3551 242E-05 144 973E-06 147 906E-06 584 127E-06 5879 191E-06

179 408E-05 3574 241E-05 145 960E-06 148 894E-06 5879 124E-06 5918 187E-06

179 405E-05 3598 239E-05 146 948E-06 149 884E-06 5918 120E-06 5957 184E-06

181 405E-05 3621 237E-05 147 935E-06 15 872E-06 5957 117E-06 5996 181E-06

188 396E-05 3762 229E-05 1528 863E-06 156 815E-06 6191 998E-07 623 163E-06

189 394E-05 3785 228E-05 1538 851E-06 157 804E-06 623 972E-07 6269 159E-06

191 393E-05 3809 227E-05 1548 840E-06 158 794E-06 6269 946E-07 6308 156E-06

254

191 391E-05 3832 225E-05 1558 829E-06 159 784E-06 6308 921E-07 6347 153E-06

198 385E-05 3949 218E-05 1606 775E-06 164 742E-06 6504 806E-07 6543 138E-06

198 383E-05 3973 217E-05 1616 765E-06 165 733E-06 6543 784E-07 6582 135E-06

20 382E-05 3996 216E-05 1626 755E-06 166 723E-06 6582 764E-07 6621 133E-06

20 380E-05 402 214E-05 1636 745E-06 166 716E-06 6621 743E-07 666 130E-06

207 372E-05 416 207E-05 1694 688E-06 172 666E-06 6855 633E-07 6894 118E-06

209 372E-05 4184 206E-05 1704 678E-06 173 658E-06 6894 616E-07 6933 116E-06

21 369E-05 4207 205E-05 1714 669E-06 174 650E-06 6933 600E-07 6972 115E-06

212 369E-05 423 203E-05 1724 660E-06 175 642E-06 6972 584E-07 7011 112E-06

212 367E-05 4254 202E-05 1733 652E-06 176 635E-06 7011 569E-07 705 111E-06

27 309E-05 5402 153E-05 2212 338E-06 224 369E-06 8925 153E-07 8964 605E-07

271 307E-05 5426 152E-05 2222 334E-06 225 364E-06 8964 149E-07 9003 605E-07

277 302E-05 5543 148E-05 227 312E-06 23 344E-06 916 130E-07 9199 574E-07

278 300E-05 5566 148E-05 228 308E-06 231 341E-06 9199 127E-07 9238 566E-07

28 300E-05 559 147E-05 229 304E-06 232 337E-06 9238 124E-07 9277 570E-07

28 298E-05 5613 146E-05 23 300E-06 233 333E-06 9277 120E-07 9316 565E-07

282 298E-05 5637 145E-05 231 296E-06 234 329E-06 9316 117E-07 9355 563E-07

313 271E-05 6246 126E-05 2563 209E-06 259 250E-06 1033 584E-08 1037 467E-07

322 264E-05 6434 121E-05 2642 188E-06 267 229E-06 1064 471E-08 1068 454E-07

327 258E-05 6551 118E-05 269 176E-06 272 217E-06 1084 412E-08 1088 437E-07

329 258E-05 6574 117E-05 27 173E-06 273 215E-06 1088 401E-08 1092 450E-07

329 257E-05 6598 117E-05 271 171E-06 274 213E-06 1092 391E-08 1096 446E-07

331 256E-05 6621 116E-05 272 169E-06 275 211E-06 1096 380E-08 11 442E-07

332 255E-05 6645 115E-05 2729 167E-06 276 209E-06 11 370E-08 1104 430E-07

339 249E-05 6785 112E-05 2788 154E-06 282 196E-06 1123 315E-08 1127 442E-07

346 244E-05 6926 109E-05 2847 142E-06 288 185E-06 1146 269E-08 115 426E-07

348 244E-05 6949 108E-05 2856 140E-06 289 185E-06 115 262E-08 1154 423E-07

348 242E-05 6973 107E-05 2866 138E-06 29 182E-06 1154 255E-08 1158 422E-07

35 242E-05 6996 107E-05 2876 136E-06 291 180E-06 1158 248E-08 1162 412E-07

36 234E-05 7207 102E-05 2964 121E-06 299 166E-06 1193 195E-08 1197 419E-07

362 234E-05 7231 102E-05 2974 119E-06 30 164E-06 1197 190E-08 1201 404E-07

362 232E-05 7254 101E-05 2983 118E-06 301 161E-06 1201 185E-08 1205 410E-07

364 232E-05 7277 101E-05 2993 116E-06 302 160E-06 1205 180E-08 1209 415E-07

369 229E-05 7371 985E-06 3032 110E-06 306 153E-06 1221 162E-08 1225 408E-07

369 227E-05 7395 981E-06 3042 109E-06 307 150E-06 1225 157E-08 1229 395E-07

378 222E-05 7559 947E-06 311 989E-07 314 139E-06 1252 130E-08 1256 401E-07

379 221E-05 7582 943E-06 312 976E-07 315 138E-06 1256 127E-08 126 394E-07

381 221E-05 7606 937E-06 313 963E-07 316 136E-06 126 124E-08 1264 397E-07

386 216E-05 7723 915E-06 3179 901E-07 321 131E-06 1279 108E-08 1283 393E-07

388 216E-05 7746 909E-06 3188 889E-07 322 13E-06 1283 105E-08 1287 395E-07

388 215E-05 777 905E-06 3198 877E-07 323 129E-06 1287 102E-08 1291 391E-07

255

39 214E-05 7793 900E-06 3208 866E-07 324 127E-06 1291 997E-09 1295 382E-07

39 213E-05 7816 895E-06 3218 854E-07 325 127E-06 1295 970E-09 1299 379E-07

399 208E-05 7981 866E-06 3286 778E-07 332 120E-06 1322 805E-09 1326 384E-07

40 207E-05 8004 862E-06 3296 768E-07 333 118E-06 1326 784E-09 133 381E-07

402 207E-05 8027 858E-06 3306 757E-07 333 117E-06 133 763E-09 1334 387E-07

432 188E-05 866 752E-06 3569 528E-07 36 903E-07 1436 370E-09 1439 359E-07

451 178E-05 9012 697E-06 3716 432E-07 375 811E-07 1494 248E-09 1498 368E-07

451 177E-05 9035 694E-06 3725 426E-07 375 811E-07 1498 241E-09 1502 365E-07

458 173E-05 9176 673E-06 3784 393E-07 381 775E-07 1521 205E-09 1525 365E-07

46 173E-05 9199 670E-06 3794 388E-07 382 758E-07 1525 200E-09 1529 362E-07

461 172E-05 9223 666E-06 3804 383E-07 383 757E-07 1529 195E-09 1533 365E-07

463 172E-05 9246 665E-06 3813 378E-07 384 752E-07 1533 190E-09 1537 356E-07

47 167E-05 941 642E-06 3882 344E-07 391 715E-07 1561 157E-09 1564 356E-07

472 167E-05 9434 639E-06 3891 340E-07 392 711E-07 1564 153E-09 1568 349E-07

481 162E-05 9621 618E-06 397 305E-07 40 663E-07 1596 124E-09 16 358E-07

495 156E-05 9902 582E-06 4087 260E-07 412 615E-07 1643 895E-10 1646 347E-07

496 155E-05 9926 579E-06 4097 256E-07 413 613E-07 1646 872E-10 165 346E-07

498 155E-05 9949 577E-06 4106 253E-07 414 610E-07 165 849E-10 1654 341E-07

498 154E-05 9973 575E-06 4116 250E-07 415 599E-07 1654 826E-10 1658 353E-07

50 153E-05 9996 572E-06 4126 246E-07 416 590E-07 1658 805E-10 1662 341E-07

50 153E-05 1002 569E-06 4136 243E-07 416 590E-07 1662 783E-10 1666 352E-07

502 152E-05 1004 567E-06 4145 240E-07 417 593E-07 1666 763E-10 167 351E-07

503 151E-05 1007 565E-06 4155 237E-07 418 585E-07 167 742E-10 1674 352E-07

51 148E-05 1021 549E-06 4214 218E-07 424 565E-07 1693 632E-10 1697 349E-07

54 136E-05 1079 489E-06 4458 156E-07 449 483E-07 1791 324E-10 1795 330E-07

549 132E-05 1098 472E-06 4536 141E-07 457 468E-07 1822 261E-10 1826 340E-07

55 131E-05 110 470E-06 4546 139E-07 458 467E-07 1826 254E-10 183 333E-07

552 131E-05 1103 469E-06 4556 137E-07 458 457E-07 183 248E-10 1834 342E-07

552 130E-05 1105 466E-06 4565 135E-07 459 458E-07 1834 241E-10 1838 334E-07

561 127E-05 1122 451E-06 4634 123E-07 466 433E-07 1861 200E-10 1865 339E-07

568 124E-05 1138 437E-06 4702 112E-07 473 427E-07 1889 166E-10 1893 330E-07

57 124E-05 114 435E-06 4712 110E-07 474 431E-07 1893 161E-10 1896 331E-07

571 123E-05 1143 433E-06 4722 109E-07 475 419E-07 1896 157E-10 19 330E-07

573 123E-05 1145 432E-06 4731 108E-07 476 424E-07 19 153E-10 1904 338E-07

573 122E-05 1147 43E-06 4741 106E-07 477 423E-07 1904 149E-10 1908 328E-07

58 120E-05 1159 421E-06 479 993E-08 482 407E-07 1924 130E-10 1928 330E-07

58 120E-05 1161 419E-06 48 979E-08 483 410E-07 1928 127E-10 1932 326E-07

589 116E-05 118 404E-06 4878 880E-08 491 398E-07 1959 102E-10 1963 328E-07

591 116E-05 1182 403E-06 4888 868E-08 492 398E-07 1963 997E-11 1967 326E-07

598 114E-05 1197 392E-06 4946 801E-08 498 369E-07 1986 849E-11 199 318E-07

599 113E-05 1199 390E-06 4956 791E-08 499 373E-07 199 826E-11 1994 321E-07

256



041 528E-05 276E-07 172E-05 170E-05 170E-05

049 500E-05 164E-07 200E-05 198E-05 198E-05

053 487E-05 136E-07 213E-05 212E-05 212E-05

057 474E-05 116E-07 226E-05 225E-05 225E-05

061 461E-05 101E-07 239E-05 238E-05 238E-05

064 449E-05 891E-08 251E-05 250E-05 250E-05

068 437E-05 795E-08 263E-05 262E-05 262E-05

072 426E-05 717E-08 274E-05 274E-05 274E-05

076 414E-05 651E-08 286E-05 285E-05 285E-05

08 403E-05 595E-08 297E-05 296E-05 296E-05

084 393E-05 547E-08 307E-05 307E-05 307E-05

088 382E-05 505E-08 318E-05 317E-05 317E-05

092 372E-05 468E-08 328E-05 327E-05 327E-05

096 362E-05 436E-08 338E-05 337E-05 337E-05

1 353E-05 407E-08 347E-05 347E-05 347E-05

103 344E-05 381E-08 356E-05 356E-05 356E-05

107 334E-05 357E-08 366E-05 365E-05 365E-05

111 326E-05 336E-08 374E-05 374E-05 374E-05

115 317E-05 317E-08 383E-05 383E-05 383E-05

119 309E-05 299E-08 391E-05 391E-05 391E-05

123 301E-05 283E-08 399E-05 399E-05 399E-05

127 293E-05 268E-08 407E-05 407E-05 407E-05

186 196E-05 135E-08 504E-05 504E-05 504E-05

189 191E-05 130E-08 509E-05 509E-05 509E-05

193 186E-05 125E-08 514E-05 514E-05 514E-05

197 181E-05 120E-08 519E-05 519E-05 519E-05

201 176E-05 116E-08 524E-05 524E-05 524E-05

205 171E-05 111E-08 529E-05 528E-05 528E-05

209 167E-05 107E-08 533E-05 533E-05 533E-05

213 163E-05 103E-08 537E-05 537E-05 537E-05

248 128E-05 752E-09 572E-05 572E-05 572E-05

252 124E-05 727E-09 576E-05 575E-05 575E-05

256 121E-05 703E-09 579E-05 579E-05 579E-05

26 118E-05 680E-09 582E-05 582E-05 582E-05

264 115E-05 658E-09 585E-05 585E-05 585E-05

268 112E-05 636E-09 588E-05 588E-05 588E-05

271 109E-05 616E-09 591E-05 591E-05 591E-05

275 106E-05 596E-09 594E-05 594E-05 594E-05

279 103E-05 577E-09 597E-05 597E-05 597E-05

283 101E-05 559E-09 599E-05 599E-05 599E-05

287 979E-06 541E-09 602E-05 602E-05 602E-05

303 880E-06 477E-09 612E-05 612E-05 612E-05

307 857E-06 462E-09 614E-05 614E-05 614E-05

311 835E-06 448E-09 617E-05 616E-05 616E-05

314 813E-06 434E-09 619E-05 619E-05 619E-05

318 791E-06 421E-09 621E-05 621E-05 621E-05

322 771E-06 408E-09 623E-05 623E-05 623E-05

326 750E-06 396E-09 625E-05 625E-05 625E-05

33 731E-06 384E-09 627E-05 627E-05 627E-05

353 623E-06 321E-09 638E-05 638E-05 638E-05

357 606E-06 311E-09 639E-05 639E-05 639E-05

361 590E-06 302E-09 641E-05 641E-05 641E-05

365 575E-06 293E-09 643E-05 642E-05 642E-05

369 560E-06 285E-09 644E-05 644E-05 644E-05

373 545E-06 277E-09 645E-05 645E-05 645E-05

377 531E-06 269E-09 647E-05 647E-05 647E-05

381 517E-06 261E-09 648E-05 648E-05 648E-05

385 503E-06 253E-09 650E-05 650E-05 650E-05

389 490E-06 246E-09 651E-05 651E-05 651E-05

393 477E-06 239E-09 652E-05 652E-05 652E-05

396 465E-06 232E-09 654E-05 654E-05 654E-05

4 452E-06 226E-09 655E-05 655E-05 655E-05

428 375E-06 185E-09 662E-05 662E-05 662E-05

432 366E-06 180E-09 663E-05 663E-05 663E-05

436 356E-06 175E-09 664E-05 664E-05 664E-05

439 347E-06 170E-09 665E-05 665E-05 665E-05

443 338E-06 165E-09 666E-05 666E-05 666E-05

447 329E-06 160E-09 667E-05 667E-05 667E-05

451 320E-06 156E-09 668E-05 668E-05 668E-05

486 252E-06 121E-09 675E-05 675E-05 675E-05

49 245E-06 118E-09 675E-05 675E-05 675E-05

494 239E-06 115E-09 676E-05 676E-05 676E-05

498 233E-06 112E-09 677E-05 677E-05 677E-05

502 226E-06 108E-09 677E-05 677E-05 677E-05

506 221E-06 106E-09 678E-05 678E-05 678E-05

51 215E-06 103E-09 679E-05 679E-05 679E-05

514 209E-06 998E-10 679E-05 679E-05 679E-05

257

518 204E-06 971E-10 680E-05 680E-05 680E-05

521 198E-06 945E-10 680E-05 680E-05 680E-05

561 152E-06 718E-10 685E-05 685E-05 685E-05

564 148E-06 699E-10 685E-05 685E-05 685E-05

568 144E-06 680E-10 686E-05 686E-05 686E-05

572 140E-06 662E-10 686E-05 686E-05 686E-05

576 137E-06 644E-10 686E-05 686E-05 686E-05

588 126E-06 594E-10 687E-05 687E-05 687E-05

592 123E-06 578E-10 688E-05 688E-05 688E-05

596 120E-06 562E-10 688E-05 688E-05 688E-05

6 116E-06 547E-10 688E-05 688E-05 688E-05

603 113E-06 532E-10 689E-05 689E-05 689E-05

607 110E-06 518E-10 689E-05 689E-05 689E-05

611 108E-06 504E-10 689E-05 689E-05 689E-05

682 666E-07 310E-10 693E-05 693E-05 693E-05

686 649E-07 302E-10 694E-05 694E-05 694E-05

689 632E-07 294E-10 694E-05 694E-05 694E-05

693 615E-07 286E-10 694E-05 694E-05 694E-05

697 599E-07 279E-10 694E-05 694E-05 694E-05

701 583E-07 271E-10 694E-05 694E-05 694E-05

705 568E-07 264E-10 694E-05 694E-05 694E-05

744 435E-07 202E-10 696E-05 696E-05 696E-05

752 413E-07 191E-10 696E-05 696E-05 696E-05

787 325E-07 150E-10 697E-05 697E-05 697E-05

791 316E-07 146E-10 697E-05 697E-05 697E-05

795 308E-07 143E-10 697E-05 697E-05 697E-05

799 300E-07 139E-10 697E-05 697E-05 697E-05

803 292E-07 135E-10 697E-05 697E-05 697E-05

807 284E-07 132E-10 697E-05 697E-05 697E-05

811 277E-07 128E-10 697E-05 697E-05 697E-05

877 176E-07 814E-11 698E-05 698E-05 698E-05

908 142E-07 657E-11 699E-05 699E-05 699E-05

912 139E-07 640E-11 699E-05 699E-05 699E-05

971 931E-08 429E-11 699E-05 699E-05 699E-05

975 906E-08 418E-11 699E-05 699E-05 699E-05

978 882E-08 407E-11 699E-05 699E-05 699E-05

982 859E-08 396E-11 699E-05 699E-05 699E-05

986 837E-08 386E-11 699E-05 699E-05 699E-05

99 815E-08 376E-11 699E-05 699E-05 699E-05

994 793E-08 366E-11 699E-05 699E-05 699E-05

998 772E-08 356E-11 699E-05 699E-05 699E-05

10 752E-08 347E-11 699E-05 699E-05 699E-05

107 466E-08 215E-11 700E-05 700E-05 700E-05

133 806E-09 371E-12 700E-05 700E-05 700E-05

133 784E-09 361E-12 700E-05 700E-05 700E-05

141 473E-09 218E-12 700E-05 700E-05 700E-05

141 461E-09 212E-12 700E-05 700E-05 700E-05

142 449E-09 207E-12 700E-05 700E-05 700E-05

142 437E-09 201E-12 700E-05 700E-05 700E-05

142 425E-09 196E-12 700E-05 700E-05 700E-05

15 257E-09 118E-12 700E-05 700E-05 700E-05

15 250E-09 115E-12 700E-05 700E-05 700E-05

151 243E-09 112E-12 700E-05 700E-05 700E-05

153 202E-09 931E-13 700E-05 700E-05 700E-05

154 197E-09 906E-13 700E-05 700E-05 700E-05

154 192E-09 883E-13 700E-05 700E-05 700E-05

155 182E-09 836E-13 700E-05 700E-05 700E-05

155 177E-09 814E-13 700E-05 700E-05 700E-05

156 172E-09 793E-13 700E-05 700E-05 700E-05

156 168E-09 772E-13 700E-05 700E-05 700E-05

156 163E-09 752E-13 700E-05 700E-05 700E-05

157 159E-09 732E-13 700E-05 700E-05 700E-05

157 155E-09 713E-13 700E-05 700E-05 700E-05

158 151E-09 695E-13 700E-05 700E-05 700E-05

158 147E-09 676E-13 700E-05 700E-05 700E-05

16 129E-09 592E-13 700E-05 700E-05 700E-05

16 125E-09 577E-13 700E-05 700E-05 700E-05

161 122E-09 561E-13 700E-05 700E-05 700E-05

161 119E-09 547E-13 700E-05 700E-05 700E-05

162 116E-09 532E-13 700E-05 700E-05 700E-05

162 113E-09 518E-13 700E-05 700E-05 700E-05

162 110E-09 505E-13 700E-05 700E-05 700E-05

163 107E-09 491E-13 700E-05 700E-05 700E-05

171 611E-10 281E-13 700E-05 700E-05 700E-05

18 331E-10 152E-13 700E-05 700E-05 700E-05

18 322E-10 148E-13 700E-05 700E-05 700E-05

181 314E-10 145E-13 700E-05 700E-05 700E-05

181 298E-10 137E-13 700E-05 700E-05 700E-05

196 114E-10 526E-14 700E-05 700E-05 700E-05

196 111E-10 513E-14 700E-05 700E-05 700E-05

199 899E-11 414E-14 700E-05 700E-05 700E-05

199 876E-11 403E-14 700E-05 700E-05 700E-05

258



259


260


261


262


263


264


265


266


267



023193 526E-05 586E-05 011597 445E-05 558E-05 0057982 271E-05 561E-05

070068 627E-05 580E-05 035035 614E-05 544E-05 017517 483E-05 548E-05

11694 601E-05 565E-05 058473 617E-05 531E-05 029235 567E-05 537E-05

16382 576E-05 551E-05 08191 601E-05 52E-05 040953 584E-05 526E-05

21069 554E-05 537E-05 10535 584E-05 509E-05 052672 576E-05 516E-05

25757 533E-05 524E-05 12879 567E-05 498E-05 06439 562E-05 506E-05

30444 514E-05 511E-05 15222 552E-05 489E-05 076109 547E-05 496E-05

35132 495E-05 498E-05 17566 538E-05 479E-05 087827 532E-05 487E-05

39819 479E-05 486E-05 1991 524E-05 47E-05 099545 517E-05 477E-05

44507 462E-05 474E-05 22254 511E-05 461E-05 11126 504E-05 468E-05

49194 447E-05 462E-05 24598 499E-05 452E-05 12298 491E-05 459E-05

53881 433E-05 450E-05 26941 486E-05 444E-05 1347 478E-05 451E-05

58569 419E-05 439E-05 29285 475E-05 436E-05 14642 466E-05 442E-05

63256 406E-05 428E-05 31629 464E-05 428E-05 15814 454E-05 434E-05

67944 393E-05 418E-05 33973 453E-05 42E-05 16986 444E-05 426E-05

72631 382E-05 408E-05 36316 443E-05 412E-05 18157 433E-05 418E-05

77319 37E-05 398E-05 3866 434E-05 405E-05 19329 423E-05 410E-05

82006 36E-05 388E-05 41004 424E-05 397E-05 20501 413E-05 403E-05

86694 35E-05 378E-05 43348 415E-05 39E-05 21673 404E-05 395E-05

14294 255E-05 282E-05 71473 326E-05 315E-05 35735 312E-05 319E-05

14763 249E-05 275E-05 73817 319E-05 309E-05 36907 306E-05 313E-05

15232 243E-05 268E-05 76161 314E-05 304E-05 38079 3E-05 308E-05

15701 237E-05 262E-05 78505 308E-05 298E-05 39251 294E-05 302E-05

16169 232E-05 256E-05 80848 302E-05 293E-05 40422 288E-05 297E-05

16638 226E-05 250E-05 83192 296E-05 288E-05 41594 283E-05 292E-05

17107 221E-05 244E-05 85536 292E-05 283E-05 42766 277E-05 287E-05

17576 216E-05 238E-05 8788 286E-05 278E-05 43938 272E-05 282E-05

18044 211E-05 232E-05 90224 281E-05 273E-05 4511 267E-05 277E-05

18513 207E-05 227E-05 92567 276E-05 268E-05 46282 262E-05 272E-05

18982 202E-05 221E-05 94911 271E-05 264E-05 47453 257E-05 268E-05

19451 198E-05 216E-05 97255 267E-05 259E-05 48625 252E-05 263E-05

19919 194E-05 211E-05 99599 262E-05 255E-05 49797 248E-05 259E-05

20388 19E-05 206E-05 10194 257E-05 25E-05 50969 243E-05 255E-05

20857 186E-05 201E-05 10429 253E-05 246E-05 52141 239E-05 250E-05

21326 182E-05 196E-05 10663 249E-05 242E-05 53313 234E-05 246E-05

21794 179E-05 192E-05 10897 244E-05 237E-05 54484 23E-05 242E-05

22263 176E-05 187E-05 11132 24E-05 233E-05 55656 226E-05 238E-05

22732 172E-05 183E-05 11366 236E-05 229E-05 56828 222E-05 234E-05

268

27888 142E-05 141E-05 13944 198E-05 189E-05 69718 183E-05 195E-05

28357 14E-05 137E-05 14179 195E-05 186E-05 7089 18E-05 192E-05

28825 138E-05 134E-05 14413 192E-05 183E-05 72062 177E-05 189E-05

29294 135E-05 131E-05 14647 189E-05 18E-05 73234 175E-05 186E-05

29763 133E-05 128E-05 14882 186E-05 177E-05 74406 172E-05 183E-05

30232 131E-05 125E-05 15116 183E-05 174E-05 75578 169E-05 180E-05

307 13E-05 122E-05 15351 181E-05 171E-05 76749 166E-05 177E-05

31169 128E-05 119E-05 15585 178E-05 168E-05 77921 163E-05 174E-05

31638 126E-05 116E-05 15819 175E-05 165E-05 79093 161E-05 171E-05

32107 124E-05 114E-05 16054 173E-05 162E-05 80265 158E-05 169E-05

32575 122E-05 111E-05 16288 171E-05 159E-05 81437 156E-05 166E-05

48982 785E-06 490E-06 24491 111E-05 877E-06 12245 949E-06 959E-06

4945 776E-06 478E-06 24726 11E-05 862E-06 12362 936E-06 944E-06

49919 767E-06 467E-06 2496 109E-05 848E-06 12479 919E-06 930E-06

50388 76E-06 457E-06 25194 107E-05 833E-06 12597 907E-06 916E-06

50857 748E-06 446E-06 25429 106E-05 819E-06 12714 896E-06 902E-06

51325 74E-06 436E-06 25663 105E-05 805E-06 12831 884E-06 888E-06

56482 652E-06 338E-06 28241 946E-06 669E-06 1412 771E-06 752E-06

5695 645E-06 330E-06 28476 934E-06 658E-06 14237 761E-06 740E-06

72888 458E-06 150E-06 36445 67E-06 371E-06 18222 515E-06 445E-06

77575 417E-06 119E-06 38788 611E-06 314E-06 19393 464E-06 384E-06

78044 414E-06 117E-06 39023 606E-06 308E-06 19511 459E-06 379E-06

78513 412E-06 114E-06 39257 601E-06 303E-06 19628 454E-06 373E-06

99606 299E-06 404E-07 49804 411E-06 143E-06 24901 313E-06 193E-06

10007 295E-06 395E-07 50039 409E-06 14E-06 25018 311E-06 190E-06

10054 295E-06 386E-07 50273 406E-06 138E-06 25135 309E-06 188E-06

10101 294E-06 377E-07 50507 402E-06 136E-06 25253 306E-06 185E-06

10148 293E-06 368E-07 50742 399E-06 134E-06 2537 303E-06 182E-06

10195 29E-06 360E-07 50976 398E-06 131E-06 25487 302E-06 180E-06

10242 288E-06 352E-07 51211 392E-06 129E-06 25604 299E-06 177E-06

10289 287E-06 344E-07 51445 393E-06 127E-06 25721 298E-06 174E-06

10336 284E-06 336E-07 51679 387E-06 125E-06 25838 296E-06 172E-06

12914 231E-06 946E-08 6457 278E-06 499E-07 32284 227E-06 775E-07

12961 23E-06 924E-08 64804 276E-06 491E-07 32401 225E-06 764E-07

13007 23E-06 904E-08 65039 277E-06 483E-07 32518 225E-06 753E-07

13054 229E-06 883E-08 65273 275E-06 475E-07 32635 224E-06 742E-07

13101 228E-06 863E-08 65508 274E-06 467E-07 32752 224E-06 732E-07

13148 227E-06 843E-08 65742 273E-06 459E-07 3287 222E-06 721E-07

13523 223E-06 701E-08 67617 264E-06 402E-07 33807 218E-06 643E-07

15117 206E-06 321E-08 75586 231E-06 228E-07 37791 197E-06 394E-07

15164 205E-06 313E-08 7582 231E-06 224E-07 37908 196E-06 388E-07

269

15211 205E-06 306E-08 76055 23E-06 22E-07 38026 197E-06 383E-07

16429 194E-06 168E-08 82149 215E-06 143E-07 41072 181E-06 263E-07

16476 194E-06 164E-08 82383 214E-06 141E-07 4119 181E-06 260E-07

16523 193E-06 161E-08 82617 215E-06 138E-07 41307 18E-06 256E-07

1657 192E-06 157E-08 82852 214E-06 136E-07 41424 181E-06 252E-07

16617 193E-06 153E-08 83086 214E-06 134E-07 41541 179E-06 249E-07

16664 192E-06 150E-08 8332 213E-06 132E-07 41658 179E-06 245E-07

16711 192E-06 147E-08 83555 212E-06 129E-07 41775 18E-06 241E-07

18539 179E-06 597E-09 92696 193E-06 675E-08 46346 164E-06 138E-07

18586 178E-06 583E-09 9293 193E-06 664E-08 46463 165E-06 136E-07

18632 178E-06 570E-09 93164 192E-06 653E-08 4658 163E-06 134E-07

18679 18E-06 557E-09 93399 192E-06 642E-08 46697 164E-06 132E-07

18726 178E-06 545E-09 93633 191E-06 632E-08 46814 163E-06 130E-07

18773 177E-06 532E-09 93867 192E-06 621E-08 46932 163E-06 128E-07

1882 178E-06 520E-09 94102 189E-06 611E-08 47049 162E-06 126E-07

18867 175E-06 508E-09 94336 19E-06 601E-08 47166 163E-06 125E-07

18914 177E-06 497E-09 94571 189E-06 591E-08 47283 162E-06 123E-07

18961 178E-06 485E-09 94805 189E-06 581E-08 474 162E-06 121E-07

19007 176E-06 474E-09 95039 188E-06 572E-08 47518 162E-06 119E-07

19054 177E-06 464E-09 95274 188E-06 562E-08 47635 162E-06 118E-07

19101 176E-06 453E-09 95508 187E-06 553E-08 47752 161E-06 116E-07

19148 175E-06 443E-09 95742 188E-06 544E-08 47869 16E-06 114E-07

19195 175E-06 433E-09 95977 187E-06 535E-08 47986 16E-06 113E-07

19242 175E-06 423E-09 96211 186E-06 526E-08 48103 16E-06 111E-07

19289 175E-06 413E-09 96446 186E-06 517E-08 48221 161E-06 110E-07

19336 175E-06 404E-09 9668 185E-06 509E-08 48338 16E-06 108E-07

19382 174E-06 395E-09 96914 184E-06 5E-08 48455 159E-06 106E-07

19429 174E-06 386E-09 97149 185E-06 492E-08 48572 16E-06 105E-07

19476 174E-06 377E-09 97383 185E-06 484E-08 48689 158E-06 103E-07

19523 173E-06 368E-09 97617 182E-06 476E-08 48807 157E-06 102E-07

1957 174E-06 360E-09 97852 185E-06 468E-08 48924 159E-06 101E-07

19617 173E-06 352E-09 98086 183E-06 46E-08 49041 159E-06 991E-08

19664 173E-06 344E-09 98321 182E-06 453E-08 49158 157E-06 977E-08

19711 172E-06 336E-09 98555 182E-06 445E-08 49275 158E-06 963E-08

19757 172E-06 328E-09 98789 183E-06 438E-08 49392 157E-06 949E-08

23695 154E-06 474E-10 11848 158E-06 108E-08 59236 136E-06 284E-08

23836 155E-06 443E-10 11918 157E-06 103E-08 59587 135E-06 272E-08

23882 155E-06 433E-10 11941 157E-06 101E-08 59705 135E-06 268E-08

23929 156E-06 423E-10 11965 157E-06 994E-09 59822 135E-06 264E-08

270


017517 170E-05 104E-03 385E-06 561E-05 385E-06 486E-07 337E-06

029235 198E-05 108E-03 515E-06 548E-05 515E-06 348E-07 480E-06

040953 212E-05 109E-03 630E-06 537E-05 630E-06 308E-07 599E-06

052672 225E-05 109E-03 738E-06 526E-05 738E-06 290E-07 709E-06

06439 238E-05 109E-03 841E-06 516E-05 841E-06 279E-07 813E-06

076109 250E-05 109E-03 942E-06 506E-05 942E-06 271E-07 915E-06

087827 262E-05 109E-03 104E-05 496E-05 104E-05 264E-07 101E-05

22845 274E-05 108E-03 205E-05 395E-05 205E-05 201E-07 203E-05

24017 285E-05 108E-03 212E-05 388E-05 212E-05 196E-07 210E-05

25188 296E-05 108E-03 219E-05 381E-05 219E-05 192E-07 217E-05

2636 307E-05 108E-03 226E-05 374E-05 226E-05 188E-07 224E-05

27532 317E-05 108E-03 232E-05 368E-05 232E-05 184E-07 231E-05

28704 327E-05 108E-03 239E-05 361E-05 239E-05 180E-07 237E-05

29876 337E-05 108E-03 245E-05 355E-05 245E-05 176E-07 244E-05

31048 347E-05 107E-03 252E-05 348E-05 252E-05 173E-07 250E-05

32219 356E-05 107E-03 258E-05 342E-05 258E-05 169E-07 256E-05

33391 365E-05 107E-03 264E-05 336E-05 264E-05 166E-07 262E-05

34563 374E-05 107E-03 270E-05 330E-05 270E-05 162E-07 268E-05

35735 383E-05 107E-03 276E-05 324E-05 276E-05 159E-07 274E-05

36907 391E-05 107E-03 281E-05 319E-05 281E-05 156E-07 280E-05

38079 399E-05 107E-03 287E-05 313E-05 287E-05 153E-07 285E-05

39251 407E-05 107E-03 292E-05 308E-05 292E-05 150E-07 291E-05

61515 504E-05 106E-03 377E-05 223E-05 377E-05 104E-07 376E-05

66203 524E-05 106E-03 392E-05 208E-05 392E-05 962E-08 391E-05

67375 528E-05 106E-03 395E-05 205E-05 395E-05 945E-08 394E-05

68547 533E-05 106E-03 398E-05 202E-05 398E-05 928E-08 398E-05

69718 537E-05 106E-03 402E-05 198E-05 402E-05 911E-08 401E-05

7089 572E-05 106E-03 405E-05 195E-05 405E-05 895E-08 404E-05

72062 575E-05 106E-03 408E-05 192E-05 408E-05 879E-08 407E-05

73234 579E-05 106E-03 411E-05 189E-05 411E-05 863E-08 410E-05

74406 582E-05 106E-03 414E-05 186E-05 414E-05 848E-08 413E-05

75578 585E-05 106E-03 417E-05 183E-05 417E-05 833E-08 416E-05

76749 588E-05 106E-03 420E-05 180E-05 420E-05 818E-08 419E-05

77921 591E-05 106E-03 423E-05 177E-05 423E-05 804E-08 422E-05

79093 594E-05 106E-03 426E-05 174E-05 426E-05 790E-08 425E-05

80265 597E-05 106E-03 429E-05 171E-05 429E-05 776E-08 428E-05

81437 599E-05 106E-03 431E-05 169E-05 431E-05 762E-08 431E-05

82609 602E-05 106E-03 434E-05 166E-05 434E-05 749E-08 433E-05

271

8378 612E-05 106E-03 437E-05 163E-05 437E-05 736E-08 436E-05

84952 614E-05 106E-03 439E-05 161E-05 439E-05 723E-08 439E-05

86124 616E-05 106E-03 442E-05 158E-05 442E-05 711E-08 441E-05

87296 619E-05 106E-03 444E-05 156E-05 444E-05 699E-08 444E-05

88468 621E-05 106E-03 447E-05 153E-05 447E-05 687E-08 446E-05

8964 623E-05 106E-03 449E-05 151E-05 449E-05 675E-08 449E-05

90811 625E-05 105E-03 452E-05 148E-05 452E-05 663E-08 451E-05

91983 627E-05 105E-03 454E-05 146E-05 454E-05 652E-08 453E-05

12831 645E-05 105E-03 510E-05 902E-06 510E-05 390E-08 509E-05

12948 647E-05 105E-03 511E-05 888E-06 511E-05 384E-08 511E-05

13065 648E-05 105E-03 513E-05 875E-06 513E-05 378E-08 512E-05

13183 650E-05 105E-03 514E-05 861E-06 514E-05 372E-08 513E-05

133 651E-05 105E-03 515E-05 848E-06 515E-05 366E-08 515E-05

13417 652E-05 105E-03 516E-05 836E-06 516E-05 360E-08 516E-05

13534 654E-05 105E-03 518E-05 823E-06 518E-05 355E-08 517E-05

13651 655E-05 105E-03 519E-05 811E-06 519E-05 349E-08 519E-05

15878 662E-05 105E-03 539E-05 609E-06 539E-05 259E-08 539E-05

15995 663E-05 105E-03 540E-05 600E-06 540E-05 255E-08 540E-05

16112 664E-05 105E-03 541E-05 591E-06 541E-05 251E-08 541E-05

16698 665E-05 105E-03 545E-05 548E-06 545E-05 232E-08 545E-05

16815 666E-05 105E-03 546E-05 540E-06 546E-05 229E-08 546E-05

16932 667E-05 105E-03 547E-05 532E-06 547E-05 225E-08 547E-05

1705 668E-05 105E-03 548E-05 524E-06 548E-05 222E-08 547E-05

17167 675E-05 105E-03 548E-05 517E-06 548E-05 219E-08 548E-05

17987 675E-05 104E-03 553E-05 466E-06 553E-05 196E-08 553E-05

20096 676E-05 104E-03 564E-05 357E-06 564E-05 150E-08 564E-05

21971 685E-05 104E-03 572E-05 282E-06 572E-05 118E-08 572E-05

25135 686E-05 104E-03 581E-05 190E-06 581E-05 789E-09 581E-05

25253 686E-05 104E-03 581E-05 188E-06 581E-05 778E-09 581E-05

2537 686E-05 104E-03 582E-05 185E-06 582E-05 766E-09 581E-05

25487 687E-05 104E-03 582E-05 182E-06 582E-05 755E-09 582E-05

25604 688E-05 104E-03 582E-05 180E-06 582E-05 744E-09 582E-05

25721 688E-05 104E-03 582E-05 177E-06 582E-05 733E-09 582E-05

25838 688E-05 104E-03 583E-05 174E-06 583E-05 723E-09 582E-05

25956 689E-05 104E-03 583E-05 172E-06 583E-05 712E-09 583E-05

26073 689E-05 104E-03 583E-05 169E-06 583E-05 702E-09 583E-05

2619 689E-05 104E-03 583E-05 167E-06 583E-05 691E-09 583E-05

26307 693E-05 104E-03 584E-05 165E-06 584E-05 681E-09 583E-05

26424 694E-05 104E-03 584E-05 162E-06 584E-05 672E-09 584E-05

28182 694E-05 104E-03 587E-05 130E-06 587E-05 539E-09 587E-05

29706 694E-05 104E-03 589E-05 108E-06 589E-05 446E-09 589E-05

272

29823 694E-05 104E-03 589E-05 107E-06 589E-05 440E-09 589E-05

2994 694E-05 104E-03 589E-05 105E-06 589E-05 433E-09 589E-05

30057 694E-05 104E-03 590E-05 104E-06 590E-05 427E-09 590E-05

30174 696E-05 104E-03 590E-05 102E-06 590E-05 421E-09 590E-05

34627 697E-05 104E-03 594E-05 590E-07 594E-05 243E-09 594E-05

4119 698E-05 104E-03 597E-05 263E-07 597E-05 108E-09 597E-05

41307 698E-05 104E-03 597E-05 260E-07 597E-05 107E-09 597E-05

41424 698E-05 104E-03 597E-05 256E-07 597E-05 105E-09 597E-05

41541 699E-05 104E-03 597E-05 252E-07 597E-05 104E-09 597E-05

41658 699E-05 104E-03 598E-05 249E-07 598E-05 102E-09 598E-05

41775 699E-05 104E-03 598E-05 245E-07 598E-05 101E-09 598E-05

41893 699E-05 104E-03 598E-05 241E-07 598E-05 991E-10 598E-05

4201 699E-05 104E-03 598E-05 238E-07 598E-05 977E-10 598E-05

42947 699E-05 104E-03 598E-05 212E-07 598E-05 871E-10 598E-05

43533 699E-05 104E-03 598E-05 197E-07 598E-05 811E-10 598E-05

4365 699E-05 104E-03 598E-05 195E-07 598E-05 799E-10 598E-05

43768 699E-05 104E-03 598E-05 192E-07 598E-05 787E-10 598E-05

4576 699E-05 104E-03 598E-05 150E-07 598E-05 617E-10 598E-05

45877 699E-05 104E-03 599E-05 148E-07 599E-05 608E-10 599E-05

45994 700E-05 104E-03 599E-05 146E-07 599E-05 599E-10 599E-05

46111 700E-05 104E-03 599E-05 144E-07 599E-05 591E-10 599E-05

48103 700E-05 104E-03 599E-05 113E-07 599E-05 463E-10 599E-05

54783 700E-05 104E-03 600E-05 497E-08 600E-05 204E-10 600E-05

549 700E-05 104E-03 600E-05 490E-08 600E-05 201E-10 600E-05

55017 700E-05 104E-03 600E-05 483E-08 600E-05 198E-10 600E-05

55134 700E-05 104E-03 600E-05 476E-08 600E-05 195E-10 600E-05

56189 700E-05 104E-03 600E-05 419E-08 600E-05 172E-10 600E-05

56306 700E-05 104E-03 600E-05 413E-08 600E-05 169E-10 600E-05

56423 700E-05 104E-03 600E-05 407E-08 600E-05 167E-10 600E-05

5865 700E-05 104E-03 600E-05 310E-08 600E-05 127E-10 600E-05

58767 700E-05 104E-03 600E-05 305E-08 600E-05 125E-10 600E-05

58884 700E-05 104E-03 600E-05 301E-08 600E-05 123E-10 600E-05

59002 700E-05 104E-03 600E-05 297E-08 600E-05 122E-10 600E-05

59939 700E-05 104E-03 600E-05 264E-08 600E-05 108E-10 600E-05

60439 700E-05 104E-03 600E-05 249E-08 600E-05 102E-10 600E-05

273



274


275


276



02899 192E-05 0 000002 017395 168E-05 0 000002 0087 126E-05 0 000002

08759 199E-05 02 199E-05 052551 194E-05 02 198E-05 02628 182E-05 02 198E-05

14618 195E-05 04 198E-05 087708 189E-05 04 197E-05 04385 191E-05 02628 197E-05

20477 192E-05 06 198E-05 12286 184E-05 05255 196E-05 06143 189E-05 04385 195E-05

26337 188E-05 08 197E-05 15802 18E-05 07255 194E-05 07901 185E-05 06143 193E-05

32196 186E-05 0876 197E-05 19318 177E-05 08771 193E-05 09659 182E-05 07901 191E-05

38056 183E-05 1076 196E-05 22833 173E-05 10771 192E-05 11416 179E-05 09659 189E-05

43915 18E-05 1276 195E-05 26349 171E-05 12286 191E-05 13174 176E-05 11416 187E-05

49774 177E-05 1462 194E-05 29865 168E-05 14286 189E-05 14932 173E-05 13174 185E-05

55634 175E-05 1662 193E-05 3338 165E-05 15802 188E-05 1669 171E-05 14932 183E-05

61493 172E-05 1862 193E-05 36896 163E-05 17802 187E-05 18447 169E-05 1669 181E-05

67353 17E-05 2048 192E-05 40411 161E-05 19318 185E-05 20205 167E-05 18447 179E-05

73212 167E-05 2248 191E-05 43927 158E-05 21318 184E-05 21963 165E-05 20205 177E-05

79072 165E-05 2448 19E-05 47443 156E-05 22833 183E-05 23721 163E-05 21963 176E-05

84931 163E-05 2634 19E-05 50958 154E-05 24833 182E-05 25478 161E-05 23721 174E-05

9079 161E-05 2834 189E-05 54474 152E-05 26349 18E-05 27236 159E-05 25478 172E-05

9665 158E-05 3034 188E-05 5799 15E-05 28349 179E-05 28994 157E-05 27236 17E-05

10251 156E-05 322 187E-05 61505 148E-05 29865 178E-05 30752 156E-05 28994 168E-05

10837 154E-05 342 187E-05 65021 146E-05 31865 177E-05 32509 154E-05 30752 167E-05

11423 152E-05 362 186E-05 68536 144E-05 3338 176E-05 34267 153E-05 32509 165E-05

12009 15E-05 3806 185E-05 72052 142E-05 3538 174E-05 36025 151E-05 34267 163E-05

12595 148E-05 4006 184E-05 75568 14E-05 36896 173E-05 37783 149E-05 36025 161E-05

13181 146E-05 4206 184E-05 79083 138E-05 38896 172E-05 3954 148E-05 37783 16E-05

13767 145E-05 4392 183E-05 82599 137E-05 40411 171E-05 41298 147E-05 3954 158E-05

14353 143E-05 4592 182E-05 86115 135E-05 42411 17E-05 43056 145E-05 41298 157E-05

14938 141E-05 4792 182E-05 8963 133E-05 43927 169E-05 44814 143E-05 43056 155E-05

15524 139E-05 4977 181E-05 93146 132E-05 45927 167E-05 46571 142E-05 44814 153E-05

1611 138E-05 5177 18E-05 96661 13E-05 47443 166E-05 48329 141E-05 46571 152E-05

16696 136E-05 5377 179E-05 10018 128E-05 49443 165E-05 50087 139E-05 48329 15E-05

17282 134E-05 5563 179E-05 10369 127E-05 50958 164E-05 51845 138E-05 50087 149E-05

17868 133E-05 5763 178E-05 10721 125E-05 52958 163E-05 53603 137E-05 51845 147E-05

18454 131E-05 5963 177E-05 11072 124E-05 54474 162E-05 5536 135E-05 53603 146E-05

1904 13E-05 6149 177E-05 11424 122E-05 56474 161E-05 57118 134E-05 5536 144E-05

23728 118E-05 7721 171E-05 14236 111E-05 70536 152E-05 7118 124E-05 69422 132E-05

24314 117E-05 7907 17E-05 14588 11E-05 72052 151E-05 72938 123E-05 7118 131E-05

24899 116E-05 8107 17E-05 1494 108E-05 74052 15E-05 74696 122E-05 72938 13E-05

25485 114E-05 8307 169E-05 15291 107E-05 75568 149E-05 76453 121E-05 74696 128E-05

26071 113E-05 8493 168E-05 15643 106E-05 77568 148E-05 78211 12E-05 76453 127E-05

277

26657 112E-05 8693 168E-05 15994 104E-05 79083 147E-05 79969 119E-05 78211 126E-05

30173 105E-05 9865 164E-05 18104 972E-06 8963 141E-05 90515 112E-05 88758 118E-05

30759 104E-05 1007 163E-05 18455 96E-06 9163 14E-05 92273 111E-05 90515 117E-05

31345 103E-05 1025 162E-05 18807 95E-06 93146 139E-05 94031 11E-05 92273 116E-05

31931 102E-05 1045 162E-05 19158 938E-06 95146 138E-05 95789 109E-05 94031 114E-05

44236 816E-06 1455 149E-05 26541 737E-06 13182 12E-05 1327 904E-06 13094 92E-06

44821 808E-06 1475 148E-05 26893 729E-06 13382 119E-05 13446 896E-06 1327 91E-06

45407 8E-06 1494 148E-05 27244 721E-06 13533 118E-05 13622 889E-06 13446 901E-06

45993 792E-06 1514 147E-05 27596 712E-06 13733 117E-05 13798 88E-06 13622 892E-06

50095 738E-06 1651 143E-05 30057 657E-06 1494 112E-05 15028 827E-06 14852 829E-06

50681 731E-06 167 143E-05 30408 651E-06 1514 111E-05 15204 82E-06 15028 82E-06

51267 724E-06 169 142E-05 3076 643E-06 15291 11E-05 15379 813E-06 15204 812E-06

72947 508E-06 2413 123E-05 43768 428E-06 21819 858E-06 21883 589E-06 21707 552E-06

73533 503E-06 2431 122E-05 44119 424E-06 21971 853E-06 22059 584E-06 21883 547E-06

78806 462E-06 2607 118E-05 47283 384E-06 23577 801E-06 23641 541E-06 23465 498E-06

79392 458E-06 2627 117E-05 47635 38E-06 23729 796E-06 23817 536E-06 23641 493E-06

79978 454E-06 2647 117E-05 47986 376E-06 23929 79E-06 23993 531E-06 23817 488E-06

80564 45E-06 2666 117E-05 48338 371E-06 2408 786E-06 24168 527E-06 23993 483E-06

8115 446E-06 2686 116E-05 4869 367E-06 2428 78E-06 24344 523E-06 24168 478E-06

81736 441E-06 2706 116E-05 49041 363E-06 24432 775E-06 2452 518E-06 24344 473E-06

82322 438E-06 2724 115E-05 49393 36E-06 24632 769E-06 24696 514E-06 2452 468E-06

82908 433E-06 2744 115E-05 49744 356E-06 24783 765E-06 24871 51E-06 24696 463E-06

90525 384E-06 2999 109E-05 54315 31E-06 27093 699E-06 27156 456E-06 26981 404E-06

91111 381E-06 3017 109E-05 54666 307E-06 27244 695E-06 27332 453E-06 27156 4E-06

91697 378E-06 3037 108E-05 55018 303E-06 27444 69E-06 27508 449E-06 27332 396E-06

95212 358E-06 3155 106E-05 57127 284E-06 28499 662E-06 28563 427E-06 28387 372E-06

95798 354E-06 3175 105E-05 57479 282E-06 28651 659E-06 28738 423E-06 28563 368E-06

96384 351E-06 3193 105E-05 5783 279E-06 28851 653E-06 28914 42E-06 28738 364E-06

9697 348E-06 3213 104E-05 58182 276E-06 29002 65E-06 2909 417E-06 28914 361E-06

10752 297E-06 3565 972E-06 6451 228E-06 32166 575E-06 32254 358E-06 32078 299E-06

1081 294E-06 3585 968E-06 64861 226E-06 32366 571E-06 3243 355E-06 32254 296E-06

10869 292E-06 3603 964E-06 65213 223E-06 32518 567E-06 32606 352E-06 3243 293E-06

10928 289E-06 3623 96E-06 65565 221E-06 32718 563E-06 32781 349E-06 32606 29E-06

10986 287E-06 3643 956E-06 65916 219E-06 32869 56E-06 32957 346E-06 32781 287E-06

11045 284E-06 3662 953E-06 66268 217E-06 33069 555E-06 33133 343E-06 32957 284E-06

11103 281E-06 3682 949E-06 66619 214E-06 33221 552E-06 33309 34E-06 33133 281E-06

11162 279E-06 3702 945E-06 66971 212E-06 33421 548E-06 33484 338E-06 33309 278E-06

1122 277E-06 372 941E-06 67322 21E-06 33572 545E-06 3366 335E-06 33484 275E-06

11279 274E-06 374 938E-06 67674 208E-06 33772 54E-06 33836 333E-06 3366 272E-06

11338 272E-06 376 934E-06 68026 206E-06 33924 537E-06 34012 33E-06 33836 27E-06

11396 269E-06 3779 93E-06 68377 203E-06 34124 533E-06 34188 327E-06 34012 267E-06

278

13857 187E-06 4599 788E-06 83143 131E-06 41507 401E-06 4157 232E-06 41394 172E-06

13916 186E-06 4619 785E-06 83494 13E-06 41658 399E-06 41746 23E-06 4157 171E-06

13974 184E-06 4639 782E-06 83846 129E-06 41858 396E-06 41922 228E-06 41746 169E-06

14033 183E-06 4658 779E-06 84197 128E-06 4201 393E-06 42097 227E-06 41922 167E-06

14092 182E-06 4678 776E-06 84549 126E-06 4221 39E-06 42273 225E-06 42097 165E-06

1415 18E-06 4698 773E-06 84901 125E-06 42361 388E-06 42449 223E-06 42273 164E-06

14209 178E-06 4717 77E-06 85252 124E-06 42561 385E-06 42625 221E-06 42449 162E-06

14267 177E-06 4737 767E-06 85604 122E-06 42713 383E-06 42801 219E-06 42625 16E-06

14736 164E-06 4892 743E-06 88416 113E-06 44119 363E-06 44207 205E-06 44031 148E-06

14795 163E-06 4912 74E-06 88768 112E-06 44319 36E-06 44383 203E-06 44207 146E-06

14853 162E-06 4932 737E-06 89119 111E-06 44471 358E-06 44558 202E-06 44383 144E-06

14912 16E-06 4951 734E-06 89471 11E-06 44671 355E-06 44734 201E-06 44558 143E-06

1626 133E-06 5401 671E-06 97557 866E-07 4869 304E-06 48777 166E-06 48601 113E-06

16318 132E-06 542 668E-06 97908 862E-07 4889 302E-06 48953 165E-06 48777 111E-06

16377 131E-06 544 666E-06 9826 855E-07 49041 3E-06 49128 164E-06 48953 11E-06

16435 13E-06 546 663E-06 98611 847E-07 49241 298E-06 49304 162E-06 49128 109E-06

16494 129E-06 5478 66E-06 98963 837E-07 49393 296E-06 4948 161E-06 49304 108E-06

16553 127E-06 5498 658E-06 99315 829E-07 49593 294E-06 49656 16E-06 4948 107E-06

16611 127E-06 5518 655E-06 99666 82E-07 49744 292E-06 49832 158E-06 49656 106E-06

1667 126E-06 5537 653E-06 10002 814E-07 49944 29E-06 50007 157E-06 49832 105E-06

16728 124E-06 5557 65E-06 10037 806E-07 50096 288E-06 50183 156E-06 50007 104E-06

17373 114E-06 5771 623E-06 10424 721E-07 52054 267E-06 52117 143E-06 51941 924E-07

1831 101E-06 6084 585E-06 10986 623E-07 54866 24E-06 54929 126E-06 54753 783E-07

18838 934E-07 626 564E-06 11303 574E-07 56424 226E-06 56511 117E-06 56335 713E-07

18896 928E-07 628 562E-06 11338 568E-07 56624 224E-06 56687 117E-06 56511 705E-07

19951 812E-07 6632 524E-06 11971 481E-07 59788 198E-06 59851 102E-06 59675 585E-07

2001 804E-07 665 522E-06 12006 474E-07 5994 197E-06 60027 101E-06 59851 579E-07

20068 799E-07 667 519E-06 12041 472E-07 6014 196E-06 60202 995E-07 60027 573E-07

20127 792E-07 669 517E-06 12076 466E-07 60291 195E-06 60378 989E-07 60202 567E-07

20537 755E-07 6826 503E-06 12322 441E-07 61546 185E-06 61609 942E-07 61433 527E-07

20596 747E-07 6846 501E-06 12357 435E-07 61697 184E-06 61784 935E-07 61609 522E-07

20654 743E-07 6866 499E-06 12392 43E-07 61897 183E-06 6196 926E-07 61784 516E-07

20713 74E-07 6885 498E-06 12428 427E-07 62049 182E-06 62136 921E-07 6196 511E-07

20771 731E-07 6905 496E-06 12463 423E-07 62249 18E-06 62312 911E-07 62136 506E-07

2083 727E-07 6925 494E-06 12498 422E-07 62401 179E-06 62487 904E-07 62312 501E-07

20889 718E-07 6943 492E-06 12533 417E-07 62601 178E-06 62663 899E-07 62487 495E-07

20947 714E-07 6963 49E-06 12568 415E-07 62752 177E-06 62839 89E-07 62663 49E-07

21006 707E-07 6983 488E-06 12603 41E-07 62952 176E-06 63015 885E-07 62839 485E-07

21064 699E-07 7002 486E-06 12638 406E-07 63104 175E-06 63191 882E-07 63015 48E-07

21123 695E-07 7022 484E-06 12674 403E-07 63304 173E-06 63366 877E-07 63191 475E-07

22705 575E-07 7549 435E-06 13623 318E-07 68026 144E-06 68112 714E-07 67937 359E-07

279

22764 57E-07 7569 433E-06 13658 316E-07 68226 143E-06 68288 707E-07 68112 355E-07

22822 57E-07 7588 432E-06 13693 313E-07 68377 143E-06 68464 702E-07 68288 352E-07

22881 565E-07 7608 43E-06 13728 311E-07 68577 141E-06 6864 695E-07 68464 348E-07

22939 562E-07 7628 428E-06 13763 311E-07 68729 141E-06 68815 693E-07 6864 344E-07

22998 557E-07 7646 427E-06 13799 306E-07 68929 14E-06 68991 686E-07 68815 341E-07

23056 554E-07 7666 425E-06 13834 303E-07 6908 139E-06 69167 681E-07 68991 337E-07

23115 547E-07 7686 423E-06 13869 304E-07 6928 138E-06 69343 68E-07 69167 334E-07

23994 494E-07 7979 399E-06 14396 267E-07 71893 125E-06 71979 607E-07 71804 286E-07

24053 489E-07 7998 398E-06 14431 264E-07 72093 124E-06 72155 606E-07 71979 283E-07

24697 45E-07 8214 381E-06 14818 239E-07 74002 115E-06 74089 562E-07 73913 252E-07

25342 417E-07 8428 365E-06 15205 22E-07 7596 106E-06 76022 513E-07 75846 225E-07

254 416E-07 8448 363E-06 1524 217E-07 76111 106E-06 76198 512E-07 76022 223E-07

25459 412E-07 8467 362E-06 15275 217E-07 76311 105E-06 76374 507E-07 76198 22E-07

25517 408E-07 8487 36E-06 1531 216E-07 76463 104E-06 7655 504E-07 76374 218E-07

26865 355E-07 8935 329E-06 16119 186E-07 8053 893E-07 80592 431E-07 80417 172E-07

26924 35E-07 8955 328E-06 16154 181E-07 80682 888E-07 80768 425E-07 80592 17E-07

26982 351E-07 8975 327E-06 16189 182E-07 80882 881E-07 80944 424E-07 80768 168E-07

27041 35E-07 8994 325E-06 16224 183E-07 81033 876E-07 8112 42E-07 80944 166E-07

27099 346E-07 9014 324E-06 1626 178E-07 81233 869E-07 81295 419E-07 8112 165E-07

2792 318E-07 9287 307E-06 16752 163E-07 83694 791E-07 83756 375E-07 83581 142E-07

27978 319E-07 9307 306E-06 16787 16E-07 83846 786E-07 83932 376E-07 83756 141E-07

28037 316E-07 9327 304E-06 16822 16E-07 84046 78E-07 84108 378E-07 83932 139E-07

29092 283E-07 9678 284E-06 17455 143E-07 8721 691E-07 87272 331E-07 87096 116E-07

2915 281E-07 9697 283E-06 1749 145E-07 87361 687E-07 87448 335E-07 87272 114E-07

29267 276E-07 9737 28E-06 1756 141E-07 87713 678E-07 87799 331E-07 87623 112E-07

29326 275E-07 9756 279E-06 17596 136E-07 87913 673E-07 87975 324E-07 87799 111E-07

29385 272E-07 9776 278E-06 17631 138E-07 88065 669E-07 88151 321E-07 87975 11E-07

29443 276E-07 9796 277E-06 17666 14E-07 88265 663E-07 88327 321E-07 88151 109E-07

29795 267E-07 9913 271E-06 17877 133E-07 89319 637E-07 89381 312E-07 89205 102E-07

29853 265E-07 9931 27E-06 17912 132E-07 89471 633E-07 89557 31E-07 89381 101E-07

29912 262E-07 9951 269E-06 17947 133E-07 89671 629E-07 89733 302E-07 89557 1E-07

29971 262E-07 9971 267E-06 17982 133E-07 89822 625E-07 89909 301E-07 89733 99E-08

280


200E-05 000E+00 000E+00 000E+00

02 198E-05 235E-07 910E-09 226E-07

026275 197E-05 308E-07 907E-09 299E-07

043852 195E-05 513E-07 898E-09 504E-07

06143 193E-05 715E-07 888E-09 706E-07

079008 191E-05 916E-07 879E-09 907E-07

096585 189E-05 111E-06 870E-09 111E-06

11416 187E-05 131E-06 861E-09 130E-06

13174 185E-05 150E-06 852E-09 150E-06

14932 183E-05 170E-06 843E-09 169E-06

1669 181E-05 189E-06 834E-09 188E-06

62391 138E-05 619E-06 636E-09 618E-06

64149 137E-05 633E-06 630E-09 633E-06

65907 135E-05 647E-06 623E-09 647E-06

67665 134E-05 661E-06 617E-09 661E-06

69422 132E-05 675E-06 610E-09 675E-06

7118 131E-05 689E-06 604E-09 688E-06

72938 130E-05 703E-06 598E-09 702E-06

74696 128E-05 716E-06 592E-09 715E-06

76453 127E-05 729E-06 586E-09 729E-06

78211 126E-05 743E-06 580E-09 742E-06

79969 124E-05 756E-06 574E-09 755E-06

81727 123E-05 768E-06 568E-09 768E-06

83484 122E-05 781E-06 562E-09 781E-06

14852 829E-06 117E-05 382E-09 117E-05

15028 820E-06 118E-05 378E-09 118E-05

15204 812E-06 119E-05 374E-09 119E-05

15379 804E-06 120E-05 370E-09 120E-05

15555 795E-06 120E-05 367E-09 120E-05

15731 787E-06 121E-05 363E-09 121E-05

15907 779E-06 122E-05 359E-09 122E-05

16083 771E-06 123E-05 355E-09 123E-05

16258 763E-06 124E-05 352E-09 124E-05

16434 755E-06 125E-05 348E-09 124E-05

1661 747E-06 125E-05 344E-09 125E-05

23465 498E-06 150E-05 230E-09 150E-05

23641 493E-06 151E-05 227E-09 151E-05

26453 417E-06 158E-05 192E-09 158E-05

26629 413E-06 159E-05 190E-09 159E-05

26805 409E-06 159E-05 188E-09 159E-05

26981 404E-06 160E-05 186E-09 160E-05

27156 400E-06 160E-05 185E-09 160E-05

27332 396E-06 160E-05 183E-09 160E-05

27508 392E-06 161E-05 181E-09 161E-05

27684 388E-06 161E-05 179E-09 161E-05

2786 384E-06 162E-05 177E-09 162E-05

28035 380E-06 162E-05 175E-09 162E-05

32957 284E-06 172E-05 131E-09 172E-05

33133 281E-06 172E-05 130E-09 172E-05

33309 278E-06 172E-05 128E-09 172E-05

33484 275E-06 172E-05 127E-09 172E-05

3366 272E-06 173E-05 126E-09 173E-05

33836 270E-06 173E-05 124E-09 173E-05

34012 267E-06 173E-05 123E-09 173E-05

34188 264E-06 174E-05 122E-09 174E-05

34363 261E-06 174E-05 121E-09 174E-05

34539 259E-06 174E-05 119E-09 174E-05

34715 256E-06 174E-05 118E-09 174E-05

34891 253E-06 175E-05 117E-09 175E-05

35066 251E-06 175E-05 116E-09 175E-05

38055 210E-06 179E-05 969E-10 179E-05

3823 208E-06 179E-05 959E-10 179E-05

38406 206E-06 179E-05 949E-10 179E-05

38582 204E-06 180E-05 939E-10 180E-05

38758 201E-06 180E-05 929E-10 180E-05

38933 199E-06 180E-05 920E-10 180E-05

44734 142E-06 186E-05 653E-10 186E-05

4491 140E-06 186E-05 646E-10 186E-05

45086 139E-06 186E-05 639E-10 186E-05

45261 137E-06 186E-05 633E-10 186E-05

45437 136E-06 186E-05 626E-10 186E-05

45613 134E-06 187E-05 620E-10 187E-05

45789 133E-06 187E-05 613E-10 187E-05

45965 132E-06 187E-05 607E-10 187E-05

4614 130E-06 187E-05 601E-10 187E-05

46316 129E-06 187E-05 595E-10 187E-05

46492 128E-06 187E-05 588E-10 187E-05

281

46668 126E-06 187E-05 582E-10 187E-05

46843 125E-06 188E-05 576E-10 188E-05

47019 124E-06 188E-05 570E-10 188E-05

47195 122E-06 188E-05 564E-10 188E-05

47371 121E-06 188E-05 559E-10 188E-05

52292 905E-07 191E-05 418E-10 191E-05

52468 896E-07 191E-05 413E-10 191E-05

52644 886E-07 191E-05 409E-10 191E-05

5282 877E-07 191E-05 405E-10 191E-05

52996 868E-07 191E-05 401E-10 191E-05

53171 859E-07 191E-05 396E-10 191E-05

53347 850E-07 191E-05 392E-10 191E-05

5616 720E-07 193E-05 332E-10 193E-05

56335 713E-07 193E-05 329E-10 193E-05

56511 705E-07 193E-05 325E-10 193E-05

56687 698E-07 193E-05 322E-10 193E-05

56863 691E-07 193E-05 319E-10 193E-05

57038 684E-07 193E-05 315E-10 193E-05

57214 677E-07 193E-05 312E-10 193E-05

5739 670E-07 193E-05 309E-10 193E-05

57566 663E-07 193E-05 306E-10 193E-05

57742 656E-07 193E-05 303E-10 193E-05

57917 649E-07 194E-05 299E-10 194E-05

58093 642E-07 194E-05 296E-10 194E-05

58269 636E-07 194E-05 293E-10 194E-05

58445 629E-07 194E-05 290E-10 194E-05

5862 623E-07 194E-05 287E-10 194E-05

58796 616E-07 194E-05 284E-10 194E-05

61784 516E-07 195E-05 238E-10 195E-05

6196 511E-07 195E-05 236E-10 195E-05

62136 506E-07 195E-05 233E-10 195E-05

62312 501E-07 195E-05 231E-10 195E-05

62487 495E-07 195E-05 229E-10 195E-05

62663 490E-07 195E-05 226E-10 195E-05

62839 485E-07 195E-05 224E-10 195E-05

63015 480E-07 195E-05 222E-10 195E-05

63191 475E-07 195E-05 219E-10 195E-05

63366 470E-07 195E-05 217E-10 195E-05

63542 465E-07 195E-05 215E-10 195E-05

63718 461E-07 195E-05 213E-10 195E-05

63894 456E-07 195E-05 210E-10 195E-05

64069 451E-07 195E-05 208E-10 195E-05

64245 446E-07 196E-05 206E-10 196E-05

64421 442E-07 196E-05 204E-10 196E-05

64597 437E-07 196E-05 202E-10 196E-05

70749 304E-07 197E-05 140E-10 197E-05

70925 301E-07 197E-05 139E-10 197E-05

711 298E-07 197E-05 137E-10 197E-05

73913 252E-07 197E-05 116E-10 197E-05

80065 175E-07 198E-05 809E-11 198E-05

80241 173E-07 198E-05 800E-11 198E-05

80417 172E-07 198E-05 792E-11 198E-05

80592 170E-07 198E-05 784E-11 198E-05

80768 168E-07 198E-05 776E-11 198E-05

80944 166E-07 198E-05 768E-11 198E-05

8112 165E-07 198E-05 760E-11 198E-05

81295 163E-07 198E-05 752E-11 198E-05

81471 161E-07 198E-05 744E-11 198E-05

81647 160E-07 198E-05 736E-11 198E-05

81823 158E-07 198E-05 729E-11 198E-05

81999 156E-07 198E-05 721E-11 198E-05

82174 155E-07 198E-05 714E-11 198E-05

8235 153E-07 198E-05 706E-11 198E-05

82526 152E-07 198E-05 699E-11 198E-05

82702 150E-07 199E-05 692E-11 198E-05

82877 148E-07 199E-05 685E-11 199E-05

83053 147E-07 199E-05 678E-11 199E-05

83229 145E-07 199E-05 671E-11 199E-05

86393 121E-07 199E-05 556E-11 199E-05

86569 119E-07 199E-05 551E-11 199E-05

86745 118E-07 199E-05 545E-11 199E-05

282




283


284


285



0 700E-05 00019 621E-05 0002 596E-05 0 700E-05 00146 670E-05 0005 713E-05

0018 633E-05 00215 578E-05 0021 495E-05 00136 612E-05 00635 587E-05 0054 605E-05

0021 619E-05 00254 568E-05 0025 478E-05 00175 589E-05 00732 572E-05 0063 59E-05

0025 606E-05 00293 558E-05 0029 462E-05 00215 568E-05 0083 559E-05 0073 575E-05

0029 594E-05 00332 548E-05 0033 446E-05 00254 548E-05 00928 546E-05 0083 561E-05

0033 582E-05 00371 538E-05 0037 431E-05 00293 529E-05 01025 533E-05 0093 548E-05

0037 570E-05 0041 529E-05 0041 417E-05 00332 511E-05 01123 521E-05 0103 537E-05

0041 559E-05 00449 52E-05 0045 404E-05 00371 494E-05 01221 510E-05 0112 525E-05

0045 548E-05 00488 51E-05 0049 391E-05 0041 477E-05 01319 499E-05 0122 514E-05

0049 537E-05 00527 501E-05 0053 379E-05 00449 461E-05 01416 489E-05 0132 503E-05

0053 527E-05 00566 492E-05 0057 367E-05 00488 446E-05 01514 479E-05 0142 493E-05

0057 517E-05 00605 484E-05 006 355E-05 00527 432E-05 01612 469E-05 0151 484E-05

006 508E-05 00644 477E-05 0064 345E-05 00566 418E-05 01709 460E-05 0161 474E-05

0092 441E-05 00956 419E-05 0096 272E-05 00878 326E-05 02491 397E-05 0239 411E-05

0096 433E-05 00995 412E-05 01 264E-05 00917 317E-05 02589 390E-05 0249 404E-05

01 426E-05 01034 406E-05 0103 256E-05 00956 307E-05 02686 383E-05 0259 397E-05

0103 419E-05 01073 4E-05 0107 249E-05 00995 299E-05 02784 377E-05 0269 391E-05

0107 412E-05 01112 393E-05 0111 242E-05 01034 290E-05 02882 371E-05 0278 384E-05

0228 265E-05 02323 252E-05 0232 111E-05 02245 127E-05 05911 244E-05 0581 248E-05

0232 262E-05 02362 249E-05 0236 108E-05 02284 124E-05 06009 242E-05 0591 245E-05

0236 259E-05 02401 246E-05 024 106E-05 02323 121E-05 06106 239E-05 0601 242E-05

024 256E-05 0244 243E-05 0244 104E-05 02362 118E-05 06204 236E-05 0611 24E-05

0244 253E-05 02479 239E-05 0248 101E-05 02401 115E-05 06302 234E-05 062 237E-05

0248 249E-05 02518 236E-05 0252 992E-06 0244 113E-05 06399 231E-05 063 234E-05

0252 246E-05 02557 233E-05 0256 971E-06 02479 110E-05 06497 229E-05 064 231E-05

0256 243E-05 02596 23E-05 026 950E-06 02518 107E-05 06595 226E-05 065 228E-05

026 241E-05 02635 227E-05 0264 929E-06 02557 105E-05 06692 224E-05 0659 226E-05

0264 238E-05 02674 224E-05 0267 91E-06 02596 102E-05 0679 222E-05 0669 223E-05

0267 235E-05 02713 221E-05 0271 891E-06 02635 997E-06 06888 219E-05 0679 22E-05

0271 232E-05 02752 218E-05 0275 870E-06 02674 973E-06 06986 217E-05 0689 218E-05

0275 229E-05 02791 216E-05 0279 853E-06 02713 950E-06 07083 215E-05 0699 215E-05

0279 227E-05 0283 213E-05 0283 836E-06 02752 927E-06 07181 213E-05 0708 213E-05

0435 148E-05 04392 13E-05 0439 403E-06 04314 367E-06 11089 150E-05 1099 14E-05

0439 146E-05 04431 129E-05 0443 396E-06 04353 359E-06 11187 149E-05 1109 139E-05

0611 975E-06 06149 794E-06 0615 232E-06 06071 135E-06 15486 110E-05 1539 956E-06

0701 802E-06 07047 633E-06 0705 193E-06 06968 814E-07 17733 960E-06 1764 81E-06

0705 795E-06 07086 626E-06 0709 192E-06 07008 796E-07 17831 955E-06 1773 805E-06

0752 720E-06 07554 559E-06 0755 177E-06 07476 613E-07 19003 894E-06 1891 742E-06

286

0755 715E-06 07593 555E-06 0759 177E-06 07515 600E-07 19101 889E-06 19 738E-06

0759 709E-06 07632 55E-06 0763 176E-06 07554 587E-07 19199 884E-06 191 734E-06

0763 703E-06 07671 545E-06 0767 176E-06 07593 574E-07 19297 879E-06 192 729E-06

0841 600E-06 08452 456E-06 0845 161E-06 08374 371E-07 21251 793E-06 2115 644E-06

0845 595E-06 08491 453E-06 0849 162E-06 08413 363E-07 21348 789E-06 2125 641E-06

0935 498E-06 09389 377E-06 0939 150E-06 09311 221E-07 23596 705E-06 235 564E-06

0939 494E-06 09428 375E-06 0943 151E-06 0935 216E-07 23693 702E-06 236 56E-06

1103 362E-06 11068 282E-06 1107 140E-06 1099 869E-08 27797 582E-06 277 458E-06

1107 359E-06 11107 279E-06 1111 141E-06 11029 850E-08 27895 579E-06 278 455E-06

1111 357E-06 11146 277E-06 1115 140E-06 11068 832E-08 27992 577E-06 279 455E-06

1716 121E-06 17197 16E-06 172 132E-06 17119 294E-09 43137 325E-06 4304 3E-06

172 121E-06 17236 161E-06 1724 134E-06 17158 288E-09 43235 324E-06 4314 299E-06

1724 120E-06 17275 16E-06 1728 132E-06 17197 281E-09 43332 323E-06 4324 299E-06

1728 119E-06 17314 159E-06 1731 134E-06 17236 275E-09 4343 322E-06 4333 3E-06

1731 118E-06 17353 159E-06 1735 133E-06 17275 270E-09 43528 321E-06 4343 297E-06

1888 904E-07 18915 152E-06 1892 133E-06 18837 114E-09 47436 282E-06 4734 284E-06

1892 898E-07 18954 151E-06 1895 132E-06 18876 112E-09 47534 281E-06 4744 283E-06

1931 840E-07 19344 148E-06 1934 132E-06 19266 900E-10 48511 273E-06 4841 28E-06

1934 835E-07 19383 148E-06 1938 133E-06 19305 881E-10 48609 272E-06 4851 28E-06

1938 829E-07 19422 148E-06 1942 133E-06 19344 862E-10 48706 271E-06 4861 279E-06

1942 824E-07 19461 149E-06 1946 132E-06 19383 844E-10 48804 270E-06 4871 28E-06

1946 818E-07 195 148E-06 195 132E-06 19422 826E-10 48902 269E-06 488 279E-06

1981 771E-07 19852 148E-06 1985 131E-06 19774 680E-10 49781 262E-06 4968 276E-06

287


TIME AM- P1 I1 P2

0 700E-05 413E-13 237E-11 242E-11

577E-08 700E-05 238E-06 675E-10 238E-06

584E-03 676E-05 389E-06 658E-10 389E-06

974E-03 661E-05 534E-06 643E-10 534E-06

0013644 647E-05 674E-06 628E-10 674E-06

0017548 633E-05 809E-06 614E-10 809E-06

0021452 619E-05 939E-06 600E-10 939E-06

0025356 606E-05 106E-05 587E-10 106E-05

002926 594E-05 118E-05 574E-10 118E-05

0033164 582E-05 130E-05 562E-10 130E-05

0037068 570E-05 141E-05 551E-10 141E-05

0040972 559E-05 152E-05 539E-10 152E-05

0044876 548E-05 163E-05 528E-10 163E-05

004878 537E-05 173E-05 518E-10 173E-05

0052684 527E-05 183E-05 507E-10 183E-05

0056588 517E-05 192E-05 498E-10 192E-05

0060492 508E-05 202E-05 488E-10 202E-05

0064396 498E-05 211E-05 479E-10 211E-05

00683 489E-05 219E-05 470E-10 219E-05

0072204 481E-05 228E-05 461E-10 228E-05

0076108 472E-05 236E-05 453E-10 236E-05

0080012 464E-05 244E-05 444E-10 244E-05

0083916 456E-05 252E-05 437E-10 252E-05

008782 448E-05 259E-05 429E-10 259E-05

0091724 441E-05 267E-05 421E-10 267E-05

0095628 433E-05 274E-05 414E-10 274E-05

0099532 426E-05 281E-05 407E-10 281E-05

010344 419E-05 288E-05 400E-10 288E-05

010734 412E-05 294E-05 394E-10 294E-05

011124 406E-05 301E-05 387E-10 301E-05

011515 399E-05 307E-05 381E-10 307E-05

011905 393E-05 313E-05 375E-10 313E-05

012296 387E-05 319E-05 369E-10 319E-05

012686 381E-05 325E-05 363E-10 325E-05

013076 375E-05 330E-05 357E-10 330E-05

013467 370E-05 336E-05 351E-10 336E-05

0162 333E-05 371E-05 316E-10 371E-05

021275 279E-05 424E-05 264E-10 424E-05

021665 276E-05 428E-05 260E-10 428E-05

022056 272E-05 431E-05 257E-10 431E-05

022446 269E-05 435E-05 253E-10 434E-05

022836 265E-05 438E-05 250E-10 438E-05

023227 262E-05 441E-05 247E-10 441E-05

023617 259E-05 444E-05 244E-10 444E-05

024008 256E-05 447E-05 241E-10 447E-05

024398 253E-05 451E-05 238E-10 451E-05

038452 168E-05 533E-05 157E-10 533E-05

038843 167E-05 535E-05 156E-10 535E-05

039233 165E-05 537E-05 154E-10 537E-05

039624 163E-05 538E-05 152E-10 538E-05

040014 162E-05 540E-05 151E-10 540E-05

040404 160E-05 542E-05 149E-10 542E-05

040795 158E-05 543E-05 148E-10 543E-05

041185 157E-05 545E-05 146E-10 545E-05

041576 155E-05 546E-05 145E-10 546E-05

061486 966E-06 604E-05 896E-11 604E-05

061876 958E-06 605E-05 888E-11 605E-05

062267 950E-06 606E-05 880E-11 606E-05

062657 941E-06 607E-05 872E-11 607E-05

063048 933E-06 607E-05 865E-11 607E-05

063438 925E-06 608E-05 857E-11 608E-05

080616 644E-06 636E-05 594E-11 636E-05

081006 639E-06 637E-05 590E-11 637E-05

081396 634E-06 637E-05 585E-11 637E-05

081787 629E-06 638E-05 580E-11 638E-05

082177 624E-06 638E-05 576E-11 638E-05

082568 619E-06 639E-05 571E-11 639E-05

082958 614E-06 639E-05 567E-11 639E-05

083348 609E-06 640E-05 562E-11 640E-05

083739 604E-06 640E-05 558E-11 640E-05

084129 600E-06 640E-05 553E-11 640E-05

08452 595E-06 641E-05 549E-11 641E-05

08491 590E-06 641E-05 545E-11 641E-05

0853 586E-06 642E-05 540E-11 642E-05

098574 452E-06 655E-05 416E-11 655E-05

098964 448E-06 656E-05 413E-11 655E-05

099355 445E-06 656E-05 410E-11 656E-05

288

12161 294E-06 671E-05 269E-11 671E-05

122 291E-06 671E-05 268E-11 671E-05

12239 289E-06 671E-05 266E-11 671E-05

12278 287E-06 671E-05 264E-11 671E-05

12317 285E-06 672E-05 262E-11 672E-05

12356 283E-06 672E-05 260E-11 672E-05

12395 281E-06 672E-05 258E-11 672E-05

12434 279E-06 672E-05 256E-11 672E-05

12473 277E-06 672E-05 254E-11 672E-05

12512 275E-06 673E-05 253E-11 673E-05

12551 273E-06 673E-05 251E-11 673E-05

1259 271E-06 673E-05 249E-11 673E-05

12903 257E-06 675E-05 235E-11 675E-05

12942 255E-06 675E-05 234E-11 675E-05

12981 253E-06 675E-05 232E-11 675E-05

1302 251E-06 675E-05 230E-11 675E-05

13059 249E-06 675E-05 229E-11 675E-05

13098 248E-06 675E-05 227E-11 675E-05

13137 246E-06 676E-05 226E-11 676E-05

13176 244E-06 676E-05 224E-11 676E-05

13215 243E-06 676E-05 222E-11 676E-05

1665 132E-06 687E-05 121E-11 687E-05

16689 132E-06 687E-05 120E-11 687E-05

16728 131E-06 687E-05 120E-11 687E-05

16767 130E-06 687E-05 119E-11 687E-05

16807 129E-06 687E-05 118E-11 687E-05

17002 125E-06 688E-05 114E-11 688E-05

17041 124E-06 688E-05 113E-11 688E-05

17861 108E-06 689E-05 982E-12 689E-05

179 107E-06 689E-05 976E-12 689E-05

17939 106E-06 689E-05 969E-12 689E-05

19774 776E-07 692E-05 708E-12 692E-05

19813 771E-07 692E-05 703E-12 692E-05

19852 766E-07 692E-05 699E-12 692E-05

19891 761E-07 692E-05 694E-12 692E-05

1993 756E-07 692E-05 690E-12 692E-05

289



290


291


292


293


294


295



0004834 495E-05 486E-05 0009664 617E-05 681777E-05 0019327 477357E-05 682E-05

0014605 476E-05 476E-05 0029194 52E-05 518738E-05 0058389 463358E-05 519E-05

0024376 457E-05 467E-05 0048725 496E-05 473146E-05 009745 450185E-05 473E-05

0034146 447E-05 459E-05 0068256 496E-05 455748E-05 013651 437765E-05 456E-05

0043917 44E-05 450E-05 0087786 496E-05 442709E-05 017557 426036E-05 443E-05

0053688 433E-05 442E-05 010732 489E-05 430699E-05 021463 414937E-05 431E-05

0063458 427E-05 434E-05 012685 478E-05 419942E-05 02537 404425E-05 42E-05

0073229 422E-05 427E-05 014638 465E-05 410301E-05 029276 394451E-05 41E-05

0083 417E-05 419E-05 016591 456E-05 00000401 033182 384973E-05 401E-05

009277 41E-05 412E-05 018544 446E-05 392408E-05 037088 375956E-05 392E-05

010254 405E-05 405E-05 020497 435E-05 383981E-05 040994 367367E-05 384E-05

026864 328E-05 312E-05 053699 288E-05 262757E-05 1074 265557E-05 263E-05

027841 323E-05 308E-05 055652 28E-05 256845E-05 1113 261337E-05 257E-05

036635 287E-05 273E-05 07323 231E-05 21068E-05 14646 228778E-05 211E-05

037612 283E-05 270E-05 075183 227E-05 206311E-05 15037 22567E-05 206E-05

038589 279E-05 266E-05 077136 223E-05 202184E-05 15427 222639E-05 202E-05

039566 275E-05 263E-05 079089 219E-05 198641E-05 15818 219698E-05 199E-05

040543 271E-05 260E-05 081042 215E-05 195068E-05 16208 216827E-05 195E-05

04152 267E-05 256E-05 082995 211E-05 191573E-05 16599 214032E-05 192E-05

042497 263E-05 253E-05 084948 208E-05 188126E-05 1699 211316E-05 188E-05

043474 26E-05 250E-05 086901 205E-05 00000185 1738 208662E-05 185E-05

044451 256E-05 247E-05 088854 201E-05 182233E-05 17771 206082E-05 182E-05

045429 253E-05 244E-05 090807 198E-05 179369E-05 18161 203559E-05 179E-05

046406 249E-05 241E-05 09276 195E-05 176583E-05 18552 201098E-05 177E-05

047383 245E-05 239E-05 094714 192E-05 173689E-05 18943 198702E-05 174E-05

04836 242E-05 236E-05 096667 189E-05 171087E-05 19333 196357E-05 171E-05

049337 238E-05 233E-05 09862 186E-05 168544E-05 19724 194068E-05 169E-05

06497 192E-05 195E-05 12987 152E-05 137592E-05 25974 163591E-05 138E-05

065947 19E-05 193E-05 13182 151E-05 136291E-05 26364 161998E-05 136E-05

075718 169E-05 175E-05 15135 137E-05 123689E-05 3027 147607E-05 124E-05

076695 167E-05 173E-05 15331 136E-05 122854E-05 30661 146303E-05 123E-05

077672 166E-05 171E-05 15526 135E-05 121641E-05 31052 145025E-05 122E-05

078649 164E-05 170E-05 15721 134E-05 120544E-05 31442 143764E-05 121E-05

079626 163E-05 168E-05 15916 133E-05 119485E-05 31833 142525E-05 119E-05

080603 161E-05 166E-05 16112 132E-05 118612E-05 32224 141309E-05 119E-05

10112 133E-05 137E-05 20213 115E-05 103592E-05 40426 119668E-05 104E-05

1021 132E-05 136E-05 20409 114E-05 103184E-05 40817 118793E-05 103E-05

10308 131E-05 135E-05 20604 113E-05 102689E-05 41208 117931E-05 103E-05

296

10405 129E-05 134E-05 20799 113E-05 102165E-05 41598 117079E-05 102E-05

10503 128E-05 132E-05 20994 112E-05 101563E-05 41989 116239E-05 102E-05

10601 128E-05 131E-05 2119 112E-05 101272E-05 4238 115412E-05 101E-05

10698 126E-05 130E-05 21385 111E-05 100835E-05 4277 114593E-05 101E-05

10796 126E-05 129E-05 2158 11E-05 100204E-05 43161 113788E-05 1E-05

10894 125E-05 128E-05 21776 11E-05 998155E-06 43551 11299E-05 998E-06

10991 124E-05 127E-05 21971 109E-05 994369E-06 43942 112203E-05 994E-06

11089 123E-05 126E-05 22166 108E-05 00000099 44333 111428E-05 99E-06

11187 122E-05 125E-05 22362 108E-05 983883E-06 44723 110661E-05 984E-06

11285 121E-05 124E-05 22557 107E-05 97932E-06 45114 109905E-05 979E-06

14216 101E-05 974E-06 28416 916E-06 871214E-06 56832 908951E-06 871E-06

14314 998E-06 967E-06 28611 909E-06 869524E-06 57223 903641E-06 87E-06

15584 937E-06 878E-06 3115 854E-06 82734E-06 62301 839142E-06 827E-06

15681 934E-06 871E-06 31346 852E-06 823903E-06 62691 834507E-06 824E-06

17245 875E-06 777E-06 34471 787E-06 781398E-06 68941 765966E-06 781E-06

17342 874E-06 772E-06 34666 784E-06 779631E-06 69332 762007E-06 78E-06

1744 87E-06 766E-06 34861 779E-06 777728E-06 69722 758072E-06 778E-06

17538 867E-06 761E-06 35057 776E-06 775835E-06 70113 754171E-06 776E-06

18613 833E-06 705E-06 37205 737E-06 746932E-06 7441 713428E-06 747E-06

1871 83E-06 700E-06 374 733E-06 746184E-06 748 709902E-06 746E-06

18808 828E-06 696E-06 37596 731E-06 74301E-06 75191 706404E-06 743E-06

20176 791E-06 634E-06 4033 684E-06 708932E-06 8066 660314E-06 709E-06

20274 789E-06 629E-06 40525 68E-06 707864E-06 8105 657207E-06 708E-06

20371 786E-06 625E-06 4072 677E-06 706194E-06 81441 654132E-06 706E-06

20469 786E-06 621E-06 40916 675E-06 702583E-06 81831 651072E-06 703E-06

20567 784E-06 617E-06 41111 672E-06 699786E-06 82222 648036E-06 7E-06

20664 78E-06 613E-06 41306 668E-06 699029E-06 82613 645029E-06 699E-06

20762 778E-06 609E-06 41502 665E-06 696427E-06 83003 642038E-06 696E-06

2086 777E-06 605E-06 41697 664E-06 694243E-06 83394 639069E-06 694E-06

20958 775E-06 601E-06 41892 662E-06 692194E-06 83785 63613E-06 692E-06

21055 771E-06 597E-06 42088 657E-06 689592E-06 84175 633205E-06 69E-06

21153 77E-06 593E-06 42283 655E-06 688728E-06 84566 630308E-06 689E-06

21251 767E-06 590E-06 42478 653E-06 686583E-06 84956 627426E-06 687E-06

21348 765E-06 586E-06 42673 651E-06 683583E-06 85347 624565E-06 684E-06

21446 762E-06 582E-06 42869 647E-06 680806E-06 85738 621732E-06 681E-06

21544 759E-06 578E-06 43064 645E-06 67965E-06 86128 618912E-06 68E-06

21642 758E-06 575E-06 43259 641E-06 678641E-06 86519 61612E-06 679E-06

23498 715E-06 510E-06 4697 586E-06 635291E-06 9394 566574E-06 635E-06

23596 716E-06 506E-06 47166 584E-06 63368E-06 94331 564139E-06 634E-06

2467 692E-06 473E-06 49314 559E-06 612437E-06 98628 538433E-06 612E-06

24768 691E-06 470E-06 49509 554E-06 611058E-06 99018 536184E-06 611E-06

297

24866 688E-06 467E-06 49705 553E-06 606748E-06 99409 533949E-06 607E-06

24964 688E-06 465E-06 499 551E-06 605126E-06 998 531735E-06 605E-06

25061 688E-06 462E-06 50095 547E-06 602544E-06 10019 529535E-06 603E-06

25159 686E-06 459E-06 5029 544E-06 599796E-06 10058 527349E-06 6E-06

25257 682E-06 456E-06 50486 544E-06 598806E-06 10097 525176E-06 599E-06

25354 681E-06 453E-06 50681 541E-06 597971E-06 10136 523018E-06 598E-06

28188 631E-06 382E-06 56345 479E-06 549631E-06 11269 465777E-06 55E-06

28286 627E-06 379E-06 5654 476E-06 545534E-06 11308 463978E-06 546E-06

28383 627E-06 377E-06 56736 475E-06 544553E-06 11347 46219E-06 545E-06

28481 627E-06 375E-06 56931 473E-06 542951E-06 11386 460412E-06 543E-06

37177 49E-06 229E-06 74313 327E-06 418437E-06 14863 334824E-06 418E-06

37275 491E-06 227E-06 74508 325E-06 418573E-06 14902 333709E-06 419E-06

3874 472E-06 210E-06 77438 304E-06 39634E-06 15488 317572E-06 396E-06

38838 471E-06 209E-06 77633 304E-06 395951E-06 15527 316537E-06 396E-06

3962 461E-06 200E-06 79196 292E-06 388699E-06 15839 308422E-06 389E-06

39717 459E-06 199E-06 79391 29E-06 385291E-06 15878 307429E-06 385E-06

39815 458E-06 198E-06 79586 29E-06 383272E-06 15917 306439E-06 383E-06

39913 458E-06 197E-06 79782 289E-06 381495E-06 15956 305454E-06 381E-06

4001 458E-06 196E-06 79977 287E-06 380689E-06 15995 304473E-06 381E-06

40108 456E-06 195E-06 80172 286E-06 381107E-06 16034 303472E-06 381E-06

41671 437E-06 179E-06 83297 265E-06 363777E-06 16659 288398E-06 364E-06

41769 434E-06 179E-06 83493 265E-06 362039E-06 16699 287492E-06 362E-06

41867 436E-06 178E-06 83688 265E-06 363845E-06 16738 286589E-06 364E-06

41965 435E-06 177E-06 83883 262E-06 360757E-06 16777 285691E-06 361E-06

42062 433E-06 176E-06 84079 261E-06 360291E-06 16816 284796E-06 36E-06

4558 393E-06 146E-06 9111 225E-06 322903E-06 18222 254927E-06 323E-06

45677 392E-06 145E-06 91305 224E-06 322165E-06 18261 25416E-06 322E-06

45775 389E-06 145E-06 915 221E-06 322165E-06 183 253396E-06 322E-06

48315 364E-06 127E-06 96578 194E-06 29535E-06 19316 234527E-06 295E-06

48413 364E-06 126E-06 96773 193E-06 293796E-06 19355 233841E-06 294E-06

48511 362E-06 126E-06 96969 192E-06 293524E-06 19394 233157E-06 294E-06

48609 362E-06 125E-06 97164 193E-06 292427E-06 19433 232476E-06 292E-06

48706 361E-06 124E-06 97359 19E-06 290796E-06 19472 231797E-06 291E-06

48804 361E-06 124E-06 97555 188E-06 290136E-06 19511 231121E-06 29E-06

48902 36E-06 123E-06 9775 188E-06 289602E-06 1955 230447E-06 29E-06

48999 358E-06 123E-06 97945 187E-06 288282E-06 19589 229776E-06 288E-06

49097 357E-06 122E-06 98141 186E-06 286951E-06 19628 229108E-06 287E-06

49781 351E-06 118E-06 99508 18E-06 280621E-06 19902 224484E-06 281E-06

49879 349E-06 117E-06 99703 179E-06 278709E-06 19941 223836E-06 279E-06

49976 348E-06 911E-07 99898 178E-06 278019E-06 1998 215738E-06 278E-06

298


TIME OH- P1 P2

0029194 527E-05 230E-06 230E-06

0048725 513E-05 373E-06 373E-06

0068256 499E-05 507E-06 507E-06

0087786 487E-05 634E-06 634E-06

010732 475E-05 754E-06 754E-06

012685 463E-05 867E-06 867E-06

014638 452E-05 975E-06 975E-06

016591 442E-05 108E-05 108E-05

018544 433E-05 117E-05 117E-05

020497 423E-05 127E-05 127E-05

02245 414E-05 136E-05 136E-05

024403 406E-05 144E-05 144E-05

026356 398E-05 152E-05 152E-05

077136 269E-05 160E-05 281E-05

079089 266E-05 167E-05 284E-05

081042 263E-05 174E-05 287E-05

082995 260E-05 181E-05 290E-05

090807 249E-05 205E-05 301E-05

09276 246E-05 211E-05 304E-05

094714 244E-05 216E-05 306E-05

096667 241E-05 221E-05 309E-05

09862 239E-05 226E-05 311E-05

10057 236E-05 231E-05 314E-05

10253 234E-05 236E-05 316E-05

10448 232E-05 240E-05 318E-05

10643 230E-05 245E-05 320E-05

10839 228E-05 249E-05 322E-05

11034 226E-05 253E-05 324E-05

11229 224E-05 257E-05 326E-05

11424 222E-05 261E-05 328E-05

1162 220E-05 264E-05 330E-05

11815 218E-05 268E-05 332E-05

1201 216E-05 271E-05 334E-05

12206 214E-05 275E-05 336E-05

12401 212E-05 278E-05 338E-05

12596 210E-05 281E-05 340E-05

12792 209E-05 284E-05 341E-05

12987 207E-05 287E-05 343E-05

13182 205E-05 290E-05 345E-05

13377 204E-05 293E-05 346E-05

14745 193E-05 311E-05 357E-05

1494 192E-05 314E-05 358E-05

15135 191E-05 316E-05 359E-05

15331 189E-05 318E-05 361E-05

15526 188E-05 320E-05 362E-05

15721 187E-05 322E-05 363E-05

15916 185E-05 324E-05 364E-05

16112 184E-05 326E-05 366E-05

16307 183E-05 328E-05 367E-05

16502 182E-05 330E-05 368E-05

16698 181E-05 332E-05 369E-05

16893 180E-05 334E-05 370E-05

17088 178E-05 336E-05 372E-05

17284 177E-05 338E-05 373E-05

17479 176E-05 340E-05 374E-05

299

22166 154E-05 341E-05 396E-05

23924 148E-05 355E-05 402E-05

24119 147E-05 357E-05 403E-05

24315 146E-05 358E-05 404E-05

2451 146E-05 359E-05 404E-05

27049 138E-05 361E-05 412E-05

27244 137E-05 362E-05 413E-05

44822 104E-05 372E-05 446E-05

45017 104E-05 373E-05 446E-05

45212 104E-05 374E-05 446E-05

45408 104E-05 375E-05 446E-05

47361 101E-05 385E-05 449E-05

55759 929E-06 386E-05 457E-05

55954 928E-06 387E-05 457E-05

5615 926E-06 388E-05 457E-05

57517 915E-06 393E-05 458E-05

57712 913E-06 394E-05 459E-05

57907 911E-06 395E-05 459E-05

58103 910E-06 396E-05 459E-05

58298 908E-06 397E-05 459E-05

58493 907E-06 397E-05 459E-05

58689 905E-06 398E-05 459E-05

58884 904E-06 399E-05 459E-05

59079 902E-06 399E-05 460E-05

59275 901E-06 400E-05 460E-05

5947 899E-06 401E-05 460E-05

59665 898E-06 402E-05 460E-05

5986 896E-06 402E-05 460E-05

60056 895E-06 403E-05 460E-05

68845 836E-06 404E-05 466E-05

6904 835E-06 404E-05 466E-05

7236 816E-06 405E-05 468E-05

72555 815E-06 406E-05 468E-05

72751 814E-06 406E-05 468E-05

76071 797E-06 407E-05 470E-05

76266 796E-06 407E-05 470E-05

76462 795E-06 408E-05 470E-05

80368 777E-06 409E-05 472E-05

80563 776E-06 409E-05 472E-05

80954 774E-06 410E-05 472E-05

81149 773E-06 411E-05 472E-05

89742 739E-06 412E-05 476E-05

90133 738E-06 413E-05 476E-05

90914 735E-06 415E-05 476E-05

9111 734E-06 415E-05 476E-05

91305 733E-06 416E-05 476E-05

915 733E-06 416E-05 477E-05

98141 711E-06 419E-05 479E-05

98336 710E-06 419E-05 479E-05

98531 710E-06 420E-05 479E-05

98727 709E-06 420E-05 479E-05

98922 708E-06 421E-05 479E-05

99117 708E-06 421E-05 479E-05

99703 706E-06 423E-05 479E-05

99898 706E-06 423E-05 479E-05

104898 691E-06 423E-05 481E-05

300



301


302


303



00048 73E-05 00029 738E-05 00029 729E-05 00048 000007 00029 000007 00029 000007

00146 72E-05 00088 735E-05 00088 727E-05 00146 678E-05 00088 683E-05 000875 67E-05

00244 7E-05 00146 723E-05 00146 713E-05 00244 664E-05 00146 671E-05 001461 65E-05

00341 68E-05 00205 71E-05 00205 697E-05 00341 651E-05 00205 661E-05 002047 63E-05

02784 39E-05 01669 537E-05 01669 438E-05 02784 392E-05 01669 467E-05 016687 35E-05

02882 38E-05 01727 531E-05 01727 431E-05 02882 384E-05 01727 461E-05 017272 35E-05

0298 38E-05 01786 524E-05 01786 424E-05 0298 376E-05 01786 455E-05 017858 34E-05

03077 37E-05 01844 518E-05 01844 417E-05 03077 369E-05 01844 45E-05 018443 33E-05

03175 36E-05 01903 513E-05 01903 41E-05 03175 362E-05 01903 445E-05 019029 33E-05

03273 35E-05 01962 507E-05 01962 404E-05 03273 355E-05 01962 44E-05 019615 32E-05

0337 35E-05 0202 501E-05 0202 396E-05 0337 348E-05 0202 435E-05 0202 32E-05

03468 34E-05 02079 495E-05 02079 39E-05 03468 342E-05 02079 43E-05 020786 31E-05

03566 34E-05 02137 489E-05 02137 384E-05 03566 335E-05 02137 425E-05 021371 31E-05

04738 27E-05 0284 428E-05 0284 318E-05 04738 267E-05 0284 374E-05 028399 25E-05

04836 26E-05 02898 424E-05 02898 314E-05 04836 262E-05 02898 37E-05 028984 25E-05

04934 26E-05 02957 419E-05 02957 309E-05 04934 258E-05 02957 366E-05 02957 25E-05

05031 26E-05 03016 414E-05 03016 304E-05 05031 253E-05 03016 363E-05 030155 24E-05

05129 25E-05 03074 41E-05 03074 3E-05 05129 248E-05 03074 359E-05 030741 24E-05

05227 25E-05 03133 406E-05 03133 296E-05 05227 244E-05 03133 356E-05 031327 24E-05

05325 24E-05 03191 401E-05 03191 291E-05 05325 239E-05 03191 352E-05 031912 23E-05

05422 24E-05 0325 396E-05 0325 287E-05 05422 235E-05 0325 349E-05 032498 23E-05

0552 23E-05 03308 392E-05 03308 283E-05 0552 231E-05 03308 346E-05 033083 23E-05

07474 17E-05 0448 322E-05 0448 212E-05 07474 163E-05 0448 289E-05 044795 18E-05

07572 17E-05 04538 318E-05 04538 21E-05 07572 16E-05 04538 286E-05 045381 17E-05

0767 16E-05 04597 315E-05 04597 207E-05 0767 158E-05 04597 284E-05 045967 17E-05

07767 16E-05 04655 312E-05 04655 204E-05 07767 155E-05 04655 282E-05 046552 17E-05

07865 16E-05 04714 309E-05 04714 201E-05 07865 153E-05 04714 279E-05 047138 17E-05

07963 16E-05 04772 306E-05 04772 198E-05 07963 15E-05 04772 277E-05 047723 17E-05

0806 15E-05 04831 303E-05 04831 196E-05 0806 148E-05 04831 275E-05 048309 17E-05

08158 15E-05 0489 3E-05 0489 193E-05 08158 145E-05 0489 273E-05 048895 16E-05

08256 15E-05 04948 298E-05 04948 191E-05 08256 143E-05 04948 271E-05 04948 16E-05

08353 15E-05 05007 295E-05 05007 188E-05 08353 141E-05 05007 268E-05 050066 16E-05

08451 15E-05 05065 292E-05 05065 185E-05 08451 138E-05 05065 266E-05 050651 16E-05

08549 14E-05 05124 289E-05 05124 183E-05 08549 136E-05 05124 264E-05 051237 16E-05

08647 14E-05 05182 287E-05 05182 181E-05 08647 134E-05 05182 262E-05 051823 15E-05

08744 14E-05 05241 284E-05 05241 178E-05 08744 132E-05 05241 26E-05 052408 15E-05

08842 14E-05 05299 282E-05 05299 176E-05 08842 13E-05 05299 258E-05 052994 15E-05

0894 14E-05 05358 279E-05 05358 174E-05 0894 128E-05 05358 256E-05 053579 15E-05

304

09037 13E-05 05417 276E-05 05417 171E-05 09037 126E-05 05417 254E-05 054165 15E-05

09135 13E-05 05475 274E-05 05475 169E-05 09135 124E-05 05475 252E-05 054751 15E-05

09233 13E-05 05534 272E-05 05534 167E-05 09233 122E-05 05534 25E-05 055336 15E-05

09331 13E-05 05592 269E-05 05592 165E-05 09331 12E-05 05592 248E-05 055922 14E-05

09428 13E-05 05651 267E-05 05651 163E-05 09428 118E-05 05651 246E-05 056507 14E-05

11187 98E-06 06705 228E-05 06705 13E-05 11187 9E-06 06705 217E-05 067048 12E-05

11285 97E-06 06763 226E-05 06763 129E-05 11285 887E-06 06763 215E-05 067634 12E-05

11382 96E-06 06822 225E-05 06822 127E-05 11382 874E-06 06822 214E-05 068219 12E-05

15291 61E-06 09164 165E-05 09164 819E-06 15291 509E-06 09164 166E-05 091643 83E-06

15388 6E-06 09223 164E-05 09223 809E-06 15388 503E-06 09223 165E-05 092229 83E-06

15486 59E-06 09282 163E-05 09282 803E-06 15486 497E-06 09282 164E-05 092815 82E-06

15584 58E-06 0934 161E-05 0934 797E-06 15584 49E-06 0934 163E-05 0934 82E-06

15681 58E-06 09399 16E-05 09399 787E-06 15681 484E-06 09399 162E-05 093986 81E-06

15779 57E-06 09457 159E-05 09457 78E-06 15779 478E-06 09457 161E-05 094571 8E-06

15877 57E-06 09516 158E-05 09516 774E-06 15877 473E-06 09516 16E-05 095157 8E-06

15975 56E-06 09574 157E-05 09574 765E-06 15975 467E-06 09574 16E-05 095743 79E-06

16072 56E-06 09633 156E-05 09633 758E-06 16072 461E-06 09633 159E-05 096328 78E-06

1617 55E-06 09691 155E-05 09691 75E-06 1617 456E-06 09691 158E-05 096914 78E-06

16268 55E-06 0975 154E-05 0975 743E-06 16268 45E-06 0975 157E-05 097499 77E-06

21251 37E-06 12736 112E-05 12736 487E-06 21251 255E-06 12736 12E-05 12736 54E-06

21348 36E-06 12795 111E-05 12795 482E-06 21348 252E-06 12795 12E-05 12795 54E-06

21446 36E-06 12854 111E-05 12854 479E-06 21446 249E-06 12854 119E-05 12854 53E-06

21544 36E-06 12912 11E-05 12912 477E-06 21544 247E-06 12912 118E-05 12912 53E-06

21642 36E-06 12971 109E-05 12971 473E-06 21642 244E-06 12971 118E-05 12971 52E-06

21739 36E-06 13029 109E-05 13029 469E-06 21739 242E-06 13029 117E-05 13029 52E-06

21837 35E-06 13088 109E-05 13088 466E-06 21837 239E-06 13088 117E-05 13088 52E-06

21935 35E-06 13146 108E-05 13146 463E-06 21935 237E-06 13146 116E-05 13146 51E-06

22032 35E-06 13205 107E-05 13205 459E-06 22032 235E-06 13205 116E-05 13205 51E-06

2213 35E-06 13264 107E-05 13264 457E-06 2213 232E-06 13264 115E-05 13264 51E-06

22228 35E-06 13322 106E-05 13322 455E-06 22228 23E-06 13322 115E-05 13322 5E-06

22325 34E-06 13381 105E-05 13381 449E-06 22325 228E-06 13381 114E-05 13381 5E-06

2555 29E-06 15313 894E-06 15313 372E-06 2555 167E-06 15313 981E-06 15313 41E-06

25647 29E-06 15372 888E-06 15372 369E-06 25647 165E-06 15372 977E-06 15372 41E-06

25745 29E-06 1543 884E-06 1543 368E-06 25745 164E-06 1543 973E-06 1543 4E-06

25843 29E-06 15489 882E-06 15489 368E-06 25843 162E-06 15489 968E-06 15489 4E-06

25941 29E-06 15547 878E-06 15547 365E-06 25941 161E-06 15547 964E-06 15547 4E-06

26038 29E-06 15606 872E-06 15606 363E-06 26038 16E-06 15606 96E-06 15606 4E-06

26136 28E-06 15664 869E-06 15664 361E-06 26136 158E-06 15664 956E-06 15664 39E-06

26234 29E-06 15723 865E-06 15723 36E-06 26234 157E-06 15723 952E-06 15723 39E-06

26331 28E-06 15782 861E-06 15782 359E-06 26331 155E-06 15782 947E-06 15782 39E-06

26429 28E-06 1584 858E-06 1584 357E-06 26429 154E-06 1584 943E-06 1584 39E-06

305

26527 28E-06 15899 855E-06 15899 357E-06 26527 153E-06 15899 939E-06 15899 38E-06

26625 28E-06 15957 85E-06 15957 355E-06 26625 151E-06 15957 935E-06 15957 38E-06

26722 28E-06 16016 845E-06 16016 352E-06 26722 15E-06 16016 931E-06 16016 38E-06

2682 28E-06 16074 844E-06 16074 352E-06 2682 149E-06 16074 927E-06 16074 38E-06

26918 28E-06 16133 84E-06 16133 351E-06 26918 147E-06 16133 923E-06 16133 38E-06

27015 28E-06 16192 835E-06 16192 348E-06 27015 146E-06 16192 919E-06 16192 37E-06

27113 28E-06 1625 832E-06 1625 346E-06 27113 145E-06 1625 916E-06 1625 37E-06

27211 27E-06 16309 829E-06 16309 345E-06 27211 144E-06 16309 912E-06 16309 37E-06

27309 28E-06 16367 823E-06 16367 344E-06 27309 142E-06 16367 908E-06 16367 37E-06

27406 27E-06 16426 82E-06 16426 341E-06 27406 141E-06 16426 904E-06 16426 36E-06

32096 24E-06 19237 686E-06 19237 288E-06 32096 963E-07 19237 744E-06 19237 28E-06

32194 24E-06 19295 683E-06 19295 29E-06 32194 956E-07 19295 741E-06 19295 28E-06

32292 24E-06 19354 681E-06 19354 288E-06 32292 949E-07 19354 739E-06 19354 27E-06

32389 24E-06 19412 679E-06 19412 284E-06 32389 942E-07 19412 736E-06 19412 27E-06

32487 24E-06 19471 677E-06 19471 285E-06 32487 935E-07 19471 733E-06 19471 27E-06

41574 22E-06 24917 53E-06 24917 243E-06 41574 506E-07 24917 523E-06 24917 17E-06

41671 22E-06 24976 528E-06 24976 241E-06 41671 503E-07 24976 522E-06 24976 17E-06

41769 22E-06 25034 527E-06 25034 241E-06 41769 5E-07 25034 52E-06 25034 17E-06

41867 22E-06 25093 526E-06 25093 242E-06 41867 497E-07 25093 518E-06 25093 17E-06

41965 22E-06 25151 525E-06 25151 24E-06 41965 494E-07 25151 516E-06 25151 16E-06

42062 22E-06 2521 523E-06 2521 241E-06 42062 491E-07 2521 515E-06 2521 16E-06

4216 22E-06 25268 524E-06 25268 242E-06 4216 488E-07 25268 513E-06 25268 16E-06

42258 22E-06 25327 52E-06 25327 241E-06 42258 486E-07 25327 511E-06 25327 16E-06

45287 21E-06 27142 488E-06 27142 237E-06 45287 408E-07 27142 461E-06 27142 14E-06

45384 21E-06 27201 486E-06 27201 236E-06 45384 406E-07 27201 46E-06 27201 14E-06

45482 21E-06 27259 488E-06 27259 237E-06 45482 404E-07 27259 458E-06 27259 14E-06

4558 21E-06 27318 486E-06 27318 236E-06 4558 401E-07 27318 457E-06 27318 14E-06

45677 21E-06 27376 486E-06 27376 235E-06 45677 399E-07 27376 455E-06 27376 14E-06

45775 21E-06 27435 485E-06 27435 234E-06 45775 397E-07 27435 454E-06 27435 14E-06

48804 21E-06 2925 463E-06 2925 231E-06 48804 338E-07 2925 411E-06 2925 12E-06

48902 21E-06 29309 462E-06 29309 23E-06 48902 336E-07 29309 409E-06 29309 12E-06

48999 21E-06 29368 46E-06 29368 229E-06 48999 335E-07 29368 408E-06 29368 12E-06

49097 21E-06 29426 46E-06 29426 229E-06 49097 333E-07 29426 407E-06 29426 12E-06

49195 21E-06 29485 46E-06 29485 229E-06 49195 331E-07 29485 406E-06 29485 12E-06

49293 21E-06 29543 458E-06 29543 23E-06 49293 33E-07 29543 404E-06 29543 12E-06

4939 21E-06 29602 459E-06 29602 229E-06 4939 328E-07 29602 403E-06 29602 11E-06

49586 21E-06 29719 458E-06 29719 23E-06 49586 325E-07 29719 4E-06 29719 11E-06

49683 21E-06 29777 455E-06 29777 229E-06 49683 323E-07 29777 399E-06 29777 11E-06

49781 21E-06 29836 456E-06 29836 228E-06 49781 322E-07 29836 398E-06 29836 11E-06

49879 21E-06 29895 455E-06 29895 23E-06 49879 32E-07 29895 397E-06 29895 11E-06

49976 21E-06 29953 451E-06 29953 229E-06 49976 318E-07 29953 395E-06 29953 11E-06

306



0014605 216E-06 121E-09 215E-06 496E-09

0024376 356E-06 199E-09 355E-06 137E-08

0034146 493E-06 276E-09 490E-06 266E-08

0043917 628E-06 351E-09 623E-06 437E-08

0053688 759E-06 424E-09 752E-06 647E-08

0063458 887E-06 496E-09 878E-06 897E-08

0073229 101E-05 567E-09 100E-05 118E-07

0083 114E-05 635E-09 112E-05 151E-07

009277 126E-05 703E-09 124E-05 187E-07

010254 137E-05 768E-09 135E-05 226E-07

011231 149E-05 833E-09 146E-05 269E-07

012208 160E-05 896E-09 157E-05 315E-07

063993 503E-05 289E-08 448E-05 551E-06

06497 507E-05 291E-08 450E-05 564E-06

065947 510E-05 293E-08 452E-05 576E-06

066924 513E-05 295E-08 454E-05 588E-06

067901 516E-05 297E-08 456E-05 601E-06

068878 519E-05 299E-08 458E-05 613E-06

069855 523E-05 301E-08 460E-05 626E-06

070832 526E-05 303E-08 461E-05 638E-06

071809 528E-05 305E-08 463E-05 651E-06

072786 531E-05 307E-08 465E-05 663E-06

073763 534E-05 309E-08 466E-05 676E-06

074741 537E-05 310E-08 468E-05 688E-06

075718 540E-05 312E-08 469E-05 701E-06

076695 542E-05 314E-08 471E-05 713E-06

077672 545E-05 316E-08 472E-05 726E-06

078649 547E-05 317E-08 473E-05 738E-06

079626 550E-05 319E-08 474E-05 751E-06

080603 552E-05 320E-08 476E-05 763E-06

08158 555E-05 322E-08 477E-05 776E-06

082557 557E-05 324E-08 478E-05 789E-06

083534 559E-05 325E-08 479E-05 801E-06

10308 597E-05 350E-08 492E-05 105E-05

10405 599E-05 351E-08 492E-05 106E-05

10503 600E-05 352E-08 493E-05 107E-05

10601 602E-05 354E-08 493E-05 109E-05

10698 603E-05 355E-08 493E-05 110E-05

10796 605E-05 356E-08 493E-05 111E-05

15681 652E-05 390E-08 484E-05 167E-05

15779 652E-05 391E-08 484E-05 168E-05

15877 653E-05 391E-08 483E-05 169E-05

15975 653E-05 392E-08 483E-05 170E-05

16072 654E-05 392E-08 482E-05 171E-05

1617 654E-05 393E-08 482E-05 172E-05

16268 655E-05 393E-08 481E-05 173E-05

16365 656E-05 394E-08 481E-05 174E-05

16463 656E-05 394E-08 480E-05 175E-05

16561 657E-05 395E-08 480E-05 176E-05

16658 657E-05 395E-08 479E-05 177E-05

16756 658E-05 395E-08 479E-05 178E-05

16854 658E-05 396E-08 479E-05 179E-05

16952 659E-05 396E-08 478E-05 180E-05

17049 659E-05 397E-08 478E-05 181E-05

17147 660E-05 397E-08 477E-05 182E-05

17245 660E-05 397E-08 477E-05 183E-05

17342 661E-05 398E-08 476E-05 184E-05

1744 661E-05 398E-08 476E-05 185E-05

17538 661E-05 399E-08 475E-05 186E-05

17636 662E-05 399E-08 474E-05 187E-05

17733 662E-05 399E-08 474E-05 188E-05

17831 663E-05 400E-08 473E-05 189E-05

17929 663E-05 400E-08 473E-05 190E-05

18026 664E-05 400E-08 472E-05 191E-05

18124 664E-05 401E-08 472E-05 192E-05

18222 664E-05 401E-08 471E-05 193E-05

18319 665E-05 401E-08 471E-05 194E-05

18417 665E-05 402E-08 470E-05 195E-05

18515 666E-05 402E-08 470E-05 195E-05

18613 666E-05 402E-08 469E-05 196E-05

28676 687E-05 423E-08 412E-05 275E-05

28774 687E-05 423E-08 411E-05 276E-05

28872 688E-05 423E-08 411E-05 277E-05

2897 688E-05 423E-08 410E-05 277E-05

29067 688E-05 424E-08 410E-05 278E-05

307

29165 688E-05 424E-08 409E-05 278E-05

29263 688E-05 424E-08 408E-05 279E-05

2936 688E-05 424E-08 408E-05 280E-05

29458 688E-05 424E-08 407E-05 280E-05

29556 688E-05 424E-08 407E-05 281E-05

29653 688E-05 424E-08 406E-05 281E-05

29751 688E-05 424E-08 406E-05 282E-05

29849 689E-05 424E-08 405E-05 283E-05

29947 689E-05 425E-08 405E-05 283E-05

30044 689E-05 425E-08 404E-05 284E-05

30142 689E-05 425E-08 404E-05 284E-05

3024 689E-05 425E-08 403E-05 285E-05

31705 690E-05 426E-08 396E-05 294E-05

31803 690E-05 426E-08 395E-05 294E-05

31901 690E-05 426E-08 395E-05 295E-05

34246 692E-05 428E-08 384E-05 308E-05

34343 692E-05 428E-08 383E-05 308E-05

34441 692E-05 429E-08 383E-05 309E-05

34539 692E-05 429E-08 382E-05 309E-05

35027 692E-05 429E-08 380E-05 312E-05

35125 692E-05 429E-08 379E-05 312E-05

35223 692E-05 429E-08 379E-05 313E-05

3532 692E-05 429E-08 379E-05 313E-05

35418 693E-05 429E-08 378E-05 314E-05

35516 693E-05 429E-08 378E-05 314E-05

36786 693E-05 430E-08 372E-05 321E-05

36884 693E-05 430E-08 372E-05 321E-05

40597 695E-05 432E-08 356E-05 338E-05

40694 695E-05 432E-08 356E-05 339E-05

40792 695E-05 432E-08 355E-05 339E-05

4089 695E-05 432E-08 355E-05 339E-05

40987 695E-05 432E-08 355E-05 340E-05

41085 695E-05 432E-08 354E-05 340E-05

41183 695E-05 432E-08 354E-05 341E-05

41281 695E-05 433E-08 353E-05 341E-05

41378 695E-05 433E-08 353E-05 341E-05

41476 695E-05 433E-08 353E-05 342E-05

41574 695E-05 433E-08 352E-05 342E-05

41671 695E-05 433E-08 352E-05 343E-05

41769 695E-05 433E-08 352E-05 343E-05

41867 695E-05 433E-08 351E-05 343E-05

41965 695E-05 433E-08 351E-05 344E-05

42062 695E-05 433E-08 350E-05 344E-05

44016 696E-05 434E-08 343E-05 352E-05

44114 696E-05 434E-08 343E-05 352E-05

44212 696E-05 434E-08 342E-05 353E-05

44309 696E-05 434E-08 342E-05 353E-05

44407 696E-05 434E-08 342E-05 354E-05

44505 696E-05 434E-08 341E-05 354E-05

44603 696E-05 434E-08 341E-05 354E-05

447 696E-05 434E-08 341E-05 355E-05

44798 696E-05 434E-08 340E-05 355E-05

44896 696E-05 434E-08 340E-05 355E-05

44993 696E-05 434E-08 340E-05 356E-05

45091 696E-05 434E-08 339E-05 356E-05

45189 696E-05 434E-08 339E-05 357E-05

45287 696E-05 434E-08 339E-05 357E-05

45384 696E-05 434E-08 338E-05 357E-05

45482 696E-05 434E-08 338E-05 358E-05

4558 696E-05 434E-08 338E-05 358E-05

45677 696E-05 434E-08 337E-05 358E-05

48804 697E-05 435E-08 327E-05 369E-05

48902 697E-05 435E-08 327E-05 370E-05

48999 697E-05 435E-08 326E-05 370E-05

49097 697E-05 435E-08 326E-05 370E-05

49195 697E-05 435E-08 326E-05 371E-05

49293 697E-05 435E-08 325E-05 371E-05

4939 697E-05 435E-08 325E-05 371E-05

49488 697E-05 436E-08 325E-05 372E-05

49586 697E-05 436E-08 324E-05 372E-05

49683 697E-05 436E-08 324E-05 372E-05

49879 697E-05 436E-08 323E-05 373E-05

49976 697E-05 436E-08 323E-05 373E-05







Abstract



1 Introduction










2 Experimental







+ 2OHminus(aq)

and





22 Kinetics





32 BOD5 and COD










Time sec

0 20 40 60

[BB

+ ] M

0

5e-6

1e-5

2e-5

2e-5

3e-5

3e-5



a

d










117 223 310 1909 375 790 88 2107234 513 135 2194 750 1595 43 2127351 739 94 2106 938 1929 36 2058468 1073 65 2294 1125 2411 29 2143585 1313 53 2244 150 3345 21 2230









0 1066 320 300210 1166 345 295920 1266 371 293130 1366 403 295140 1464 449 306650 1499 462 3082Mean= 2999plusmn 063


a k = kprime[HOCl]











4 Conclusions




Acknowledgements


References
















Coverpagepdf

Table of Contents

LIST OF FIGURES

CHAPTER1AND2FINAL



Conclusions

references

Appendix

PUBLICATION


Introduction

Experimental


Kinetics



BOD5 and COD


Conclusions

Acknowledgements

References










iii











iv

ACKNOWLEDGEMENTS












encouragement


and help





social environment



v

PUBLICATIONS




Oral Presentations



Dioxiderdquo




Local





International



vi

TABLE OF CONTENTS

Abstract xiv


List of tables xxvi


CHAPTER 1

11 Introduction 1


121 Ozonation 5

122 Chlorination 6










171 Acid dyes 16

vii

172 Direct dyes 17


174 Sulfur dyes 18


176 Basic dyes 20

177 Vat dyes 20



181 Azo dyes 25


183 Azine dyes 26










viii








1141 Simulations 45






CHAPTER 2

21 Experimental 52






ix










CHAPTER 3











x





3113 Rate law 99















3213 Rate law 125

xi















3313 Rate law 152


CHAPTER 4




xii












4113 Rate law 179









xiii







4213 Rate law 204














xiv


4313 Rate law 228


CHAPTER 5

Conclusions 231

References 237

Appendix 248

xv

ABSTRACT





















xvi




















xvii

LIST OF FIGURES













[AM-]0 (70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 51


















(70 x 10-5 M) with [OCl-]t (15 x 10-3 M)) 75

xviii



b = 170 c = 255 d = 340 and e = 510) at pH = 90 76



c = 0145 d = 0175 and e = 0322)) 77




(145 x 10-3 M) [H+]eq (199x10-9- 7752 x 10-4 M) 79


[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 81




and I (012 M)) 82




[H+]0 (996 x 10-9 M) and I (012 M) 83



775 x 10-3 M) [OCl-]eq (114 x 10-3 -153 x 10-6 M) 85



[OCl-]eq (276 x 10-2 -33 x 10-6 M) 85



strength (I = 0009 - 0039 M) 87

xix








(70 x 10-5 M) with [OCl-]t (145x10-3 M) 101


hypochlorite 102






(70 x 10-5 M) with [OCl-]t (15 x 10-3 M) 104



145 c = 218 d = 290 and e = 435) at pH 90 105



c = 0037 d = 0046 and e = 0086) 106









[OCl-]t (145 x 10-3 M) [H+]0 (996 x 10-9 M) and I (013 M) 111

xx




(996 x 10-9M) and I (012 M) 112



[OCl-]eq (114 x 10-3 -153 x 10-6M) 114



[HOClˉ]eq (276 x 10-2 -33 x 10-6 M) 114











hypochlorite 124


[BB+]0 (70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 128





519 nm 130



xxi


[OCl-]t (15 x 10-3 M) 131



170 c = 255 d = 340 and e = 510) at pH = 90 132



0027 c = 0034 d = 0043 and e = 0052) 133




[OCl-]t (145 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 135


[OCl-]t (145 x 10-3 M) [H+]eq (199x 10-9- 7752 x 10-4 M) 136



[OCl-]t (145 x 10- 3M) [H+] (996 x 10-9 M) and I (0128 M) 138



[OCl-]t (145 x 10-3 M) [H+] (996 x 10-9 M) and I (0128M) 138








0039 M) 144



fixed acid [H+] (45 x 10-3 M) 145

xxii






[SO+]0 (30 x10-5M) with [OCl-]t (145 x 10-3 M) 154


hypochlorite 155






C y = -A exp (-k x) + C) 157



379 c = 505 d = 631 and e = 757) at pH = 90 158




e = 480) 159




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9 - 7752 x 10-4 M) 162





[ClO2]t (115 x 10-3 M) [OH-]eq (10 x 10-8- 631 x 10-7 M) 166

xxiii










(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 181











c = 303 d = 328 and e = 353) 185



k s (a = 332 b = 374 c = 399 d = 422 and e = 467) 186




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 189


(115 x 10-3 M) 190

xxiv













(70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 206


(E2 S2) 207








(a = 252 b= 278 c= 303 d = 328 and e = 353) 210



(a = 252 b= 278 c = 303 d = 328 and e = 353) 211




[ClO2]t (115 x 10-3 M) [H+]eq (199 x 10-9- 7752 x 10-4 M) 214

xxv


with [ClO2]t (115 x 10-3 M) 214



[ClO2]t (115 x 10-3 M) [OH-]eq (18 x 10-8- 251 x 10-7 M) 217




[ClO2]t (115 x 10-3 M) at I (0009 - 004 M) 221


(115 x 10-3 M) 223


dioxide 226






xxvi

LIST OF TABLES






[OCl-]t (145 x 10-3 M) 81



[AM-]0 (70 x 10-5 M) pH = 90 87


[AM-]0 (70 x 10-5 M) [OCl-]t (145 x 10-3 M) pH = 310 88


with [OCl-]t (145 x 10-3 M) [Cl-] = 1x10-1M 89


(70 x 10-5 M) with [OCl-]t (145 x 10-3 M) 90



Simulations 107


[BB+]0 (70 x 10-5 M) [OCl-]t (0725 x 10-3 -435 x 10-3 M) pH = 90 107




[BB+]0 (70 x 10-5 M) pH = 90 116


[BB+]0 (70 x10-5 M) [OCl-]t (145 x 10-3 M) pH = 31 117


[OCl-]t (145 x 10-3 M) [Cl-] (1x10-1 M) 118




xxvii



simulations 126


strength 134


[OCl-]t (145 x 10-3) 135



[OCl-]t (145 x 10-3 M) pH =90 143


[OCl-]t (145 x 10-3M) pH = 40 145


(30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146


[SO+]0 (30 x 10-5 M) with [OCl-]t (145 x 10-3 M) 146




simulations 153








[ClO2]t (115 x10-3 M) 169


[ClO2]t (115 x 10-3 M) pH = 80 171



xxviii



(115 x 10-3 M) 173







[ClO2]t (25 x 10- 3-35 x10-3 M) 188




[BB+]0 (70 x 10-5 M) with [ClO2]t (115 x 10-3 M) 194


[ClO2]t (115 x 10-3 M) pH = 90 196





[ClO2]t (115 x 10-3 M) 198




simulations 205





xxix




[SO+]0 (30 x 10-5 M) with [ClO2]t (115 x10-3 M) 218


[ClO2]t (115 x 10-3 M) pH = 80) 220






simulations 229

xxx




I ionic strength



AM- amaranth




ClO2- chlorite

ClO3- chlorate

cm centimetre

activation enthalpy

activation entropy

e- electron


Exp exponential

g gram

gL gram per litre



HOCl hypochlorite

K Kelvin






L litre


M-1 s-1 mol L sec

mg milligrams

mL millilitre


ng nano gram

nm nano metre

xxxi






s second

SO+ safranine-O dye

t time


TM trade mark

UV ultraviolet

V volt

z ionic charge


1

CHAPTER 1

11 Introduction





















2
























3























4
























5













121 Ozonation








harmful compounds31

6






















7

122 Chlorination























with chlorine gas44

8
















formed








9
















produced on-site








10











streams5960












11






















12






















13
























14























15
























16


















171 Acid dyes






17



NSO3

-

NN

O

SO3-

H


172 Direct dyes








OH

H2N

N

SO3Na

N NHCONH N N

OH

SO3NaNaO3S

NH2


18

173 Disperse dyes










Figure 11394

NaO3SSO3Na

N

NOH

N

CH3

NaO3S N

N

Cl

N

Cl


174 Sulfur dyes






19



NO-O

N

O-

O

OH


175 Reactive dyes









NaO3SOCH2CH2O2S

OCH3

N N

OH

SO3Na


20

176 Basic dyes











Figure 11697

N

N CH3

NH2H2N

H3C


177 Vat dyes







21



O

O HN

O

ONH

OO














22

























23























24























25



is given below


181 Azo dyes


















26














183 Azine dyes







27







3 OCl- = ClO3- + 2 Cl- (19)

OCl (110)




OCl- + ClO2- ClO3

- + Cl- (fast) (112)












28





stoichiometry128

2 HOCl + OCl- ClO3- + 2 H+ + 2 Cl- (114)


















29



visible light131132








In alkali

OCl- + H2O + 2e- Cl- + 2OH- (115)

In acid

OCl- + 2H+ + 2e- Cl- + H2O (116)







30


pH [OCl-] [HOCl]

20 045 9955

30 121 9879

40 323 9677

50 832 9168

60 1978 8022

70 4013 5987

80 6457 3543

90 8320 1680

100 9309 691













lights

31












ClO2 + 4H+ + 4e- rarr Cl- + 2H2O (118)




-144145


- 137


- + H2O (119)





- (036 to 097 mgL)


32


not contain ClO3-






- (121)
















33





















34

















rarr (124)



(125)


35


(126)


(127)


ln

(128)


129 to 130)

ln ln (129)

or

(130)








36

(131)




(132)

(133)




(134)


(135)


0 (136)


(137)


which implies that

(138)


37

(139)


(140)


(141)

which affords

(142)


ln ln (143)


ndash (kf + kb)



(144)


(145)



38






For the reaction

rarr

(146)


(147)




(148)









39


ndash ndash

(151)


x

ndash x ndash x

(152)


ln ndash

(153)

1ln (154)









conditions


=


(155)

40








(156)







(157)




(158)

and

(159)

41

At equilibrium

(160)


0 (161)

This implies that

(162)


as

(163)

Resulting in

(164)


(165)


(166)


(167)

Which results in

42

ln

(168)








rarr rarr

(169)


(170)

(171)

(172)


for has two terms


[A] [A]0 [B]0 = 0 [C]0 = 0 (173)

and at any time t

43

(174)


(175)


(176)



(176) yields

(177)




1

(178)






44















(181)







45







1131 Simulations









circumstances161







46
























47













constant








48



















49




















50













51





52

CHAPTER 2

21 Experimental















N N SO3-

O-

-O3S

-O3S


53













‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

54

NSO3

-

NN

O

SO3-

H









0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorabnce

Wavelength (nm)

55






N

N CH3

NH2H2N

H3C






‐01

0

01

02

03

04

05

06

07

08

300 400 500 600 700 800 900

Absorban

ce

Wavelength (nm)

56
















57









air


Anode 2Cl- (aq) Cl2 (g) + 2e- (21)



58





















59















2 OCl- + As2O3 As2O5 + 2 Cl- (25)








60


















61
















mgmL ClO

A B N 1349

mL sample titrated

(26)

mgmL Cl

A B N 3545

mL sample titrated

(27)


mgL ClO

A B N 13490

mL sample

(28)

62

mgL Cl

A B N 35450

mL sample

(29)





















63











64


65


66


67


68























69























70
























71





x1 x2 x3 xn-1 xn


ā = x1 + x2 + x3 + + xn-1 + xn

n (210)



n ndash 1 (211)




n ndash 1


form

12

N1 N2 N3



i=1 j=1 k=1

N1 + N2 + N3 + - Ns

(212)



72

2110 Variance (s2)








CV = (s ā) x 100








73

CHAPTER 3





















74


(15 x 10-3 M) at pH = 90 and 520 nm












‐01

0

01

02

03

04

05

06

07

08

0 20 40 60 80 100 120 140

Absorban

ce

Times

75


(15 x 10-3 M)














76






‐01

0

01

02

03

04

05

06

0 20 40 60 80 100 120

Absorban

ce

Time s

a

b

c

de

77

(a) (b)

(c) (d)

(e)


78



and pH equals to 90


[OCl-]t 10-3 M ks-1

050 0041

170 0093

255 0145

340 0175

510 0322



y = 11072x + 46582Rsup2 = 09928

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4

lnk`

ln [OCl‐]t

79















0

01

02

03

04

05

06

07

08

09

1

3 4 5 6 7 8 9 10

k

pH

80


pH ks-1

989 0005

972 0011

945 0015

912 0021

881 0028

863 0039

815 0110

784 0199

755 0320

739 0398

693 0599

685 0638

650 0745

485 0847

420 0854

365 0865

344 0875

317 0878

315 0897






81














y = 02711x + 37842Rsup2 = 09618

‐12

‐1

‐08

‐06

‐04

‐02

0

‐20 ‐15 ‐10 ‐5 0

ln k

acute

ln [H+]

82




313






83










84


respectively



-1 k1M-1s-1 k2M

-1s-1

863 234 x 10-9 340 x 10-3 194 x 10-3 80 x 10-2 0039 234 1990

815 706 x 10-9 307 x 10-3 530 x 10-3 71 x 10-2 0110 232 2077

784 144 x 10-8 266 x 10-3 938 x 10-3 65 x 10-2 0199 247 2132

755 281 x 10-8 213 x 10-3 147 x 10-2 52 x 10-2 0320 245 2183

739 406 x 10-8 180 x 10-3 179 x 10-2 47 x 10-2 0398 261 2219

693 117 x 10-7 930 x 10-4 267 x 10-2 25 x 10-2 0599 273 2244

685 141 x 10-7 810 x 10-4 279 x 10-2 17 x 10-2 0638 216 2288

650 315 x 10-7 410 x 10-4 319 x 10-2 80 x 10-3 0745 199 2338

485 141 x 10-5 100 x 10-5 359 x 10-2 20 x 10-5 0847 176 2360

420 630 x 10-5 234 x 10-5 360 x 10-2 39 x 10-5 0854 168 2375

365 224 x 10-5 659 x 10-6 360 x 10-2 10 x 10-5 0864 159 2402

344 363 x 10-5 406 x 10-6 360 x 10-2 57 x 10-6 0875 143 2431

317 675 x 10-5 218 x 10-6 360 x 10-2 26 x 10-6 0878 123 2439

315 707 x 10-5 208 x 10-6 360 x 10-2 25 x 10-6 0897 122 2493

314 723 x 10-5 204 x 10-6 360 x 10-2 24 x 10-6 0912 119 2535


plusmn 06 232

plusmn 18





85






3111





y = 10717x + 11753Rsup2 = 09996

‐16

‐14

‐12

‐10

‐8

‐6

‐4

‐2

0

‐15 ‐10 ‐5 0

ln k

acute

ln [OCl‐]eq

y = 09297x + 28534Rsup2 = 09958

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐8 ‐7 ‐6 ‐5 ‐4 ‐3

ln k

ln [HOCl]eq

86













rate











87





-1

00092 0043 0047

00167 0050 0048

00242 0052 0048

00317 0054 0050

00392 0059 0051




y = 12169x ‐ 14689Rsup2 = 09833

y = 07935x ‐ 31338Rsup2 = 09402

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

005 01 015 02

ln k

radicI

88











00167 0048

00242 0048

00317 0050

00392 0051



y = 01333x + 00459Rsup2 = 09544

004650047

004750048

004850049

00495005

005050051

00515

0 001 002 003 004 005

k

IM

89





HOCl as anticipated








Table 316


[Cl-]M ks-1 0100 0107 0148 0109 0298 0107 0447 0104 0597 0104 0725 0104




90














-1 kM-2 s-1

283 0015 130 0033 287

288 0016 139 0052 452

293 0017 139 0060 522

298 0025 217 0072 626

303 0031 269 0091 791



91



(Figure 3114)






Hǂk J mol-1


SǂJ K-1 mol-1


Eak J mol-1




y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

92























93




mz 130(M-2)




O

NaO3S

NaO3S

OH

Na+

(P1)


sodium salt

OO

Cl Cl

(P2)


OO

O

(P3)


94
























95











+ Na+ + N2 + H3O+ + 3HCl (31)











96










97

N

ONaSO3

NaO3S

H

N SO3Na N

NaO3S

NaO3S

N SO3Na

OHO Cl

I1

N

NaO3S

NaO3S

N SO3Na

OO

H

HOCl

H+O

HH

ONaO3S

NaO3S

N

O H

SO3NaN

I3

I2

O

NaO3S

NaO3S

OH

P1

+ SO3NaNN

O

HH

I4

NN O H

H

Cl O

H

I5

HOCl

-N2Cl O O H

I6

OO

I7

HOCl OO

O

Cl2OO

Cl Cl P3P2

H+-

N

ONaO3S

N SO3Na

OHH

NaO3S


98





H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2


I1 + H+ rarr I2+


+

I3 + H2O + H+ rarr P1 + I4+

I4+ + H2O rarr I5

+ + Na+ + SO32- + H+


I6 rarr I7 + HCl

I7 + Cl2 rarr P2


R1

R2

R3

R4

R5

R6

R7

R8

R9



+ Na+ + N2 + 3HCl (32)

3113 Rate law





99











(33)

(34)



(35)

3114 Simulations






100







C1 H+ + OCl- HOCl 397 x 10-4 M-1s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1s-1 11 s-1



C5 I1+ H+ rarr I2+ 430 x 109 M-1s-1 --


+ 415 x 109 M-2s-1 --

C7 I2+ rarr P1 + I5

+ + Na+ + SO32- + H+ 301 x108 s-1 --


C9 I7 + Cl2 rarr P2 435 x 108 M-1s-1 --








101



000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 20 40 60 80 100 120 140

ConcentrationM

Times

E1 S1

E2 S2

E3 S3

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 5 10 15 20 25 30

Concentration M

Times



Intermediates(I)



102











103










(15 x 10-3) at pH = 90 and 555 nm






0

01

02

03

04

05

06

07

0 20 40 60 80 100

Absorban

ce

Times

104













105








0

01

02

03

04

05

06

07

08

0 50 100 150 200 250 300

Absorban

ce

Time s

(a)

(b)

(c)

(d)(e)

106

(a) (b)

(c) (d)

(e)


107




[OCl-]t 10-3 M ks-1 073 0012 145 0030 218 0037 290 0046 435 0086








y = 10323x ‐ 0408Rsup2 = 09746

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐5 ‐4 ‐3 ‐2 ‐1 0

ln k

ln [OCl‐]t

108







(145 x 10-3 M) with [H+]e (199 x 10-9- 7752 x 10-4 M)





322

0

01

02

03

04

05

06

07

08

2 4 6 8 10

k

pH

109


pH ks-1

900 00347

870 00345

835 00411

800 00491

770 00574

745 00640

720 00780

700 01018

675 01226

650 01425

600 02027

540 03160

370 05900

331 06704

329 06955

322 07093

311 07309






110








y = 02414x + 15266Rsup2 = 09858

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

‐25 ‐20 ‐15 ‐10 ‐5 0

ln k

ln [H+]

111







112











113



-1 k1M-1s-1 k2M

-1s-1

870 199 x 10-9 276 x 10-2 134 x 10-3 00390 00270 141 2008

835 445 x 10-9 261 x 10-2 285 x 10-3 00360 00610 137 2143

800 997 x 10-9 233 x 10-2 568 x 10-3 00303 01400 129 2464

770 199 x 10-8 195 x 10-2 949 x 10-3 00250 02050 128 2161

745 354 x 10-8 155 x 10-2 134 x 10-2 00190 02799 122 2081

720 629 x 10-8 114 x 10-2 176 x 10-2 00135 03670 118 2088

700 997 x 10-8 843 x 10-3 206 x 10-2 00094 04275 112 2079

675 177 x 10-7 543 x 10-3 236 x 10-2 00060 04930 110 2092

650 315 x 10-7 332 x 10-3 257 x 10-2 00035 05390 105 2100

600 998 x 10-7 114 x 10-3 279 x 10-2 00011 05880 100 2111

540 397 x 10-6 294 x 10-4 287 x 10-2 00002 06459 084 2250

370 199 x 10-4 595 x 10-6 290 x 10-2 -- 06582 -- 2270

331 489 x 10-4 242 x 10-6 290 x 10-2 -- 06652 -- 2294

329 512 x 10-4 232 x 10-6 290 x 10-2 -- 06725 -- 2319

322 602 x 10-4 197 x 10-6 290 x 10-2 -- 06842 -- 2359

311 775 x 10-4 153 x 10-6 290 x 10-2 -- 06910 -- 2383









114


30 to 90


[OClˉ]eq (114 x 10-3 ndash 153 x 10-6 M)








y = 1101x + 09865Rsup2 = 09135

‐01

6E‐16

01

02

03

04

05

06

‐5 ‐45 ‐4 ‐35 ‐3

ln k

`

ln [OCl‐]eq

y = 1034x + 32194Rsup2 = 09979

‐4

‐35

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐7 ‐6 ‐5 ‐4 ‐3 ‐2

ln k

`

ln [HOCl]eq

115




















116



-1

00099 0035 00452

00188 0035 00459

00225 0037 00471

00263 0038 00485

00338 0040 00499







y = ‐10346x ‐ 11666Rsup2 = 09931

y = ‐07456x ‐ 11354Rsup2 = 09937

‐148

‐146

‐144

‐142

‐14

‐138

‐136

‐134

‐132

‐13

‐128

022 023 024 025 026 027 028

log k

radicI

A

B

117


shown in Table 325


(145 x 10-3 M) pH = 31


00510 161

00547 157

00585 155

00622 153

00697 150








y = 57679x + 12139Rsup2 = 09752

148

15

152

154

156

158

16

162

164

003 004 005 006 007 008

k

IM

118





reaction


[Cl-]M ks-1 0000 0125 0148 0126 0298 0126 0447 0126 0597 0127 0725 0127










same

119



-1 kM-2 s-1

283 0014 121 0041 356

288 0019 165 0058 504

293 0028 165 0064 556

298 0033 286 0079 686

303 0037 321 0098 852




y = ‐32326x + 11578Rsup2 = 08397

y = ‐40483x + 15448Rsup2 = 09598

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

120



HǂkJ mol-1


SǂJK-1 mol-1


EakJ mol-1








compact nature













121











(C7H9N)












122















NH2

O

(P1)


N

SO3H

H

(P2)


123

NSO3H

Cl

(P3)


acid

OH OH

OH

(P4)









+ 3HCl + OH- + H+ (36)






124


formation of P4

NSO3

-

NN

O

SO3-

H

HOCl

NSO3H

NN

O

SO3H

HH

-OCl

NSO3H

N

SO3H

ClO

NH2

O

HOCl

-OCl

NSO3H

ClO OCl

N

SO3H

H

ClO OCl

NSO3H

ClO

OCl-

HO Cl

ClO OCl

OCl

NSO3H

Cl

H+OH-

OH OH

OH

+

SO3H

NSO3H

NClO H

P1I1

I2I3

P2

I5

P4

P3

I4


125




H+ + OCl- HOCl

HOCl + Cl- + H+ Cl2


I1+ + HOCl rarr I1

2+ + OCl- R2

I22+ + OCl- rarr I3

+ + P2 R3



I3+ + 3H2O rarr P4

+ + 3HCl R6



+ 3HCl + OH- + H+

(37)

3213 Rate law



(38)



(39)

126

(310)

and where (311)

(312)

3214 Simulations











curves203


Reaction

No


Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-2 s-1 11 s-1


127

Table 3210 contd

Reaction

No


Reverse rate

C5 BB+ + OCl- rarr I1 122 M-1 s-1 --

C6 I1 + H+ rarr I1+ + P1 330 x 109 M-1 s-1 --


2+ + OCl- 230 x 109 M-1 s-1 --


+ + P2 430 x 109 M-1 s-1 --



C11 I3+ rarr P4

+ + 3HCl 417 x 108 s-1 --








128





0

000001

000002

000003

000004

000005

000006

000007

0 50 100 150 200 250

ConcentrationM

Times

E1S1

E2S2

E3S3



129








0

000001

000002

000003

000004

000005

000006

000007

0 10 20 30 40 50 60 70

ConcentrationM

Times


Intermediates (I)


130

















0

01

02

03

04

05

06

0 50 100 150

Absorban

ce

Times

131


(15 x 10-3 M)










132








‐01

6E‐16

01

02

03

04

05

06

07

0 50 100 150 200 250 300

Absorban

ce

Time s

(b)(c)(d)(e)

(a)

133

(a) (b)

(c) (d)

(e)





134


[OCl-]t 10-3 M ks-1

0085 0010

170 0026

255 0034

340 0043

510 0052









y = 09193x + 20384Rsup2 = 09533

‐5

‐45

‐4

‐35

‐3

‐25

‐2

‐15

‐8 ‐7 ‐6 ‐5 ‐4

ln k´

ln [OCl‐]t

135







pH ks-1

873 008

826 012

786 023

754 044

722 054

710 082

668 125

664 221

450 1975

‐45

05

55

105

155

205

255

305

355

405

275 375 475 575 675 775 875

k

pH

136

Table 332 contd

pH ks-1

390 2827

351 3256

361 3347

315 3571

313 3699

295 3964

285 4087






(Figure 337)


y = 04715x + 7247Rsup2 = 09727

‐3

‐2

‐1

0

1

2

3

4

5

‐20 ‐15 ‐10 ‐5

ln k

ln[H+]

137

















138






139








y = 1013x + 33473Rsup2 = 09936

‐3

‐25

‐2

‐15

‐1

‐05

0

05

‐6 ‐55 ‐5 ‐45 ‐4 ‐35 ‐3

ln k

ln[HOCl]eq

y = 05112x ‐ 2502Rsup2 = 09709

‐25

‐15

‐05

05

15

25

35

‐13 ‐11 ‐9 ‐7 ‐5 ‐3 ‐1

ln k

ln[OCl]eq

140



-1 k1M-1 s-1 k2M

-1 s-1

873 186 x 10-9 156 x 10-3 340 x 10-2 0064 0093 195 2922

826 548 x 10-9 440 x 10-3 310 x 10-2 0066 0127 209 2999

786 138 x 10-8 921 x 10-3 260 x 10-2 0058 0276 217 3048

754 288 x 10-8 150 x 10-2 210 x 10-2 0053 0458 254 3087

722 601 x 10-8 215 x 10-2 140 x 10-2 0040 0676 279 3157

710 792 x 10-8 239 x 10-2 120 x 10-2 0035 0761 291 3209

668 208 x 10-8 301 x 10-2 590 x 10-2 0018 0985 318 3274

664 228 x 10-8 306 x 10-2 545 x 10-2 -- 107 -- 3528

405 890 x 10-5 360 x 10-2 164 x 10-5 -- 129 -- 3596

390 126 x 10-4 360 x 10-2 120 x 10-5 -- 130 -- 3624

351 309 x 10-4 360 x 10-2 455 x 10-6 -- 133 -- 3713

361 245 x 10-4 360 x 10-2 589 x 10-6 -- 136 -- 3780

315 707 x 10-4 360 x 10-2 203 x 10-6 -- 138 -- 3831

313 740 x 10-4 360 x 10-2 198 x 10-6 -- 141 -- 3922

295 112 x 10-3 360 x 10-2 134 x 10-6 -- 143 -- 3974

285 141 x 10-3 360 x 10-2 107 x 10-6 -- 144 -- 4005










141










as follows

(313)



(314)

Thus


(316)




(317)

142















(318)

(319)

(320)

and



143











y = 71649x + 31127Rsup2 = 09658

32

33

34

35

36

37

38

39

40

41

00002 00004 00006 00008 0001 00012 00014

k

[H+]eq

144



-1 00092 0047 063

00167 0042 062

00242 0039 060

00317 0037 056

00392 0034 054








and SO+

y = ‐12866x ‐ 1202Rsup2 = 09955

y = ‐07248x ‐ 01187Rsup2 = 09181

‐16

‐14

‐12

‐1

‐08

‐06

‐04

‐02

0

008 01 012 014 016 018 02

log kacute

radicI

B

A

145









00167 062

00242 060

00317 056

00392 054



y = ‐34x + 06745Rsup2 = 09635

052

054

056

058

06

062

064

066

0005 001 0015 002 0025 003 0035 004

k

IM

146








value (Table 336)


[Cl-]M ks-1 0000 0901 0148 0901 0298 0902 0447 0902 0597 0902 0725 0903








147





-1 kM-2 s-1

283 0019 172 0049 426

288 0022 200 0062 539

293 0037 336 0075 652

298 0041 372 0082 713

303 0051 463 0098 852



y = ‐44611x + 16295Rsup2 = 09509

y = ‐28627x + 11599Rsup2 = 09829

0

05

1

15

2

25

000325 00033 000335 00034 000345 00035 000355

ln k

1T

A

B

148



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1





















in Table 339

149


H3C

H2N

OCl

OCl

(P1)


N

N CH3

NH2

OH

ClOH

(P2)



dienone oxime











150





















1 Figure 1116)


Figure 3316

151

N

N CH3

NH2H2N

H3C

OCl-N

N CH3

NH2H2N

H3C

OCl

H

N

N CH3

NH2

H

N

N CH3

NH2

OH

ClOH

H3C

H2N

OCl

OCl

OCl

N

N CH3

NH2

OH

H

I1

P1

I2

I3

P2

H+

HO Cl

HOCl

Cl- +

+ H+





+ R1




152





3313 Rate law







be proposed as

(323)

3314 Simulations








153





Reaction

No

Reaction Mechanism

Forward rate

Reverse rate

C1 H+ + OCl- HOCl 397 x 10-4 M-1 s-1 10 x 10-4 s-1

C2 HOCl + Cl- + H+ Cl2 363 x 10-3 M-1 s-1 11 s-1


C4 SO+ + OCl- rarr I1 302 M-1 s-1 --

C5 I1 + H + rarr I1+ 23x 109 M-1 s-1 --









154






0

0000005

000001

0000015

000002

0000025

0 50 100 150 200

ConcentrationM

Times



E2S2

E3S3

E1 S1

155








16)

000E+00

500E‐06

100E‐05

150E‐05

200E‐05

250E‐05

0 20 40 60 80 100

Concentration M

Time s

Products (P1P2)


Intermediates (I)

156

CHAPTER 4





















157





fitted curve



005

015

025

035

045

055

065

075

0 05 1 15 2

Absorban

ce

Times

158













10-3 M (a = 252 b = 379 c = 505 d = 631 and e = 757) at pH = 90

0

01

02

03

04

05

06

07

08

09

0 05 1 15 2

Absorban

ce

Times

a

b

cd

e

159




(a) (b)

(c) (d)

(e)


160






[ClO2] 10-3 M ks-1

252 3320

379 3740

505 3990

631 4340

757 4800



y = 10719x ‐ 07905Rsup2 = 09967

04

06

08

1

12

14

16

18

125 145 165 185 205 225

ln [ClO2] t

ln kacute

161



[ClO2]0














from 60 to 90

162



pH ks-1

60 0409

64 0411

66 0411

68 0480

70 0490

72 0946

74 1552

76 1928

78 2250

80 2500

04

09

14

19

24

29

34

6 65 7 75 8 85 9

k

pH

163


82 2790

84 2910

86 3150

88 3290

90 3310










y = 08321x + 12573Rsup2 = 08844

‐4

‐3

‐2

‐1

0

1

2

‐185 ‐175 ‐165 ‐155 ‐145 ‐135 ‐125

ln k

ln(OH‐)

164









(41)







y = 10825x + 72892Rsup2 = 09915

y = 06802x + 45703Rsup2 = 08898

y = 01227x + 11484Rsup2 = 09362

‐2

‐15

‐1

‐05

0

05

1

15

2

‐8 ‐6 ‐4 ‐2 0

log k

log[OH‐]

165








794 x 10-9 008 03

158 x 10-8 012 05

251 x 10-8 015 10

631 x 10-8 017 18

178 x 10-7 049 33

631 x 10-7 130 63

316 x 10-6 430 104

794 x 10-6 580 129


166














y = 4E+09xRsup2 = 09711

0

200

400

600

800

1000

1200

1400

1600

‐1E‐07 358E‐20 1E‐07 2E‐07 3E‐07 4E‐07 5E‐07

kM

‐2s‐1

[OH‐]M

167





-+ H2O (43)














HOO- + 2ClO2 + OH- 2ClO2- + H2O (47)



168





















169


pH = 70

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 049 1944 194 x 108

277 078 2058 206 x 108

303 093 1841 184 x 108

328 130 2060 206 x 108

353 150 1981 198 x 108


pH = 80

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 250 9920 99 x 107

277 260 9386 94 x 107

303 290 9570 96 x 107

328 320 9756 98 x 107

353 350 9915 99 x 107


pH = 90

[ClO2] x 10-3 M k s-1 k2M-1s-1 k

252 332 13174 13 x 107

278 374 13453 13 x 107

303 399 13168 13 x 107

328 422 12865 13 x 107

353 480 13597 14 x 107



170





mechanism








y = 10131x + 30233Rsup2 = 09891

y = 10371x + 47055Rsup2 = 09724

y = 10193x + 49541Rsup2 = 09759

‐1

‐05

0

05

1

15

2

25

‐39 ‐37 ‐35 ‐33 ‐31 ‐29 ‐27 ‐25

ln k

ln [ClO2]

a

b

c

171



00096 311

00174 341

00262 357

00354 375

00397 395






AM-

y = 09499x + 04017Rsup2 = 09814

048

05

052

054

056

058

06

008 01 012 014 016 018 02

log k

radicI

172






[Cl-]M ks-1

0148 0486

0298 0496

0447 0502

0597 0512

0725 0530












173


417


TK ks-1 k3 M-2 s-1

283 0050 333 x 106

288 0090 600 x 106

293 0120 800 x 106

298 0170 110 x 107

303 0210 140 x 107





y = ‐60224x + 3641Rsup2 = 09739

148

15

152

154

156

158

16

162

164

166

168

000325 00033 000335 00034 000345 00035 000355

ln k

1T

174



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

AM- with ClO2 4758 -65873 5006














175









2- + Na+ (49)


HO3S

NaO3S

O

O

(P1)


O O

(P2)


176


















Figure 4113

177

N N SO3Na

OHNaO3S

NaO3S

ClO2 N N SO3Na

OH-O3S

NaO3S

N N SO3Na

OHO3S

NaO3S

I1

N

HO3S

NaO3S

N SO3Na

O

-OH

-OH

HO3S

NaO3S

O

N N SO3Na

OH ClO23

HO3S

NaO3S

O

N

O

N SO3Na

H

HO3S

NaO3S

O

O

SO3NaNN

-OH-OH

SO3NaOH

OHOH

-OH

H

I2I3

P1

P2

-OH

H+ +

I4

O O


178





- + AM (very slow)



HO AM ClO2



- R1


- R2

I2 + ClO2rarr I3+

+ ClO2- R3

I3+ + ClO2rarr I4

2+ + ClO2- R4

I42+ rarr P1 + I5

+ + H+ + N2 R5

I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ R6



SO32-

+ Na+

(410)

179

4113 Rate law








as


where kOH-k2

[OH-]



k AM-


k = k1 + kOH- [OH-][ClO2] (414)

180

4114 Simulations













- 40 x 109 M-1s-1


+ ClO2- 534 x 109 M-1 s-1

C4 I3


-

4 97 x 109 M-1s-1


+ + H+ + N2 4 54 x 109 s-1

C6 I5+ + H2O rarr P2 + 2H+ + SO3

2- + Na+ 517 x 109 M-1s-1

181






000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Time s

E1 S1 E2 S2

E3 S3



182







000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

‐1 0 1 2 3 4 5 6 7

Concentration M

Times


Intermediates(I)


183










0

01

02

03

04

05

06

07

08

0 2 4 6 8 10

Absorban

ce

Time (sec)

184










185









‐01

6E‐16

01

02

03

04

05

06

07

0 1 2 3 4 5

Absorban

ce

Time ( Sec)

c

b

d

e

186

(a) (b)

(c) (d)

(e)


187



in the Table 421


[ClO2]t 10-3 M ks-1 252 332 278 374 303 399 328 422

353 467







y = 10308x ‐ 49235Rsup2 = 09865

‐37

‐365

‐36

‐355

‐35

‐345

‐34

‐335

‐33

119 129 139 149

ln[ClO

2] t

ln k

188






pH ks-1

60 029

63 032

67 038

69 047

72 082

74 096

79 134

81 160

82 169

84 171

86 179

88 175

90 186





189






02

04

06

08

1

12

14

16

18

2

6 65 7 75 8 85 9

k

pH

190







y = 08011x + 11389Rsup2 = 09487

04

06

08

1

12

14

‐135 ‐13 ‐125 ‐12

ln k

ln(OH‐)

y = 02213x + 12206Rsup2 = 09432

y = 04638x + 29978Rsup2 = 09704

y = 08011x + 49463Rsup2 = 09487

‐08

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐8 ‐75 ‐7 ‐65 ‐6 ‐55 ‐5

log k

log [OH‐]

191





















192


[OH-]0M ks-1 k 102 M-1s-1

100 x 10-8 029 193

200 x 10-8 032 213

257 x 10-8 035 237

501 x 10-8 038 253

794 x 10-8 047 314

132 x 10-7 062 413

195 x 10-7 082 546







193






products


OH-] (417)






y = 2E+09x + 17235Rsup2 = 09947

100

150

200

250

300

350

400

450

500

550

600

‐5E‐08 18E‐21 5E‐08 1E‐07 15E‐07 2E‐07

kM

‐2s‐1

[OH‐]

194


pH = 70

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 029 1150 115 x 108

277 044 1160 116 x 108

303 059 1168 117 x 108

328 075 1188 119 x 108

353 091 1202 120 x 108


pH = 80

[ClO2] x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 108 4285 430 x 107

277 115 4151 420 x 107

303 124 4092 410 x 107

328 138 4207 420 x 107

353 141 3994 400 x 107


pH = 90

[ClO2]x 10-3M ks-1 k2M-1s-1 k3 M

-2s-1

252 298 11825 118 x 107

278 324 11510 115 x 107

303 352 11551 115 x 107

328 381 11585 115 x 107

353 425 11898 118 x 107




195










Table 425

y = 1039x + 25823Rsup2 = 09999

y = 08489x + 3195Rsup2 = 09763

y = 1016x + 48161Rsup2 = 09881

‐15

‐1

‐05

0

05

1

15

2

25

3

‐4 ‐35 ‐3 ‐25 ‐2

ln k

ln [ClO2]

A

B

C

196



00096 0091

00174 0095

00262 0105

00354 0109

00397 0111







y = 09016x ‐ 11324Rsup2 = 0974

‐106

‐104

‐102

‐1

‐098

‐096

‐094

009 011 013 015 017 019

logk

radicI

197





salt


[Cl-]M ks-1

0148 0720

0298 0730

0447 0710

0597 0710

0725 0720









198


TK ks-1 k3 M-2s-1

283 0100 70 x 106

288 0136 90 x 106

293 0172 11 x 107

298 0260 17 x 107

303 0329 22 x 107






y = ‐51842x + 34016Rsup2 = 0992

156

158

16

162

164

166

168

17

000325 00033 000335 00034 000345 00035 000355

ln k

1T

199



HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

BB+ with ClO2 4758 -67636 5006

















200



















201


N

O

H

COOH

(P1)


N

SO3

NSO3

(P2)










hydroxylamine

202






amine analog P2


Figure 4213

203

NSO3

N

O

H

N

SO3

ClO2

N

O

H

N

SO3

NSO3

OH

N

O

H

N

SO3

NSO3

N

O

H

N

SO3

NSO3

O

H

OH

N

O

H

N

SO3

O

NSO3

HO-N

O

H

COOH

N

SO3

NSO3

I1

I2

P1 P2

ClO2








- + HO BB+

Rate limiting step

(420)

204



- R1


R2




4213 Rate law






k1[ClO2][BB+ ] + k2 [ClO2][OH-] [BB+

] (423)


as


205

where kOH-k2

[OH-]

r k1 + kOH- [OH-][ClO2] [BB+] (425)


k [BB+] (426)


k = k1 + kOH- [OH-] ClO2 (427)

4214 Simulations









- 172 x 102 M-1 s-1


200 x 109 M-2 s-1


206






0

000001

000002

000003

000004

000005

000006

000007

000008

0 5 10 15 20 25

Concentration M

Times

E1S1

E2S2

E3S3


207









24)

000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

0 2 4 6 8 10 12

Concentration M

Time s

Products (P1P2 P3)


Intermediates (I)

208












0

01

02

03

04

05

06

07

08

09

0 2 4 6 8 10 12

Absorban

ce

Time (sec)

209












210


10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)




0

01

02

03

04

05

06

07

08

0 1 2 3 4 5

Absorban

ce

Time s

ecb

a

d

211

(a) (b)

(c) (d)

(e)


10-3 M (a = 252 b = 278 c = 303 d = 328 and e = 353)



212


[ClO2]t 10-3 M ks-1

252 2100

278 2310

303 2610

328 2820

353 3010




[ClO2]0


y = 1097x + 4779Rsup2 = 0994

06

07

08

09

1

11

12

13

14

15

16

‐37 ‐36 ‐35 ‐34 ‐33

ln k

ln [ClO2]t

213

434 Effect of pH





pH ks-1

60 0405

63 041

66 0421

68 0475

70 0499

72 0956

74 1752

76 1828

78 211

80 245

82 269

84 281

86 325

88 349

90 361




higher pH range

214









0

05

1

15

2

25

3

35

4

45

5

6 65 7 75 8 85 9

ks

‐1

pH

215








y = 081x + 11269Rsup2 = 0953

0

05

1

15

2

25

‐135 ‐13 ‐125 ‐12 ‐115 ‐11

ln k

ln(OH‐)

y = 01651x + 08533Rsup2 = 09089

y = 01944x + 13006Rsup2 = 09979

y = 0809x + 48942Rsup2 = 0953

‐06

‐04

‐02

0

02

04

06

08

1

‐85 ‐75 ‐65 ‐55 ‐45

log k

log [OH‐]

216








= k1 +KkOH- [OH-][ClO2] [SO+] (429)

= k [ClO2] [SO+] (430)













217


[OH-]eq k k 102M-1s-1

182 x 10-8 0369 246

251 x 10-8 0411 274

398 x 10-8 0411 274

631 x 10-8 0480 320

100 x 10-7 0490 326

158 x 10-7 0946 630

251 x 10-7 1052 701




y = 2E+09x + 19826Rsup2 = 0915

0

100

200

300

400

500

600

700

800

0 5E‐08 00000001 15E‐07 00000002 25E‐07 00000003

kM

‐2s‐1

[OH‐] M

218













Table 434


pH = 70

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 049 1944 194 x 108

278 059 2122 212 x 108

303 065 2145 215 x 108

328 069 2104 21 0x 108

353 074 2096 21 0x 108


219

Table 434 contd

pH = 80

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 115 4563 456 x 108

278 135 4856 486 x 108

303 145 4785 479 x 108

328 160 4878 488 x 108

353 175 4972 497 x 108


pH = 90

[ClO2]t x 10-3M ks-1 k2M-1s-1 k3M

-2s-1

252 190 7540 754 x 108

278 208 7482 748 x 108

303 222 7327 733 x 108

328 250 7622 762 x 108

353 280 7932 793 x 108





y = 11338x + 47969Rsup2 = 09766

y = 12126x + 4618Rsup2 = 09907

y = 1181x + 36698Rsup2 = 09632 ‐1

‐05

0

05

1

15

‐37 ‐36 ‐35 ‐34 ‐33 ‐32

ln k

ln[ClO2]

220










ionic strength



00096 0126

00174 0109

00262 0105

00354 0096

00397 0093


221










y = ‐12368x ‐ 07853Rsup2 = 09731

‐104

‐102

‐1

‐098

‐096

‐094

‐092

‐09

‐088

009 011 013 015 017 019

log k

radicI

222


IM ks-1

0060 0153

0061 0155

0062 0160

0063 0175

0064 0176








pH 90

TK ks-1 k3 M-2s-1

283 125 83 x 107

288 152 10 x 108

293 179 12 x 108

298 193 13 x 108


223




HǂkJ mol-1


SǂJ K-1 mol-1


EakJ mol-1

SO+ with ClO2 1508 -74836 1755





y = ‐21128x + 2575Rsup2 = 09501

182

183

184

185

186

187

188

189

000325 00033 000335 00034 000345 00035 000355

ln k

1T

224


















product P2

225


OH

(P1)

phenol

N

N CH3H3C

OHOH

(P2)











226



and GC-MS spectrum

N

N CH3

NH2H2N

H3C

ClO2

H3C

H2N N NH2

CH3N

OH

N

N CH3

N

H3C

H

HH2N

OH

OHI1

P1ClO2

N

N CH3

N

H3C

H

H

OHH2N

HO

N

N CH3H3C

OHH2N

I2

I3

N

N CH3

OH N

H3C

H

H

OH

N

N CH3H3C

OHN

H

H

OH

ClO2

OH-

ClO2

OH-

OH

N

N CH3H3C

OHOH

I4

P2


227





limiting

(434)



+ + ClO2

- R1

I1+ + ClO2 + OH-

rarr I2+ + ClO2

- R2

I2+ + OH- rarr I3

+ NH2OH R3

I3 + ClO2 + OH-

rarr I4 + ClO2- R4


- R5



228

4313 Rate law





k1 [ClO2][SO+] + k2 [ClO2][OH-] [SO+] (436)


as

k1 ClO2 SO+ ‐ ClO2 [OH-] SO+ (437)

where kOH-k2

[OH-]



k SO+ (439)


k k1 kOH‐ [OH-] ClO2 (440)

229

4314 Simulations










+ + ClO2

- 198 x 102 M-1 s-1

C2 I1+ + ClO2 + OH-

rarr I2+ + ClO2

- 200 x 109 M-2s-1


+ NH2OH 456 x 109 M-2s-1

C4 I3 + ClO2 + OH-

rarr I4 + ClO2- 590 x 109 M-2s-1


- 675 x 109 M-2s-1


0

000001

000002

000003

000004

000005

000006

000007

000008

0 05 1 15 2 25 3 35 4

ConcentrationM

Times

E1 S1

E2 S2

E3 S3


230











000E+00

100E‐05

200E‐05

300E‐05

400E‐05

500E‐05

600E‐05

700E‐05

800E‐05

0 1 2 3 4 5 6

Concentration M

Times

Products (P1P2P3)


Intermediates (I)

231

CHAPTER 5

CONCLUSIONS





















232

























233











oxime













234




















substrate




235














hydroxylamine








236













shorter durations

237

REFERENCES












77 247-255




Mater 2009 161 974-981

















238



917-929




2008 194 275-285








44(1) 48-56







71-75




410




1(2) 203 -206




239
















3541







1389-1393






297-307


773


240


2002 9(1) 5-14




1992 92(6) 82-88





77 275-286





1972 p230-256



Denver CO AWWA 1996









105-114




Assoc 2008 58 647-656

241


2000 21(3) 241-248


160-165









1981 p 144


Science 2006 293 16-26



195


34(3) 227-241


173-179



2007 73 47-54








197-200

242


349-352


Chem Res 2000 39(9) 3241-3248


45(14) 4898-4904






1972 p 604




pigments 2004 62(2) 181-195





2006 27(1-3) 121-134


352


142-149






1663-1665



243


81-88
















1965 p245-267






p207-220


397





66(11) 703-706


943-957

244






69-77














2004 p140-144 268 -280











221-230



245









82-85


Educ 1982 12 885-886





VCH New York 1990 p1-22 57-68 177-180




Boston 1999 p365-385 598





1989 p340-359








Chemistry 2003 27 147-152

246




644-651







190 H Eyring Chem Rev 1935 17(1) 65-77





38-44






1703-1731





1833-1836



Sons 2001 p526-528


8126-8127


247


6500-6506



248




249


250


251


252



02 700E-05 1757 646E-05 0 700E-05 063 612E-05 0 700E-05 0254 596E-05

04 696E-05 1991 640E-05 02 681E-05 073 601E-05 02 610E-05 0293 580E-05

06 692E-05 2225 635E-05 04 663E-05 083 592E-05 0293 573E-05 0332 564E-05

08 687E-05 246 630E-05 06 645E-05 093 582E-05 0332 557E-05 0371 549E-05

1 683E-05 2694 625E-05 0732 633E-05 102 573E-05 0371 543E-05 041 533E-05

12 679E-05 2929 620E-05 083 625E-05 112 563E-05 041 528E-05 0449 519E-05

14 675E-05 3163 615E-05 0927 617E-05 122 554E-05 0449 514E-05 0488 505E-05

16 671E-05 3397 611E-05 1025 608E-05 132 546E-05 0488 500E-05 0527 492E-05

176 667E-05 3632 605E-05 1123 600E-05 142 537E-05 0527 487E-05 0566 478E-05

196 663E-05 3866 6E-05 122 592E-05 151 529E-05 0566 474E-05 0605 465E-05

199 659E-05 41 596E-05 1318 585E-05 161 521E-05 0605 462E-05 0644 453E-05

269 645E-05 5507 570E-05 1904 539E-05 22 475E-05 084 393E-05 0879 386E-05

313 640E-05 621 558E-05 2197 518E-05 249 454E-05 0957 362E-05 0996 356E-05

316 636E-05 6444 554E-05 2294 511E-05 259 447E-05 0996 353E-05 1035 347E-05

336 635E-05 6679 550E-05 2392 504E-05 269 440E-05 1035 343E-05 1074 338E-05

34 632E-05 6913 546E-05 249 498E-05 278 434E-05 1074 334E-05 1113 329E-05

387 623E-05 7851 530E-05 288 472E-05 317 41E-05 123 300E-05 1269 297E-05

407 622E-05 8085 526E-05 2978 466E-05 327 404E-05 1269 292E-05 1308 289E-05

41 618E-05 8319 523E-05 3076 459E-05 337 398E-05 1308 285E-05 1347 282E-05

43 618E-05 8554 519E-05 3173 453E-05 347 392E-05 1347 277E-05 1387 274E-05

48 605E-05 9726 501E-05 3662 424E-05 395 365E-05 1543 242E-05 1582 241E-05

5 604E-05 996 497E-05 3759 418E-05 405 360E-05 1582 236E-05 1621 235E-05

504 601E-05 1019 494E-05 3857 413E-05 415 355E-05 1621 230E-05 166 230E-05

524 600E-05 1043 490E-05 3955 407E-05 425 351E-05 166 223E-05 1699 224E-05

527 596E-05 1066 486E-05 4052 402E-05 435 346E-05 1699 218E-05 1738 218E-05

574 588E-05 116 473E-05 4443 381E-05 474 327E-05 1855 195E-05 1894 197E-05

594 587E-05 1184 469E-05 454 376E-05 483 322E-05 1894 190E-05 1933 192E-05

598 584E-05 1207 466E-05 4638 371E-05 493 318E-05 1933 185E-05 1972 187E-05

618 583E-05 123 463E-05 4736 366E-05 503 314E-05 1972 180E-05 2012 183E-05

621 580E-05 1254 46E-05 4833 361E-05 513 310E-05 2012 176E-05 2051 178E-05

641 579E-05 1277 456E-05 4931 356E-05 522 306E-05 2051 171E-05 209 174E-05

688 571E-05 1371 444E-05 5322 338E-05 561 290E-05 2207 153E-05 2246 157E-05

691 567E-05 1394 441E-05 5419 333E-05 571 285E-05 2246 149E-05 2285 154E-05

738 559E-05 1488 429E-05 581 316E-05 61 271E-05 2402 134E-05 2441 139E-05

758 559E-05 1512 426E-05 5908 312E-05 62 267E-05 2441 131E-05 248 136E-05

762 555E-05 1535 423E-05 6005 307E-05 63 264E-05 248 127E-05 2519 132E-05

782 555E-05 1559 420E-05 6103 303E-05 64 260E-05 2519 124E-05 2558 129E-05

785 551E-05 1582 417E-05 6201 299E-05 649 257E-05 2558 121E-05 2597 126E-05

253

805 551E-05 1605 414E-05 6298 295E-05 659 254E-05 2597 117E-05 2636 123E-05

902 532E-05 1816 390E-05 7177 262E-05 747 226E-05 2949 922E-06 2988 989E-06

996 517E-05 2004 369E-05 7958 235E-05 825 203E-05 3261 744E-06 3301 818E-06

102 516E-05 2027 367E-05 8056 232E-05 835 201E-05 3301 725E-06 334 798E-06

102 513E-05 2051 364E-05 8154 229E-05 845 198E-05 334 705E-06 3379 778E-06

104 513E-05 2074 362E-05 8251 226E-05 854 196E-05 3379 687E-06 3418 761E-06

104 509E-05 2098 359E-05 8349 223E-05 864 193E-05 3418 669E-06 3457 743E-06

106 509E-05 2121 357E-05 8447 220E-05 874 191E-05 3457 651E-06 3496 726E-06

107 506E-05 2144 355E-05 8544 217E-05 884 188E-05 3496 634E-06 3535 708E-06

109 505E-05 2168 352E-05 8642 214E-05 893 186E-05 3535 617E-06 3574 691E-06

109 502E-05 2191 35E-05 874 211E-05 903 184E-05 3574 601E-06 3613 675E-06

118 488E-05 2379 331E-05 9521 190E-05 981 166E-05 3886 485E-06 3926 56E-06

12 488E-05 2402 329E-05 9618 187E-05 991 164E-05 3926 472E-06 3965 548E-06

121 485E-05 2426 327E-05 9716 185E-05 10 162E-05 3965 459E-06 4004 535E-06

123 484E-05 2449 325E-05 9814 182E-05 101 160E-05 4004 447E-06 4043 524E-06

123 481E-05 2473 323E-05 9911 180E-05 102 158E-05 4043 435E-06 4082 512E-06

125 481E-05 2496 321E-05 1001 178E-05 103 156E-05 4082 424E-06 4121 500E-06

13 474E-05 259 313E-05 104 168E-05 107 149E-05 4238 381E-06 4277 457E-06

13 471E-05 2613 311E-05 105 166E-05 108 147E-05 4277 371E-06 4316 446E-06

132 470E-05 2637 309E-05 106 164E-05 109 145E-05 4316 361E-06 4355 437E-06

137 461E-05 2754 299E-05 1108 153E-05 114 136E-05 4511 316E-06 455 390E-06

148 447E-05 2965 282E-05 1196 136E-05 123 122E-05 4863 248E-06 4902 320E-06

149 445E-05 2988 281E-05 1206 134E-05 124 121E-05 4902 242E-06 4941 314E-06

151 444E-05 3012 279E-05 1216 132E-05 125 119E-05 4941 235E-06 498 307E-06

151 442E-05 3035 277E-05 1226 131E-05 125 118E-05 498 229E-06 5019 301E-06

153 441E-05 3059 275E-05 1235 129E-05 126 116E-05 5019 223E-06 5058 295E-06

158 432E-05 3176 267E-05 1284 121E-05 131 109E-05 5215 195E-06 5254 265E-06

16 432E-05 3199 265E-05 1294 119E-05 132 108E-05 5254 190E-06 5293 259E-06

161 429E-05 3223 264E-05 1304 117E-05 133 107E-05 5293 185E-06 5332 253E-06

163 429E-05 3246 262E-05 1313 116E-05 134 106E-05 5332 180E-06 5371 249E-06

163 426E-05 327 260E-05 1323 114E-05 135 104E-05 5371 175E-06 541 243E-06

168 420E-05 3363 254E-05 1362 108E-05 139 996E-06 5527 157E-06 5566 225E-06

17 420E-05 3387 253E-05 1372 107E-05 14 984E-06 5566 153E-06 5605 219E-06

17 417E-05 341 251E-05 1382 105E-05 141 973E-06 5605 149E-06 5644 216E-06

177 408E-05 3551 242E-05 144 973E-06 147 906E-06 584 127E-06 5879 191E-06

179 408E-05 3574 241E-05 145 960E-06 148 894E-06 5879 124E-06 5918 187E-06

179 405E-05 3598 239E-05 146 948E-06 149 884E-06 5918 120E-06 5957 184E-06

181 405E-05 3621 237E-05 147 935E-06 15 872E-06 5957 117E-06 5996 181E-06

188 396E-05 3762 229E-05 1528 863E-06 156 815E-06 6191 998E-07 623 163E-06

189 394E-05 3785 228E-05 1538 851E-06 157 804E-06 623 972E-07 6269 159E-06

191 393E-05 3809 227E-05 1548 840E-06 158 794E-06 6269 946E-07 6308 156E-06

254

191 391E-05 3832 225E-05 1558 829E-06 159 784E-06 6308 921E-07 6347 153E-06

198 385E-05 3949 218E-05 1606 775E-06 164 742E-06 6504 806E-07 6543 138E-06

198 383E-05 3973 217E-05 1616 765E-06 165 733E-06 6543 784E-07 6582 135E-06

20 382E-05 3996 216E-05 1626 755E-06 166 723E-06 6582 764E-07 6621 133E-06

20 380E-05 402 214E-05 1636 745E-06 166 716E-06 6621 743E-07 666 130E-06

207 372E-05 416 207E-05 1694 688E-06 172 666E-06 6855 633E-07 6894 118E-06

209 372E-05 4184 206E-05 1704 678E-06 173 658E-06 6894 616E-07 6933 116E-06

21 369E-05 4207 205E-05 1714 669E-06 174 650E-06 6933 600E-07 6972 115E-06

212 369E-05 423 203E-05 1724 660E-06 175 642E-06 6972 584E-07 7011 112E-06

212 367E-05 4254 202E-05 1733 652E-06 176 635E-06 7011 569E-07 705 111E-06

27 309E-05 5402 153E-05 2212 338E-06 224 369E-06 8925 153E-07 8964 605E-07

271 307E-05 5426 152E-05 2222 334E-06 225 364E-06 8964 149E-07 9003 605E-07

277 302E-05 5543 148E-05 227 312E-06 23 344E-06 916 130E-07 9199 574E-07

278 300E-05 5566 148E-05 228 308E-06 231 341E-06 9199 127E-07 9238 566E-07

28 300E-05 559 147E-05 229 304E-06 232 337E-06 9238 124E-07 9277 570E-07

28 298E-05 5613 146E-05 23 300E-06 233 333E-06 9277 120E-07 9316 565E-07

282 298E-05 5637 145E-05 231 296E-06 234 329E-06 9316 117E-07 9355 563E-07

313 271E-05 6246 126E-05 2563 209E-06 259 250E-06 1033 584E-08 1037 467E-07

322 264E-05 6434 121E-05 2642 188E-06 267 229E-06 1064 471E-08 1068 454E-07

327 258E-05 6551 118E-05 269 176E-06 272 217E-06 1084 412E-08 1088 437E-07

329 258E-05 6574 117E-05 27 173E-06 273 215E-06 1088 401E-08 1092 450E-07

329 257E-05 6598 117E-05 271 171E-06 274 213E-06 1092 391E-08 1096 446E-07

331 256E-05 6621 116E-05 272 169E-06 275 211E-06 1096 380E-08 11 442E-07

332 255E-05 6645 115E-05 2729 167E-06 276 209E-06 11 370E-08 1104 430E-07

339 249E-05 6785 112E-05 2788 154E-06 282 196E-06 1123 315E-08 1127 442E-07

346 244E-05 6926 109E-05 2847 142E-06 288 185E-06 1146 269E-08 115 426E-07

348 244E-05 6949 108E-05 2856 140E-06 289 185E-06 115 262E-08 1154 423E-07

348 242E-05 6973 107E-05 2866 138E-06 29 182E-06 1154 255E-08 1158 422E-07

35 242E-05 6996 107E-05 2876 136E-06 291 180E-06 1158 248E-08 1162 412E-07

36 234E-05 7207 102E-05 2964 121E-06 299 166E-06 1193 195E-08 1197 419E-07

362 234E-05 7231 102E-05 2974 119E-06 30 164E-06 1197 190E-08 1201 404E-07

362 232E-05 7254 101E-05 2983 118E-06 301 161E-06 1201 185E-08 1205 410E-07

364 232E-05 7277 101E-05 2993 116E-06 302 160E-06 1205 180E-08 1209 415E-07

369 229E-05 7371 985E-06 3032 110E-06 306 153E-06 1221 162E-08 1225 408E-07

369 227E-05 7395 981E-06 3042 109E-06 307 150E-06 1225 157E-08 1229 395E-07

378 222E-05 7559 947E-06 311 989E-07 314 139E-06 1252 130E-08 1256 401E-07

379 221E-05 7582 943E-06 312 976E-07 315 138E-06 1256 127E-08 126 394E-07

381 221E-05 7606 937E-06 313 963E-07 316 136E-06 126 124E-08 1264 397E-07

386 216E-05 7723 915E-06 3179 901E-07 321 131E-06 1279 108E-08 1283 393E-07

388 216E-05 7746 909E-06 3188 889E-07 322 13E-06 1283 105E-08 1287 395E-07

388 215E-05 777 905E-06 3198 877E-07 323 129E-06 1287 102E-08 1291 391E-07

255

39 214E-05 7793 900E-06 3208 866E-07 324 127E-06 1291 997E-09 1295 382E-07

39 213E-05 7816 895E-06 3218 854E-07 325 127E-06 1295 970E-09 1299 379E-07

399 208E-05 7981 866E-06 3286 778E-07 332 120E-06 1322 805E-09 1326 384E-07

40 207E-05 8004 862E-06 3296 768E-07 333 118E-06 1326 784E-09 133 381E-07

402 207E-05 8027 858E-06 3306 757E-07 333 117E-06 133 763E-09 1334 387E-07

432 188E-05 866 752E-06 3569 528E-07 36 903E-07 1436 370E-09 1439 359E-07

451 178E-05 9012 697E-06 3716 432E-07 375 811E-07 1494 248E-09 1498 368E-07

451 177E-05 9035 694E-06 3725 426E-07 375 811E-07 1498 241E-09 1502 365E-07

458 173E-05 9176 673E-06 3784 393E-07 381 775E-07 1521 205E-09 1525 365E-07

46 173E-05 9199 670E-06 3794 388E-07 382 758E-07 1525 200E-09 1529 362E-07

461 172E-05 9223 666E-06 3804 383E-07 383 757E-07 1529 195E-09 1533 365E-07

463 172E-05 9246 665E-06 3813 378E-07 384 752E-07 1533 190E-09 1537 356E-07

47 167E-05 941 642E-06 3882 344E-07 391 715E-07 1561 157E-09 1564 356E-07

472 167E-05 9434 639E-06 3891 340E-07 392 711E-07 1564 153E-09 1568 349E-07

481 162E-05 9621 618E-06 397 305E-07 40 663E-07 1596 124E-09 16 358E-07

495 156E-05 9902 582E-06 4087 260E-07 412 615E-07 1643 895E-10 1646 347E-07

496 155E-05 9926 579E-06 4097 256E-07 413 613E-07 1646 872E-10 165 346E-07

498 155E-05 9949 577E-06 4106 253E-07 414 610E-07 165 849E-10 1654 341E-07

498 154E-05 9973 575E-06 4116 250E-07 415 599E-07 1654 826E-10 1658 353E-07

50 153E-05 9996 572E-06 4126 246E-07 416 590E-07 1658 805E-10 1662 341E-07

50 153E-05 1002 569E-06 4136 243E-07 416 590E-07 1662 783E-10 1666 352E-07

502 152E-05 1004 567E-06 4145 240E-07 417 593E-07 1666 763E-10 167 351E-07

503 151E-05 1007 565E-06 4155 237E-07 418 585E-07 167 742E-10 1674 352E-07

51 148E-05 1021 549E-06 4214 218E-07 424 565E-07 1693 632E-10 1697 349E-07

54 136E-05 1079 489E-06 4458 156E-07 449 483E-07 1791 324E-10 1795 330E-07

549 132E-05 1098 472E-06 4536 141E-07 457 468E-07 1822 261E-10 1826 340E-07

55 131E-05 110 470E-06 4546 139E-07 458 467E-07 1826 254E-10 183 333E-07

552 131E-05 1103 469E-06 4556 137E-07 458 457E-07 183 248E-10 1834 342E-07

552 130E-05 1105 466E-06 4565 135E-07 459 458E-07 1834 241E-10 1838 334E-07

561 127E-05 1122 451E-06 4634 123E-07 466 433E-07 1861 200E-10 1865 339E-07

568 124E-05 1138 437E-06 4702 112E-07 473 427E-07 1889 166E-10 1893 330E-07

57 124E-05 114 435E-06 4712 110E-07 474 431E-07 1893 161E-10 1896 331E-07

571 123E-05 1143 433E-06 4722 109E-07 475 419E-07 1896 157E-10 19 330E-07

573 123E-05 1145 432E-06 4731 108E-07 476 424E-07 19 153E-10 1904 338E-07

573 122E-05 1147 43E-06 4741 106E-07 477 423E-07 1904 149E-10 1908 328E-07

58 120E-05 1159 421E-06 479 993E-08 482 407E-07 1924 130E-10 1928 330E-07

58 120E-05 1161 419E-06 48 979E-08 483 410E-07 1928 127E-10 1932 326E-07

589 116E-05 118 404E-06 4878 880E-08 491 398E-07 1959 102E-10 1963 328E-07

591 116E-05 1182 403E-06 4888 868E-08 492 398E-07 1963 997E-11 1967 326E-07

598 114E-05 1197 392E-06 4946 801E-08 498 369E-07 1986 849E-11 199 318E-07

599 113E-05 1199 390E-06 4956 791E-08 499 373E-07 199 826E-11 1994 321E-07

256



041 528E-05 276E-07 172E-05 170E-05 170E-05

049 500E-05 164E-07 200E-05 198E-05 198E-05

053 487E-05 136E-07 213E-05 212E-05 212E-05

057 474E-05 116E-07 226E-05 225E-05 225E-05

061 461E-05 101E-07 239E-05 238E-05 238E-05

064 449E-05 891E-08 251E-05 250E-05 250E-05

068 437E-05 795E-08 263E-05 262E-05 262E-05

072 426E-05 717E-08 274E-05 274E-05 274E-05

076 414E-05 651E-08 286E-05 285E-05 285E-05

08 403E-05 595E-08 297E-05 296E-05 296E-05

084 393E-05 547E-08 307E-05 307E-05 307E-05

088 382E-05 505E-08 318E-05 317E-05 317E-05

092 372E-05 468E-08 328E-05 327E-05 327E-05

096 362E-05 436E-08 338E-05 337E-05 337E-05

1 353E-05 407E-08 347E-05 347E-05 347E-05

103 344E-05 381E-08 356E-05 356E-05 356E-05

107 334E-05 357E-08 366E-05 365E-05 365E-05

111 326E-05 336E-08 374E-05 374E-05 374E-05

115 317E-05 317E-08 383E-05 383E-05 383E-05

119 309E-05 299E-08 391E-05 391E-05 391E-05

123 301E-05 283E-08 399E-05 399E-05 399E-05

127 293E-05 268E-08 407E-05 407E-05 407E-05

186 196E-05 135E-08 504E-05 504E-05 504E-05

189 191E-05 130E-08 509E-05 509E-05 509E-05

193 186E-05 125E-08 514E-05 514E-05 514E-05

197 181E-05 120E-08 519E-05 519E-05 519E-05

201 176E-05 116E-08 524E-05 524E-05 524E-05

205 171E-05 111E-08 529E-05 528E-05 528E-05

209 167E-05 107E-08 533E-05 533E-05 533E-05

213 163E-05 103E-08 537E-05 537E-05 537E-05

248 128E-05 752E-09 572E-05 572E-05 572E-05

252 124E-05 727E-09 576E-05 575E-05 575E-05

256 121E-05 703E-09 579E-05 579E-05 579E-05

26 118E-05 680E-09 582E-05 582E-05 582E-05

264 115E-05 658E-09 585E-05 585E-05 585E-05

268 112E-05 636E-09 588E-05 588E-05 588E-05

271 109E-05 616E-09 591E-05 591E-05 591E-05

275 106E-05 596E-09 594E-05 594E-05 594E-05

279 103E-05 577E-09 597E-05 597E-05 597E-05

283 101E-05 559E-09 599E-05 599E-05 599E-05

287 979E-06 541E-09 602E-05 602E-05 602E-05

303 880E-06 477E-09 612E-05 612E-05 612E-05

307 857E-06 462E-09 614E-05 614E-05 614E-05

311 835E-06 448E-09 617E-05 616E-05 616E-05

314 813E-06 434E-09 619E-05 619E-05 619E-05

318 791E-06 421E-09 621E-05 621E-05 621E-05

322 771E-06 408E-09 623E-05 623E-05 623E-05

326 750E-06 396E-09 625E-05 625E-05 625E-05

33 731E-06 384E-09 627E-05 627E-05 627E-05

353 623E-06 321E-09 638E-05 638E-05 638E-05

357 606E-06 311E-09 639E-05 639E-05 639E-05

361 590E-06 302E-09 641E-05 641E-05 641E-05

365 575E-06 293E-09 643E-05 642E-05 642E-05

369 560E-06 285E-09 644E-05 644E-05 644E-05

373 545E-06 277E-09 645E-05 645E-05 645E-05

377 531E-06 269E-09 647E-05 647E-05 647E-05

381 517E-06 261E-09 648E-05 648E-05 648E-05

385 503E-06 253E-09 650E-05 650E-05 650E-05

389 490E-06 246E-09 651E-05 651E-05 651E-05

393 477E-06 239E-09 652E-05 652E-05 652E-05

396 465E-06 232E-09 654E-05 654E-05 654E-05

4 452E-06 226E-09 655E-05 655E-05 655E-05

428 375E-06 185E-09 662E-05 662E-05 662E-05

432 366E-06 180E-09 663E-05 663E-05 663E-05

436 356E-06 175E-09 664E-05 664E-05 664E-05

439 347E-06 170E-09 665E-05 665E-05 665E-05

443 338E-06 165E-09 666E-05 666E-05 666E-05

447 329E-06 160E-09 667E-05 667E-05 667E-05

451 320E-06 156E-09 668E-05 668E-05 668E-05

486 252E-06 121E-09 675E-05 675E-05 675E-05

49 245E-06 118E-09 675E-05 675E-05 675E-05

494 239E-06 115E-09 676E-05 676E-05 676E-05

498 233E-06 112E-09 677E-05 677E-05 677E-05

502 226E-06 108E-09 677E-05 677E-05 677E-05

506 221E-06 106E-09 678E-05 678E-05 678E-05

51 215E-06 103E-09 679E-05 679E-05 679E-05

514 209E-06 998E-10 679E-05 679E-05 679E-05

257

518 204E-06 971E-10 680E-05 680E-05 680E-05

521 198E-06 945E-10 680E-05 680E-05 680E-05

561 152E-06 718E-10 685E-05 685E-05 685E-05

564 148E-06 699E-10 685E-05 685E-05 685E-05

568 144E-06 680E-10 686E-05 686E-05 686E-05

572 140E-06 662E-10 686E-05 686E-05 686E-05

576 137E-06 644E-10 686E-05 686E-05 686E-05

588 126E-06 594E-10 687E-05 687E-05 687E-05

592 123E-06 578E-10 688E-05 688E-05 688E-05

596 120E-06 562E-10 688E-05 688E-05 688E-05

6 116E-06 547E-10 688E-05 688E-05 688E-05

603 113E-06 532E-10 689E-05 689E-05 689E-05

607 110E-06 518E-10 689E-05 689E-05 689E-05

611 108E-06 504E-10 689E-05 689E-05 689E-05

682 666E-07 310E-10 693E-05 693E-05 693E-05

686 649E-07 302E-10 694E-05 694E-05 694E-05

689 632E-07 294E-10 694E-05 694E-05 694E-05

693 615E-07 286E-10 694E-05 694E-05 694E-05

697 599E-07 279E-10 694E-05 694E-05 694E-05

701 583E-07 271E-10 694E-05 694E-05 694E-05

705 568E-07 264E-10 694E-05 694E-05 694E-05

744 435E-07 202E-10 696E-05 696E-05 696E-05

752 413E-07 191E-10 696E-05 696E-05 696E-05

787 325E-07 150E-10 697E-05 697E-05 697E-05

791 316E-07 146E-10 697E-05 697E-05 697E-05

795 308E-07 143E-10 697E-05 697E-05 697E-05

799 300E-07 139E-10 697E-05 697E-05 697E-05

803 292E-07 135E-10 697E-05 697E-05 697E-05

807 284E-07 132E-10 697E-05 697E-05 697E-05

811 277E-07 128E-10 697E-05 697E-05 697E-05

877 176E-07 814E-11 698E-05 698E-05 698E-05

908 142E-07 657E-11 699E-05 699E-05 699E-05

912 139E-07 640E-11 699E-05 699E-05 699E-05

971 931E-08 429E-11 699E-05 699E-05 699E-05

975 906E-08 418E-11 699E-05 699E-05 699E-05

978 882E-08 407E-11 699E-05 699E-05 699E-05

982 859E-08 396E-11 699E-05 699E-05 699E-05

986 837E-08 386E-11 699E-05 699E-05 699E-05

99 815E-08 376E-11 699E-05 699E-05 699E-05

994 793E-08 366E-11 699E-05 699E-05 699E-05

998 772E-08 356E-11 699E-05 699E-05 699E-05

10 752E-08 347E-11 699E-05 699E-05 699E-05

107 466E-08 215E-11 700E-05 700E-05 700E-05

133 806E-09 371E-12 700E-05 700E-05 700E-05

133 784E-09 361E-12 700E-05 700E-05 700E-05

141 473E-09 218E-12 700E-05 700E-05 700E-05

141 461E-09 212E-12 700E-05 700E-05 700E-05

142 449E-09 207E-12 700E-05 700E-05 700E-05

142 437E-09 201E-12 700E-05 700E-05 700E-05

142 425E-09 196E-12 700E-05 700E-05 700E-05

15 257E-09 118E-12 700E-05 700E-05 700E-05

15 250E-09 115E-12 700E-05 700E-05 700E-05

151 243E-09 112E-12 700E-05 700E-05 700E-05

153 202E-09 931E-13 700E-05 700E-05 700E-05

154 197E-09 906E-13 700E-05 700E-05 700E-05

154 192E-09 883E-13 700E-05 700E-05 700E-05

155 182E-09 836E-13 700E-05 700E-05 700E-05

155 177E-09 814E-13 700E-05 700E-05 700E-05

156 172E-09 793E-13 700E-05 700E-05 700E-05

156 168E-09 772E-13 700E-05 700E-05 700E-05

156 163E-09 752E-13 700E-05 700E-05 700E-05

157 159E-09 732E-13 700E-05 700E-05 700E-05

157 155E-09 713E-13 700E-05 700E-05 700E-05

158 151E-09 695E-13 700E-05 700E-05 700E-05

158 147E-09 676E-13 700E-05 700E-05 700E-05

16 129E-09 592E-13 700E-05 700E-05 700E-05

16 125E-09 577E-13 700E-05 700E-05 700E-05

161 122E-09 561E-13 700E-05 700E-05 700E-05

161 119E-09 547E-13 700E-05 700E-05 700E-05

162 116E-09 532E-13 700E-05 700E-05 700E-05

162 113E-09 518E-13 700E-05 700E-05 700E-05

162 110E-09 505E-13 700E-05 700E-05 700E-05

163 107E-09 491E-13 700E-05 700E-05 700E-05

171 611E-10 281E-13 700E-05 700E-05 700E-05

18 331E-10 152E-13 700E-05 700E-05 700E-05

18 322E-10 148E-13 700E-05 700E-05 700E-05

181 314E-10 145E-13 700E-05 700E-05 700E-05

181 298E-10 137E-13 700E-05 700E-05 700E-05

196 114E-10 526E-14 700E-05 700E-05 700E-05

196 111E-10 513E-14 700E-05 700E-05 700E-05

199 899E-11 414E-14 700E-05 700E-05 700E-05

199 876E-11 403E-14 700E-05 700E-05 700E-05

258



259


260


261


262


263


264


265


266


267



023193 526E-05 586E-05 011597 445E-05 558E-05 0057982 271E-05 561E-05

070068 627E-05 580E-05 035035 614E-05 544E-05 017517 483E-05 548E-05

11694 601E-05 565E-05 058473 617E-05 531E-05 029235 567E-05 537E-05

16382 576E-05 551E-05 08191 601E-05 52E-05 040953 584E-05 526E-05

21069 554E-05 537E-05 10535 584E-05 509E-05 052672 576E-05 516E-05

25757 533E-05 524E-05 12879 567E-05 498E-05 06439 562E-05 506E-05

30444 514E-05 511E-05 15222 552E-05 489E-05 076109 547E-05 496E-05

35132 495E-05 498E-05 17566 538E-05 479E-05 087827 532E-05 487E-05

39819 479E-05 486E-05 1991 524E-05 47E-05 099545 517E-05 477E-05

44507 462E-05 474E-05 22254 511E-05 461E-05 11126 504E-05 468E-05

49194 447E-05 462E-05 24598 499E-05 452E-05 12298 491E-05 459E-05

53881 433E-05 450E-05 26941 486E-05 444E-05 1347 478E-05 451E-05

58569 419E-05 439E-05 29285 475E-05 436E-05 14642 466E-05 442E-05

63256 406E-05 428E-05 31629 464E-05 428E-05 15814 454E-05 434E-05

67944 393E-05 418E-05 33973 453E-05 42E-05 16986 444E-05 426E-05

72631 382E-05 408E-05 36316 443E-05 412E-05 18157 433E-05 418E-05

77319 37E-05 398E-05 3866 434E-05 405E-05 19329 423E-05 410E-05

82006 36E-05 388E-05 41004 424E-05 397E-05 20501 413E-05 403E-05

86694 35E-05 378E-05 43348 415E-05 39E-05 21673 404E-05 395E-05

14294 255E-05 282E-05 71473 326E-05 315E-05 35735 312E-05 319E-05

14763 249E-05 275E-05 73817 319E-05 309E-05 36907 306E-05 313E-05

15232 243E-05 268E-05 76161 314E-05 304E-05 38079 3E-05 308E-05

15701 237E-05 262E-05 78505 308E-05 298E-05 39251 294E-05 302E-05

16169 232E-05 256E-05 80848 302E-05 293E-05 40422 288E-05 297E-05

16638 226E-05 250E-05 83192 296E-05 288E-05 41594 283E-05 292E-05

17107 221E-05 244E-05 85536 292E-05 283E-05 42766 277E-05 287E-05

17576 216E-05 238E-05 8788 286E-05 278E-05 43938 272E-05 282E-05

18044 211E-05 232E-05 90224 281E-05 273E-05 4511 267E-05 277E-05

18513 207E-05 227E-05 92567 276E-05 268E-05 46282 262E-05 272E-05

18982 202E-05 221E-05 94911 271E-05 264E-05 47453 257E-05 268E-05

19451 198E-05 216E-05 97255 267E-05 259E-05 48625 252E-05 263E-05

19919 194E-05 211E-05 99599 262E-05 255E-05 49797 248E-05 259E-05

20388 19E-05 206E-05 10194 257E-05 25E-05 50969 243E-05 255E-05

20857 186E-05 201E-05 10429 253E-05 246E-05 52141 239E-05 250E-05

21326 182E-05 196E-05 10663 249E-05 242E-05 53313 234E-05 246E-05

21794 179E-05 192E-05 10897 244E-05 237E-05 54484 23E-05 242E-05

22263 176E-05 187E-05 11132 24E-05 233E-05 55656 226E-05 238E-05

22732 172E-05 183E-05 11366 236E-05 229E-05 56828 222E-05 234E-05

268

27888 142E-05 141E-05 13944 198E-05 189E-05 69718 183E-05 195E-05

28357 14E-05 137E-05 14179 195E-05 186E-05 7089 18E-05 192E-05

28825 138E-05 134E-05 14413 192E-05 183E-05 72062 177E-05 189E-05

29294 135E-05 131E-05 14647 189E-05 18E-05 73234 175E-05 186E-05

29763 133E-05 128E-05 14882 186E-05 177E-05 74406 172E-05 183E-05

30232 131E-05 125E-05 15116 183E-05 174E-05 75578 169E-05 180E-05

307 13E-05 122E-05 15351 181E-05 171E-05 76749 166E-05 177E-05

31169 128E-05 119E-05 15585 178E-05 168E-05 77921 163E-05 174E-05

31638 126E-05 116E-05 15819 175E-05 165E-05 79093 161E-05 171E-05

32107 124E-05 114E-05 16054 173E-05 162E-05 80265 158E-05 169E-05

32575 122E-05 111E-05 16288 171E-05 159E-05 81437 156E-05 166E-05

48982 785E-06 490E-06 24491 111E-05 877E-06 12245 949E-06 959E-06

4945 776E-06 478E-06 24726 11E-05 862E-06 12362 936E-06 944E-06

49919 767E-06 467E-06 2496 109E-05 848E-06 12479 919E-06 930E-06

50388 76E-06 457E-06 25194 107E-05 833E-06 12597 907E-06 916E-06

50857 748E-06 446E-06 25429 106E-05 819E-06 12714 896E-06 902E-06

51325 74E-06 436E-06 25663 105E-05 805E-06 12831 884E-06 888E-06

56482 652E-06 338E-06 28241 946E-06 669E-06 1412 771E-06 752E-06

5695 645E-06 330E-06 28476 934E-06 658E-06 14237 761E-06 740E-06

72888 458E-06 150E-06 36445 67E-06 371E-06 18222 515E-06 445E-06

77575 417E-06 119E-06 38788 611E-06 314E-06 19393 464E-06 384E-06

78044 414E-06 117E-06 39023 606E-06 308E-06 19511 459E-06 379E-06

78513 412E-06 114E-06 39257 601E-06 303E-06 19628 454E-06 373E-06

99606 299E-06 404E-07 49804 411E-06 143E-06 24901 313E-06 193E-06

10007 295E-06 395E-07 50039 409E-06 14E-06 25018 311E-06 190E-06

10054 295E-06 386E-07 50273 406E-06 138E-06 25135 309E-06 188E-06

10101 294E-06 377E-07 50507 402E-06 136E-06 25253 306E-06 185E-06

10148 293E-06 368E-07 50742 399E-06 134E-06 2537 303E-06 182E-06

10195 29E-06 360E-07 50976 398E-06 131E-06 25487 302E-06 180E-06

10242 288E-06 352E-07 51211 392E-06 129E-06 25604 299E-06 177E-06

10289 287E-06 344E-07 51445 393E-06 127E-06 25721 298E-06 174E-06

10336 284E-06 336E-07 51679 387E-06 125E-06 25838 296E-06 172E-06

12914 231E-06 946E-08 6457 278E-06 499E-07 32284 227E-06 775E-07

12961 23E-06 924E-08 64804 276E-06 491E-07 32401 225E-06 764E-07

13007 23E-06 904E-08 65039 277E-06 483E-07 32518 225E-06 753E-07

13054 229E-06 883E-08 65273 275E-06 475E-07 32635 224E-06 742E-07

13101 228E-06 863E-08 65508 274E-06 467E-07 32752 224E-06 732E-07

13148 227E-06 843E-08 65742 273E-06 459E-07 3287 222E-06 721E-07

13523 223E-06 701E-08 67617 264E-06 402E-07 33807 218E-06 643E-07

15117 206E-06 321E-08 75586 231E-06 228E-07 37791 197E-06 394E-07

15164 205E-06 313E-08 7582 231E-06 224E-07 37908 196E-06 388E-07

269

15211 205E-06 306E-08 76055 23E-06 22E-07 38026 197E-06 383E-07

16429 194E-06 168E-08 82149 215E-06 143E-07 41072 181E-06 263E-07

16476 194E-06 164E-08 82383 214E-06 141E-07 4119 181E-06 260E-07

16523 193E-06 161E-08 82617 215E-06 138E-07 41307 18E-06 256E-07

1657 192E-06 157E-08 82852 214E-06 136E-07 41424 181E-06 252E-07

16617 193E-06 153E-08 83086 214E-06 134E-07 41541 179E-06 249E-07

16664 192E-06 150E-08 8332 213E-06 132E-07 41658 179E-06 245E-07

16711 192E-06 147E-08 83555 212E-06 129E-07 41775 18E-06 241E-07

18539 179E-06 597E-09 92696 193E-06 675E-08 46346 164E-06 138E-07

18586 178E-06 583E-09 9293 193E-06 664E-08 46463 165E-06 136E-07

18632 178E-06 570E-09 93164 192E-06 653E-08 4658 163E-06 134E-07

18679 18E-06 557E-09 93399 192E-06 642E-08 46697 164E-06 132E-07

18726 178E-06 545E-09 93633 191E-06 632E-08 46814 163E-06 130E-07

18773 177E-06 532E-09 93867 192E-06 621E-08 46932 163E-06 128E-07

1882 178E-06 520E-09 94102 189E-06 611E-08 47049 162E-06 126E-07

18867 175E-06 508E-09 94336 19E-06 601E-08 47166 163E-06 125E-07

18914 177E-06 497E-09 94571 189E-06 591E-08 47283 162E-06 123E-07

18961 178E-06 485E-09 94805 189E-06 581E-08 474 162E-06 121E-07

19007 176E-06 474E-09 95039 188E-06 572E-08 47518 162E-06 119E-07

19054 177E-06 464E-09 95274 188E-06 562E-08 47635 162E-06 118E-07

19101 176E-06 453E-09 95508 187E-06 553E-08 47752 161E-06 116E-07

19148 175E-06 443E-09 95742 188E-06 544E-08 47869 16E-06 114E-07

19195 175E-06 433E-09 95977 187E-06 535E-08 47986 16E-06 113E-07

19242 175E-06 423E-09 96211 186E-06 526E-08 48103 16E-06 111E-07

19289 175E-06 413E-09 96446 186E-06 517E-08 48221 161E-06 110E-07

19336 175E-06 404E-09 9668 185E-06 509E-08 48338 16E-06 108E-07

19382 174E-06 395E-09 96914 184E-06 5E-08 48455 159E-06 106E-07

19429 174E-06 386E-09 97149 185E-06 492E-08 48572 16E-06 105E-07

19476 174E-06 377E-09 97383 185E-06 484E-08 48689 158E-06 103E-07

19523 173E-06 368E-09 97617 182E-06 476E-08 48807 157E-06 102E-07

1957 174E-06 360E-09 97852 185E-06 468E-08 48924 159E-06 101E-07

19617 173E-06 352E-09 98086 183E-06 46E-08 49041 159E-06 991E-08

19664 173E-06 344E-09 98321 182E-06 453E-08 49158 157E-06 977E-08

19711 172E-06 336E-09 98555 182E-06 445E-08 49275 158E-06 963E-08

19757 172E-06 328E-09 98789 183E-06 438E-08 49392 157E-06 949E-08

23695 154E-06 474E-10 11848 158E-06 108E-08 59236 136E-06 284E-08

23836 155E-06 443E-10 11918 157E-06 103E-08 59587 135E-06 272E-08

23882 155E-06 433E-10 11941 157E-06 101E-08 59705 135E-06 268E-08

23929 156E-06 423E-10 11965 157E-06 994E-09 59822 135E-06 264E-08

270


017517 170E-05 104E-03 385E-06 561E-05 385E-06 486E-07 337E-06

029235 198E-05 108E-03 515E-06 548E-05 515E-06 348E-07 480E-06

040953 212E-05 109E-03 630E-06 537E-05 630E-06 308E-07 599E-06

052672 225E-05 109E-03 738E-06 526E-05 738E-06 290E-07 709E-06

06439 238E-05 109E-03 841E-06 516E-05 841E-06 279E-07 813E-06

076109 250E-05 109E-03 942E-06 506E-05 942E-06 271E-07 915E-06

087827 262E-05 109E-03 104E-05 496E-05 104E-05 264E-07 101E-05

22845 274E-05 108E-03 205E-05 395E-05 205E-05 201E-07 203E-05

24017 285E-05 108E-03 212E-05 388E-05 212E-05 196E-07 210E-05

25188 296E-05 108E-03 219E-05 381E-05 219E-05 192E-07 217E-05

2636 307E-05 108E-03 226E-05 374E-05 226E-05 188E-07 224E-05

27532 317E-05 108E-03 232E-05 368E-05 232E-05 184E-07 231E-05

28704 327E-05 108E-03 239E-05 361E-05 239E-05 180E-07 237E-05

29876 337E-05 108E-03 245E-05 355E-05 245E-05 176E-07 244E-05

31048 347E-05 107E-03 252E-05 348E-05 252E-05 173E-07 250E-05

32219 356E-05 107E-03 258E-05 342E-05 258E-05 169E-07 256E-05

33391 365E-05 107E-03 264E-05 336E-05 264E-05 166E-07 262E-05

34563 374E-05 107E-03 270E-05 330E-05 270E-05 162E-07 268E-05

35735 383E-05 107E-03 276E-05 324E-05 276E-05 159E-07 274E-05

36907 391E-05 107E-03 281E-05 319E-05 281E-05 156E-07 280E-05

38079 399E-05 107E-03 287E-05 313E-05 287E-05 153E-07 285E-05

39251 407E-05 107E-03 292E-05 308E-05 292E-05 150E-07 291E-05

61515 504E-05 106E-03 377E-05 223E-05 377E-05 104E-07 376E-05

66203 524E-05 106E-03 392E-05 208E-05 392E-05 962E-08 391E-05

67375 528E-05 106E-03 395E-05 205E-05 395E-05 945E-08 394E-05

68547 533E-05 106E-03 398E-05 202E-05 398E-05 928E-08 398E-05

69718 537E-05 106E-03 402E-05 198E-05 402E-05 911E-08 401E-05

7089 572E-05 106E-03 405E-05 195E-05 405E-05 895E-08 404E-05

72062 575E-05 106E-03 408E-05 192E-05 408E-05 879E-08 407E-05

73234 579E-05 106E-03 411E-05 189E-05 411E-05 863E-08 410E-05

74406 582E-05 106E-03 414E-05 186E-05 414E-05 848E-08 413E-05

75578 585E-05 106E-03 417E-05 183E-05 417E-05 833E-08 416E-05

76749 588E-05 106E-03 420E-05 180E-05 420E-05 818E-08 419E-05

77921 591E-05 106E-03 423E-05 177E-05 423E-05 804E-08 422E-05

79093 594E-05 106E-03 426E-05 174E-05 426E-05 790E-08 425E-05

80265 597E-05 106E-03 429E-05 171E-05 429E-05 776E-08 428E-05

81437 599E-05 106E-03 431E-05 169E-05 431E-05 762E-08 431E-05

82609 602E-05 106E-03 434E-05 166E-05 434E-05 749E-08 433E-05

271

8378 612E-05 106E-03 437E-05 163E-05 437E-05 736E-08 436E-05

84952 614E-05 106E-03 439E-05 161E-05 439E-05 723E-08 439E-05

86124 616E-05 106E-03 442E-05 158E-05 442E-05 711E-08 441E-05

87296 619E-05 106E-03 444E-05 156E-05 444E-05 699E-08 444E-05

88468 621E-05 106E-03 447E-05 153E-05 447E-05 687E-08 446E-05

8964 623E-05 106E-03 449E-05 151E-05 449E-05 675E-08 449E-05

90811 625E-05 105E-03 452E-05 148E-05 452E-05 663E-08 451E-05

91983 627E-05 105E-03 454E-05 146E-05 454E-05 652E-08 453E-05

12831 645E-05 105E-03 510E-05 902E-06 510E-05 390E-08 509E-05

12948 647E-05 105E-03 511E-05 888E-06 511E-05 384E-08 511E-05

13065 648E-05 105E-03 513E-05 875E-06 513E-05 378E-08 512E-05

13183 650E-05 105E-03 514E-05 861E-06 514E-05 372E-08 513E-05

133 651E-05 105E-03 515E-05 848E-06 515E-05 366E-08 515E-05

13417 652E-05 105E-03 516E-05 836E-06 516E-05 360E-08 516E-05

13534 654E-05 105E-03 518E-05 823E-06 518E-05 355E-08 517E-05

13651 655E-05 105E-03 519E-05 811E-06 519E-05 349E-08 519E-05

15878 662E-05 105E-03 539E-05 609E-06 539E-05 259E-08 539E-05

15995 663E-05 105E-03 540E-05 600E-06 540E-05 255E-08 540E-05

16112 664E-05 105E-03 541E-05 591E-06 541E-05 251E-08 541E-05

16698 665E-05 105E-03 545E-05 548E-06 545E-05 232E-08 545E-05

16815 666E-05 105E-03 546E-05 540E-06 546E-05 229E-08 546E-05

16932 667E-05 105E-03 547E-05 532E-06 547E-05 225E-08 547E-05

1705 668E-05 105E-03 548E-05 524E-06 548E-05 222E-08 547E-05

17167 675E-05 105E-03 548E-05 517E-06 548E-05 219E-08 548E-05

17987 675E-05 104E-03 553E-05 466E-06 553E-05 196E-08 553E-05

20096 676E-05 104E-03 564E-05 357E-06 564E-05 150E-08 564E-05

21971 685E-05 104E-03 572E-05 282E-06 572E-05 118E-08 572E-05

25135 686E-05 104E-03 581E-05 190E-06 581E-05 789E-09 581E-05

25253 686E-05 104E-03 581E-05 188E-06 581E-05 778E-09 581E-05

2537 686E-05 104E-03 582E-05 185E-06 582E-05 766E-09 581E-05

25487 687E-05 104E-03 582E-05 182E-06 582E-05 755E-09 582E-05

25604 688E-05 104E-03 582E-05 180E-06 582E-05 744E-09 582E-05

25721 688E-05 104E-03 582E-05 177E-06 582E-05 733E-09 582E-05

25838 688E-05 104E-03 583E-05 174E-06 583E-05 723E-09 582E-05

25956 689E-05 104E-03 583E-05 172E-06 583E-05 712E-09 583E-05

26073 689E-05 104E-03 583E-05 169E-06 583E-05 702E-09 583E-05

2619 689E-05 104E-03 583E-05 167E-06 583E-05 691E-09 583E-05

26307 693E-05 104E-03 584E-05 165E-06 584E-05 681E-09 583E-05

26424 694E-05 104E-03 584E-05 162E-06 584E-05 672E-09 584E-05

28182 694E-05 104E-03 587E-05 130E-06 587E-05 539E-09 587E-05

29706 694E-05 104E-03 589E-05 108E-06 589E-05 446E-09 589E-05

272

29823 694E-05 104E-03 589E-05 107E-06 589E-05 440E-09 589E-05

2994 694E-05 104E-03 589E-05 105E-06 589E-05 433E-09 589E-05

30057 694E-05 104E-03 590E-05 104E-06 590E-05 427E-09 590E-05

30174 696E-05 104E-03 590E-05 102E-06 590E-05 421E-09 590E-05

34627 697E-05 104E-03 594E-05 590E-07 594E-05 243E-09 594E-05

4119 698E-05 104E-03 597E-05 263E-07 597E-05 108E-09 597E-05

41307 698E-05 104E-03 597E-05 260E-07 597E-05 107E-09 597E-05

41424 698E-05 104E-03 597E-05 256E-07 597E-05 105E-09 597E-05

41541 699E-05 104E-03 597E-05 252E-07 597E-05 104E-09 597E-05

41658 699E-05 104E-03 598E-05 249E-07 598E-05 102E-09 598E-05

41775 699E-05 104E-03 598E-05 245E-07 598E-05 101E-09 598E-05

41893 699E-05 104E-03 598E-05 241E-07 598E-05 991E-10 598E-05

4201 699E-05 104E-03 598E-05 238E-07 598E-05 977E-10 598E-05

42947 699E-05 104E-03 598E-05 212E-07 598E-05 871E-10 598E-05

43533 699E-05 104E-03 598E-05 197E-07 598E-05 811E-10 598E-05

4365 699E-05 104E-03 598E-05 195E-07 598E-05 799E-10 598E-05

43768 699E-05 104E-03 598E-05 192E-07 598E-05 787E-10 598E-05

4576 699E-05 104E-03 598E-05 150E-07 598E-05 617E-10 598E-05

45877 699E-05 104E-03 599E-05 148E-07 599E-05 608E-10 599E-05

45994 700E-05 104E-03 599E-05 146E-07 599E-05 599E-10 599E-05

46111 700E-05 104E-03 599E-05 144E-07 599E-05 591E-10 599E-05

48103 700E-05 104E-03 599E-05 113E-07 599E-05 463E-10 599E-05

54783 700E-05 104E-03 600E-05 497E-08 600E-05 204E-10 600E-05

549 700E-05 104E-03 600E-05 490E-08 600E-05 201E-10 600E-05

55017 700E-05 104E-03 600E-05 483E-08 600E-05 198E-10 600E-05

55134 700E-05 104E-03 600E-05 476E-08 600E-05 195E-10 600E-05

56189 700E-05 104E-03 600E-05 419E-08 600E-05 172E-10 600E-05

56306 700E-05 104E-03 600E-05 413E-08 600E-05 169E-10 600E-05

56423 700E-05 104E-03 600E-05 407E-08 600E-05 167E-10 600E-05

5865 700E-05 104E-03 600E-05 310E-08 600E-05 127E-10 600E-05

58767 700E-05 104E-03 600E-05 305E-08 600E-05 125E-10 600E-05

58884 700E-05 104E-03 600E-05 301E-08 600E-05 123E-10 600E-05

59002 700E-05 104E-03 600E-05 297E-08 600E-05 122E-10 600E-05

59939 700E-05 104E-03 600E-05 264E-08 600E-05 108E-10 600E-05

60439 700E-05 104E-03 600E-05 249E-08 600E-05 102E-10 600E-05

273



274


275


276



02899 192E-05 0 000002 017395 168E-05 0 000002 0087 126E-05 0 000002

08759 199E-05 02 199E-05 052551 194E-05 02 198E-05 02628 182E-05 02 198E-05

14618 195E-05 04 198E-05 087708 189E-05 04 197E-05 04385 191E-05 02628 197E-05

20477 192E-05 06 198E-05 12286 184E-05 05255 196E-05 06143 189E-05 04385 195E-05

26337 188E-05 08 197E-05 15802 18E-05 07255 194E-05 07901 185E-05 06143 193E-05

32196 186E-05 0876 197E-05 19318 177E-05 08771 193E-05 09659 182E-05 07901 191E-05

38056 183E-05 1076 196E-05 22833 173E-05 10771 192E-05 11416 179E-05 09659 189E-05

43915 18E-05 1276 195E-05 26349 171E-05 12286 191E-05 13174 176E-05 11416 187E-05

49774 177E-05 1462 194E-05 29865 168E-05 14286 189E-05 14932 173E-05 13174 185E-05

55634 175E-05 1662 193E-05 3338 165E-05 15802 188E-05 1669 171E-05 14932 183E-05

61493 172E-05 1862 193E-05 36896 163E-05 17802 187E-05 18447 169E-05 1669 181E-05

67353 17E-05 2048 192E-05 40411 161E-05 19318 185E-05 20205 167E-05 18447 179E-05

73212 167E-05 2248 191E-05 43927 158E-05 21318 184E-05 21963 165E-05 20205 177E-05

79072 165E-05 2448 19E-05 47443 156E-05 22833 183E-05 23721 163E-05 21963 176E-05

84931 163E-05 2634 19E-05 50958 154E-05 24833 182E-05 25478 161E-05 23721 174E-05

9079 161E-05 2834 189E-05 54474 152E-05 26349 18E-05 27236 159E-05 25478 172E-05

9665 158E-05 3034 188E-05 5799 15E-05 28349 179E-05 28994 157E-05 27236 17E-05

10251 156E-05 322 187E-05 61505 148E-05 29865 178E-05 30752 156E-05 28994 168E-05

10837 154E-05 342 187E-05 65021 146E-05 31865 177E-05 32509 154E-05 30752 167E-05

11423 152E-05 362 186E-05 68536 144E-05 3338 176E-05 34267 153E-05 32509 165E-05

12009 15E-05 3806 185E-05 72052 142E-05 3538 174E-05 36025 151E-05 34267 163E-05

12595 148E-05 4006 184E-05 75568 14E-05 36896 173E-05 37783 149E-05 36025 161E-05

13181 146E-05 4206 184E-05 79083 138E-05 38896 172E-05 3954 148E-05 37783 16E-05

13767 145E-05 4392 183E-05 82599 137E-05 40411 171E-05 41298 147E-05 3954 158E-05

14353 143E-05 4592 182E-05 86115 135E-05 42411 17E-05 43056 145E-05 41298 157E-05

14938 141E-05 4792 182E-05 8963 133E-05 43927 169E-05 44814 143E-05 43056 155E-05

15524 139E-05 4977 181E-05 93146 132E-05 45927 167E-05 46571 142E-05 44814 153E-05

1611 138E-05 5177 18E-05 96661 13E-05 47443 166E-05 48329 141E-05 46571 152E-05

16696 136E-05 5377 179E-05 10018 128E-05 49443 165E-05 50087 139E-05 48329 15E-05

17282 134E-05 5563 179E-05 10369 127E-05 50958 164E-05 51845 138E-05 50087 149E-05

17868 133E-05 5763 178E-05 10721 125E-05 52958 163E-05 53603 137E-05 51845 147E-05

18454 131E-05 5963 177E-05 11072 124E-05 54474 162E-05 5536 135E-05 53603 146E-05

1904 13E-05 6149 177E-05 11424 122E-05 56474 161E-05 57118 134E-05 5536 144E-05

23728 118E-05 7721 171E-05 14236 111E-05 70536 152E-05 7118 124E-05 69422 132E-05

24314 117E-05 7907 17E-05 14588 11E-05 72052 151E-05 72938 123E-05 7118 131E-05

24899 116E-05 8107 17E-05 1494 108E-05 74052 15E-05 74696 122E-05 72938 13E-05

25485 114E-05 8307 169E-05 15291 107E-05 75568 149E-05 76453 121E-05 74696 128E-05

26071 113E-05 8493 168E-05 15643 106E-05 77568 148E-05 78211 12E-05 76453 127E-05

277

26657 112E-05 8693 168E-05 15994 104E-05 79083 147E-05 79969 119E-05 78211 126E-05

30173 105E-05 9865 164E-05 18104 972E-06 8963 141E-05 90515 112E-05 88758 118E-05

30759 104E-05 1007 163E-05 18455 96E-06 9163 14E-05 92273 111E-05 90515 117E-05

31345 103E-05 1025 162E-05 18807 95E-06 93146 139E-05 94031 11E-05 92273 116E-05

31931 102E-05 1045 162E-05 19158 938E-06 95146 138E-05 95789 109E-05 94031 114E-05

44236 816E-06 1455 149E-05 26541 737E-06 13182 12E-05 1327 904E-06 13094 92E-06

44821 808E-06 1475 148E-05 26893 729E-06 13382 119E-05 13446 896E-06 1327 91E-06

45407 8E-06 1494 148E-05 27244 721E-06 13533 118E-05 13622 889E-06 13446 901E-06

45993 792E-06 1514 147E-05 27596 712E-06 13733 117E-05 13798 88E-06 13622 892E-06

50095 738E-06 1651 143E-05 30057 657E-06 1494 112E-05 15028 827E-06 14852 829E-06

50681 731E-06 167 143E-05 30408 651E-06 1514 111E-05 15204 82E-06 15028 82E-06

51267 724E-06 169 142E-05 3076 643E-06 15291 11E-05 15379 813E-06 15204 812E-06

72947 508E-06 2413 123E-05 43768 428E-06 21819 858E-06 21883 589E-06 21707 552E-06

73533 503E-06 2431 122E-05 44119 424E-06 21971 853E-06 22059 584E-06 21883 547E-06

78806 462E-06 2607 118E-05 47283 384E-06 23577 801E-06 23641 541E-06 23465 498E-06

79392 458E-06 2627 117E-05 47635 38E-06 23729 796E-06 23817 536E-06 23641 493E-06

79978 454E-06 2647 117E-05 47986 376E-06 23929 79E-06 23993 531E-06 23817 488E-06

80564 45E-06 2666 117E-05 48338 371E-06 2408 786E-06 24168 527E-06 23993 483E-06

8115 446E-06 2686 116E-05 4869 367E-06 2428 78E-06 24344 523E-06 24168 478E-06

81736 441E-06 2706 116E-05 49041 363E-06 24432 775E-06 2452 518E-06 24344 473E-06

82322 438E-06 2724 115E-05 49393 36E-06 24632 769E-06 24696 514E-06 2452 468E-06

82908 433E-06 2744 115E-05 49744 356E-06 24783 765E-06 24871 51E-06 24696 463E-06

90525 384E-06 2999 109E-05 54315 31E-06 27093 699E-06 27156 456E-06 26981 404E-06

91111 381E-06 3017 109E-05 54666 307E-06 27244 695E-06 27332 453E-06 27156 4E-06

91697 378E-06 3037 108E-05 55018 303E-06 27444 69E-06 27508 449E-06 27332 396E-06

95212 358E-06 3155 106E-05 57127 284E-06 28499 662E-06 28563 427E-06 28387 372E-06

95798 354E-06 3175 105E-05 57479 282E-06 28651 659E-06 28738 423E-06 28563 368E-06

96384 351E-06 3193 105E-05 5783 279E-06 28851 653E-06 28914 42E-06 28738 364E-06

9697 348E-06 3213 104E-05 58182 276E-06 29002 65E-06 2909 417E-06 28914 361E-06

10752 297E-06 3565 972E-06 6451 228E-06 32166 575E-06 32254 358E-06 32078 299E-06

1081 294E-06 3585 968E-06 64861 226E-06 32366 571E-06 3243 355E-06 32254 296E-06

10869 292E-06 3603 964E-06 65213 223E-06 32518 567E-06 32606 352E-06 3243 293E-06

10928 289E-06 3623 96E-06 65565 221E-06 32718 563E-06 32781 349E-06 32606 29E-06

10986 287E-06 3643 956E-06 65916 219E-06 32869 56E-06 32957 346E-06 32781 287E-06

11045 284E-06 3662 953E-06 66268 217E-06 33069 555E-06 33133 343E-06 32957 284E-06

11103 281E-06 3682 949E-06 66619 214E-06 33221 552E-06 33309 34E-06 33133 281E-06

11162 279E-06 3702 945E-06 66971 212E-06 33421 548E-06 33484 338E-06 33309 278E-06

1122 277E-06 372 941E-06 67322 21E-06 33572 545E-06 3366 335E-06 33484 275E-06

11279 274E-06 374 938E-06 67674 208E-06 33772 54E-06 33836 333E-06 3366 272E-06

11338 272E-06 376 934E-06 68026 206E-06 33924 537E-06 34012 33E-06 33836 27E-06

11396 269E-06 3779 93E-06 68377 203E-06 34124 533E-06 34188 327E-06 34012 267E-06

278

13857 187E-06 4599 788E-06 83143 131E-06 41507 401E-06 4157 232E-06 41394 172E-06

13916 186E-06 4619 785E-06 83494 13E-06 41658 399E-06 41746 23E-06 4157 171E-06

13974 184E-06 4639 782E-06 83846 129E-06 41858 396E-06 41922 228E-06 41746 169E-06

14033 183E-06 4658 779E-06 84197 128E-06 4201 393E-06 42097 227E-06 41922 167E-06

14092 182E-06 4678 776E-06 84549 126E-06 4221 39E-06 42273 225E-06 42097 165E-06

1415 18E-06 4698 773E-06 84901 125E-06 42361 388E-06 42449 223E-06 42273 164E-06

14209 178E-06 4717 77E-06 85252 124E-06 42561 385E-06 42625 221E-06 42449 162E-06

14267 177E-06 4737 767E-06 85604 122E-06 42713 383E-06 42801 219E-06 42625 16E-06

14736 164E-06 4892 743E-06 88416 113E-06 44119 363E-06 44207 205E-06 44031 148E-06

14795 163E-06 4912 74E-06 88768 112E-06 44319 36E-06 44383 203E-06 44207 146E-06

14853 162E-06 4932 737E-06 89119 111E-06 44471 358E-06 44558 202E-06 44383 144E-06

14912 16E-06 4951 734E-06 89471 11E-06 44671 355E-06 44734 201E-06 44558 143E-06

1626 133E-06 5401 671E-06 97557 866E-07 4869 304E-06 48777 166E-06 48601 113E-06

16318 132E-06 542 668E-06 97908 862E-07 4889 302E-06 48953 165E-06 48777 111E-06

16377 131E-06 544 666E-06 9826 855E-07 49041 3E-06 49128 164E-06 48953 11E-06

16435 13E-06 546 663E-06 98611 847E-07 49241 298E-06 49304 162E-06 49128 109E-06

16494 129E-06 5478 66E-06 98963 837E-07 49393 296E-06 4948 161E-06 49304 108E-06

16553 127E-06 5498 658E-06 99315 829E-07 49593 294E-06 49656 16E-06 4948 107E-06

16611 127E-06 5518 655E-06 99666 82E-07 49744 292E-06 49832 158E-06 49656 106E-06

1667 126E-06 5537 653E-06 10002 814E-07 49944 29E-06 50007 157E-06 49832 105E-06

16728 124E-06 5557 65E-06 10037 806E-07 50096 288E-06 50183 156E-06 50007 104E-06

17373 114E-06 5771 623E-06 10424 721E-07 52054 267E-06 52117 143E-06 51941 924E-07

1831 101E-06 6084 585E-06 10986 623E-07 54866 24E-06 54929 126E-06 54753 783E-07

18838 934E-07 626 564E-06 11303 574E-07 56424 226E-06 56511 117E-06 56335 713E-07

18896 928E-07 628 562E-06 11338 568E-07 56624 224E-06 56687 117E-06 56511 705E-07

19951 812E-07 6632 524E-06 11971 481E-07 59788 198E-06 59851 102E-06 59675 585E-07

2001 804E-07 665 522E-06 12006 474E-07 5994 197E-06 60027 101E-06 59851 579E-07

20068 799E-07 667 519E-06 12041 472E-07 6014 196E-06 60202 995E-07 60027 573E-07

20127 792E-07 669 517E-06 12076 466E-07 60291 195E-06 60378 989E-07 60202 567E-07

20537 755E-07 6826 503E-06 12322 441E-07 61546 185E-06 61609 942E-07 61433 527E-07

20596 747E-07 6846 501E-06 12357 435E-07 61697 184E-06 61784 935E-07 61609 522E-07

20654 743E-07 6866 499E-06 12392 43E-07 61897 183E-06 6196 926E-07 61784 516E-07

20713 74E-07 6885 498E-06 12428 427E-07 62049 182E-06 62136 921E-07 6196 511E-07

20771 731E-07 6905 496E-06 12463 423E-07 62249 18E-06 62312 911E-07 62136 506E-07

2083 727E-07 6925 494E-06 12498 422E-07 62401 179E-06 62487 904E-07 62312 501E-07

20889 718E-07 6943 492E-06 12533 417E-07 62601 178E-06 62663 899E-07 62487 495E-07

20947 714E-07 6963 49E-06 12568 415E-07 62752 177E-06 62839 89E-07 62663 49E-07

21006 707E-07 6983 488E-06 12603 41E-07 62952 176E-06 63015 885E-07 62839 485E-07

21064 699E-07 7002 486E-06 12638 406E-07 63104 175E-06 63191 882E-07 63015 48E-07

21123 695E-07 7022 484E-06 12674 403E-07 63304 173E-06 63366 877E-07 63191 475E-07

22705 575E-07 7549 435E-06 13623 318E-07 68026 144E-06 68112 714E-07 67937 359E-07

279

22764 57E-07 7569 433E-06 13658 316E-07 68226 143E-06 68288 707E-07 68112 355E-07

22822 57E-07 7588 432E-06 13693 313E-07 68377 143E-06 68464 702E-07 68288 352E-07

22881 565E-07 7608 43E-06 13728 311E-07 68577 141E-06 6864 695E-07 68464 348E-07

22939 562E-07 7628 428E-06 13763 311E-07 68729 141E-06 68815 693E-07 6864 344E-07

22998 557E-07 7646 427E-06 13799 306E-07 68929 14E-06 68991 686E-07 68815 341E-07

23056 554E-07 7666 425E-06 13834 303E-07 6908 139E-06 69167 681E-07 68991 337E-07

23115 547E-07 7686 423E-06 13869 304E-07 6928 138E-06 69343 68E-07 69167 334E-07

23994 494E-07 7979 399E-06 14396 267E-07 71893 125E-06 71979 607E-07 71804 286E-07

24053 489E-07 7998 398E-06 14431 264E-07 72093 124E-06 72155 606E-07 71979 283E-07

24697 45E-07 8214 381E-06 14818 239E-07 74002 115E-06 74089 562E-07 73913 252E-07

25342 417E-07 8428 365E-06 15205 22E-07 7596 106E-06 76022 513E-07 75846 225E-07

254 416E-07 8448 363E-06 1524 217E-07 76111 106E-06 76198 512E-07 76022 223E-07

25459 412E-07 8467 362E-06 15275 217E-07 76311 105E-06 76374 507E-07 76198 22E-07

25517 408E-07 8487 36E-06 1531 216E-07 76463 104E-06 7655 504E-07 76374 218E-07

26865 355E-07 8935 329E-06 16119 186E-07 8053 893E-07 80592 431E-07 80417 172E-07

26924 35E-07 8955 328E-06 16154 181E-07 80682 888E-07 80768 425E-07 80592 17E-07

26982 351E-07 8975 327E-06 16189 182E-07 80882 881E-07 80944 424E-07 80768 168E-07

27041 35E-07 8994 325E-06 16224 183E-07 81033 876E-07 8112 42E-07 80944 166E-07

27099 346E-07 9014 324E-06 1626 178E-07 81233 869E-07 81295 419E-07 8112 165E-07

2792 318E-07 9287 307E-06 16752 163E-07 83694 791E-07 83756 375E-07 83581 142E-07

27978 319E-07 9307 306E-06 16787 16E-07 83846 786E-07 83932 376E-07 83756 141E-07

28037 316E-07 9327 304E-06 16822 16E-07 84046 78E-07 84108 378E-07 83932 139E-07

29092 283E-07 9678 284E-06 17455 143E-07 8721 691E-07 87272 331E-07 87096 116E-07

2915 281E-07 9697 283E-06 1749 145E-07 87361 687E-07 87448 335E-07 87272 114E-07

29267 276E-07 9737 28E-06 1756 141E-07 87713 678E-07 87799 331E-07 87623 112E-07

29326 275E-07 9756 279E-06 17596 136E-07 87913 673E-07 87975 324E-07 87799 111E-07

29385 272E-07 9776 278E-06 17631 138E-07 88065 669E-07 88151 321E-07 87975 11E-07

29443 276E-07 9796 277E-06 17666 14E-07 88265 663E-07 88327 321E-07 88151 109E-07

29795 267E-07 9913 271E-06 17877 133E-07 89319 637E-07 89381 312E-07 89205 102E-07

29853 265E-07 9931 27E-06 17912 132E-07 89471 633E-07 89557 31E-07 89381 101E-07

29912 262E-07 9951 269E-06 17947 133E-07 89671 629E-07 89733 302E-07 89557 1E-07

29971 262E-07 9971 267E-06 17982 133E-07 89822 625E-07 89909 301E-07 89733 99E-08

280


200E-05 000E+00 000E+00 000E+00

02 198E-05 235E-07 910E-09 226E-07

026275 197E-05 308E-07 907E-09 299E-07

043852 195E-05 513E-07 898E-09 504E-07

06143 193E-05 715E-07 888E-09 706E-07

079008 191E-05 916E-07 879E-09 907E-07

096585 189E-05 111E-06 870E-09 111E-06

11416 187E-05 131E-06 861E-09 130E-06

13174 185E-05 150E-06 852E-09 150E-06

14932 183E-05 170E-06 843E-09 169E-06

1669 181E-05 189E-06 834E-09 188E-06

62391 138E-05 619E-06 636E-09 618E-06

64149 137E-05 633E-06 630E-09 633E-06

65907 135E-05 647E-06 623E-09 647E-06

67665 134E-05 661E-06 617E-09 661E-06

69422 132E-05 675E-06 610E-09 675E-06

7118 131E-05 689E-06 604E-09 688E-06

72938 130E-05 703E-06 598E-09 702E-06

74696 128E-05 716E-06 592E-09 715E-06

76453 127E-05 729E-06 586E-09 729E-06

78211 126E-05 743E-06 580E-09 742E-06

79969 124E-05 756E-06 574E-09 755E-06

81727 123E-05 768E-06 568E-09 768E-06

83484 122E-05 781E-06 562E-09 781E-06

14852 829E-06 117E-05 382E-09 117E-05

15028 820E-06 118E-05 378E-09 118E-05

15204 812E-06 119E-05 374E-09 119E-05

15379 804E-06 120E-05 370E-09 120E-05

15555 795E-06 120E-05 367E-09 120E-05

15731 787E-06 121E-05 363E-09 121E-05

15907 779E-06 122E-05 359E-09 122E-05

16083 771E-06 123E-05 355E-09 123E-05

16258 763E-06 124E-05 352E-09 124E-05

16434 755E-06 125E-05 348E-09 124E-05

1661 747E-06 125E-05 344E-09 125E-05

23465 498E-06 150E-05 230E-09 150E-05

23641 493E-06 151E-05 227E-09 151E-05

26453 417E-06 158E-05 192E-09 158E-05

26629 413E-06 159E-05 190E-09 159E-05

26805 409E-06 159E-05 188E-09 159E-05

26981 404E-06 160E-05 186E-09 160E-05

27156 400E-06 160E-05 185E-09 160E-05

27332 396E-06 160E-05 183E-09 160E-05

27508 392E-06 161E-05 181E-09 161E-05

27684 388E-06 161E-05 179E-09 161E-05

2786 384E-06 162E-05 177E-09 162E-05

28035 380E-06 162E-05 175E-09 162E-05

32957 284E-06 172E-05 131E-09 172E-05

33133 281E-06 172E-05 130E-09 172E-05

33309 278E-06 172E-05 128E-09 172E-05

33484 275E-06 172E-05 127E-09 172E-05

3366 272E-06 173E-05 126E-09 173E-05

33836 270E-06 173E-05 124E-09 173E-05

34012 267E-06 173E-05 123E-09 173E-05

34188 264E-06 174E-05 122E-09 174E-05

34363 261E-06 174E-05 121E-09 174E-05

34539 259E-06 174E-05 119E-09 174E-05

34715 256E-06 174E-05 118E-09 174E-05

34891 253E-06 175E-05 117E-09 175E-05

35066 251E-06 175E-05 116E-09 175E-05

38055 210E-06 179E-05 969E-10 179E-05

3823 208E-06 179E-05 959E-10 179E-05

38406 206E-06 179E-05 949E-10 179E-05

38582 204E-06 180E-05 939E-10 180E-05

38758 201E-06 180E-05 929E-10 180E-05

38933 199E-06 180E-05 920E-10 180E-05

44734 142E-06 186E-05 653E-10 186E-05

4491 140E-06 186E-05 646E-10 186E-05

45086 139E-06 186E-05 639E-10 186E-05

45261 137E-06 186E-05 633E-10 186E-05

45437 136E-06 186E-05 626E-10 186E-05

45613 134E-06 187E-05 620E-10 187E-05

45789 133E-06 187E-05 613E-10 187E-05

45965 132E-06 187E-05 607E-10 187E-05

4614 130E-06 187E-05 601E-10 187E-05

46316 129E-06 187E-05 595E-10 187E-05

46492 128E-06 187E-05 588E-10 187E-05

281

46668 126E-06 187E-05 582E-10 187E-05

46843 125E-06 188E-05 576E-10 188E-05

47019 124E-06 188E-05 570E-10 188E-05

47195 122E-06 188E-05 564E-10 188E-05

47371 121E-06 188E-05 559E-10 188E-05

52292 905E-07 191E-05 418E-10 191E-05

52468 896E-07 191E-05 413E-10 191E-05

52644 886E-07 191E-05 409E-10 191E-05

5282 877E-07 191E-05 405E-10 191E-05

52996 868E-07 191E-05 401E-10 191E-05

53171 859E-07 191E-05 396E-10 191E-05

53347 850E-07 191E-05 392E-10 191E-05

5616 720E-07 193E-05 332E-10 193E-05

56335 713E-07 193E-05 329E-10 193E-05

56511 705E-07 193E-05 325E-10 193E-05

56687 698E-07 193E-05 322E-10 193E-05

56863 691E-07 193E-05 319E-10 193E-05

57038 684E-07 193E-05 315E-10 193E-05

57214 677E-07 193E-05 312E-10 193E-05

5739 670E-07 193E-05 309E-10 193E-05

57566 663E-07 193E-05 306E-10 193E-05

57742 656E-07 193E-05 303E-10 193E-05

57917 649E-07 194E-05 299E-10 194E-05

58093 642E-07 194E-05 296E-10 194E-05

58269 636E-07 194E-05 293E-10 194E-05

58445 629E-07 194E-05 290E-10 194E-05

5862 623E-07 194E-05 287E-10 194E-05

58796 616E-07 194E-05 284E-10 194E-05

61784 516E-07 195E-05 238E-10 195E-05

6196 511E-07 195E-05 236E-10 195E-05

62136 506E-07 195E-05 233E-10 195E-05

62312 501E-07 195E-05 231E-10 195E-05

62487 495E-07 195E-05 229E-10 195E-05

62663 490E-07 195E-05 226E-10 195E-05

62839 485E-07 195E-05 224E-10 195E-05

63015 480E-07 195E-05 222E-10 195E-05

63191 475E-07 195E-05 219E-10 195E-05

63366 470E-07 195E-05 217E-10 195E-05

63542 465E-07 195E-05 215E-10 195E-05

63718 461E-07 195E-05 213E-10 195E-05

63894 456E-07 195E-05 210E-10 195E-05

64069 451E-07 195E-05 208E-10 195E-05

64245 446E-07 196E-05 206E-10 196E-05

64421 442E-07 196E-05 204E-10 196E-05

64597 437E-07 196E-05 202E-10 196E-05

70749 304E-07 197E-05 140E-10 197E-05

70925 301E-07 197E-05 139E-10 197E-05

711 298E-07 197E-05 137E-10 197E-05

73913 252E-07 197E-05 116E-10 197E-05

80065 175E-07 198E-05 809E-11 198E-05

80241 173E-07 198E-05 800E-11 198E-05

80417 172E-07 198E-05 792E-11 198E-05

80592 170E-07 198E-05 784E-11 198E-05

80768 168E-07 198E-05 776E-11 198E-05

80944 166E-07 198E-05 768E-11 198E-05

8112 165E-07 198E-05 760E-11 198E-05

81295 163E-07 198E-05 752E-11 198E-05

81471 161E-07 198E-05 744E-11 198E-05

81647 160E-07 198E-05 736E-11 198E-05

81823 158E-07 198E-05 729E-11 198E-05

81999 156E-07 198E-05 721E-11 198E-05

82174 155E-07 198E-05 714E-11 198E-05

8235 153E-07 198E-05 706E-11 198E-05

82526 152E-07 198E-05 699E-11 198E-05

82702 150E-07 199E-05 692E-11 198E-05

82877 148E-07 199E-05 685E-11 199E-05

83053 147E-07 199E-05 678E-11 199E-05

83229 145E-07 199E-05 671E-11 199E-05

86393 121E-07 199E-05 556E-11 199E-05

86569 119E-07 199E-05 551E-11 199E-05

86745 118E-07 199E-05 545E-11 199E-05

282




283


284


285



0 700E-05 00019 621E-05 0002 596E-05 0 700E-05 00146 670E-05 0005 713E-05

0018 633E-05 00215 578E-05 0021 495E-05 00136 612E-05 00635 587E-05 0054 605E-05

0021 619E-05 00254 568E-05 0025 478E-05 00175 589E-05 00732 572E-05 0063 59E-05

0025 606E-05 00293 558E-05 0029 462E-05 00215 568E-05 0083 559E-05 0073 575E-05

0029 594E-05 00332 548E-05 0033 446E-05 00254 548E-05 00928 546E-05 0083 561E-05

0033 582E-05 00371 538E-05 0037 431E-05 00293 529E-05 01025 533E-05 0093 548E-05

0037 570E-05 0041 529E-05 0041 417E-05 00332 511E-05 01123 521E-05 0103 537E-05

0041 559E-05 00449 52E-05 0045 404E-05 00371 494E-05 01221 510E-05 0112 525E-05

0045 548E-05 00488 51E-05 0049 391E-05 0041 477E-05 01319 499E-05 0122 514E-05

0049 537E-05 00527 501E-05 0053 379E-05 00449 461E-05 01416 489E-05 0132 503E-05

0053 527E-05 00566 492E-05 0057 367E-05 00488 446E-05 01514 479E-05 0142 493E-05

0057 517E-05 00605 484E-05 006 355E-05 00527 432E-05 01612 469E-05 0151 484E-05

006 508E-05 00644 477E-05 0064 345E-05 00566 418E-05 01709 460E-05 0161 474E-05

0092 441E-05 00956 419E-05 0096 272E-05 00878 326E-05 02491 397E-05 0239 411E-05

0096 433E-05 00995 412E-05 01 264E-05 00917 317E-05 02589 390E-05 0249 404E-05

01 426E-05 01034 406E-05 0103 256E-05 00956 307E-05 02686 383E-05 0259 397E-05

0103 419E-05 01073 4E-05 0107 249E-05 00995 299E-05 02784 377E-05 0269 391E-05

0107 412E-05 01112 393E-05 0111 242E-05 01034 290E-05 02882 371E-05 0278 384E-05

0228 265E-05 02323 252E-05 0232 111E-05 02245 127E-05 05911 244E-05 0581 248E-05

0232 262E-05 02362 249E-05 0236 108E-05 02284 124E-05 06009 242E-05 0591 245E-05

0236 259E-05 02401 246E-05 024 106E-05 02323 121E-05 06106 239E-05 0601 242E-05

024 256E-05 0244 243E-05 0244 104E-05 02362 118E-05 06204 236E-05 0611 24E-05

0244 253E-05 02479 239E-05 0248 101E-05 02401 115E-05 06302 234E-05 062 237E-05

0248 249E-05 02518 236E-05 0252 992E-06 0244 113E-05 06399 231E-05 063 234E-05

0252 246E-05 02557 233E-05 0256 971E-06 02479 110E-05 06497 229E-05 064 231E-05

0256 243E-05 02596 23E-05 026 950E-06 02518 107E-05 06595 226E-05 065 228E-05

026 241E-05 02635 227E-05 0264 929E-06 02557 105E-05 06692 224E-05 0659 226E-05

0264 238E-05 02674 224E-05 0267 91E-06 02596 102E-05 0679 222E-05 0669 223E-05

0267 235E-05 02713 221E-05 0271 891E-06 02635 997E-06 06888 219E-05 0679 22E-05

0271 232E-05 02752 218E-05 0275 870E-06 02674 973E-06 06986 217E-05 0689 218E-05

0275 229E-05 02791 216E-05 0279 853E-06 02713 950E-06 07083 215E-05 0699 215E-05

0279 227E-05 0283 213E-05 0283 836E-06 02752 927E-06 07181 213E-05 0708 213E-05

0435 148E-05 04392 13E-05 0439 403E-06 04314 367E-06 11089 150E-05 1099 14E-05

0439 146E-05 04431 129E-05 0443 396E-06 04353 359E-06 11187 149E-05 1109 139E-05

0611 975E-06 06149 794E-06 0615 232E-06 06071 135E-06 15486 110E-05 1539 956E-06

0701 802E-06 07047 633E-06 0705 193E-06 06968 814E-07 17733 960E-06 1764 81E-06

0705 795E-06 07086 626E-06 0709 192E-06 07008 796E-07 17831 955E-06 1773 805E-06

0752 720E-06 07554 559E-06 0755 177E-06 07476 613E-07 19003 894E-06 1891 742E-06

286

0755 715E-06 07593 555E-06 0759 177E-06 07515 600E-07 19101 889E-06 19 738E-06

0759 709E-06 07632 55E-06 0763 176E-06 07554 587E-07 19199 884E-06 191 734E-06

0763 703E-06 07671 545E-06 0767 176E-06 07593 574E-07 19297 879E-06 192 729E-06

0841 600E-06 08452 456E-06 0845 161E-06 08374 371E-07 21251 793E-06 2115 644E-06

0845 595E-06 08491 453E-06 0849 162E-06 08413 363E-07 21348 789E-06 2125 641E-06

0935 498E-06 09389 377E-06 0939 150E-06 09311 221E-07 23596 705E-06 235 564E-06

0939 494E-06 09428 375E-06 0943 151E-06 0935 216E-07 23693 702E-06 236 56E-06

1103 362E-06 11068 282E-06 1107 140E-06 1099 869E-08 27797 582E-06 277 458E-06

1107 359E-06 11107 279E-06 1111 141E-06 11029 850E-08 27895 579E-06 278 455E-06

1111 357E-06 11146 277E-06 1115 140E-06 11068 832E-08 27992 577E-06 279 455E-06

1716 121E-06 17197 16E-06 172 132E-06 17119 294E-09 43137 325E-06 4304 3E-06

172 121E-06 17236 161E-06 1724 134E-06 17158 288E-09 43235 324E-06 4314 299E-06

1724 120E-06 17275 16E-06 1728 132E-06 17197 281E-09 43332 323E-06 4324 299E-06

1728 119E-06 17314 159E-06 1731 134E-06 17236 275E-09 4343 322E-06 4333 3E-06

1731 118E-06 17353 159E-06 1735 133E-06 17275 270E-09 43528 321E-06 4343 297E-06

1888 904E-07 18915 152E-06 1892 133E-06 18837 114E-09 47436 282E-06 4734 284E-06

1892 898E-07 18954 151E-06 1895 132E-06 18876 112E-09 47534 281E-06 4744 283E-06

1931 840E-07 19344 148E-06 1934 132E-06 19266 900E-10 48511 273E-06 4841 28E-06

1934 835E-07 19383 148E-06 1938 133E-06 19305 881E-10 48609 272E-06 4851 28E-06

1938 829E-07 19422 148E-06 1942 133E-06 19344 862E-10 48706 271E-06 4861 279E-06

1942 824E-07 19461 149E-06 1946 132E-06 19383 844E-10 48804 270E-06 4871 28E-06

1946 818E-07 195 148E-06 195 132E-06 19422 826E-10 48902 269E-06 488 279E-06

1981 771E-07 19852 148E-06 1985 131E-06 19774 680E-10 49781 262E-06 4968 276E-06

287


TIME AM- P1 I1 P2

0 700E-05 413E-13 237E-11 242E-11

577E-08 700E-05 238E-06 675E-10 238E-06

584E-03 676E-05 389E-06 658E-10 389E-06

974E-03 661E-05 534E-06 643E-10 534E-06

0013644 647E-05 674E-06 628E-10 674E-06

0017548 633E-05 809E-06 614E-10 809E-06

0021452 619E-05 939E-06 600E-10 939E-06

0025356 606E-05 106E-05 587E-10 106E-05

002926 594E-05 118E-05 574E-10 118E-05

0033164 582E-05 130E-05 562E-10 130E-05

0037068 570E-05 141E-05 551E-10 141E-05

0040972 559E-05 152E-05 539E-10 152E-05

0044876 548E-05 163E-05 528E-10 163E-05

004878 537E-05 173E-05 518E-10 173E-05

0052684 527E-05 183E-05 507E-10 183E-05

0056588 517E-05 192E-05 498E-10 192E-05

0060492 508E-05 202E-05 488E-10 202E-05

0064396 498E-05 211E-05 479E-10 211E-05

00683 489E-05 219E-05 470E-10 219E-05

0072204 481E-05 228E-05 461E-10 228E-05

0076108 472E-05 236E-05 453E-10 236E-05

0080012 464E-05 244E-05 444E-10 244E-05

0083916 456E-05 252E-05 437E-10 252E-05

008782 448E-05 259E-05 429E-10 259E-05

0091724 441E-05 267E-05 421E-10 267E-05

0095628 433E-05 274E-05 414E-10 274E-05

0099532 426E-05 281E-05 407E-10 281E-05

010344 419E-05 288E-05 400E-10 288E-05

010734 412E-05 294E-05 394E-10 294E-05

011124 406E-05 301E-05 387E-10 301E-05

011515 399E-05 307E-05 381E-10 307E-05

011905 393E-05 313E-05 375E-10 313E-05

012296 387E-05 319E-05 369E-10 319E-05

012686 381E-05 325E-05 363E-10 325E-05

013076 375E-05 330E-05 357E-10 330E-05

013467 370E-05 336E-05 351E-10 336E-05

0162 333E-05 371E-05 316E-10 371E-05

021275 279E-05 424E-05 264E-10 424E-05

021665 276E-05 428E-05 260E-10 428E-05

022056 272E-05 431E-05 257E-10 431E-05

022446 269E-05 435E-05 253E-10 434E-05

022836 265E-05 438E-05 250E-10 438E-05

023227 262E-05 441E-05 247E-10 441E-05

023617 259E-05 444E-05 244E-10 444E-05

024008 256E-05 447E-05 241E-10 447E-05

024398 253E-05 451E-05 238E-10 451E-05

038452 168E-05 533E-05 157E-10 533E-05

038843 167E-05 535E-05 156E-10 535E-05

039233 165E-05 537E-05 154E-10 537E-05

039624 163E-05 538E-05 152E-10 538E-05

040014 162E-05 540E-05 151E-10 540E-05

040404 160E-05 542E-05 149E-10 542E-05

040795 158E-05 543E-05 148E-10 543E-05

041185 157E-05 545E-05 146E-10 545E-05

041576 155E-05 546E-05 145E-10 546E-05

061486 966E-06 604E-05 896E-11 604E-05

061876 958E-06 605E-05 888E-11 605E-05

062267 950E-06 606E-05 880E-11 606E-05

062657 941E-06 607E-05 872E-11 607E-05

063048 933E-06 607E-05 865E-11 607E-05

063438 925E-06 608E-05 857E-11 608E-05

080616 644E-06 636E-05 594E-11 636E-05

081006 639E-06 637E-05 590E-11 637E-05

081396 634E-06 637E-05 585E-11 637E-05

081787 629E-06 638E-05 580E-11 638E-05

082177 624E-06 638E-05 576E-11 638E-05

082568 619E-06 639E-05 571E-11 639E-05

082958 614E-06 639E-05 567E-11 639E-05

083348 609E-06 640E-05 562E-11 640E-05

083739 604E-06 640E-05 558E-11 640E-05

084129 600E-06 640E-05 553E-11 640E-05

08452 595E-06 641E-05 549E-11 641E-05

08491 590E-06 641E-05 545E-11 641E-05

0853 586E-06 642E-05 540E-11 642E-05

098574 452E-06 655E-05 416E-11 655E-05

098964 448E-06 656E-05 413E-11 655E-05

099355 445E-06 656E-05 410E-11 656E-05

288

12161 294E-06 671E-05 269E-11 671E-05

122 291E-06 671E-05 268E-11 671E-05

12239 289E-06 671E-05 266E-11 671E-05

12278 287E-06 671E-05 264E-11 671E-05

12317 285E-06 672E-05 262E-11 672E-05

12356 283E-06 672E-05 260E-11 672E-05

12395 281E-06 672E-05 258E-11 672E-05

12434 279E-06 672E-05 256E-11 672E-05

12473 277E-06 672E-05 254E-11 672E-05

12512 275E-06 673E-05 253E-11 673E-05

12551 273E-06 673E-05 251E-11 673E-05

1259 271E-06 673E-05 249E-11 673E-05

12903 257E-06 675E-05 235E-11 675E-05

12942 255E-06 675E-05 234E-11 675E-05

12981 253E-06 675E-05 232E-11 675E-05

1302 251E-06 675E-05 230E-11 675E-05

13059 249E-06 675E-05 229E-11 675E-05

13098 248E-06 675E-05 227E-11 675E-05

13137 246E-06 676E-05 226E-11 676E-05

13176 244E-06 676E-05 224E-11 676E-05

13215 243E-06 676E-05 222E-11 676E-05

1665 132E-06 687E-05 121E-11 687E-05

16689 132E-06 687E-05 120E-11 687E-05

16728 131E-06 687E-05 120E-11 687E-05

16767 130E-06 687E-05 119E-11 687E-05

16807 129E-06 687E-05 118E-11 687E-05

17002 125E-06 688E-05 114E-11 688E-05

17041 124E-06 688E-05 113E-11 688E-05

17861 108E-06 689E-05 982E-12 689E-05

179 107E-06 689E-05 976E-12 689E-05

17939 106E-06 689E-05 969E-12 689E-05

19774 776E-07 692E-05 708E-12 692E-05

19813 771E-07 692E-05 703E-12 692E-05

19852 766E-07 692E-05 699E-12 692E-05

19891 761E-07 692E-05 694E-12 692E-05

1993 756E-07 692E-05 690E-12 692E-05

289



290


291


292


293


294


295



0004834 495E-05 486E-05 0009664 617E-05 681777E-05 0019327 477357E-05 682E-05

0014605 476E-05 476E-05 0029194 52E-05 518738E-05 0058389 463358E-05 519E-05

0024376 457E-05 467E-05 0048725 496E-05 473146E-05 009745 450185E-05 473E-05

0034146 447E-05 459E-05 0068256 496E-05 455748E-05 013651 437765E-05 456E-05

0043917 44E-05 450E-05 0087786 496E-05 442709E-05 017557 426036E-05 443E-05

0053688 433E-05 442E-05 010732 489E-05 430699E-05 021463 414937E-05 431E-05

0063458 427E-05 434E-05 012685 478E-05 419942E-05 02537 404425E-05 42E-05

0073229 422E-05 427E-05 014638 465E-05 410301E-05 029276 394451E-05 41E-05

0083 417E-05 419E-05 016591 456E-05 00000401 033182 384973E-05 401E-05

009277 41E-05 412E-05 018544 446E-05 392408E-05 037088 375956E-05 392E-05

010254 405E-05 405E-05 020497 435E-05 383981E-05 040994 367367E-05 384E-05

026864 328E-05 312E-05 053699 288E-05 262757E-05 1074 265557E-05 263E-05

027841 323E-05 308E-05 055652 28E-05 256845E-05 1113 261337E-05 257E-05

036635 287E-05 273E-05 07323 231E-05 21068E-05 14646 228778E-05 211E-05

037612 283E-05 270E-05 075183 227E-05 206311E-05 15037 22567E-05 206E-05

038589 279E-05 266E-05 077136 223E-05 202184E-05 15427 222639E-05 202E-05

039566 275E-05 263E-05 079089 219E-05 198641E-05 15818 219698E-05 199E-05

040543 271E-05 260E-05 081042 215E-05 195068E-05 16208 216827E-05 195E-05

04152 267E-05 256E-05 082995 211E-05 191573E-05 16599 214032E-05 192E-05

042497 263E-05 253E-05 084948 208E-05 188126E-05 1699 211316E-05 188E-05

043474 26E-05 250E-05 086901 205E-05 00000185 1738 208662E-05 185E-05

044451 256E-05 247E-05 088854 201E-05 182233E-05 17771 206082E-05 182E-05

045429 253E-05 244E-05 090807 198E-05 179369E-05 18161 203559E-05 179E-05

046406 249E-05 241E-05 09276 195E-05 176583E-05 18552 201098E-05 177E-05

047383 245E-05 239E-05 094714 192E-05 173689E-05 18943 198702E-05 174E-05

04836 242E-05 236E-05 096667 189E-05 171087E-05 19333 196357E-05 171E-05

049337 238E-05 233E-05 09862 186E-05 168544E-05 19724 194068E-05 169E-05

06497 192E-05 195E-05 12987 152E-05 137592E-05 25974 163591E-05 138E-05

065947 19E-05 193E-05 13182 151E-05 136291E-05 26364 161998E-05 136E-05

075718 169E-05 175E-05 15135 137E-05 123689E-05 3027 147607E-05 124E-05

076695 167E-05 173E-05 15331 136E-05 122854E-05 30661 146303E-05 123E-05

077672 166E-05 171E-05 15526 135E-05 121641E-05 31052 145025E-05 122E-05

078649 164E-05 170E-05 15721 134E-05 120544E-05 31442 143764E-05 121E-05

079626 163E-05 168E-05 15916 133E-05 119485E-05 31833 142525E-05 119E-05

080603 161E-05 166E-05 16112 132E-05 118612E-05 32224 141309E-05 119E-05

10112 133E-05 137E-05 20213 115E-05 103592E-05 40426 119668E-05 104E-05

1021 132E-05 136E-05 20409 114E-05 103184E-05 40817 118793E-05 103E-05

10308 131E-05 135E-05 20604 113E-05 102689E-05 41208 117931E-05 103E-05

296

10405 129E-05 134E-05 20799 113E-05 102165E-05 41598 117079E-05 102E-05

10503 128E-05 132E-05 20994 112E-05 101563E-05 41989 116239E-05 102E-05

10601 128E-05 131E-05 2119 112E-05 101272E-05 4238 115412E-05 101E-05

10698 126E-05 130E-05 21385 111E-05 100835E-05 4277 114593E-05 101E-05

10796 126E-05 129E-05 2158 11E-05 100204E-05 43161 113788E-05 1E-05

10894 125E-05 128E-05 21776 11E-05 998155E-06 43551 11299E-05 998E-06

10991 124E-05 127E-05 21971 109E-05 994369E-06 43942 112203E-05 994E-06

11089 123E-05 126E-05 22166 108E-05 00000099 44333 111428E-05 99E-06

11187 122E-05 125E-05 22362 108E-05 983883E-06 44723 110661E-05 984E-06

11285 121E-05 124E-05 22557 107E-05 97932E-06 45114 109905E-05 979E-06

14216 101E-05 974E-06 28416 916E-06 871214E-06 56832 908951E-06 871E-06

14314 998E-06 967E-06 28611 909E-06 869524E-06 57223 903641E-06 87E-06

15584 937E-06 878E-06 3115 854E-06 82734E-06 62301 839142E-06 827E-06

15681 934E-06 871E-06 31346 852E-06 823903E-06 62691 834507E-06 824E-06

17245 875E-06 777E-06 34471 787E-06 781398E-06 68941 765966E-06 781E-06

17342 874E-06 772E-06 34666 784E-06 779631E-06 69332 762007E-06 78E-06

1744 87E-06 766E-06 34861 779E-06 777728E-06 69722 758072E-06 778E-06

17538 867E-06 761E-06 35057 776E-06 775835E-06 70113 754171E-06 776E-06

18613 833E-06 705E-06 37205 737E-06 746932E-06 7441 713428E-06 747E-06

1871 83E-06 700E-06 374 733E-06 746184E-06 748 709902E-06 746E-06

18808 828E-06 696E-06 37596 731E-06 74301E-06 75191 706404E-06 743E-06

20176 791E-06 634E-06 4033 684E-06 708932E-06 8066 660314E-06 709E-06

20274 789E-06 629E-06 40525 68E-06 707864E-06 8105 657207E-06 708E-06

20371 786E-06 625E-06 4072 677E-06 706194E-06 81441 654132E-06 706E-06

20469 786E-06 621E-06 40916 675E-06 702583E-06 81831 651072E-06 703E-06

20567 784E-06 617E-06 41111 672E-06 699786E-06 82222 648036E-06 7E-06

20664 78E-06 613E-06 41306 668E-06 699029E-06 82613 645029E-06 699E-06

20762 778E-06 609E-06 41502 665E-06 696427E-06 83003 642038E-06 696E-06

2086 777E-06 605E-06 41697 664E-06 694243E-06 83394 639069E-06 694E-06

20958 775E-06 601E-06 41892 662E-06 692194E-06 83785 63613E-06 692E-06

21055 771E-06 597E-06 42088 657E-06 689592E-06 84175 633205E-06 69E-06

21153 77E-06 593E-06 42283 655E-06 688728E-06 84566 630308E-06 689E-06

21251 767E-06 590E-06 42478 653E-06 686583E-06 84956 627426E-06 687E-06

21348 765E-06 586E-06 42673 651E-06 683583E-06 85347 624565E-06 684E-06

21446 762E-06 582E-06 42869 647E-06 680806E-06 85738 621732E-06 681E-06

21544 759E-06 578E-06 43064 645E-06 67965E-06 86128 618912E-06 68E-06

21642 758E-06 575E-06 43259 641E-06 678641E-06 86519 61612E-06 679E-06

23498 715E-06 510E-06 4697 586E-06 635291E-06 9394 566574E-06 635E-06

23596 716E-06 506E-06 47166 584E-06 63368E-06 94331 564139E-06 634E-06

2467 692E-06 473E-06 49314 559E-06 612437E-06 98628 538433E-06 612E-06

24768 691E-06 470E-06 49509 554E-06 611058E-06 99018 536184E-06 611E-06

297

24866 688E-06 467E-06 49705 553E-06 606748E-06 99409 533949E-06 607E-06

24964 688E-06 465E-06 499 551E-06 605126E-06 998 531735E-06 605E-06

25061 688E-06 462E-06 50095 547E-06 602544E-06 10019 529535E-06 603E-06

25159 686E-06 459E-06 5029 544E-06 599796E-06 10058 527349E-06 6E-06

25257 682E-06 456E-06 50486 544E-06 598806E-06 10097 525176E-06 599E-06

25354 681E-06 453E-06 50681 541E-06 597971E-06 10136 523018E-06 598E-06

28188 631E-06 382E-06 56345 479E-06 549631E-06 11269 465777E-06 55E-06

28286 627E-06 379E-06 5654 476E-06 545534E-06 11308 463978E-06 546E-06

28383 627E-06 377E-06 56736 475E-06 544553E-06 11347 46219E-06 545E-06

28481 627E-06 375E-06 56931 473E-06 542951E-06 11386 460412E-06 543E-06

37177 49E-06 229E-06 74313 327E-06 418437E-06 14863 334824E-06 418E-06

37275 491E-06 227E-06 74508 325E-06 418573E-06 14902 333709E-06 419E-06

3874 472E-06 210E-06 77438 304E-06 39634E-06 15488 317572E-06 396E-06

38838 471E-06 209E-06 77633 304E-06 395951E-06 15527 316537E-06 396E-06

3962 461E-06 200E-06 79196 292E-06 388699E-06 15839 308422E-06 389E-06

39717 459E-06 199E-06 79391 29E-06 385291E-06 15878 307429E-06 385E-06

39815 458E-06 198E-06 79586 29E-06 383272E-06 15917 306439E-06 383E-06

39913 458E-06 197E-06 79782 289E-06 381495E-06 15956 305454E-06 381E-06

4001 458E-06 196E-06 79977 287E-06 380689E-06 15995 304473E-06 381E-06

40108 456E-06 195E-06 80172 286E-06 381107E-06 16034 303472E-06 381E-06

41671 437E-06 179E-06 83297 265E-06 363777E-06 16659 288398E-06 364E-06

41769 434E-06 179E-06 83493 265E-06 362039E-06 16699 287492E-06 362E-06

41867 436E-06 178E-06 83688 265E-06 363845E-06 16738 286589E-06 364E-06

41965 435E-06 177E-06 83883 262E-06 360757E-06 16777 285691E-06 361E-06

42062 433E-06 176E-06 84079 261E-06 360291E-06 16816 284796E-06 36E-06

4558 393E-06 146E-06 9111 225E-06 322903E-06 18222 254927E-06 323E-06

45677 392E-06 145E-06 91305 224E-06 322165E-06 18261 25416E-06 322E-06

45775 389E-06 145E-06 915 221E-06 322165E-06 183 253396E-06 322E-06

48315 364E-06 127E-06 96578 194E-06 29535E-06 19316 234527E-06 295E-06

48413 364E-06 126E-06 96773 193E-06 293796E-06 19355 233841E-06 294E-06

48511 362E-06 126E-06 96969 192E-06 293524E-06 19394 233157E-06 294E-06

48609 362E-06 125E-06 97164 193E-06 292427E-06 19433 232476E-06 292E-06

48706 361E-06 124E-06 97359 19E-06 290796E-06 19472 231797E-06 291E-06

48804 361E-06 124E-06 97555 188E-06 290136E-06 19511 231121E-06 29E-06

48902 36E-06 123E-06 9775 188E-06 289602E-06 1955 230447E-06 29E-06

48999 358E-06 123E-06 97945 187E-06 288282E-06 19589 229776E-06 288E-06

49097 357E-06 122E-06 98141 186E-06 286951E-06 19628 229108E-06 287E-06

49781 351E-06 118E-06 99508 18E-06 280621E-06 19902 224484E-06 281E-06

49879 349E-06 117E-06 99703 179E-06 278709E-06 19941 223836E-06 279E-06

49976 348E-06 911E-07 99898 178E-06 278019E-06 1998 215738E-06 278E-06

298


TIME OH- P1 P2

0029194 527E-05 230E-06 230E-06

0048725 513E-05 373E-06 373E-06

0068256 499E-05 507E-06 507E-06

0087786 487E-05 634E-06 634E-06

010732 475E-05 754E-06 754E-06

012685 463E-05 867E-06 867E-06

014638 452E-05 975E-06 975E-06

016591 442E-05 108E-05 108E-05

018544 433E-05 117E-05 117E-05

020497 423E-05 127E-05 127E-05

02245 414E-05 136E-05 136E-05

024403 406E-05 144E-05 144E-05

026356 398E-05 152E-05 152E-05

077136 269E-05 160E-05 281E-05

079089 266E-05 167E-05 284E-05

081042 263E-05 174E-05 287E-05

082995 260E-05 181E-05 290E-05

090807 249E-05 205E-05 301E-05

09276 246E-05 211E-05 304E-05

094714 244E-05 216E-05 306E-05

096667 241E-05 221E-05 309E-05

09862 239E-05 226E-05 311E-05

10057 236E-05 231E-05 314E-05

10253 234E-05 236E-05 316E-05

10448 232E-05 240E-05 318E-05

10643 230E-05 245E-05 320E-05

10839 228E-05 249E-05 322E-05

11034 226E-05 253E-05 324E-05

11229 224E-05 257E-05 326E-05

11424 222E-05 261E-05 328E-05

1162 220E-05 264E-05 330E-05

11815 218E-05 268E-05 332E-05

1201 216E-05 271E-05 334E-05

12206 214E-05 275E-05 336E-05

12401 212E-05 278E-05 338E-05

12596 210E-05 281E-05 340E-05

12792 209E-05 284E-05 341E-05

12987 207E-05 287E-05 343E-05

13182 205E-05 290E-05 345E-05

13377 204E-05 293E-05 346E-05

14745 193E-05 311E-05 357E-05

1494 192E-05 314E-05 358E-05

15135 191E-05 316E-05 359E-05

15331 189E-05 318E-05 361E-05

15526 188E-05 320E-05 362E-05

15721 187E-05 322E-05 363E-05

15916 185E-05 324E-05 364E-05

16112 184E-05 326E-05 366E-05

16307 183E-05 328E-05 367E-05

16502 182E-05 330E-05 368E-05

16698 181E-05 332E-05 369E-05

16893 180E-05 334E-05 370E-05

17088 178E-05 336E-05 372E-05

17284 177E-05 338E-05 373E-05

17479 176E-05 340E-05 374E-05

299

22166 154E-05 341E-05 396E-05

23924 148E-05 355E-05 402E-05

24119 147E-05 357E-05 403E-05

24315 146E-05 358E-05 404E-05

2451 146E-05 359E-05 404E-05

27049 138E-05 361E-05 412E-05

27244 137E-05 362E-05 413E-05

44822 104E-05 372E-05 446E-05

45017 104E-05 373E-05 446E-05

45212 104E-05 374E-05 446E-05

45408 104E-05 375E-05 446E-05

47361 101E-05 385E-05 449E-05

55759 929E-06 386E-05 457E-05

55954 928E-06 387E-05 457E-05

5615 926E-06 388E-05 457E-05

57517 915E-06 393E-05 458E-05

57712 913E-06 394E-05 459E-05

57907 911E-06 395E-05 459E-05

58103 910E-06 396E-05 459E-05

58298 908E-06 397E-05 459E-05

58493 907E-06 397E-05 459E-05

58689 905E-06 398E-05 459E-05

58884 904E-06 399E-05 459E-05

59079 902E-06 399E-05 460E-05

59275 901E-06 400E-05 460E-05

5947 899E-06 401E-05 460E-05

59665 898E-06 402E-05 460E-05

5986 896E-06 402E-05 460E-05

60056 895E-06 403E-05 460E-05

68845 836E-06 404E-05 466E-05

6904 835E-06 404E-05 466E-05

7236 816E-06 405E-05 468E-05

72555 815E-06 406E-05 468E-05

72751 814E-06 406E-05 468E-05

76071 797E-06 407E-05 470E-05

76266 796E-06 407E-05 470E-05

76462 795E-06 408E-05 470E-05

80368 777E-06 409E-05 472E-05

80563 776E-06 409E-05 472E-05

80954 774E-06 410E-05 472E-05

81149 773E-06 411E-05 472E-05

89742 739E-06 412E-05 476E-05

90133 738E-06 413E-05 476E-05

90914 735E-06 415E-05 476E-05

9111 734E-06 415E-05 476E-05

91305 733E-06 416E-05 476E-05

915 733E-06 416E-05 477E-05

98141 711E-06 419E-05 479E-05

98336 710E-06 419E-05 479E-05

98531 710E-06 420E-05 479E-05

98727 709E-06 420E-05 479E-05

98922 708E-06 421E-05 479E-05

99117 708E-06 421E-05 479E-05

99703 706E-06 423E-05 479E-05

99898 706E-06 423E-05 479E-05

104898 691E-06 423E-05 481E-05

300



301


302


303



00048 73E-05 00029 738E-05 00029 729E-05 00048 000007 00029 000007 00029 000007

00146 72E-05 00088 735E-05 00088 727E-05 00146 678E-05 00088 683E-05 000875 67E-05

00244 7E-05 00146 723E-05 00146 713E-05 00244 664E-05 00146 671E-05 001461 65E-05

00341 68E-05 00205 71E-05 00205 697E-05 00341 651E-05 00205 661E-05 002047 63E-05

02784 39E-05 01669 537E-05 01669 438E-05 02784 392E-05 01669 467E-05 016687 35E-05

02882 38E-05 01727 531E-05 01727 431E-05 02882 384E-05 01727 461E-05 017272 35E-05

0298 38E-05 01786 524E-05 01786 424E-05 0298 376E-05 01786 455E-05 017858 34E-05

03077 37E-05 01844 518E-05 01844 417E-05 03077 369E-05 01844 45E-05 018443 33E-05

03175 36E-05 01903 513E-05 01903 41E-05 03175 362E-05 01903 445E-05 019029 33E-05

03273 35E-05 01962 507E-05 01962 404E-05 03273 355E-05 01962 44E-05 019615 32E-05

0337 35E-05 0202 501E-05 0202 396E-05 0337 348E-05 0202 435E-05 0202 32E-05

03468 34E-05 02079 495E-05 02079 39E-05 03468 342E-05 02079 43E-05 020786 31E-05

03566 34E-05 02137 489E-05 02137 384E-05 03566 335E-05 02137 425E-05 021371 31E-05

04738 27E-05 0284 428E-05 0284 318E-05 04738 267E-05 0284 374E-05 028399 25E-05

04836 26E-05 02898 424E-05 02898 314E-05 04836 262E-05 02898 37E-05 028984 25E-05

04934 26E-05 02957 419E-05 02957 309E-05 04934 258E-05 02957 366E-05 02957 25E-05

05031 26E-05 03016 414E-05 03016 304E-05 05031 253E-05 03016 363E-05 030155 24E-05

05129 25E-05 03074 41E-05 03074 3E-05 05129 248E-05 03074 359E-05 030741 24E-05

05227 25E-05 03133 406E-05 03133 296E-05 05227 244E-05 03133 356E-05 031327 24E-05

05325 24E-05 03191 401E-05 03191 291E-05 05325 239E-05 03191 352E-05 031912 23E-05

05422 24E-05 0325 396E-05 0325 287E-05 05422 235E-05 0325 349E-05 032498 23E-05

0552 23E-05 03308 392E-05 03308 283E-05 0552 231E-05 03308 346E-05 033083 23E-05

07474 17E-05 0448 322E-05 0448 212E-05 07474 163E-05 0448 289E-05 044795 18E-05

07572 17E-05 04538 318E-05 04538 21E-05 07572 16E-05 04538 286E-05 045381 17E-05

0767 16E-05 04597 315E-05 04597 207E-05 0767 158E-05 04597 284E-05 045967 17E-05

07767 16E-05 04655 312E-05 04655 204E-05 07767 155E-05 04655 282E-05 046552 17E-05

07865 16E-05 04714 309E-05 04714 201E-05 07865 153E-05 04714 279E-05 047138 17E-05

07963 16E-05 04772 306E-05 04772 198E-05 07963 15E-05 04772 277E-05 047723 17E-05

0806 15E-05 04831 303E-05 04831 196E-05 0806 148E-05 04831 275E-05 048309 17E-05

08158 15E-05 0489 3E-05 0489 193E-05 08158 145E-05 0489 273E-05 048895 16E-05

08256 15E-05 04948 298E-05 04948 191E-05 08256 143E-05 04948 271E-05 04948 16E-05

08353 15E-05 05007 295E-05 05007 188E-05 08353 141E-05 05007 268E-05 050066 16E-05

08451 15E-05 05065 292E-05 05065 185E-05 08451 138E-05 05065 266E-05 050651 16E-05

08549 14E-05 05124 289E-05 05124 183E-05 08549 136E-05 05124 264E-05 051237 16E-05

08647 14E-05 05182 287E-05 05182 181E-05 08647 134E-05 05182 262E-05 051823 15E-05

08744 14E-05 05241 284E-05 05241 178E-05 08744 132E-05 05241 26E-05 052408 15E-05

08842 14E-05 05299 282E-05 05299 176E-05 08842 13E-05 05299 258E-05 052994 15E-05

0894 14E-05 05358 279E-05 05358 174E-05 0894 128E-05 05358 256E-05 053579 15E-05

304

09037 13E-05 05417 276E-05 05417 171E-05 09037 126E-05 05417 254E-05 054165 15E-05

09135 13E-05 05475 274E-05 05475 169E-05 09135 124E-05 05475 252E-05 054751 15E-05

09233 13E-05 05534 272E-05 05534 167E-05 09233 122E-05 05534 25E-05 055336 15E-05

09331 13E-05 05592 269E-05 05592 165E-05 09331 12E-05 05592 248E-05 055922 14E-05

09428 13E-05 05651 267E-05 05651 163E-05 09428 118E-05 05651 246E-05 056507 14E-05

11187 98E-06 06705 228E-05 06705 13E-05 11187 9E-06 06705 217E-05 067048 12E-05

11285 97E-06 06763 226E-05 06763 129E-05 11285 887E-06 06763 215E-05 067634 12E-05

11382 96E-06 06822 225E-05 06822 127E-05 11382 874E-06 06822 214E-05 068219 12E-05

15291 61E-06 09164 165E-05 09164 819E-06 15291 509E-06 09164 166E-05 091643 83E-06

15388 6E-06 09223 164E-05 09223 809E-06 15388 503E-06 09223 165E-05 092229 83E-06

15486 59E-06 09282 163E-05 09282 803E-06 15486 497E-06 09282 164E-05 092815 82E-06

15584 58E-06 0934 161E-05 0934 797E-06 15584 49E-06 0934 163E-05 0934 82E-06

15681 58E-06 09399 16E-05 09399 787E-06 15681 484E-06 09399 162E-05 093986 81E-06

15779 57E-06 09457 159E-05 09457 78E-06 15779 478E-06 09457 161E-05 094571 8E-06

15877 57E-06 09516 158E-05 09516 774E-06 15877 473E-06 09516 16E-05 095157 8E-06

15975 56E-06 09574 157E-05 09574 765E-06 15975 467E-06 09574 16E-05 095743 79E-06

16072 56E-06 09633 156E-05 09633 758E-06 16072 461E-06 09633 159E-05 096328 78E-06

1617 55E-06 09691 155E-05 09691 75E-06 1617 456E-06 09691 158E-05 096914 78E-06

16268 55E-06 0975 154E-05 0975 743E-06 16268 45E-06 0975 157E-05 097499 77E-06

21251 37E-06 12736 112E-05 12736 487E-06 21251 255E-06 12736 12E-05 12736 54E-06

21348 36E-06 12795 111E-05 12795 482E-06 21348 252E-06 12795 12E-05 12795 54E-06

21446 36E-06 12854 111E-05 12854 479E-06 21446 249E-06 12854 119E-05 12854 53E-06

21544 36E-06 12912 11E-05 12912 477E-06 21544 247E-06 12912 118E-05 12912 53E-06

21642 36E-06 12971 109E-05 12971 473E-06 21642 244E-06 12971 118E-05 12971 52E-06

21739 36E-06 13029 109E-05 13029 469E-06 21739 242E-06 13029 117E-05 13029 52E-06

21837 35E-06 13088 109E-05 13088 466E-06 21837 239E-06 13088 117E-05 13088 52E-06

21935 35E-06 13146 108E-05 13146 463E-06 21935 237E-06 13146 116E-05 13146 51E-06

22032 35E-06 13205 107E-05 13205 459E-06 22032 235E-06 13205 116E-05 13205 51E-06

2213 35E-06 13264 107E-05 13264 457E-06 2213 232E-06 13264 115E-05 13264 51E-06

22228 35E-06 13322 106E-05 13322 455E-06 22228 23E-06 13322 115E-05 13322 5E-06

22325 34E-06 13381 105E-05 13381 449E-06 22325 228E-06 13381 114E-05 13381 5E-06

2555 29E-06 15313 894E-06 15313 372E-06 2555 167E-06 15313 981E-06 15313 41E-06

25647 29E-06 15372 888E-06 15372 369E-06 25647 165E-06 15372 977E-06 15372 41E-06

25745 29E-06 1543 884E-06 1543 368E-06 25745 164E-06 1543 973E-06 1543 4E-06

25843 29E-06 15489 882E-06 15489 368E-06 25843 162E-06 15489 968E-06 15489 4E-06

25941 29E-06 15547 878E-06 15547 365E-06 25941 161E-06 15547 964E-06 15547 4E-06

26038 29E-06 15606 872E-06 15606 363E-06 26038 16E-06 15606 96E-06 15606 4E-06

26136 28E-06 15664 869E-06 15664 361E-06 26136 158E-06 15664 956E-06 15664 39E-06

26234 29E-06 15723 865E-06 15723 36E-06 26234 157E-06 15723 952E-06 15723 39E-06

26331 28E-06 15782 861E-06 15782 359E-06 26331 155E-06 15782 947E-06 15782 39E-06

26429 28E-06 1584 858E-06 1584 357E-06 26429 154E-06 1584 943E-06 1584 39E-06

305

26527 28E-06 15899 855E-06 15899 357E-06 26527 153E-06 15899 939E-06 15899 38E-06

26625 28E-06 15957 85E-06 15957 355E-06 26625 151E-06 15957 935E-06 15957 38E-06

26722 28E-06 16016 845E-06 16016 352E-06 26722 15E-06 16016 931E-06 16016 38E-06

2682 28E-06 16074 844E-06 16074 352E-06 2682 149E-06 16074 927E-06 16074 38E-06

26918 28E-06 16133 84E-06 16133 351E-06 26918 147E-06 16133 923E-06 16133 38E-06

27015 28E-06 16192 835E-06 16192 348E-06 27015 146E-06 16192 919E-06 16192 37E-06

27113 28E-06 1625 832E-06 1625 346E-06 27113 145E-06 1625 916E-06 1625 37E-06

27211 27E-06 16309 829E-06 16309 345E-06 27211 144E-06 16309 912E-06 16309 37E-06

27309 28E-06 16367 823E-06 16367 344E-06 27309 142E-06 16367 908E-06 16367 37E-06

27406 27E-06 16426 82E-06 16426 341E-06 27406 141E-06 16426 904E-06 16426 36E-06

32096 24E-06 19237 686E-06 19237 288E-06 32096 963E-07 19237 744E-06 19237 28E-06

32194 24E-06 19295 683E-06 19295 29E-06 32194 956E-07 19295 741E-06 19295 28E-06

32292 24E-06 19354 681E-06 19354 288E-06 32292 949E-07 19354 739E-06 19354 27E-06

32389 24E-06 19412 679E-06 19412 284E-06 32389 942E-07 19412 736E-06 19412 27E-06

32487 24E-06 19471 677E-06 19471 285E-06 32487 935E-07 19471 733E-06 19471 27E-06

41574 22E-06 24917 53E-06 24917 243E-06 41574 506E-07 24917 523E-06 24917 17E-06

41671 22E-06 24976 528E-06 24976 241E-06 41671 503E-07 24976 522E-06 24976 17E-06

41769 22E-06 25034 527E-06 25034 241E-06 41769 5E-07 25034 52E-06 25034 17E-06

41867 22E-06 25093 526E-06 25093 242E-06 41867 497E-07 25093 518E-06 25093 17E-06

41965 22E-06 25151 525E-06 25151 24E-06 41965 494E-07 25151 516E-06 25151 16E-06

42062 22E-06 2521 523E-06 2521 241E-06 42062 491E-07 2521 515E-06 2521 16E-06

4216 22E-06 25268 524E-06 25268 242E-06 4216 488E-07 25268 513E-06 25268 16E-06

42258 22E-06 25327 52E-06 25327 241E-06 42258 486E-07 25327 511E-06 25327 16E-06

45287 21E-06 27142 488E-06 27142 237E-06 45287 408E-07 27142 461E-06 27142 14E-06

45384 21E-06 27201 486E-06 27201 236E-06 45384 406E-07 27201 46E-06 27201 14E-06

45482 21E-06 27259 488E-06 27259 237E-06 45482 404E-07 27259 458E-06 27259 14E-06

4558 21E-06 27318 486E-06 27318 236E-06 4558 401E-07 27318 457E-06 27318 14E-06

45677 21E-06 27376 486E-06 27376 235E-06 45677 399E-07 27376 455E-06 27376 14E-06

45775 21E-06 27435 485E-06 27435 234E-06 45775 397E-07 27435 454E-06 27435 14E-06

48804 21E-06 2925 463E-06 2925 231E-06 48804 338E-07 2925 411E-06 2925 12E-06

48902 21E-06 29309 462E-06 29309 23E-06 48902 336E-07 29309 409E-06 29309 12E-06

48999 21E-06 29368 46E-06 29368 229E-06 48999 335E-07 29368 408E-06 29368 12E-06

49097 21E-06 29426 46E-06 29426 229E-06 49097 333E-07 29426 407E-06 29426 12E-06

49195 21E-06 29485 46E-06 29485 229E-06 49195 331E-07 29485 406E-06 29485 12E-06

49293 21E-06 29543 458E-06 29543 23E-06 49293 33E-07 29543 404E-06 29543 12E-06

4939 21E-06 29602 459E-06 29602 229E-06 4939 328E-07 29602 403E-06 29602 11E-06

49586 21E-06 29719 458E-06 29719 23E-06 49586 325E-07 29719 4E-06 29719 11E-06

49683 21E-06 29777 455E-06 29777 229E-06 49683 323E-07 29777 399E-06 29777 11E-06

49781 21E-06 29836 456E-06 29836 228E-06 49781 322E-07 29836 398E-06 29836 11E-06

49879 21E-06 29895 455E-06 29895 23E-06 49879 32E-07 29895 397E-06 29895 11E-06

49976 21E-06 29953 451E-06 29953 229E-06 49976 318E-07 29953 395E-06 29953 11E-06

306



0014605 216E-06 121E-09 215E-06 496E-09

0024376 356E-06 199E-09 355E-06 137E-08

0034146 493E-06 276E-09 490E-06 266E-08

0043917 628E-06 351E-09 623E-06 437E-08

0053688 759E-06 424E-09 752E-06 647E-08

0063458 887E-06 496E-09 878E-06 897E-08

0073229 101E-05 567E-09 100E-05 118E-07

0083 114E-05 635E-09 112E-05 151E-07

009277 126E-05 703E-09 124E-05 187E-07

010254 137E-05 768E-09 135E-05 226E-07

011231 149E-05 833E-09 146E-05 269E-07

012208 160E-05 896E-09 157E-05 315E-07

063993 503E-05 289E-08 448E-05 551E-06

06497 507E-05 291E-08 450E-05 564E-06

065947 510E-05 293E-08 452E-05 576E-06

066924 513E-05 295E-08 454E-05 588E-06

067901 516E-05 297E-08 456E-05 601E-06

068878 519E-05 299E-08 458E-05 613E-06

069855 523E-05 301E-08 460E-05 626E-06

070832 526E-05 303E-08 461E-05 638E-06

071809 528E-05 305E-08 463E-05 651E-06

072786 531E-05 307E-08 465E-05 663E-06

073763 534E-05 309E-08 466E-05 676E-06

074741 537E-05 310E-08 468E-05 688E-06

075718 540E-05 312E-08 469E-05 701E-06

076695 542E-05 314E-08 471E-05 713E-06

077672 545E-05 316E-08 472E-05 726E-06

078649 547E-05 317E-08 473E-05 738E-06

079626 550E-05 319E-08 474E-05 751E-06

080603 552E-05 320E-08 476E-05 763E-06

08158 555E-05 322E-08 477E-05 776E-06

082557 557E-05 324E-08 478E-05 789E-06

083534 559E-05 325E-08 479E-05 801E-06

10308 597E-05 350E-08 492E-05 105E-05

10405 599E-05 351E-08 492E-05 106E-05

10503 600E-05 352E-08 493E-05 107E-05

10601 602E-05 354E-08 493E-05 109E-05

10698 603E-05 355E-08 493E-05 110E-05

10796 605E-05 356E-08 493E-05 111E-05

15681 652E-05 390E-08 484E-05 167E-05

15779 652E-05 391E-08 484E-05 168E-05

15877 653E-05 391E-08 483E-05 169E-05

15975 653E-05 392E-08 483E-05 170E-05

16072 654E-05 392E-08 482E-05 171E-05

1617 654E-05 393E-08 482E-05 172E-05

16268 655E-05 393E-08 481E-05 173E-05

16365 656E-05 394E-08 481E-05 174E-05

16463 656E-05 394E-08 480E-05 175E-05

16561 657E-05 395E-08 480E-05 176E-05

16658 657E-05 395E-08 479E-05 177E-05

16756 658E-05 395E-08 479E-05 178E-05

16854 658E-05 396E-08 479E-05 179E-05

16952 659E-05 396E-08 478E-05 180E-05

17049 659E-05 397E-08 478E-05 181E-05

17147 660E-05 397E-08 477E-05 182E-05

17245 660E-05 397E-08 477E-05 183E-05

17342 661E-05 398E-08 476E-05 184E-05

1744 661E-05 398E-08 476E-05 185E-05

17538 661E-05 399E-08 475E-05 186E-05

17636 662E-05 399E-08 474E-05 187E-05

17733 662E-05 399E-08 474E-05 188E-05

17831 663E-05 400E-08 473E-05 189E-05

17929 663E-05 400E-08 473E-05 190E-05

18026 664E-05 400E-08 472E-05 191E-05

18124 664E-05 401E-08 472E-05 192E-05

18222 664E-05 401E-08 471E-05 193E-05

18319 665E-05 401E-08 471E-05 194E-05

18417 665E-05 402E-08 470E-05 195E-05

18515 666E-05 402E-08 470E-05 195E-05

18613 666E-05 402E-08 469E-05 196E-05

28676 687E-05 423E-08 412E-05 275E-05

28774 687E-05 423E-08 411E-05 276E-05

28872 688E-05 423E-08 411E-05 277E-05

2897 688E-05 423E-08 410E-05 277E-05

29067 688E-05 424E-08 410E-05 278E-05

307

29165 688E-05 424E-08 409E-05 278E-05

29263 688E-05 424E-08 408E-05 279E-05

2936 688E-05 424E-08 408E-05 280E-05

29458 688E-05 424E-08 407E-05 280E-05

29556 688E-05 424E-08 407E-05 281E-05

29653 688E-05 424E-08 406E-05 281E-05

29751 688E-05 424E-08 406E-05 282E-05

29849 689E-05 424E-08 405E-05 283E-05

29947 689E-05 425E-08 405E-05 283E-05

30044 689E-05 425E-08 404E-05 284E-05

30142 689E-05 425E-08 404E-05 284E-05

3024 689E-05 425E-08 403E-05 285E-05

31705 690E-05 426E-08 396E-05 294E-05

31803 690E-05 426E-08 395E-05 294E-05

31901 690E-05 426E-08 395E-05 295E-05

34246 692E-05 428E-08 384E-05 308E-05

34343 692E-05 428E-08 383E-05 308E-05

34441 692E-05 429E-08 383E-05 309E-05

34539 692E-05 429E-08 382E-05 309E-05

35027 692E-05 429E-08 380E-05 312E-05

35125 692E-05 429E-08 379E-05 312E-05

35223 692E-05 429E-08 379E-05 313E-05

3532 692E-05 429E-08 379E-05 313E-05

35418 693E-05 429E-08 378E-05 314E-05

35516 693E-05 429E-08 378E-05 314E-05

36786 693E-05 430E-08 372E-05 321E-05

36884 693E-05 430E-08 372E-05 321E-05

40597 695E-05 432E-08 356E-05 338E-05

40694 695E-05 432E-08 356E-05 339E-05

40792 695E-05 432E-08 355E-05 339E-05

4089 695E-05 432E-08 355E-05 339E-05

40987 695E-05 432E-08 355E-05 340E-05

41085 695E-05 432E-08 354E-05 340E-05

41183 695E-05 432E-08 354E-05 341E-05

41281 695E-05 433E-08 353E-05 341E-05

41378 695E-05 433E-08 353E-05 341E-05

41476 695E-05 433E-08 353E-05 342E-05

41574 695E-05 433E-08 352E-05 342E-05

41671 695E-05 433E-08 352E-05 343E-05

41769 695E-05 433E-08 352E-05 343E-05

41867 695E-05 433E-08 351E-05 343E-05

41965 695E-05 433E-08 351E-05 344E-05

42062 695E-05 433E-08 350E-05 344E-05

44016 696E-05 434E-08 343E-05 352E-05

44114 696E-05 434E-08 343E-05 352E-05

44212 696E-05 434E-08 342E-05 353E-05

44309 696E-05 434E-08 342E-05 353E-05

44407 696E-05 434E-08 342E-05 354E-05

44505 696E-05 434E-08 341E-05 354E-05

44603 696E-05 434E-08 341E-05 354E-05

447 696E-05 434E-08 341E-05 355E-05

44798 696E-05 434E-08 340E-05 355E-05

44896 696E-05 434E-08 340E-05 355E-05

44993 696E-05 434E-08 340E-05 356E-05

45091 696E-05 434E-08 339E-05 356E-05

45189 696E-05 434E-08 339E-05 357E-05

45287 696E-05 434E-08 339E-05 357E-05

45384 696E-05 434E-08 338E-05 357E-05

45482 696E-05 434E-08 338E-05 358E-05

4558 696E-05 434E-08 338E-05 358E-05

45677 696E-05 434E-08 337E-05 358E-05

48804 697E-05 435E-08 327E-05 369E-05

48902 697E-05 435E-08 327E-05 370E-05

48999 697E-05 435E-08 326E-05 370E-05

49097 697E-05 435E-08 326E-05 370E-05

49195 697E-05 435E-08 326E-05 371E-05

49293 697E-05 435E-08 325E-05 371E-05

4939 697E-05 435E-08 325E-05 371E-05

49488 697E-05 436E-08 325E-05 372E-05

49586 697E-05 436E-08 324E-05 372E-05

49683 697E-05 436E-08 324E-05 372E-05

49879 697E-05 436E-08 323E-05 373E-05

49976 697E-05 436E-08 323E-05 373E-05







Abstract



1 Introduction










2 Experimental







+ 2OHminus(aq)

and





22 Kinetics





32 BOD5 and COD










Time sec

0 20 40 60

[BB

+ ] M

0

5e-6

1e-5

2e-5

2e-5

3e-5

3e-5



a

d










117 223 310 1909 375 790 88 2107234 513 135 2194 750 1595 43 2127351 739 94 2106 938 1929 36 2058468 1073 65 2294 1125 2411 29 2143585 1313 53 2244 150 3345 21 2230









0 1066 320 300210 1166 345 295920 1266 371 293130 1366 403 295140 1464 449 306650 1499 462 3082Mean= 2999plusmn 063


a k = kprime[HOCl]











4 Conclusions




Acknowledgements


References
















Coverpagepdf

Table of Contents

LIST OF FIGURES

CHAPTER1AND2FINAL



Conclusions

references

Appendix

PUBLICATION


Introduction

Experimental


Kinetics



BOD5 and COD


Conclusions

Acknowledgements

References










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