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Spring 1972

A spectrophotometric study of the reactionbetween benzoyl peroxide and N, N-dimethyl-P-phenylenediamineBertha Cosby King

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Recommended CitationKing, Bertha Cosby, "A spectrophotometric study of the reaction between benzoyl peroxide and N, N-dimethyl-P-phenylenediamine"(1972). Master's Theses. Paper 359.

A SPECTROPHOTOMETRIC STUDY

OF THE REACTION BETWEEN

BENZOYL PEROXIDE AND N,N-DIMETHYL-P-PHENYLENEDIAMINE

BY

BERTHA COSBY KING

A THESIS S~8MITTED TO THE GRADUATE FACULTY .. OF THE UNIVERSITY OF RICHMOND

IN CANDIDACY FOR THE DEGREE OF

MA8TER OF SCIENCE IN CHEMISTRY

JUNE 1972

UBRARf

UM1VE:RSITY OF RICHMONv J'Ol~!~JIA

APPROVED:

ACKNOWLEDGMENT

With the completion of this work, I wish to express

my sincerest thanks to Dr. w. Allan Powell for his per­

sonal interest and guidance throughout this project.

I wish to express my appreciation to Dr. J. Stanton

. Pierce, whose wiae counsel and contagious enthusiam

helped in the completion of this wbrk.

I would like to thank the other members of the de­

partment for their patience and encouragement •

. Finally, I want to thank my family for their sup­

port and cooperation.

TABLE OF CONTENTS

' . INTRODUCTION •

HISTORICAL,., .•.•

• •

• • •

• •

• •

• • • • • • • •

• • • • • • ... • • • • •

• •

• •

• •

• •

• • •

• • •

Page \ l

4 I. Organic Peroxides. • • • • • • • • • • • • • • • • • 4

A., Classification and Stability • • • • • • • • • • 4

B. Methods of Analysis •• • • • • • • • • ••• • • 5

1. Volumetric • • • • • • • • • • • • • • • • • 6

2. Polarographic, infrared, and chromato-

,. 8 graphic • • • • • • • • • • • • • • • · • • • • " ..

3. Colorimetric • • • • • • • • • • • • • • • • 10

4 .. The spectrophotometric method using N,N­

dimethyl~p-phenylenediamine sulfate. .. • • • 15 II. Oxidation of Amines •••• ~ • • • • •

A. Formation of Free Radicals • • • •

• • • • • • •

• • • • • • •

23

24 B. Reactions of N,N-Dimethyl-p-phenylenediamine • • 28

c. Formation 'or Wurster• s Red • • • • • • • • • • •

EXPERIMENTAL • • • • • • • • • • • • • • • • • • • • • • • •

I. Reagents

II.· Apparatus

• • • • • . . .. • • • • • • • • • • • • • •

• \ • 0 . .. . . . . • • • • • • • • • • •

III. Preparation of Solutions and General Procedure •• • • IV. Data and Results •••••• • • • • • • • • • • • • •

" I

A. A Study of the Effect .of Variables on Dugan's ,; I .

Method •• • • • • • • • • • • • • • • • • • • ,,

B • N, N-D~methy.1-p-phenylenediamine Sulfate in

Methanol. • • • • • • • • o •••• 0 ••.••

• •

• •

29

36

36

37

38

40

40

43

v.

S~ARY.

APPENDIX

Page· c. N,N-Dimethyl-p-phenylenediamine·Sulfate in ,

,,•:I ..,_.:; .

• Water •••••• • • • • • • • • • • • • • • . • .. 46

D. N,N-Dimethyl-p-phenylenediamine Sulfate in

Acetone •• • • • • • • • • • • • • • • • • . ... . E. Separation of the Colored Reaction Product •••

" .

F. Reaction of the Amine with Bromine and Ferric

Ions •• • • • • • • • • • • . .• '. . . . G. P~vel~pment of a Method for the Determination

of Peroxides Substituting Pyridine for Benzene •

Discussion •••• • • • • 8 '. • • • • • • • • • • •

A.

B.

c.

' . Identification of Wurster's Red ••••••••

Identification of p,p'-Bis(dimethylamino)-

azobenzene • • • • • • • • • • • • • • • • • • '

Further Analysis of the Spectra •• • • • • • • •

•

•

•

D. The Modification of Dugan~s Method •••••••

~ • • • 0 • • • • • • • • • • • • • • • • • • • • •

eeeeee•eoeeoe~OGeee•oe•e•e

···. ··"

49

49

.51 ..

51

57

57

59 64

66

68

69

BIBLIOGRAPHY . . . .. . . (. '

• • • • • • •. '. ·. • • . • • • • • . • • • • 132 ,, AUTOBIOGRAPHY. • • • • • • • •• ·~· •• 0 ••••••••• 138 ,,

. I

(1)

INTRODUCTION

A special need for methods to determine low concen-

trations of organic peroxides originated because of their

hazardous and harmful effects, Even the small amounts of

organio peroxide~ formed by autoxidation in ethers exposed ...

to air make the ethers highly explosive and unsuitable for

use as anesthesia or laboratory solvents. The formation of

organic peroxides in fats and oils causes rancid'ity. They

have been named as pollutants, and some of them are known

to have detrimental.physiological eff~cts (47).

As organic. peroxides are oxidants and sources of free •,

radicals, within recent years they have been used commer-

cially as initiators and catalysts in polymerization, as

bleaches, as disinfectants, and as fuel additives. In

addition, they are intermediates in certain oxidation pro­

cesses for the production of alcohols and phenols (34).

In these 'processes the amount of unused peroxide requires

determination. For example, as polymeri~ation catalysts

in the synthesis of rubber or plastics, organic peroxides

may remain in the finished product, which is often used in

rood packaging, thus allowing peroxide migration into food.

With the variation in the techn<5logy of their applications~

(2)

many n~w p~rox~des are being synthesized. As more is known

of their cnemistry and behavior, they will have wider use,

requiring·. simple, rapid, reliable methods of .determination.

N,N-Dimethyl-p-phenylenediamine sulfate has been used "

in a quantitative .spectrophotometric determination for sev­

eral types. of. organic peroxides •. This method was developed

by Dugan :(12), using' benzoyl,and lauroyl peroxides in ben•

zene. A mixture ·of water. ,arid methanol was used as the sol-

vent for .the amine sulfate •. The method was later extended

to include' the.detection of traces of peroxides in ethers . .

and of other ~pacific peroxides {13, 14).

This .. mit thod needs modifies ti on. Al though the color

forms rapidly (with benzoyl peroxide maximu.~ formation oc­

curs in approximately five minutes) and the standard curves

for the peroxides studied follow Beer's Law, color fading is

apparent. Absorbance.at the.specified wavelengths changes

rapidly,. making the time 'ror measuring the absorbancesori ti•·

cal. In. determini~g benzoyl peroxide, the absorbance is ap­

proximately 70 percent of the maximum value and continues to

decrease after thirty minutes, the time allowed for color

development, by the Dugan method.

The formation of different colored products was observed

by Dugan at different pH values.' and in different solvents. .. .

Howev.er, no identificati.on of these products was made. Ac-

cording 'to' Dugan, the reaotan,ts were the amine sulfate and " I ' ',

( 3)

methanol, which formed a colored complex, and the reaction

was cats.lysed by a free radical mechanism. According to

Dugan, it involved the splitting off of -Ng~~ from the ben­

zene ring. However, this seemed to be too drastic a reac­

tion for occurrence at room temperature and an unusual reac-

tion for an aromatic tertiary amine.

The purpose of this research was to improve this method

of analysis and to determine better conditions for the meRs~··

urement of color b'y studying the separate effects of the

solvents used, and the effect of pH, the amine concentration,

and the order of addition of reagents. The' purpose also was

to learn more about the reaction that occurs and to identify,

if possible, one or more of the colored products.

(4)

HISTORICAL

I. Organic Peroxides

A. Classification and Stability

Organic peroxides are characterized by an -0-0- linkage. ~

Martin (34) divides them in~o six types.

Type Example Analog

1) Hydroperoxide · C2H5ooH C2H50H

2) Dialkyl (also diaryl) c2H5ooc2H5 c2H5oc2H5

3) Peroxyacid (or ~er-acid) CH3C~QooH CH3C~QOH

4) Peroxy ester CH3c~QOOC(CH3 )3 . 0 CH3C~-OC(GH3))

5) Diacyl (also diaroyl) . CH3C" ... Oooc~2cH3 CH3C~Qoc~QCH3

6) Peroxy derivatives of H

<e:._xO aldehydes and ketones - 0 OH

Other examples of peroxide linkage are found in polymers formed

from conjugated olefins plus oxygen, for example, ,_

+

x trans annular peroxides of terpenes ~·· sterols, and polynuclear aro­

matic hydrocarbons, for example,· · -6- ,cH3 CH3 0-0 CH 'CH .

3

(5)

and polyalkylidene peroxides, for example, the dimeric and tri~ I

meric acetone peroxides such ~s

Ozonides also have a peroxide linkage.

Organic peroxides have a wide range of stability, This class

of compounds as a whole should be treated with respect because.

ce:Dtain perr.&ides ·decG.'llpose violently when exposed to heat or

shock. N~vertheless, all organic peroxides are not dangerous as

was shown in a study by Noller and Bolton (47). They may have 11

half lives, which vary from one second to over twenty years at

50 degrees centigrade (36). Peroxides with high oxygen content

are most likely to be unstable and are extremely dangerous if the

ratio of hytlrogen .to oxygen or carbon to oxygen is three (or \

less) to one. Organic. peroxides are most stable in neutral or

slightly acidic aqueous solutions.

B. · Methods of Ana'lysis'

The usual methods of oxidation-reduction analysis have been

applied to"organic peroxide's' 1 (35). These include the· reduction

of the peroxide linkage. All methods, however, are not applica­

ble to all peroxides. In the reduction reaction of peroxides,

there is a wide range 'of' ;r~acti vi ty not predictable from their

structures, Moreover, the relative reactivities among reducing

agents are not consistent. In application, many of the usual

'methods of analysis must b'e 'modified due to s'llub~li ty problems.

(6)

The reduction of the peroxide linkage is followed by ti tra\ .. •

tion or a colorimetric estimation. These titrations are all in-

direct. It is the oxidized reducing agent or the excess reducing

agent that is titrated. In the case where eerie ions are used

to oxidize hydrogen peroxide or hydroperoxides (37), the excess

oxidizing agent is titrated. Titration endpoints are determined

visually using indicators, potentiometrically, amperometrically,

or with "dead-stop" techniques. Colorimetric methods can be a·p-,. '

plied in the case of a colored oxidation product. If the reduc­

ing agent is colored, the excess may be estimated colorimetrical­

ly.

1. Volumetric

Martin (37) describes four volumetric methods, which are io­

dometric, stannous ion reduction, arsenious oxide r·eduction, and

eerie ammonium sulfate oxidation. The iodometric method is

thought to be the most convenient, precise, and accurate method

for samples containing more than 0.05 milliequivalents of perox­

ides if they are easily reduced~ For smaller amounts, colorimet-

ric methods are· more sensitive. For example, this wes found to

be true in c~~paring the iodometric method with the ferrothiocy­

anate color'imetric method when determining peroxides in marga•

rines and edible oils {10). According to Martin, the best iodo­

metric procedure is that of Wagner, Smith, and Peters (37). The

usual sources of error for this method are loss of iodine by side

reactions,. volatilization,, and incomplete reaction, along with,

(7)

the addition of iodine to double bonds if present. • • The advantage of the stannous ion reduction method is that

it can be used in the presence of sulfur or conjugated olefinic

compounds.· Materials reduced by the stannous ion interfere.

This method will not tolerate aldehydes, thioethers or primary

alcohols. The procedure is that excess stannous ions are ti­

trated with ferric or iodine solutions, or an excess of ferric

ions is added, and the resulting ferrous ions are titrated with

pota~sium dichromate.

In the arsenious oxide reduction method, referred to as the

method of Siggia (37), the excess arsenious oxide is titrated

with iodine solution.

The eerie ammonium sulfate oxidation method (37) can be ap­

plied to hydrogen peroxide and some hydroperoxides, in which case

the eerie ion is the s_tronger oxidizing agent. This oxidation is

followed by an iodometric procedure· to determine excess eerie

ions.

An additional method, referred to by Mair and Graupner. (33),

is that of reduction using titanous chloride. I

A double titration method was used to determine benzoyl per­

oxide in carbon tetrachloride in the presence of free chlorine

(55, 56) •. The total amount of peroxide and chlorine was deter­

mined iodometrically with thiosulfate, the amount of chlorine by

titration with methyl orange in acid, and the amount of benzoyl

peroxide calculated by differen~~· The amount of organic perox­

ide was also calculated by' difference in an aqueous solution con-. I· l •11

{8)

taining aldehydes and hydrogen peroxide in addition to the or-\ I

ganic peroxide (46). The total peroxide concentration was de- ·

termined iodometrically, hydrogen peroxide was determined photo-++ metrically after reaction with acidic TiO , and silver oxide

was used to oxidize the aldehyde (RCHO to RCOOAg) followed by

titration with potassium thiocyanate. A special method, involv­

ing separate determinations of hydrogen peroxide, peracids and

total peroxide (3), was also devised to determine the peroxid& .. .. compounds which are products of furfural oxidation.

Dialkyl and diacyl peroxides were determined in the presence

of hydroperoxides {48) by their reaction with aniline. Dialkyl

peroxides reacted with the liberation of water, which was titrat­

ed with Fischer's reagent. For·diacyl peroxides, the amount of

aniline used was measured.

In the determination of peroxides used in the polymerization

of styrene, to eliminate the necessity of maintaining an inert

atmosphere, a complexonietric method was developed in which fer•o ·

rous ammonium sulfate was oxidized, and the resulting ferr_ic ions

were titrated with ethylenediaminetetraacetic acid (61).

2. Polarographic, infrared and chromatographic

For determining a wide variety of. peroxides, polarographic

methods are the most valuable. Ove.r the normal polarographic po-

tential region, only one peroxide, di-tert-butyl, is known to be

non-reducible (41). The reductions are two electron~reactions

in which the bond between the two oxygens is broken and hydroxyl

groups are formed. Mixtures .can be analysed i:t' the halt-wave

(9)

potehtials are different by at least ,0.4 volts, with the current

directly proportional to the peroxide concentration. In using •

this method, calibration is necessary for each peroxide.

,, Reference to the literature showed extensive application of

this method. The polarographic behavior of anesthesia ether due

to its aldehyde and peroxide content was studied (2)), as were

the p~oducts of radiation (52). The method was used to distin­

guish between peroxide structures in oxidized fats (32, 54) •.

These studies showed,the use of mixed solvent systems with dif­

ferent supporting electrolytes. The half-wave potentials of per­

pxides were found to be independent of pH (31).

Infrared spectroscopy as a method of analysis for organic

peroxides has been only moderately successful, as it has been

impossible to assign a band representing the stretching vibra­

tion of the 0-0 bond not influenced by the rest of the molecule

(42). Benzoyl peroxide and a series of aliphatic diacyl perox­

ides in the range of 0.2 to 0.01 moles per liter were determined

in the .presence of styrene arid polystyrene (1). Hydroperoxides

and alcohols were deter~ined in the presence of peresters· and

dialkyl peroxides, using the absorption bands of the free hy-'.­

droxyl groups (60).

Gas chromatography has been used to some extent, and further .. application is expected {7,25). Thin-layer chromatography of

organic peroxides was studied, and the peroxides arranged in a

eerie~ in decreasing order ac·cording to their Rf' values: dialkyl,

diacyl, peroxy esters, hydroperoxides, and hydrogen peroxide (8).

(10)

Infrared, dipole moment, and molecular weight studies have-,

been used in determining structures (59). W!th polarography, an

order of stability has been established which parallels reactiv­

ities with the iodide ion. The polarographic half-wave potentials

of the various classes of peroxides serve as an indication of the

st~engths of the 0-0 bonds (5). These classes, arranged in de­

creasing order according to their half-wave potentials, are as

follows: di-tert-butyl peroxide, dialkyl peroxides, tert-buty~

... peresters, hydroperoxides, diacyl peroxides, and peracids •

•

3. Colorimetric

Colorimetric methods for determining organic peroxides are

. mainly methods involving ferrous ion oxidation, iodometrio meth-

ode, or methods in which an aromatic organic compound, such as an

amine, can be oxidized to a dye form with multiple conjugation

and intense color.

The ferrous ion oxidation method has great sensitivity, as

was pointed out on page six, but poor specificity, and sometimes

poor precision and accuracy (38, 57). Kolthoff and Medalia (30)

compared this method to the iodometric method and found the lat-

ter to be more accurate. The reduction of peroxide by ferrous

ions and the colorimetric determination of ferric ions with thio-

cyanate, referred to as the method of Young (70), was recently

modified and used to determine peroxide content in radiat-ion-ox-

idized Polyvinyl chloride. Instead of determining ferric ions,

measurement has also been made of the excess ferrous ions, using

(11)

1,10-phenanthroline {38). •

A recent study was made of the iodometric method by which ' traces of peroxides in organic solvents could be determined.

This study by Banerjee and Budke (5) in 1964 modified the work

of Heaton and Uri in 1958 and the earlier work of Lea in 1931.

Dilution of the sample with an acetic acid-chloroform mixture

was followed by treatment with potassium iodide a~ter deaeration.

A one-hour reaction-time was allowed. The intens'i ty of the cdlor . of the iodine liberated was proportional to the concentration of

peroxide and was measured spectrophotometrically at 470 millimi­

crons (or nanom.eters). Peroxide concentration was determined

and reported as active oxygen in the range of 5 to 80 parts per

million. The range was extended to cover 0 to 5 parts per mil­

lion by using 1.5 centimeter cells and a wavelength of 410 milli­

microns. It is believed that the absorption is due to the 13-

ion, which has a maximum at 362 mi~limicrons. In the method de~

scribed above, absorbance was read at higher wavelengths where

fewer co.npounds interfere. or the peroxiQ.es tested, only .di-tert­

butyl and dicumyl peroxides, which have similar structures, failed

td react. Tetralkylammonium iodide has been used as the reagent ' I

instead of potassium iodide in the determination of traces of per- .

oxides in ~thers {24).

Hydroperoxidea, as well as dialkyl peroxides, were deter-·

mined in the presence of compounds which react easily with io-•• t

dine, using· triphenyl phosphine (16). The triphenyl ph~sphine

was oxidized to triphenyl phosphine oxide, and the excess was de-

{12)

termined, after treatment with formaldehyde and hydrochloric

acid to form lfh3PcH2oH] +Cl - , either gravime t;rically or photo­

metrically. at 275·millimicrons.

Welcher (68} describes a qualitative test for the detection

of peroxides and persalts, using leuco methylene blue as reagent.

Leuco methylene blue was prepared by the action of sodium thio­

sulfate on methylene blue in aqueous hydrochloric acid solution.

The method of analysis, using this reagent, was developed by Ue­berreiter and Sorge (l7, 39) in 19.56 for hydroperoxides and dia-

cyl peroxides. The reagent, however, was difficult to prepare

and relatively unstable. This method was improved by reducing

the reagent in benzene with hydrogen in the presence of a plati­

num catalyst immediately prior to use (15). Determination of

organic peroxides at the lo-6 molar concentration. level was re-

ported. A further improvement described a method for preparation

and purification of the reagent by reducing methylene blue with

phenylhydrazine, after which it was stable for several months (4).

The colorimetric determination described was carried out in a ··,'

mixed solvent of benzene and trichloroacetic acid. The time of

reaction was twelv~ to twenty-four hours. Beer' a Law was follow-··

ed for solutions containing 0 to lOmicrograms of peroxide per

millil.iter.

Eiss and Giesecke {17, 57) in 1959 substituted benzoyl leuco

methylene blue as reagent in· place of leuco methylene blue, as .. ,

it also reacts with peroxides and hydr~peroxides to form the

characteristioc;methylene blue color in a solution of benzene and

(13}

trichloroacetic acid.

+ (0) ---)

Benzoyl leuco methylene blue Methylene blue cation

Even this reagent is somewhat unstable, turning blue in ultra-.

violet light an~, ·to a lesser degree, in artificial light. or the naphthenates tried for· use as catalysts by Eiss and Giesecke,

zirconium naphthenate was found to best accelerate the peroxide '

decomposition and thereby increase the reaction rate. Benzoyl

and lauroyl peroxides, and p-menthane and cumene hydroperoxides

followed Beer's Law up to one part ·per million. Tert-butyl hy­

droperoxide deviated. Di-te~t-butyl peroxide did not react. The

times· for complete color development (in the dark at 24 degrees

centigrade) were as follows: tert-butyl hydroperoxide, 30 min­

utes; cumene hydroperoxide, 40 minutes; p-menthane hydroperoxide,

2 hours; lauroyl peroxide, 5 hours; and benzoyl peroxide, '30

hours.

A modification of this method (6) includes heating the reac- ·

tion mixture on a steam bath (in the dark) for thirty-five min­

utes. The absorbance values for benzoyl peroxide by this modifi­

cation were the same as those reported by Eiss and Giesecke (17)

after thirty hours.

An additional method described by Martin (40} was developed • by Tikkanen, using phenolphthalein as reagent. The absorbance,

however, was not linear and required the use of calibration

curves. This method was particularly useful: for the determina-

tion of hydrogen peroxide. Hydrogen peroxide may be the only pe,r~

oxide which .oxidizes this reagent, the other peroxides being

first hydrolysed to hydrogen peroxide.

Other reagents with limited use include chromic acid, phloro­

glucinol, thiofluorescein, and p-diaminodiphenylamine. This

last reagent was used in a spot test to detect artificial bleach­

ing substances in wheat flour (2). An intense blue color was . . .

formed by the reaction of organic peroxides with p,p'-diaminodi­

phenylamine sulfate in acetic.acid (57).

Qualitative tests given by Feigl {20) include the use of po-, I I '

tass iwn iodide-starch paper,. p-phenylenediamine, ferrothiocya~-<'. ~

nate, and N,N 1 -diphenylbenzidine in concentrated sulfuric acid.

Organic peroxides could be detected, using 2,7-diaminofluorene

in ace~ic ~ciq, ~nly in the presence'· of peroxidases, which_ ra:ise

their oxidizipg_pow~r (21).

H2N-~.=J 0N~2 ............ 0/. [oJ '>

H2

Feigl {19, 22)' gives three tests for benzoyl peroxide using

amines as reagents.· :'In ~ne of these, benzoyl peroxide oxidizes . I

tetramethyl-p,p'-diaminodiphenylmethane after evaporation of the j.

solvent to give a blue stain.

(15)

•

In the other two tests, the products used in the determinations

are not amines. In the reaction with diethylaniline, acetalde­

hyde is formed, and with hexamine, formaldehyde and nitrogen gas

are formed.

A method has been,developed to determine benzoyl peroxide and .

oumene hydroperoxide colorimetrically .after complexing with o-to-

luidine in the presence of styrene and dimethylaniline (29).

4. The spectrophotometric. method using N,N-dimethyl-p-

ph~nylenediamine sulfate

Dugan (12) in 1961 developed a method for the spectrophoto­

metric determination of microgram amounts of lauroyl and benzoyl

peroxide, using N,N-dime~hyl-p-phenylenediamine sulfate. The ,

reagent solution was prepared by dissolving 0.3 grams of. the a;.;.·

mine salt in 10 milliliters of redistilled water and diluting to

100 milliliters with alsolute methanol. Standard solutions of

lauroyl and benzoyl peroxide were prepared in the range of 5 to

100 micrograms per milliliter of benzene. The colorimetric, de­

terminations were carried out on either a Beckman Model DU or DKl

spectrophotometer, employing matched one-centimeter silica ab~

eorption cells.· Two milliliters of reagent solution were mixed

with two millili~ers of benzene containing peroxide. A reaction

time of thirty minutes· at'25,degrees centigrade was allowed.

(16)

Percent transmittance was then determined at 560 millimicrons, •

using a blank as reference. The precision of the method was cal-

culated to be 4.1 percent at the 95 percent confidence limit,

based upon ·eight determinations for each peroxide.

The spectrum of the reagent solution versus a solvent blank

was given. At 560 millimicrons the ·percent transmittance was

greater than 65 percent.

Absorption spectra were given for a constant peroxide con•

centration and varying amounts of reagent, 0.1, 0.3, and 0.5

percent. Transmittance was greater for 0.5 percent and approxi-

mately the same for 0.1 and O.J percent. Dugan believed that the

use of the higher concentration of reagent decreased the sensi-

tivity.

Spectra representing the standard curve for benzoyl peroxide

were given with concentrations of 5, 10, 20, 30, and 40 micro-. ,

grams per milliliter, as shown in Figure 1 in the Appendix. Ac­

cording t~.Du&a~, ~~er's Law was followed between 5 and 30 micro­

grams per milliliter with a deviation at 40 micrograms. The . .· > \ 11, 'l

spectrum for 40 micrograms per milliliter after 1.5 hours was ~ • , , t I , ,

given, and it sh9wed a d~o~ea~~ in.percent transmittance in the

400 to 525 millimicron range and an increase at 560 millimicrons.

Spectra representing the standard curve for lauroyl peroxide

were giveri with concentrations of 10, 20, 30, 40, 60, and 100

micrograms per milliliter, in which range Boer's Law was fol.i-,1:.;

lowed. In the spectra for both benzoyl and lauroyl peroxide,

there was a perc.ent transm"i ttance minimum (or an a~so:r,bance max-

' ·I, ,. I I I' '

(16)

Pere en t transmi tta.nce was then determined a.t 560 millimicrons, 1 .

• using a. bl~nk as reference. The precision of the method was cal-

culated to be 4.1 pe~cent at the 95 percent confidence limit,

based upon eight determinations for each peroxide.

The spectrum of the reagent solution versus a solvent blank

was given. At 560 millimicrons the percent transmittance was

greater than 65 percent.

Absorption spectra were given for a constant peroxide conJ

centration and varying amounts of reagent, 0.1, 0.3, and 0.5

percent. Transmittance was greater for 0.5 percent and approxi-

mately the:same for 0.1 and 0.3 percent. Dugan believed that the

use of the higher concentration of reagent decreased the sensi-

tivity.

Spectra representing the standard curve for benzoyl peroxide

were given with concentrations of 5, 10, 20, 30, and 40 micro­

grams per milliliter, as shown in Figure 1 in the Appendix. Ac­

cording to Dugan, Beer's Law was followed between 5 and 30 mi­

grams per milliliter with a deviation at 40 micrograms. The

spectrum. for 40 micrograms per milliliter after 1.5 hours was

given, and :it showed a . decrease ·in percent transmittance in the

400 to 525 millimicron range and an increase at 560 millimicrons.

Spectra representing th~ standard curve for lauroyl peroxide

were given ·with concentrations of 10, 20, 30, 40, 60, and 100.

micrograms per milliliter, in which range Beer's Law was fol•·F;

lowed. In the spectra for both benzoyl and lauroyl peroxide,

there was a percent transmittance minimum (or an absorbanoe max-

(17)

I

imum) at 525 millimicrons approximately equal to the minimum at

560 millimicrons. •

· Other ratios of reagent and peroxide solutions were found to

be satisfactory, provided they were miscible. Greater color de­

veloped with an increase in the amount of water. Dugan stated t b

that the reaction would occur in solvents for the peroxide other

than benzene, such as mineral oil.

The time allowed for color development was critical. The • . •'

temperatur~ was held constant at 25 degrees centigrade, and its

influence was not studied. According to Dugan, light affected

b"oth the peroxide solutions and the N,N-dimethyl-p-phenylenedia­

mine sulfate reagent solution. Reagent solutions were prepared

fresh'daily, and the reactions were carried out in subdued light.

No color developed with dicumyl peroxide, even when iron, co• '

balt, or rare earth naphthenates were present as catalysts.

Dugan made the following observations:

Reagent in water + lauroyl peroxide in benzene + methanol ~

rapid color deve lopmenit ,_

Reagent in water + peroxide in benzene (no methanol) ~

immiscible, no color reaction ',,

Reagent· in water + benzene + methanol ~

very slow color reaction

Reagent in methanol + benzene~very slow color reaction

Reagent in water + methanol + laurio acid ---.::..

very slow color reaction

Reagent in water + methanol + laury1· alcohol '>.

(18)

very slow color reaction

Reagent in 90~ methanol + hydrogen peroxide ~

very slow color reaction

Color complex + 0.1 N H2so4 ~ no effect

Color complex + 0.1 N NaOH ~> colorless

In summary, Dugan stated that the reaction, greatly acceler­

ated by the presence of lauroyl or benzoyl peroxide, appeared to

be: .. N,N-dimethyl-p-ptlenyl~nediamine sulfate +methanol~

blue colored complex

According to Dugan, although the reaction mechanism was not

known, it did not appear to be a simple oxidation, but rather a

reaction catalysed by a free radical mechanism, probably involv-

ing the splitting off of -Ng~3 groups by active OH. 3

The method of Dugan, developed to determine the presence of I

peroxides migrating from polymers formed using peroxide catalysts

(5), has been found to be suitable for detecting traces of per­

oxide in diethyl ether, isopropyl ether, dioxane, and tetrahydro-·,,

furan (13). Because the reagent is an aromatic amine, it will

form Schiff bases with aldehydes if present. However, the alde­

hydes tested did not interfere in concentrations less than 1000

micrograms per milliliter. They were.benzaldehyde, formaldehyde,

and glucose.

In 1963, Dugan (14) modified the method further to in~lude

other peroxides~ When added as O.l percent solutions in benzene,

the following rates of reaction were observed: for p-chloroben­

zoyl peroxide and methylethyl ketone peroxide, two minutes; tor·· . '

{19)

t-butyl hydroperoxide and 2,4-dichlorobenzoyl peroxide, up to one

hour; and for myristoyl peroxide, cyclohexanome peroxide, hydr~x-. .

yheptyl peroxide, and di-t-butyl peroxide, two hours.

According to Dugan, the reaction with many peroxides would

proceed if the following solvents were substituted for benzene:

pyridine, N,N-dimethyl formamide, benzyl alcohol, ethanol, chlo-­

roform, carbon tetrachloride, tetrachloroethane, and triacetin,

though all possible combinations of peroxide and solvent were not

studied. Di.ffere~t rates and occasionally different•:. end prod·­

ucts in the various solven~were noted. No data for solvents

other than benzene was given. The only further reference to oth-

er solvents is that di-t-butyl peroxide reacted more rapidly in

carbon tetrachloride and chloroform than in the other solvents

listed, and a "color different from the spectrum reported was

observed in trichloroethane and benzyl alcohol".

Only in the reaction with benzoyl peroxide, which is rapid,

was oxygen removed by a nitrogen purge, with negligible results.

A spectrum scan was given showing the color formation between­

fe·rric iron· and the reagent at pH 5 .5 with minimum percent

·transmittance at the same wavelengths as for peroxide. Addition­

al spectra showed the effect of ferric ions on the reagent in

the presence of peroxide at a pH of 5.5. In addition to the 520

and 560 millimicron minima with ferric ions in the absence of

peroxide or with peroxide in the absence of ferric ions, a mini­

mum occcn'ed at 720 millimicrona as well as at 520 and 560 milli-

microns when both were present. Transmittance through the solu­

tion at 720 millimicrons became'' less with time. According to

{20)

Dugan, the intense red complex, which the ferric ions formed with \

the reagent could be differentiated from the peroxide reaction., •

product by observing the absorption at 720 millimicrons,·which

formed only in the presence of peroxid~. The following ions had

no effect on the reagent at pH 5.5: ca2+, co2 +, cu2 +, Fe2+, Mg2+,

Mn2+, Ni 2+, Ti 2+, zn2+, Al)+, a'nd,:·or3+.

When 0.25 milliliters of s.aturated ammonium carbonate solu-

tion were added to two milliliters of reagent prior to adding

two milliliters of pe~oxide in benzene, ·a green color formed and

the final pH was 8.7. Spectra were given for the reaction at pH

8.7 with the following peroxide concentrations: 10, 20, 40, 60,

and 100 micrograms per milliliter of benzanep A plot of the val­

ues for percent transmittance at 675 millimicrons ind.icated that

Beer's Law was f'ollowed, The author stated that the previously

reported double band which formed in acid solution did not form

under alkaline conditions. Whereas the presence of benzaldehyde

had been shown to interfere in concentrations greater than O.l -.

percent at· pH 5.5, in the spectra of Figure 2, given for solu"' "L:.':)

tions at PH 8.7, little effect was shown on the 675 millimicron

peak for concentrations up to 1.0 percent. This is because alde­

hydes do not form Schiff bases under alkaline conditions, Ac-• J .

cordingly, organic peroxides could b~ detected in the presence

of high concentrations of aldehydes by adding alkaline buffer to

the reagen~ to yield a final pH of 7.5 to 9.1.

The following summary of reactions was given. The "reagent" . .. is 0.3 per~ent N,N-dimethyl-p-phenylenediamine sulfate in 10 per-

(21)

cent water in methanol, described previously. The "peroxide" is l

\

100 microgi;oams per ·milliliter of either benzQyl or lauroyl perox-I

ide in ben~ene. "Aldehyde" refers to a one percent solution of

benzaldehyde in ethanol. "Tris-buffer 11 is two grams of 2-amino-

2-(hydroxymethyl )-1,J-propanediol in 100 milliliters or dis tilled

water.

Reagent + peroxide~ red-violet color ~ + 0.5 ml 6 N H2S04~

stable colo'.r

Reagent (pH 5.5) + ~.5 ml 6 N H2S04 + peroxide~ NR (No observ­able color reaction)

Reagent (pH 5 .5) + 0.5 ml 6 N H2S04 + aldehyde-) Schiff color

Reagent + 0.5 ml 1 CN NaOH + peroxide~ NR

Reagent + 0.5 ml l N·NaOH + aldehyde---1 NR ' . ~ + o.5 ml 6 N H2S04

--7 Schiff color ' Reagent + 0.25 ml satd. (NH4)2C03 + peroxide~ green color

Reagent + 0.25 ml satd. (NH4 )2C03 + aldehyde~ NR

Reagent + 0.25 ml 2% tris•buffer (pH 7 .4) + peroxide~

green color

Reagent + 0.25 ml 2% tris-buffer (pH 7.4) +aldehyde~ NR

Reagent + 1 drop of cone. NH40H (pH 9.1) +peroxide ----t green color

Reagent+ l .drop of cone. NH40H (pH 9.1) +aldehyde~ NR

p-Dimethylapiinobenzaldehyde + peroxide~ NR

p-Dimethylaminopropioni trile + peroxide~ NR

Dugan concluded that "the peroxide will not react if strong

acid . C~. N H2S04) is added "to the reagent. Undoubtedly the per-

(22)

. oxide is destroyed in the acid. Strong base (l N NaOH) also

destroys the ability of the peroxide to react." •

(23)

II. Oxidation of Amines

Benzoyl peroxide is a compound known to be an oxidant and a

source of free radicals. The reagent used in this research to

determine this peroxide, N,N-dimethyl-p-phenylenediamine, is ar­

omatic and has two functional groups, one of a primary and one

of a tertiary amine. Therefore, it should be easily oxidized

in numerous ways depending upon the oxidizing agent (49).

reaction between peroxides such as benzoyl peroxide and amines

results in the production of free radicals (65). It is known

that N,N-dimethyl-p-phenylenediamine can be oxidized by such

reagents as bromine and ferric ions to a free radical, red-vio­

le t in color, that is called Wurster's red (18, 67). In the

literature with regard to Wurster's red, higher oxidation prod­

ucts are not given (45). When tertiary amines are oxidized by such oxidizing agents

as hydrogen peroxide and pe~acids, which can supply an oxygen

atom with six electrons, the amine oxide is formed (49).

'b• . . . . ~ The same reagent·s oxidize primary and secondary amines by the

following steps: ' \ ll l

RNH2 fQl) [

0 ] . OH R-~-H -4- RN-H RNO

( Rz-lf-H] ~ 0

RzNOH The primary' amine is usually oxidized all the way to the nitro

compound. The secondary amine is onl~ oxidized to the hydroxyl­

amine. In the oxidation of aniline, .the products, which may be

N-phenylhydroxylamine, nitrosobenzene, or nitrobenzene,depend

(24)

upon the temperature, and t~e amount and kind of oxidizing a-. \

gent (50). Aniline is oxidized with sodium.dichromate in dilute

sulfuric acid to _1,4-benzoquinone. With oxidizing agents that

abstract a hydrogen atom or hydride ion, the roactions are more

complex, often· giving highly colored products.

A. Formation of Free:Radicals

When peroxides, such as benzoyl .peroxide, react with amines,

a complex series.of reactions occur. In some cases free radi~als

are formed (65). Thus benzoyl peroxide and dimethylaniline have

been used to induce polymerization of monomers, such as styrene

and methyl methacrylate. However, the primary process in perox­

ide-amine reactions does not appear to be the free radical for­

mation, but rather ·a polar reaction from which the unstable in-

termediate breaks down to form radicals.

An investigation.of the products of the reaction of benzoyl

peroxide with a series of primary, secondary, and tertiary a­

mines was first made during the period 1925 to 1933 by Gambarjan

( 65}. A survey of the kinetics of the process was made .1?Y Bart­

lett and Nozaki (65) in 1947• They found the reaction to be

very rapid 1n comparison to the ordinary thermal deoomposi ti on of

peroxide. Most of our present informa~ion results from detailed

studies by Horner (65) and associ~tes.

Radical formation was clearly shown in diacyl peroxide-ter­

tiary amine systems, of which benzoyl peroxide and dimethylani­

line is an example. In a dilute solution of chloroform, the

products of this react.ion were benzoio acid, in almost quanti ta-,

(25)

tive yield, plus monomethylaniline, formaidehyde, and small a­

mounts of p-benzoyloxydimethylaniline and p,p'-di(dimethylamino) • •

diphenylmethane.

The reaction scheme for the decomposition proposed by Horner

is. the followit':g: ,,

0N(CH3~~2.' + (C6H5C0)202 ~

I

CH3 ¢000. ¢coo-I-> 0-Nt. + .. +

CH3 \... V"'

,,. II .

yH3 H20~

9H3 II~ 0~H . + 0COOH 0rj + CH20 + ¢COOH

CH20CO~ H

II~ ¢c90~ __ ,.N(CH))2 + ¢COOH

There is evidence to support only the first two steps. In . .'

support of step one, it was.found that the rate·or peroxide de-

composition was greatly accelerated by electron-supplying groups

on dimethylaniline and retarded ?Y elect~~n-withdrawing groups. j

When the concentrations '..Of peroxide and amine were o. 05 molar

in chloroform at 20 degrees centigrade, the half-life of the

perox~de was five minutes with p-methyldimethylaniline, thir­

teen minutes with dimethylaniline, and six days with p-cyanodi­

methylaniline. In addition, electron-withdrawing groups on the

peroxide accelerated the reaction. The compound, benzoylsulfo­

nyl peroxide, r·reac ted almost instantly even with p-ni tro-dimeth­

ylaniline. ·The initiation of polymerization by the system is" ·

(26)

.. evidence of radical formation along with the observation that

\ ' the system absorbed oxygen, keeping the perQxide concentration_

high. In addition, Boekelheide and Harrington {65) reported

the initiation of polymerization by acetic anhydride-dimethyl•

aniline oxide, which presumably forms a similar intermediate.

The rates found in kinetic studies of the reaction are consis-

tent with an initial bimolecular process.

Walling and Indicator {66) suggested that the unstable in~

termediate I deccimpos-ed by competing radical and non-radical

forming processes. Competing with the radical process would be

the following:

¢COOH

An inconclusive study was made by Roy and Swan (.53) of the re­

action of benzoyl peroxide with tertiary amines. They attempt­

ed, by trapping intermediates, to determine which products.re­

sulted from radicals and which from ions.

Secondary amines also react re~dily with benzoyl peroxide,

methylaniline several times' more rapidly than.dimethylaniline,

although, generally, there is no evidence for radical formation,

such as initiating polymerization or. absorbing oxygen ( 9). Fur­

ther ,studies by Denney and Denney ( 11), using benzoyl peroxide

labeled with oxygen-18 in the carbonyl position, tend to prove

that the ~echanism for the reaction with a secondary amine.in­

volves nucleoph111c attac~ by the am~ne on the peroxide to give

(27)

a pair of ions, which then undergo proton transfer.

Primary amines and benzoyl peroxide giv~ a co11plex mixture' ·

of products, which from aniline include benzoic acid, benzani­

lide, azobenzene, and a Arnall amoqnt of o-hydroxybenzanilide

(65).

However, very little is known of radical formation in the

reactions of other types of peroxides with amines. Initially,

only a few types of reactions and a limited number of types of

rad&cals were studied, avoiding the complexities of polar re­

actions (62). Indeed, it·was not until 1937 that the role of f

free radicals as reactive intermediates in ordinary tempera­

ture, liquid-phase reactions was recognized. During this year

the studies of Hey and Waters, of Kharasch, and of Flory were

published (62). Hey and Waters interpreted a number of reac~

tions, heretofore stu..~biing blocks in the development of the e-•

lectronic theory of•organic reactions, as being free radical

processes, Included was the "abnormal" addition of hydrogen

bromide to olefins, Independently, Kharasch proposed the pres-

ently accepted free radical chain mechanism for the same reac­

tion~ In his papers, Flory treated vinyl polymerization as a

free radical chain reaction. I

Like pther types of compounds~ f.ree radicals have their own

distinctive physical properties:~, including molecular weight,

absol"ption spectrum, dipole moment, melting point and so forth.

Furtpermore, due to their unique structural feature,one or more

unpaired eleotrona, free radicals as a class exhibit a unique

,. I•

(28)

property, paramagnetism. Conjugated free radicals, particular­

ly those in which the odd electron is conjugated with the aro~ •

matic ~uclei, show strong light absorption in the visible region

(63). Often in oxidation-reduction reactions the transient ap­

pearance of color can be taken as evidence of the presence of

radical intermediates. Acceleration by light is a positive in­

dication of a radical process (64).

Walling (64) gives some' general characteristics of radical .

reactions. They .wi11:, occur in polar, as well as inr" non~pol.ar,

solvents. They are generally insensitive to the ionizing power

of solvent,, since the intermediates are non-ionic and not high­

ly polarized (with the exception of some oxidation-reduction

systems). In contrast to many polar reactions, they rarely show

catalysis by acids 'or bases (with th~ exception of certain oxi­

dation-reduction systems).

B. Reactions of N,N-Dimethyl-p-phenylenediamine

'rhe free mnine::i:(51, 67) of the reagE:mt, N ,N-dimethyl-p-phen- . ·

ylenediamine _sulfate, used by Dugan can be obtained as a white

crystal from a benzene solution on the addition of ligroin. It

melts at 41 degrees centigrade and boils at 263 degrees centi­

grade. It is soluble in cold water, alcohol, benzene, and chlo-

roform, less soluble in ether, and insoluble in ligroin. It is

easily oxidized and cannot be kept indefinitely in air (28).

Its salts, however, are more stable.

According to Welcher (67), this reagent has been used for

the determination of chlorine, hydr~gen sul~ide, manganese, and

(29)

vanadium. It has been used for the detection of bromine, chlo-

rine, copper, hydrogen cyanide, hydrogen sulfide, manganese, and •

vanadium. It reacts with hydrogen sulfide in the presence of

farri'o chloride in strongly acid sol.ution to form the dye, meth­

ylene blue. It reacts with the oxidizing agents, chlorine, bro­

mine, and vanadates, to form a color ref~~red to· as Wurster's

red. In contrast, lead salts show a weak turbidity,a,nd~bismuth

salts give a yellow-orange precipitate with the reagent.

Coppe~ can be detected by the reaction of cupric salts with

potassium iodide to form free iodine, followed by reaction with

tha,· amine reagent to form the red-violet color, Wurster's red.

Spot tests to determine N,N-dimethyl-p-phenylenediamine in­

clude oxidation to Wurster's red (18), carried out best with

dilute ferric chloride solution. To a drop of alcoholic neutral

or slightly acid test solution was added a drop of 0.01 percent

ferric chlcride solutlon. The test was P?Sitive with the forma­

tion of a red-violet color.

c. Formation of Wurster's Red

In his writings of 1879 and 1886, Wurster (69) proposed the

following e:npirical formulas ·for the oxidation products of two

p-phenylenediamines •.

The red dye from p-aminod~methyl~niline:

The blue dye from tetramethyl-p-phenylenediamine:

C10H15N2Br

These two oxidized forms, correct except for the numb.er of hy-

drogena, are referred to ~s Wurster'~ salts, Wurster's red and

Wurster's blue. These compounds are examples of compounds, in• •

(JO)

termediate with. respect to oxidation level between a diarnine ~nd

a diimine, which are similar to hydroquinone and quinone (43).'

By the 1930's an increasing number of papers were being pub­

lished advocating the existence of free radicals (43) instead of

double molecules. In some cases, where a free radical exists,

such as with Gomberg's triphenylmethyl and Wieland's biphenyl­

nitride, an equilibrium was assumed to exist between the free

radical and its polymeric saturated form. · In other cases, such

as in the oxidation of aromatic diarnines, the existence of only

the free radical was assumed, as shown, for example, by boiling

point determinations of Weitz and Fischer. A large contribution

in this area was made by Michaelis (43), who in 1931 used po.ten­

tiometric analysis to study this type of oxidation, especially

oxidation by way of the two Wurster's salts mentioned above.

Bromine was used as the oxidant.

Michaelis recorded his observations. When the titration

was performed rapidly, at a certain point the color, red or

blue, which had developed disappeared again. If, after reach­

ing this point, the solution was allowed to stand, the color

gradually returned, but not to its maximum intensity. The rate

of return depended upon concentration and pH.4 Spectroscopic

analysis showed the second colored sµbstance~to be the same as

the first, recognizable by a characteristic double band, which

differed for Wurster's red and Wurster's blue only by their

spectral location. According to Michaelis, other dyes might al­

so develop· along with the. reappearance of the Wur4'.ter 1 s salts.

(31)

His interpretation of the above observations was that Wurs­

ter' a red or blue differed from the parent substance by only

one oxidation equivalent. The disappearance of dolor indicated

·a higher oxidation level, very likely a diiminoquinone, which

would be very labile, undergoing irreversible changes into sub­

stances inclined to still further oxidation.

Within a certain pH range, the most suitable pH being 4.6,

the first half of the titration could be carried out with con~

stant potentials; as ~hown in Figure 3. In the second half, no

constant potentials could be obtained under any conditions, the

potentials always drifting back to the negative side as though

the diiminoquinone spontaneously and irreversibly disappeared.

The amount of oxidant for each of the two steps was the same,

within the limits of error. The curve for the first step was

that of a regular oxidation-reduction system with the differ­

ence between the reduced and oxidized forms being one electron.

Therefore, the dye, Wurster 1s red, and also Wurster's blue are

half-reduced quinones or semiquinones with an odd number of e­

lectrons. :

A later report by Michaelis with Schubert and Granick C45) was concerned with the stability and color of Wurster's salts,

modified by substitutions at the amino groups and at the ben­

zene ring. A study of the stability of these semiquinone radi­

cals was difficult because they exist in equilibrium with the

diamines and the very labile diimines. Quinone diimines are

very unstable in all solvents not en.tirely water free. Somo ot

the free radicals a.re stable even in aqueous solution. Substi- ·

{32)

tution of methyl groups for hydrogen on the ring had no effect \

unless the methyl group was ortho to a methylated amino group,· •

in which case the stability was decreased. Substitution of

methyl groµps for hydrogen attached to nitrogen increased the

stability, the tetramethylamino compound being the most stable of

the series. Substitution on the ring by other groups such as

-OCH3 1 -Cl, and -S03H caused destabilization.

Radicals, such as Wurster's salts, are capable of existence

because of a part~cular symmetry of structure resulting in res'-._)

onance. According tp Michaelis (45), the resonance could occur

only if the aromatic ring, the two nitrogen ato~s, and the four.

atoms attached to the nitrogen were all located in one plane.

Michaelis showed that the radicals having little stability did

not have the planar structure necessary for resonance. It is

stated in a recent text by Hendrickson, Cram, and Ha~mond (26}

that these radicals are stabilized by extensive delocalization

of the electrons and that destabilization is due to steric ef-

fects or repulsion or like charges. The following structural

forms are included for Wurster's blue:

[o) -~. -e

These are not all or the possible forms. The first two were

given by Michaelis (45}.

In addition to structure, the stability of the radicals de­

pends upon pH. In aqueous solution the necessary pH range was

(33)

found to be between 3.5 and.6. Michaelis gave the following· !

figures to represent the three possible ionization states of the •

radicals.

Only formula two can exhibit the resonance necessary for stabil-

ity.

In studying the absorption spectra, it was found that each

methyl group substituted for hydrogen in the amino groups had a

bathochro~ic effect, shifting the two distinct bands of the rad-

ical toward longer wavelengths. The two bands for Wurster's red,

the spectrum of which is given . in Figure 4, showed maximum ab••:::-:.·­

sorbance at approximately 515 and 550 millimicrons. Attaching

methyl g:oups to the ring had no bathochromic effect, but

changed the pattern of the bands.

An increase in· color due to further oxidation by exposure

to the air was noted. The lifetime of these compounds was not

affected by diffuse daylight.

Accord~ng to Michaelis, in dilute solutions these radicals

did not combine with each other or with the original diamine,

but underwent condensation or other reactions with other mole-

cules in the solution, especially those on the oxidation level

of the diiminoquinones. In higher concentrations or at low

temperature, most Wurster's salts, with the exception of Wurs-

ter 's .blue, formed polymers, which d~ffered in color from the

free radicals, all .of the polymers being deep green-blue in the

{34)

crystailine state (~). In the case of Wurster's red, only the

dimer existed. For compounds, in which both ni~rogens were not •

completely methylated, a higher polymer might be possible.

As was stated earlier, benzoyl peroxide reacts with a terti­

ary amine to form an intermediate complex, which dissociates in­

to two ion radicals. Using the system, tetrrunethyl-p-phenylene

diamine (TMPD) and chloranil (C) in various mixtures of chloro­

form, 1,2-dichloroethane, and ethanol, Isenberg and Baird (27)

attempted to show by ,electron spin resonance that the similar

complex .(TMPD~C) which formed could not dissociate into the two

ion radicals TMPDt and c.- in a non•polar solvent.

Steigman and Cronkright {$8) showed that the ion radicals

did form in non-polar solvents in the presence of excess acid.

Tetramethyl-p-phenylenediamine in reduced form is a diacid base

with the acidity constants, pKl equal to 2.20 for the dissocia-2+ + tion of TMPDH2 and pK2 equal to 6.35 for TXPDH • 'The fraction

present as TMPDH+ is at its maximum at pH 4.28, very close to

the pH found to be most suitable by Michaelis (45) for nadical

formation. Therefore, with the form of the radical capable of '. '

resonance as the product, the following equation best describes

the oxidation to Wurster's blue.

H H3c,~~CH3 H3c, t .,,CH:J

N

Q ~ 0 H+ ~ + + e

'N C ).i,CH H c""-'CH

3 3 H3 .3

(35)

Steigman and Cronkright studied t.he effects of different ac­\

ids on Wurster•s blue, formed in benzene from tetramethyl-p- ' •

phenylene~iamine with chloranil as oxidant. They found that,

regardless of the number of acid molecules associated with

TMPDH+ prior to oxidation, one additional molecule of acid was

necessary for the formation of Wurster's blue. This additional

molecule was believed to stabilize the counteranion, which p~ior

to oxidation had been stabilized by hydrogen bonding with

TMPDH+. The additioQ of bases, proton acceptors, and salts ca-

pable of hydrogen bonding.caused the disappearance of blue

color.

The spectrum of Wurster's blue, in methanol containing·per­

chloric acid, by Steigman and Cronkright, shown in Figure 5, was

almost identical to those obtained by Michaelis, Schubert and

Granick (45), and by Albrecht and Si~pson (58) for the perchlo~

rate in water. In benzene containing chloranil and trichloro­

acidic acid, the 565 peak shifted to 570 millimicrons and be-

came more prominent than the second peak. A large excess of

tetramethyl-p-phenylenediamine in relation to chloranil was

used to diminish the diimine concentration.

(36)

EXPERIMENTAL

I. Reagents ,

The N,N-dimethyl-p-phenylenediamine sulfate, [NH2c6H4N(CH3)zj2·

H2so4, molecular weight 370.47, used was obtained from East-

man.

The benzoyl peroxide, (C6H5C00)2 , 99 percent pure, and the 2-

amino-2-(hydroxymethyl)-l,J-propanediol were obtained from

Matheson, Coleman and Bell.

All other chemicals used were of reagent or equivalent grade,

with the exception of purified annnonium carbonate, used only

in verifying the work done previously by Dugan.

All water used was redistilled from an alkaline permanganate

solution.

(37)

II. Apparatus

TM Scans of tho'visible spectrum were made with a Beckman Acta

III UV - Visible Spectrophotometer, employing matched one­

centimeter silica absorption cells.

Absorbance measurements at a set wavelength were made with ei­

ther the Beckman Acta™ III UV - Visible Spectrophotometer

or a Beckman Model B Spectrophotometer, employing matched

one-cef?timeter sil'ica absorption cells.

The pH me.asurements of solutions were made using a Sargent pH

Me·ter Model LS.

A scan of the infrared spectrum for the oxidation product ob­

tained was made with a Perkin-Elmer 137 B Infracor~ Spec-

trophotometer, using a potassium bromide wafer for the sam-

ple cell.

Sample weighings were made with either a Mettler Type H Analyti­

cal Balance or a Mettler Top-Loading Balance. '

Miscellaneous laboratory glassware and equipment were used, in­

cluding volumetric flasks, pipets, erlenmeyer flasks, gradu~

ated cylinders, a distilling flask and condenser, a Bunsen

burner, separatory funnels, a Buchner pyrex fritted funnel~

and a filtering flask, and a centrifuge.

{38)

III. Preparation of Solutions and General Procedure

•

All reactions were carried out under fluorescent light and

at room temperature, which varied from 21 to 25 degrees centi­

grade. All solutions were stored in the dark.

A 0.3 percent reagent solution was prepared according to the

method of Dugan, by dissolving 0.3 grams of N,N-dimethyl-p-phen­

ylenediamine sulfate in 10 milliliters of redistilled water and '

diluting to 100 milliliters with methanol in a volumetric flask.

This solution will be referred to in the sections that follow as

the reagent solution. Solutions of O.l, 0.2, and 0.5~peree~t a-

mine sulfate were prepared in a like manner as were solutions of

·0.3 and O.l percent a~ine sulfate in methanol only and in water

only. Due to their rapid color development, each of these solu­

tions was prepared as'.needed and only freshly prepared solutions

were used.

A stock solution of benzoyl peroxide was prepared by dissolv­

ing 0.0500 grams in 100 milliliters of benzene {or pyridine) af­

ter which l, 2, 3, 4, 5, 6, 7, and 8 milliliters of stock solu­

tion were diluted to 50 milliliters with solvent to make standard

benzoyl peroxide solutions, containing, respectively, 10, 20, 30,

40, 50, 60, 70, and 80 micrograms of 'benzoyl peroxide per milli-

liter. Generally, scans were made using two milliliters of an .·.

appropriate solution containing the amine sulfate, mixed with two

milliliters of benzene or pyridine containing the peroxide.

In order to have a miscible solution with the addition of

(39)

acid to the reaction mixture, sulfuric acid solutions were pre~

pared by adding concentrated sulfuric acid tQ methanol. (Aqueous

acid solutions were used with the am.ine . .in:water only.)

To prevent the formation of two layers upon the addition of

tris-buffer, the buffer solution was prepared by dissolving two

grams of 2-amino-2-(hydroxymethyl)-l,3-propanediol in 10 millili­

ters of redistilled water and diluting to 100 milliliters with

methanol. This solution will be referred to as tris-buffer. A . two percent aqueous solution of tris-buffer was used to study the

reaction with no methanol.·

For studying the reaction, rather than making a standard

curve or determining factors influencing the standard curve,

methanol was used instead of a reagent blank. In studying the

effect of the amine concentration, a separate reagent blank was

used for each concentration.

In cases where only the wavelength of the peak values was of

concern and no~ the solution concentration, no values for a~aor­

banoe are given on the scans • . ...

(40)

IV. Data and Re·s ul ts

A. A Study of the Effect of Variables on 'Dugan's Method

A preliminary investigation was carried out according to the

original method of Dugan with N,N-dimethyl-p-phenylenediamine

sulfate and benzoyl peroxide. A study was then made of the ef-

feet of the variables, time and pH, on the system.

Scans of the ~isible spectrum were made at intervals other·

than thirty minutes in order to study the development of the ab-

sorbance peaks with time. When benzoyl peroxide in benzene was

mixed with a solution of N,N-dimethyl-p-phenylenediamine sulfate,

a scan of the spectrum between 400 and Boo nanometers shows ab­

sorbance peaks at 515, 555, and.to a lesser degree at 670 nano­

meters. This scan is given in Figure 6. The 515 and 555 nano-

meter peaks increased rapidly to a maximum in approximately five

minutes and then decreased. The 670 peak increased less rapid­

ly. Scans made over a two hour period showed that the 670 peak

had become more intense by the end of that time than the 515 and 'I

555 peaks. Wit~in twenty-four hours, there were no 515 and 555

peaks, and the 670 peak had shifted to a sharp peak at 640 nano­

meters, almost identical to .the peak which developed when the

amine salt in methanol autoxidized. (See Figure 18.)

The effect of changing the pH of the solutions before and I

after mixing the reagents was studied. Dugan (12, 14) had stat-

ed that the addition of O.l N sulfuric acid to the colored prod­

uct had no effect and tha~ the addition of 0.5 milliliters of 6 N ,-'l

{41)

sulfuric acid stabilized the color. Addition of the stronger

acid solution before mixing the reagents prevented the reaction, • .

and Dugan concluded that the peroxide was destroyed in the acid1

First'the effect of the addition of acid was studied. The

concentration of acid was varied, and also the time of addition.

Adding acid to the reagent solution prior to adding the peroxide

prevented the formation of color as reported by Dugan. The

addition o~ acid at any time after the reactants were combined

stabilized the re~ction at that point. Figure 7 shows the max-,

imum absorbance, which occurped five minutes after mixing. It

shows also the effects of adding acid to the reagent solution

prior to adding peroxide and immediately after adding peroxide.

The addition of acid greatly inhibited the color formation. How-

ever, scan b shows that in the few seconds before acid was added,

a certain amount of color had a chance to form. For each of ':.,'i..::

these scans, 0.1 milliliters of 6 N sulfuric acid in methanol

were added to the reaction mixture. It was found that 1 N sul-

furic acid was as effective as 6 N for stabilizing the reaction,

but weaker solutions were not. This is shown in Figures 8, 9,

and 10. The pH_ of the reagent solution was approximately 5.5 in-

itially. The pH after addition of O.l milliliters of 1 N sul-. I

furic acid in methanol was approximately 1.8. Figure 11 shows

that, after the reaction was stabilized at· peak formation, Beer's

Law was followed at 555 nanometers for concen~rations of peroxide

from 10 to 60 micrograms per milliliter. Figure 12 shows the

variation of absorbance with time at 555 nanometers for 60 micro-, ''

/ , grams of benzoyl peroxide per milliliter of ben~ene with and

I" ' ' I ' . ... . ' ,. ' '

• I {. .,,...- . ~ , ', .', : • ! . ~ •. '· .1 .

<42)

without the addition of acid. . ~

In an attempt to stabilize the color formation by lowering, •

the pH slightly from 5.5 to 4.7, the reagent solution was made

».

up, substituting 1 N acetic acid for water. The color, which

formed in this solution after peroxide was added, showed the

same instability at 555 nanometers and slightly .less inten~ity ·

than before the substitution.

Dugan made the reaction mixture basic by the separate addi-.

tions of tris-buf,f;'er, concentrated ammonium hydroxide and satu'~·S···

rated am.~onium carbonate solution. In each case a green color

was observed, but spectra were given only for the solution to

which ammonium carbonate had been added. Dugan stated tbat the·

previously reported doubile 1-:band which occurned1 ·.ia.· acid·;solution

did not form under alkaline conditions.

Because they were not given, spectra were made of the reac~~

tion mixture to which tris-buffer was added. When 0.25 millili-

ters of tris-buffer were added to two milliliters of the rea-

gent solution (giving a pH of 7.4) ,and then two milliliters ·or

peroxide in benzene &ere added, the solution first turned a red~

violet or magenta color (as at pH 5.5) and then green in less

than five minutes, with the development 6f peaks at 465 and 670·

nanometers, which were fairly stable. Figure 13 shows the ab~

sorbance at 555, 465 and 670 nanometers with time. Figure 14

shows that· the peak values at 465 ~nd· 670 nanometers follow

Beer's Law'. (Figure 14 was made using the data from the scans

..

(43)

showed a n~gligible decrease in abaorbanoe as compared to add~

ing it before. ' ,···:

• A time 'study of the reaction, given in Figure 15, shows that

after two hours both peaks were increasing, the 465 peak more

rapidly than the 670 peak. A scan after three hours.shows· the·

465 peak increasing and the 670 peak decreasing. This was. con­

tinuing after five and a half hours.

The same color formation occurred when the, tris-buffer·.was

omitted and pyridi:ne w.as used in place of benzene to achieve ap~

proximately the same solution pH. Figure 16 shows the peaks at·

465 and 670 nanometers, along with 'the diminishing peaks at 515

and 555 nanometers when the scan was begun immediately after ' .

mixing. Figure 17 is a scan between 600 and 400 nanometers only,

begun at zero mixing time, which shows more clearly the forma-·

tion of the 515 and 555 peaks.

B. N,N-Dimethyl-p-phenylenediamine Sulfate in Methanol

An attempt was made to better understand the Dugan method and

to improve it by studying the effects of the solvents used. Du~­

gan (12) had stated that the colored reaction that occurred was ·

between the amine sulfate and methanol. However, he observed

greater color developmerot as the amount of water in the mixture

was increased. The reagent is pale pink in a freshly· prepared

water-methanol solution. Even without peroxide, noticeable col-.

or development occurs with time.

The first study involved a change to methanol as solvent for

the amine sulfate rather than the water-methanol mixture. Ben-·

(44)

zene remained the solvent for the peroxide. When the ·amine salt

was dissolved in methanol, a scan made after twenty-focir:hours~ •

given in Figure lB, shows the development of a peak at 640 nan6-·

meters, The solution at this time was dark blue as contrasted

to the pale pink color of the freshly prepared solution. A scan

after only two hours shows slight peaks at 515 and 555 n~nometers, .. . half as intense as those for the amine salt in water. (See Figure

25.) (For these scans, the concentration of the amine salt wa~

changed from 0.3 perc~nt to O.l percent due to its low solubility

in methanol.)

When two milliliters of the peroxide in benzene were com-

bined with two milliliters of the amine salt in methanol, the

same sharp peaks appeared at 515 and 555 nanometers, as shown in

Figure 19. A scan twenty minutes after mixing shows these peaks

decreasing and a 670 peak developing.

When the peroxide solution was added to a twenty-four-hour-

old solution of the amine salt in methanol, sharp peaks appeared

at 515 and 555 nanome tera in addition to the peak at 640 nano• .. -,\;. ·

meters. These can be seen in Figure 20. The 515 and 555 ~eaks ~.

were approximately the same height as from a fresh'.solution of

the amine salt in methanol, or water and methanol.

Figure 21 shows that when acid or. base (ammonium hydroxide)

was added to a twenty-four-hour-old solution of the amine salt,

in methanol, the 640 peak remained. With the addition of base,

an immediate scan showed a 465 peak forming.

When tris-buffer was added to a solutio·n of the amine· salt ., .

·,

in

(45)

methanol, a scan after twenty-four hours, given in Figure 22, '.-~

shows a peak at 465 nanometers and a slight rise near 640 nano-·-. •

meters {pH 7.7). A scan of the amine salt_ in methanol plus·one_

drop of concentrated ammonium hydroxide (giving a pH greater

than 8.3) after twenty-four hours shows only a peak at 465 nano-;

meters, more intense than for pH 7.7. Because the reaction oc-

curs very slowly without peroxide, the time interval of twenty­

four hours was allowed for sufficient color development. .

A study was made Qf the effect of. the addition of acid and

base upon a solution· of the amine salt in methanol plus peroxide

in benzene after the 515 and 555 nanometer peaks had decreased.

below the intensity of the 670 peak. For these scans, given in

Figure 2J, two milliliters of the amine salt in methanol (O.l

percent) were mixed with two milliliters of peroxide in benzene

{50 micrograms per milliliter). After ten minutes, concentrate~·

a-mmonium hydroxide was added to completely remove the 515 and

555 nanometer peaks. Scan f in Figure 2J shows only a peak at

465·nanometers, the solution was tan, and the pH was greater than

8. The pH was then varied by the dropwise addition of sulfuric

acid in methanol and concentrated ammonium hydroxide. As the

solution was made more acidic, the color changed from tan to

yellow-green (pH 7.7) to green-blue (pH 4.0) with a decrease in

the 465 peak and an increase in the 670 peak. As the color

changed from green-blue to violet (pH 1.7), the 670 peak began to

decrease and slight peaks reappeared at 515 and 555 nanometers.

As the color changed from violet to pink (pH 0.5) to red {pH les.s

(46)

than 0.5), the 670 peak c:bntinued to decrease, a peak appeared, at

510 nanometers, and the peaks at 515 and 555. nanometers were ,.n~ :' ·

longer seen. With this solution, it was possible to change. 'froni ,;

acidic to basic and back again several. times without evidence of ·

decomposition as shown by the repetition of the color changes. .,.

(In, making the scans described above, after scan: f was made,· ·the

solution was made very acidic and scan b was made. Then base ,,;, ·

was added and scans d and e were made, followed by the addition

of acid to make scans ,c and a. The ammonium sulfate which formed

in the solution had to be removed by the use of a centrifuge.)

Figure 24 shows maximum formation of the 515 and 555 peaks

from the reaction of the amine salt in methanol and the peroxid·e

in benzenel After making this scan, 0.1 milliliters of 6 N sul­

furic acid were added, which stabilized the reaction but at a

lower intensity. A continuation of the addition of acid greatly

decreased the two peaks already formed, with no appearance of

other peaks.

When acid was added to the amine salt in methanol, the solu~

tion became colorless and remained colorless after the addition

of peroxide in benzene. The addition of one drop of ammonium hy~

droxide produced a pink color, which immediately turned blue-

green.

c. N,N-Dimethyl-p-phenylenediamine Sulfate in Water

The color development of the amine salt in water only was· al-:; •·· >

. . so studied, as was the reaction between the reagent in w~ter and

benzoyl peroxide in benzene with varying pH. Soans were made of

:!

(47)

the separate layers of this two-layer system after mixing. The .

pH of these layers was changed before and af~er separation. ·'Du~ · ·

gan (12) had stated that the reagent in water and peroxide in'

benzene were immiscible and that no colored reaction occurred.

·· •.. i.

Figure 25 shows that the amine salt in water slowly formed o

peaks at 515 and 555 nanometers. After twenty-four hours, 'th~re

were sharp peaks at 515 and 555 nanometers. When tris-buffer or

a drop of concentrated ammonium hydro~ide was added to this

twenty-four-hour-old solution, a scan of this solution, give~ ih

Figure 26, shows a raised section between 515 and 555 nanometers,

but no distinct peaks and no other peaks.

When one or two drops of ammonium hydroxide were added to the

amine salt in water,•a scan after two hours, given in Figure 27,

shows a peak at 475 nanometers. In a solution containing no

methanol, the amine salt in water reacted with peroxide in pyri­

dine, forming peaks at 675 and 485 nanometers as shown in Figure·

28.

When five milliliters of the amine salt in water were shaken

with five milliliters of peroxide in benzene, the intensity of

the pink color of the wat.er layer increased, and the benzene lay­

er turned yellow. A scan of the water layer, given·in Figure 29,

shows peaks at 515 and 555 nanometers., and a scan of the benzene

layer in Figure JO shows a triple peak, centered at 445 nanome­

ters. Wit~ the addition of tris-buffer or ammonium hydroxide to

an identical two-layer sys tern, the color was extracted into the'

benzene layer. Scans of these two layers are also given in Fig-

(48)

ures 29 and 30.

Because of the intensity of this yellow ~olor in the benzene.,.·

layer, an attempt was made to use it in a quantitative test for

peroxide at the concentrations used previously and at lower con­

centrations. It was impossible, ijowever, to obtain duplicat~

results. :. Peroxide could be detected at a concentration or· two

micrograms per milliliter.

When acid was added to the amine salt in water before addipg

peroxide in benzene, ~cans of both the water and the benzene lay­

ers, given in Figures 31 and )2, show little or no color forma-

tion when compared to the same solutions without aci~.

It was possible to separate and scan a similar yellow ben-

zene layer which formed in the presence of methanol. Two or

more drops of am.~onium hydroxide were added to two milliliters

of the reagent solution used originally, turning it from pink to

blue. With the careful addition to this basic solution of two

milliliter~ of peroxide in benzene, two layers or bands of color

formed. Am.~onium sulfate precipitated from the solution. Slight. I '

agitation caused the.bands to disappear, ~giviog a uniformly col­

ored solution. A ~can or: the benzene layer, given in Figure 33,

is similar to Figure 30. A scan of the methanol layer in Figure

34 shows a peak at 465 nanometers.

In order to compare the yellow color described above with

that of a Schiff base, propionaldehyde was added to the amine

salt in water plus benzene with no peroxide. A very light co_lor

formed in the benzene layer, which was lost upon the addition of

(49)

tris-buffer. No. soans were ~ade of this soluticn ~ No further. ·:.:

tests with a~dehydes were made. •

D. N1N-Dimethyl~p-phenylenediamine Sulfate in Acetone

The behavior. of ,the amine sulfate in a solvent less polar ··~

than water or methanol was investigated. The amine sulfate was

·insoluble in ;·benzene. It was only slightly soluble in ace tone,. ,.

forming a•yellow solution with maximum absorbance at less than

400 nanomete~s, as·shown in Pigure 35. Combining this solutio,h ~ \' ', ; '

" ' with an equal amount of benzene containing peroxide caused no·

change ·in.the spectrum but showed only the effect of dilution.

No attempt·to change the pH of this solution was made.

,•:, .t

E. Separation of the Colored Reaction Product . '·

When an acid solution was added to the yello~ benzene layer ~ ' . ~

described in section C, the color was eACtracted almost complete-" ly out of this layer into the polar layer, which turned a bright

red. This occurred upon the addition of either sulfuric acid in '.; l.

water or in methanol, or an aqueous solution of hydrochlor:Irc :•.ci , ...

acid. This color was apparently due to a reaction product. Its

behavior is characteristic of an amine and its salt.

Figure 36 shows that a scan of the red aqueous layer gives a l, ·'

very intense peak at 510 nanometers, similar to Scan a in Figure

23. Addition of base to this solution caused precipitatio~:

Figur~· 37 show~ scans made of the red acidic methanol '1aye:f·, " '?}

with scan a having the same intense peak at 510 nanome tars ·~s in

Figure 36 and a slight peak near 640 nanometers. (Compare with

scans a and bin Figure 23.) Addition or one drop of ammonium

(50)

hydroxide caused a decrease in the 510 peak and an increase in

the 640 peak. /•ddition of a second drop of ~rnmoriium hydroxide I

ca~sed the .~~.O peak to decrease along with the formation of a

peak at 460 nanometers, similar to scans e and f in Figure 23 •

. When glacial acetic acid was added to the benzene layer, the

solution turned a yellow-green, with an intense peak at approx­

imately 460 nanometers and a slight peak at 650 nanometers, as

shown in Figure 38, similar to the scan for the solution ex-.

tracted into acidic m~thanol and after the addition of two drops

of ammonium hydroxide, which was just described.

The red hydrochloric acid solution was evaporated to dryness

on a steam bath, but without the formation of good crystals.

When water was added, a greenish-yellow solution formed, which

turned red upon the addit~on of acid. Figure 39 gives a scan of

this solution.

The addition of methanol to the dry red product caused a

blue solution to form, the scan of which is given in Figure 40,

with peaks similar to those seen previously in Figure 37.

The addition of ethanol to the same product caused the for-

mation of a green solution. A scan of this solution in Figure

41 is similar to but slightly different from. Figure 40. When the red hydrochloric-acid solution after separation

' . from benzene was made basic with five percent sodium hydroxide,

a greenish-yellpw precipitate formed. This precipitate appeared

to be stable. Figure 42, a scan of the infrared spectrum of

this product shows only slight pe~ks, which occur at 6.2,· 7.3,

(51)

8.7, and 12.1 microns. Although no definite identification was

made of this product with the Sadtler Spcc-Finder,(79a), it ap• •

peared to be an azo dye. In Figure 43, Scan a is the greenish­

yellow precipitate dissolved in methanol and shows the 670 peak.

Scan b, made after the addition of acid, shows the 510 peak.

F. Reaction of the Amine Sulfate with Bromine and Ferric Ions

According to the literature (18, 67), N,N-dimethyl-p-phenyl-

enediamine reacts with bromine or ferric ions to form a free ...

radical called Wurster's red. Consequently, a comparison was

made of the reddish~violet color formed by these reactions with

the color of the reaction being studied. The addition of one

drop of bromine water to a solution of the amine salt in water

caused the immediate formation of intense peaks at 515 and 555

nanometers, shown in Figure 44. The solution tur~ed from pink

to a deep magenta· color. Bromine water was added to equal

parts of the reagent solution and pyridine (no peroxide). A

similar test was made using ferric sulfate in methanol. Both

solutions turned red•violet and then green. Figures 45 and 46 ..

show these reactions with intense peaks at 465 or 475 nanometers

and at 670 nanometers.

G. Development of a Method for the D.etermination of Peroxides

Substituting Pyridine for Benz~ne

Because the peaks which occur in basic solution appeared to

be more stable than those in acid solution, because pyridine

could be used as both a solvent for the peroxide and a buffer at·

{52)

the proper pH, and because, in addition, Walling and Indicator '

{66) showed that the reaction between an aromatic amine and ben-

zoyl peroxide occurred rapidly in this solvent, the development

of a method with pyridine seemed practical. Dugan indicated l

that pyridine could be substituted for benzene when using N,N-

dimethyl-p-phenylenedia~ine sulfate as reagent.

To be sure that this system was better than the previously

tried tris-buffered solution of water, methanol and benzene, a.

comparison was made o~ these two systems. Figure 47 shows scans

made, fifteen minutes after benzoyl peroxide in benzene, with

concentrations ranging from 10 to 80 micrograms per milliliter,

was mixed with the 0.3 percent amine reagent solution to which

0,25 milliliters of tris-buffer had been added, Figure 48 shows

similar scans fQr which pyridine was substituted for benzene and

tris-buffer w~s omitted. Figure 49, corresponding to Figure 14

(the Beer's Law curve for the tris-buffered solution), shows

that the reaction in pyridine also follows Beer's Law.

The concentration of the peroxide was held constant and the

concentration of the amine was varied. Figure 50 shows that

changing the concentration:·of the amine salt which was combined

with the peroxide in benzene changed the intensity of the ab-

sorbance peaks much more than changing the concentration of the

amine salt which was combined with peroxide in pyridine. This is

shown in Figure 51. Table I gives :the absorbance at 670 nano­

meters, obtained, using the Beckman. Model B spectrophotometer, ' for 60 micrograms per milliliter of benzoyl peroxide in pyridine

(53)

TABLE I

The Absorbance for a Constant Concentration of Benzoyl Peroxide

with Different Concentrations of N,N-Dimethyl-p-phenylenediamine Sulfate

Concentrationa Absorbanceb Average Average Absorbance Deviation

0.1% 0.580 0.575 0.585 0.570 o.565 0.575 0.006

0.2% 0.570 0 .. 575 0.575 o.565 0.580 0.573 0.004

0.3% 0.550 0.545 0.555 0.560 0.555 0.553 0.004

0.5% 0.525 0.520 0.525 0.530 0.525 0.002

Percent Average Deviation

1.0

0.7

0.7

0.4

a The amine concentrations are in grams per 100 milliliters of solution, 10 milliliters of which is water and the remainder methanol. The peroxide concentration is 60 micrograms per milliliter of pyridine.

b The absorbance was measured at 670 nm, using a Beckman Model B Spectrophotometer, with a reagent blank as reference.

with 0.1, 0.2, O.J, and 0.5 percent N,N-dimethyl-p-phenylenedia-

mine sulfate in a ten percent water-methanol solution. . . A time.study was made of the reaction, using one concentra-

tion of peroxide in pyridine. This solution was mixed with the

regular 0.3 percent reagent solution. The scans in Figure 52

show a slow decrease ,in the 670 absorbance peak in the time in­

terval from fifteen minutes to one and a half hours. These

scans were made versus a reagent blank. These scans were par~~

tially repeated in Fi~ure 53, after al~owing the reagent solution

to age three hours, with no apparent change in absorbance. These

scans were repeated in Figure 54, using methanol as reference in­

stead of a reagent blank., in which case the peaK at 650 nanome­

ters increased with time. For Figure 55, scans were made two to

eighteen minutes after mixing and show the development of the

670 peak. Fo~ the scans in Figure 56, the amine reagent was dis-, • I

solved in water, omitting the methanol. Unlike Figure 52, these

scans show that the 670 peak continued to increase after fifteen

minutes.

In the solutions described above, for example, those used

for the scans in Figure 48, the green color appeared more rapid­

ly in the more concentrated solutions. However, Figure 57 shows· t'

that the absorbance became relativel~ stable after fifteen min­

utes for 10 micrograms per milliliter, as it did for 60 micro­

grams per milliliter in Figures 52 and 55. Figure 58 shows the

absorbance versus time for the reagent solution with 10, JO, 50,

and 70 micrograms per milliliter of benzoyl peroxide in pyridine.

(55)

These curves are ne.arly hori.zontal; be tween ten and thirty minut~s,

during which time absorbance measurements oowld be made.

Table II gives the absorbance after fifteen minutes for the

reagent solution with 10. 20, 30, 40, 50, 60, 701.and 80 micro­

grams per milliliter of peroxide in pyridine, based upon four

sa~ples for .. ~ach concentration. The ~verage of the percent av­

erage deviation obtained from these values is 1.6 percent. Fig­

ure 59, using the average absorbance values from Table II shows . that Beer's Law is' fol,lowed. ( The values for Figure 58 and Ta­

ble II were obtained, using the Beckman Model B spectrophotome­

ter.)

A slight coloration of the standard peroxide solutions in py-

ridine was observed several days after preparation, This was not

apparent with the benzene solutions. For a period of three days,

a fourteen percent loss in strength for 60 micrograms per milli~

liter of peroxide in pyridine was calculated from the decrease in

absorbanoe.

(56)

TABLE II

The Absorbance for Different Concentrations of Benzoyl Peroxide •

with a 0.3 Percent Reagent Solution

Concentration Absorba.ncea Average Average Percent ~g/ml) (670 nm) Absorbance Deviation Average

Deviation

10 0.113 0.113 0.102 0.108 0.109 0.0040 3.7

20 0.256 0.258 . 0.247' 0.256 0.254 0.0038 1.5

30 . 0.397 0.406 0.391 0.405 0.395 0.0068 1.7

40 0.535 0.547 0.528 0.543 0.538 0.0068 1.3

50 0.682 0.692 0.672 o.693 o.685 0.0078 1.1

60 0.824 0.833 0.814 0.840 0.828 0.0088 1.1

70 0.950 0.960 0.943 0.980 0.958 0.013 1.4

ao· 1.098 1.113 1.078 1.096 1.096 0.0093 o.85 The Average of the Percent Average 1.6 Deviation

a Absorbance measurements were made with a Beckman Model B Spectrophotometer, using a reagent blank as reference.

{57)

V. Discussion

A. Identification of Wurster's Red

Comparison of the spectra, given in Figures 6 through 10 and

also in Figure l by Dugan with those given in Figure 4 by Mi­

chaelis and in Figure 44, indicates that, when a solution of N, I

N-dimethyl-p-phenylenediamine sulfate is mixed with a solution

of benzoyl peroxi~e, the first product of the reaction is W4r$­

ter's red, and the reaction is an oxidation reaction as with the

a~ine sulfate and bromine or ferric ions.

The pH of the reagent solution, 5.5, falls within the range,

3.5 to 6, which, according to Michaelis (45), is necessary for

free radical formation. According to Steigman and Cronkright

(58), the amine salt, N,N-dimethyl-p-phenylenediamine sulfate,

used in this study is 1~ the proper ionization state for the re­

action. It would have the following structural formula,

[(cH3 J2~~-!H2] 2 [ S04:), with the extra proton on the ni­

trogen of t~e tertiary ~mine group, since the unpaired electrons

of this nitrogen are more available for sharing than those of

the nitrogen of the primary group (75a). The following equation,

similar to that of Steigman and Cronkright for Wurster's blue,

best describes the oxidation to Wurster 1 s red.

[oJ ~

+ -e

(58}

This form of Wurster's red is the ionization state which, ac­

cording to Michaelis (45), can exhibit the resonance for stabil-

ity. Other resonance forms are possible, similar to those given

for Wurster's blue on page 32.

·If Wurster's red is formed by the reaction mechanism pro­

posed by Horner (65), .a. proton is lost and the amine reao:ts "Wi.:t~h

benzoyl peroxide according to the followin~ equations.

Q-c,!'o +.~ ,.,.8 ~~o

+

+

+

.o ~-~ '~ 'o-

The electrons of the free radical can easily shift to the quino-

no id s true ture. · .·,

The appearance of color, denoting the formation of the free

radical by autoxidation, in the reagent solution with time is in

accord with the observations of Michaelis (45). It occurs when

the reagent is dissolved in methanol, as seen in Figure 18, but

it occurs twice as rapidly in water, as s~en in Figure 25, form­

ing more rapidly in the more polar solvent, which can more easily

accept a proton. No color formation characteristic of Wurster's

red is observed in acetone, as Figure 35 shows. The reaction

with or without peroxide is therefore not between the amine sul-

fate and methanol aa was 'suggested by Dugan (12).

. (59)

B. Identification ''of p,p•-Bis(diinethylamino)azobenzene

According to Micha.ells.·· (43), after the fQrmation .of Wurster '-s

' · -red, further oxidation occurs~ It was found that, in the reagent

·.· s~lutton (ptt·5.5) ~as· the peaks ·for the free radical a·t ·515 and

.. 555 nanomet'ers. decreased.;· ·a peak formed at 670 nanometers; which .·,. ., . . . ·upon standing· became sharp· and shifted to 640 nanometers. These

peaks can' 'be seen in. the scans. of Fi.gur~ · 6.

In basic s~lutlorr the~ 515 arid 555 peaks formed and then ra.p-' .. ·. . '

idl~ decreas~d(as'peaki at'670 and 465 na~omete~s ·formed, as

. shown in Figures .. 1),' 16 and' 17. Fig~re 15 shows·. that. upon stand­

i~g the 67o'peak reached a·ma.Ximum and then decreased.while the

·465 pe,~k continued to increase, This fact is not apparent from

. Figure'i3, 'which covers a short time period. As the pH of the

· solution ·~h,ang~·d, g·r~ate·z. basici ty favored the 465 nanometer

peak;' a peak at .510 'nan'ometers a·ppeared fn· strongly acid solu-.•

tion'~ with the 670 l'l'anometer peak a't' intermediate pH values, as

Figure 23 .. sh,ows. The tnree warvelengths ·at 465, 670 and 510 nano-' r,

meters appear to be pharac'teristio of the higher oxidation prod-

. uct. The stability of this' product can be seen by comparing the '-'·.,_

-_ spectrS: immediately after formation in Figures 23 and 48 with

the spectra of the salt extracted from benzene in Figure 37 and . '

the spectra of the dissolved salt i.n. Figt.lre 43. , J '~

As: the pH of the solution was changed, causing changes in the

:·intensities of these peaks, virtually the entire spectrum of col-'.:

Ors Was observed, tan ',to yellow-green··. to· green-blue to Violet to . \: . . " ; ·'.\.,.·\ "·.. , ·.-~.. .. .

pink .to red. This' c~~ be. _achieved with Just two wavelengths

: (60).

:(7ia):_if:one ~s in the yel~ow to purple rangei (5800 to 7200 -'···: ··.·. : ... \

anstroms) and th~ other is centered on a wavelength shorter by~ . ~' .

1500 ans trams •.

The products of the-reaction between benzoyl peroxide and

~dimethyianiline, a tertiary ~mi~e similar to the ·one being stud~ ' '

ied, ar·~ benzoic acid,. monomethyianiline, formaldehyde, and'

small amounts of p-benzoyloxydimethylariiline andp,p'-di(dimeth~

yl~mino)diphenylme~hane 0 (65). 'The·proddcts ·of.the ~eaction be­

tween be.nzoyl peroxid~ and -aniline·,· a primary amine similar to

the one being studied,· are.b~nz6icjacid,~benzanilide, azobenzene,

and a small amount or·o-hydroxybenzanilide (65). Of these prod-. . ~._, " ~ -

' ucts, the azo dye should have the greatest color.

Although no definit~'identitication was made~with the Sadtler

Spec-Finder of the ~oli~ product 1 i~olatea in this:researc~, three

compounds are: listed· ( 79a) with·· the same prominent peaks as the

product.''in question:·; Although comparison of their structures ' '

with that of the amineusedin'the reaction eliminated them as

possible products;. all three oi' these compounds are azo dyes.

" ' ... ,·: .''•' '· ,_

·N-o. 360_.

·-._ ··No •. 6991. - - -·

CH3 ' J l I [ CH" ~-N=N~~-N~ ) . .· ' 'CH)

(61)

Roberts and Caserio ( 78a) refer to the ,spectrum o,r ,P-dimeth-·-· .. '

ylamin.6azoben~ene •. Thi·s compound in aqueous solution, is. bright ' •, . , '·1 . ' ' , • ' '<. - '

yellow (...\.max 4200 A), but it turns intense red (A. max 5300 A) I. . - . ,' ·,•: '->.'" . LI " • ·,

~upon t~e ~ddition,of.di~ute ~~id~ :With the. addition of strong_~·

ac~'d, the red changes to' a yellow color (A. max 4300 A) different·.

· from the .. s ta~ting s<?lution. ·. The shifting to longe~ and . .then , ..

. shorter wavelengths .by this compound with ·Changing pH is indeed.··. ' .; '· '

~· • I

.similar to that observed for the second reaction product of N,N-;. . . . . ~ "

dimet~yl-p-phenylened\amine sulfate and benzoyl peroxide.

The azo dye, p,p 1 -bis(dimethylamino)-azobenzene, .. \ '

CH3 . CH3 \ ,-, ,-\ I' N-1 \-N-N-4" '\\-N

CH3" '. \::::-./ - \=.I 'cH3

a specific stain for. unbleached coniferous sulfite fibers (72a),

has been prepa?"ed by .the au toxida ti on , of N ,N-.. dimethyl-p-phenyl~ , .· •'' ' :. .,; ~, ' ' :;. ·: ·' ·'

enediamine in the presence of alkali alcoholates, particularly ",., ~

'potassium. tert-butoxi.de (73a).

In using Wurster's red, formed by.the oxidation of N,N-di-'·, ., . • ~ l,

methyl-p-phenylenedi.amine by potassium thiosulfa te, to determine , ' ' ' ' / ' . ' '

the reactivity sequence of compounds of. the gene,ral formula, ~ \ I·/ ·" . 0

XCH2Y, when attacked by free radi.~,als, Hiinig and Pie ~stocker

(74a) noted that Wurster's. red also dipierized, and. the hydrazo ' f • : ,t .. ' . ' ' . '

compound which formed was oxidized::to p,p~-bis(d~methylamino) . . . I . ' , ' '•·

azobenzene. The ease with which a.hydrazine can be oxid~zed to ' 'I' A , l

'• .·'

the corres~onding azo compound was pointed out by Roberts and·: . . ' :; , ,~ ; ' ' .

caserio (76~). · ·- "~~ .

{:: .' ~ .

: ···Figu.re. 60 is the spectra giyen by Gerson and Heilbronner t, •..•.

(62)

(71~) 'io~;· p,p'-bis(dimethylamino)-azobenzene, '.which show peaks·. - - -- • . , - l , '

at ·~·ppr:~xirp.~tely' 670, 510, 465 a~d 440 nanom~te.r.s, corresponding .

. clo'sely 'with. those, observed iri' this lab~ratory. The forms of ·~ • -<

th~"-dye''corr~espondi.ng.to these wavelengths were given as the ' .,.., ....

following: .....

. . •

.' . _, ~ ' -~ ' 'i '' ~ '·"'· ' ·'; •

T~e scans of Figure 60 sh~w the' tw~ forms giving peaks at 446 ·

and 670 nanometers' to -~e iri sol,ution in different ratios depe~d-•( ., .. ' i'ng upon the pH.

(' .. ' ·. '·

From the information given above, it was concluded that the ' ~- -~ _,,.. ' ~-·. '' ; '"'\· \ , •· ..;

second oxidation product in the reaction between N,N-dimethyl-p-

~henylen~di.aml~~, ~ul·f~ te 'is ::..p, p.' -bis ( di~~thyla~ino )-azobenz~ne ~ ~hich for~s by ·wa; ;6r .Wurs.ter 1 s red.:. This formation is sh.own in

F{g~res 1"3, '16,''·~~d 17. ·Frorn Wurst·e~'~ red the.hydrazine forms • ' '·, "J.. r \ '1 , ~ ~ • ~-. •

with 'the los's" 'or protons from tri'e nitr'ogeri anci. is further ox1.:..:

di zed. ··In acid solut1on,' t·~e oxiclati'.on of th~ hydrazine occurs .,

with the·'r~rmatio~ of the··~zo dye with structure correspondini'

to that given ro~ tne p·aak ·at. 670 nano~~ t~~~, as shown irl Figure :·.· f-:·.

6. It ·appears r~~~ the spect~a. of Figure's\ lj and ·15 'that this· _. ·, . ' .

. ·structure,:fo~s_ simultane~usiy in basic solution.with a structure

(63)

corresponding to the peak at 465 nanoneters. Considering the

structure of the.hydrazine, it would be likely for the structure

giving a peak at 670 nanometers to form firs·t and rearrange to

the latter structure.

CH3 + H 2 .·· · 'N-:/=\-N:

" '==./' .• CH3 ··. . H

+ - 2 H)

Although care must be taken in making identifications using

visible spectra, for the free radical, Wurster's red, and the azo . . . dye, p,p'-bis(dimethylamino)azobenzene, the slight deviations of

the wavelength peaks _obs·e!'ved appear ~o be due to solvent effects,

similar to those· observed by others,,such as Steigman and Cronk­

right,··as is shown in Figure' 5. (See.also Figures 40 and 41.) ,,

Of the different structures of the azo dye corresponding to

the different wavelengths, the one given for 670 nanometers seems

to fit the observed data because of the way in which the azo dye

forms, because of its existence in slightly acid solution,_ and '

because the location of the proton favors resonance •

. The structure given for the 510 nanometer peak also fits the

observ~d data, with two protons attached to the molecule and

with charges separated in such a way as to favor resonance. The

shift to the lower wavelength occurs when the proton becomes at­

tached to the unshared pair of electrons on the nitrogen of the I ", , '. I• l,;

ter~iary group, and they are no longer free to move.

{64)

The structure given for the 465 nanometer peak is in line. • • ,, : - • !_ ~

with the observed data for b~sic solutions· in which· the· color ' •

-.that for.ms also gives maximum absorbance at approximately 46.5

nanometers. depending upon the solvent. These :·a tructurea: are in ·.· .' ' ' .

:agreement with Roberts and Casario (78a), that the shifts in'the •• ·-' ...... _ •• c•

.spectrtim of p-dimethylaminoazobenzene are due to the. addition of

··one and then the second proton to the uncharged molecule.

The reaction whereby the azo dye is formed, as well as the

. f.orma.tion of .the~:LnteX'!.mediate, Wurster's red, are not specific ' ~ .

for peroxides but will occur with other mild oxidizing agents,

~s Figures 45 and 46 show.

·c. Further Analysis of the ·spectra ... ,;,

. -In light of.the above conclusions, further analysis of the

spectra ·given will be made.·· In titrating th~ amine with bromine

pa~ t the point for complete oxidation to the semiquinone, Michael· . "\ . . ;

is (43) observed the reappearance with time of the color charac-. ·.

teristic of the free radical, al~hough this color was not as in-

tense as when it was fira.t formed • He concluded that this second

. color was due to self-oxidation of the diamine by the diimine. ) - ;

.. In_· the pr:esent work, the reappearance ·or the peaks characteristic .

. of thejfree radical was observed within a narrow pH range when the:_

pH was changed and the scans for Figure 23 .. were made. The return·

of th~ magenta color was also observed when the reaction mixture ·"

;--,_ <!"':

containing pyridine was made' acidic•.:

In' the 'ten percent water.;.methanol solution at a pH or 5.5, ·'""

the amine sulfate can lose a proton and: be -oxidiz~~.to Wurster1s

(65)

red. ·This/pH also favors th~ toss of. a proton 1

t'rom Wurster•s~ ' \

:red ~nd further oxidation. Addi ti on ·or acid to the reagent , · • ' '

: solution 'prior to mixing with. the peroxide solution does not ,.1 ·

.·- ~· . ·- ,· :

des~~oy the peroxide as was reported by Dugan (14)but prevents

·the loss of the proton from·the amine salt, and in this way pre~ ' ~ : .

:vents ~adical formation. 'rhe subsequent addition of base per-..

mits the ~~r~ation of the radical, as shown by.the a~~earince of

the red-violet color, which turns blue-green, the colo~. of 'the"'.. .. .~ "" ..

azo·dye. ' ''. ·'

The addition' of acid to the reaction mixtu~e st0.bilizes' the'

reactfon at the time of additlon, as Figures 7 through 12 srfow,'.·:··>

·by preve~ting the loss of a proton froill the. Wur~t~r'~ re·d wh'.lch·

h~s formed. . With the addition or excess acid;· the 1

·~oi~ti~n 'pH

is too''low· for the stability of the rree radical,: a~d mJch 'too '

low ror the· azo dye to form •.•. Judging from' the . scans .of' Figure ;t"

. 24, with ex'c:ess acid the free· radical. is· lost and 'the resulting

p'roducta a~e not .:Colored· .... No,"atten1pt was m~de··t'o ·analyse this

·sol~tiori~

Figure· 20 shows simply that there was aurri.1

0 ier.it arriine '. su1-·.

' ' fat~, in ·~ddition to that already autoxidized~ for oxidation by

· benzoyl". per-oxi~e to occur •

,~·-, '

. The: color of the two layer water-benzene syst"e'm was .extracted· i.. ( .'">,· ' 'i ,1'

·into' the benzene layer with the addition of tris-buffer, as seen

in Fig~re .JO. · Thie tends to 'prove that this peak for the ben­

zene layer ·-is due to the uncharged form or the azo dye/ as 'is the -· - '·

, .. ·:· !

465 .. pe_~:k. b't a basic solution,. with the shift in waveletfgth. ob-~

(66)

- . . .served' due to solvents effects.

\,'

D. The Modification of Dugan's Method ··~ - .

By Dugan's method the absorbance was measured thirty minutes . - .

after mixing, at which time the color had decreased considerably

below the maximum and was decreasing rapidly. Therefore, advan-

tage was not taken of maximum color development. Taking advan-.. "

tage of the maximum color development by stabilizing the reac-

tion with ~cid was considered. Although this worked quite wel~ t . '

for standard solutions of benzoyl peroxid~ as Figure 11 shows, .-

the time of addition of acid.was critical as can be seen from

Figure 12. The fact that sample solutions might contain impuri­

ties which:would alter the rate of reaction slightly so that the~ .. , .:

would not compare well with standard solutions led to considera- ·

tion of carrying out the determination in basic solution.

When tris-buffer was added, the absorbance varied greatly

with the reagent concentration, as Figure 50 shows. Tris-buffer

could not be made up in aqueous solution because tf the ratio of ,I,<

water to methanol was' increased, two layers formed. By the use

of pyridine, this variation was greatly lesse.ned. The small

variations -which did occur with pyridine did not seem sufficient

to change the preparation of. the reagent solution • . . In the pyridine modification which has been worked out, no

": ,• .·· ,' - -'i:~.. . :· • . . - ..

change was made:in the water-methanol ratio. This amount of

water was n~9essary to dissolve the reagent; a larger amount ; . ' ~·- ''

. <?aused the \too rat: \d · oolo:c-ation of the solution by autoxidation. ~· . • '!.

·--.-,,.;.'Autoxfdation of the reagent solution along with loss· of

(67}

strength of the peroxide in pyridine necessitated the use of

fresh solutions. Altnough a nitrogen purge might have prevent• •

ed the autoxidation which occurred, the use of fresh solutions

and a reagent blank instead greatly simplified the method.

Whereas Dugan reported a deviation from Beer's Law for 40

micrograms per milliliter, Figure 59 shows that with pyridine

Beer's Law was followed up to 80 mi~rograms per milliliter.

The procedure that has been worked out using pyridine is as

follows: The reagent ... solution is. prepared by dissOl·ving O. 3

grams of N,N-dimethyl-p-phenylenediamine sulfate in 10 millili­

ters of redistilled water and diluting to 100 milliliters with

methanol.

Standard solutions of peroxide are prepared in the range

from 10 to 80 micrograms per' milliliter of pyridine from a J;OO

milliliter stock solution cbntaining 0.0500 grams of benzoyl

peroxide. Sa~ples can be dissolved in pyridine to give peroxide

concentrations in the. required range.

Two milliliters of reagent solution are mixed with two milli­

liters ot pyridine containing peroxide. A reagent blank is pre­

pared at the time of mixing. Absorbance is read at 670 nanome­

ters ten to thirty minutes after mixing.

To use this method as modified10~ Dugan's method requires a

knowledge of the reaction time for the particular peroxide to be

determined. ·

(68)

.SUMMARY

.'. _,..

The colored reaction which occurs'with N,N-dimethyl-p-phenyl­

~ enediamine sulf~te in a water-metha~ol solution and benzoyl.per-

·:.oxide ··in benzene, or some other appropriate solvent, is the ox-

idation of the amine sulfate by benzoyl peroxide, first to the . CH3 + _ ,,,, H

type, 'N:<::'):N• CH3,,... '-H

free radical of the semiquinone , ·call~d

Wurster's red, with the loss of one electron, and then by further

p,p'-bis(dimethylamino)azobenzene,

, with the loss of a second electron

(or two electrons·from the dimer which forms).

The Dugan method was modified by substituting pyridine for

, benzene as the solvent for the peroxide, and the absorbance was

read at 670 nanometers, the peak which occurs from the oxidation

· of the . amine to the azo dye.

Although different peroxides react at different rates, the

· .. ·oxidation of benzoyl peroxide with these modifications was rap-· ·'

, id, the color which formed was fairly stable, and absorbs.nee

readings could be made ten·to thirty minutes after mixing. Py­

.·ridine served as the needed buffer for the system, and Beer's

·Law·· was followed for a wider. conoe,ntration range than previous-, : ....

' (69)

APPENDIX '· '

'•,

FIGURE 1. STANDARD CUH.VE FOR BENZOYL PEBOXIDE

Uugan, Pa trick li.: Hap id Spectrophotometr1 c Determination of Nicrogrrun Am:>unts of Lauroyl and Benzoyl Peroxide, Anal. Chem., .2J., 697 (1961).

I ••

Corte. benzoyl peroxide - 50rg/rnl solvent Cone~ benzaldehyde - (1) none, (2) 0.1%, (3) 0.25%, (4) 0.5%, (5) 1 .. ()%.

F·IGURE 2. REACTION SPECTHA FOR BENZOYL PEIDXIDE AND N,N-Dil1ETHYL-P-PHENYIENEDIAMINE AT PH 8. 7 IN 'llIE PRESENCE OF BENZAIDEHYDE

, Dugan, Patrick R. and ttichard D. 0 1 Nei1l: Modified Spect.rophotornetric · reaction for Detecting Or~anic Peroxide, Anal. Chem.; .J.2, 415 (1963).

-·--- - -·--·-. -

ZA ! +600 -A 2

A +550

== A t ~ 1 :.+;

+soo-

0 0.5 1.0 1.5 2.0 Cc. of bromine.

DimethyJ-p-phenylened1amjne hydrochl~ride in acetate buffer (pH - 4.62). Arrows signify drift of potential. (A) is the tota] theoretical amount of bromine for compJete oxldation to the semi­quinone level.

FIGURE J. POTENTIOMETRIC TITHA TIO!\ CURVE FOR N ,N-DIME THYL-P-PHENYlENEDIANINE HYDhOCHLOHIDE WITH BftONINE

.

I . l 1

I 2

I I

50001

i : I

2500 ~ !

H2N 0 N(CH3)2

Cli.3

Ii2N 0 N(CH3) 2

460 540 mµ.

620

I

I !

FIGURE 4. SPECT.HA FOR T1fllRSTER 1S RED, SHOWING THE E1''1''1'~CT OF HING SUBSTITUTION

Michae11s, I., ~·j. P. Schubert, and S. granick: 'l'he Free hadicals of the Type; of Wurster's Salts, J. Amer. Ctem. Soc., g, 1987 (1939).

.. -1--1--1--T=1.:.++.+= : ,_:+_,__,._,_ -++ 1- + ~-- -~ :_ ---1-m---f~m-0::1, -ri~ -~~---- . 1~+-- - - --i-++ 1--H-+- --H--1-+---1-1--t-+-- -I- - - i-\\- -- - -H- -p l hi. L ,)Im~ ttJe "ffi~)( ir, o-1-- -1-1--1-•-'

- - -~ -t--t--- -1/t ;-t- - ;- - ; - - • - - .. -- - - ~ --rt-+--1- -H--+-

· -i-+--+--i-+-++- - -•- 1- -1\ + - ·· ra \- - - --1--1- -ltJLr.·:.JL-t.; -~, ·lchbi L!: · Jni:.i--iJ-J.alrt-:,;.;__r +- -"--J·-'---'-'

1-1-i-- -1-- !-t--1-- - -lf- - -i-- -- - f--- -~i- -1--1-- + -- -+ _ -_, dn-j~-fy-/Cl'-~he-t+ ,.. __ ,I ~--1-H-

2.1 't= ~t=~ -!~ -l=+=fj==-~1\+=-jJ :=~~I : 1~-t2= -~=f1d~~\~~~~Jl~~~1~~2~~-j'> -.-:Yi1~=:-i ~-=-H -t _] ++- -1-l\iJ- - -N-~ -1+-1-1-+-i--1-j~) J>~-hl-o,.,L-l-~--H-+-1 H--+-

H -1-f-H-f: -rl-'H -l~b-l - -J · - - ; -- -r'-'~f"['--l--J- - --t- -_.__,>-+-_,_1--+-H-- --1-1-+-f'i-'----f-1- I·-~ H--1- -1-1-- g-)--~ !rAj n.Lr-H-1-+-I-- - - -1-- -+--l-+­-f--t-i-+-1--t-H--- --!-' - -1--,-H-i - + --t-H--t-1- --rf.i..:.. -b-,-~,:;l~ 1-v1iilllri!--l-+-l-H-l- - - -H--+-

1--1-t- - H~J:+-~J~=t:I - 1--t-I I H- --+-+-1- -- _Jf1).· -p1.+~ .... ,..f-1-+ - -i-- -H--H-H +-H-t-l---j •--+-+-+--+-1'-+-+-+---1-!(1-1 +-- f +-HI -1----,..t --i-t-1-'-l•P__j!_H---+ --- -\ ~-+-+-+-<>--+--~--+-·•1t- -l--1--[t-r -I -!- - - '_ --t-+-Hf-i-H-11--1-+--l-~-l--I-+· H-f-1-1- H- -LH-t-J

1. 8 ~-+-+-t-+-1++-1--1--11- -L-1 -l- -1\i.::,; - -1--}&1- -1-+-+--1-t---1-11- --1--t-t- -1-t-H- - -+-+-1 --1-H-+- - -!=j

+-t-- ~- --l---i--l-+-~L-1 ~t-- 1 - +---1---1--1-+-1-1-- -H--+-- - -t-t- -t-. -H-- -•- -- -1-+- -l-<

1-!---+-+-+-H -+-+1r - :y- - i +-- - - II+- -+ i -- - +-+- - -~ =t-=-- - H- :.++ -- -~ fl ti +JS t- -+--I/ - -- I 1- -!-+- -- 1-t- _U

l-+--+--+--+--+--4---•-l~I- --, •. - - -L 1-+-- -j- - - -+-1- -1-f- -1 t--H-f/1- l--11·,-+-- :;i_ -t-jJ -~ -t----1- -H-+- !- -

l-+--+-"-1--1-+-1- 1-17'-- -----j\-+V-f~fi !--\-- I--+-+-·- !-1-f;\~ -- +.I- -l-l--+--l-+-~1-+--l-+--+--1-1-+ 1-t---t--1--+--1-+---1.J - -17 - IH- -1--t-\ ~ -u f-j\- t-+++ -1-+-l-- - -- +-t-1 -I~ T 1-+--1-+-'-'-'--+-+-1--'1-1--+-'--+-1 1.5 I I] II- -/---l---J-t--k-j/'-{ +·111 1-f--f---f-j-.;{.-_J -t-t-J-t_!-+--+- 1--1--+- -f-+--H-

'T -~t)1--k_--[t-i-J -+-t-~ ~-- -- -H-l- ~q.gl--~ \-- - -1-+-->-+--+---l'-LJ.' l-l---1---'"f·JJI - ![_ 1--ii--j \ ---, I/ J-1-+-t- t-- _ _ _ -+-+---_l I I t h i- +-!-- --1-+-+-~-.--t--H-1--1-+--+--l--t i-+--+--+~+--~-+-+--jf - ' - - - - ~---1 f-1+-+- - H-1-- - . IL' i..\ 1-t-+--+--i--t-+-1-~- -'--'-'---'-'--• l-+-+-1--+--l·--l--11-+I ,-'.-H-c -1-+-r-t.Hz , ~h -1--t- - - -- +-- __ ,__,__._.__._ ·'--l--l-+-!--1---1~1-+--

CV If ~-- 1...-1 11 . - H--J - - - H-t-- -+ h-+-I 11'=1-r- _ ~J I-' H--!~f- -+ J Ii- - _ -t~+--+--+-+·+, -t-t-+--ll-1!--t-Hf-1--1-1---l--1-<

0 1-t-t--t-+--~-f-+-i7 - Pf I- -H tHH- - 1---1--+- +-+ t-+-t-1-+-1-+---'-'--'-+-+-t-11-+-+-+-+--t

~ 1.2 I ,-t+-+111/1--t--,- - -~I-- - -H- Ml- -!-- -1-1--+-j-l-!---I-' -H - -!--~~ i! +i=d ),-t-1/:v J...1 - I' _L -H -l--j-1-1- - -l--1- - - ~\++-1-1-H i-+--1-1

g -~1-4+-~1 f--+--1--l-- '+-+-+-+- :,±--:::::-~,_ -~-t-t't~~-1--1--1-r-t-+---~-:-+-l--14-!l--!-~ ~ ~r-t-- - 1/-1-/ :I-++- 1--t--+- .i..-n\I i"b, - -»-->-+-<>-

i-+--+-+[l+-+[/.," fr-+- H-t- - ,· -...=t - J-i~ -[~ ~e-'lrs .... ._~--1--+--l-f-l-+-+-l-'*~ll-JW+-++- -- v \ I IS~

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0.6

500 700 750 Wavelength nm .

Benzoyi peroxioe j n benzene (80~/rnl) and .N,N-dimethyl-p-phenylenediamine a~lfate in water-methanol (0.3%) vs. methanol •

.r FIGURE 6 •. COLOR DEVELOPMENT WITH TIME IN ACID SOLUTION

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H--tJ:-t-+-+-!-1-+-+~~+-J.-+-l-+--l-l-l-+-+-+-+-++-i-+--+-t:l I~ = o.oh50I 700

Benzoyl peroxide in benzene Wavelength run

(6~g/ml) and reagent solution (0.3%) vs. methanol

FIGURE 7. THE hl'FECT OF ADDihG ACID BEFORE AND AFTER COHBll4ING ·THE 100.CTANTS . • :<

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Wavel~ngth run . Benzoyl peroxide in b~nz~ne (401"-g/ml) and reagent solution (b.3%) wit~, o-~ ml of- lN ~2S04 in metlurnol Added_ after 5 min. vs. methanol

" _FIOU}tE 8. THE EFFECT OF THE CONCE?iTRATION OF ACID

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~ Q. 6 - - "/ --t-t--l-1f-H- --+-~ ..... ~----+-<-1--+--+-t-t--- · -1-t- H---t-- -t-- .... +-

~ 1-! 11-t-+--+--+-tl--t---t--t- -+--l---t---1-+-11- -H-- t - -1-- --- _ __,_,____.__.....__. -+--t-+--__,__,,_1--- --- --- - -<--+--+--+-•--+·-+-1,_., .... 1--l-t-ltl r---r+-~' -1--+-+-t-+-t----+--+- t- -t-11--1--+---t-t--+--+-t-+-t- 1---+-t- 1- -t- --I_; -c f +- - 1-t-t- - --t--t-< I- ,1---1---+--1-1---+-1:-+-·+ -,-+-1---t-+---t-+-+--+-+---+-1-l -, I-+-+-- __,__.._.____,____,_,_,__.._._, __ _,_,I --+--- - 1-t--+----t-t-tl --+-- t- - +-- +--+-1-t---r--1

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-l--1-+--+-+--+---1--1--+---i-+- - I--++-+- -+-+-+~l-t-+-1-+--+-+ -t--

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'o.o ·450 500 550 600 650 100

. -CJ,>.

·' ·' -.

WaveJenp:th run Benzoyl peroxide in benz~ne (u0/'4-r,/ml) and r~a~~nt solution (0.3~) wi~ O.l Jill or O.lN H2S04 in methanol added after 5 min. Ve• methanol

·:,.-:'.

-FIOUHE 9• :·:THE EFFEcT ~)F -THE CONCENTRATION OF ACID

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650 100 ,. · ' Wavelengt.h run

Benzoyl peroxide in benzene (LOl"-g/mJ) and reagent solution (O.J%) with 0.1 ml of O.OlN H?S04 in metha?ol added after 5 min• vs. methanol.

FIGURE 10. 'JJIE EFFECT OF THE CONCENTRATION OF ACID

t_ jj_ ,±t_ -l~ tr1_+_\-t!Jl1·· l1Jut ·1\ll t .. t.· ll_ jJ -i~ Li . I tT _it_\1. \I· 11~-i l l I l i ll_:li1 tLl '1- \_I:_:_. ; __ 11·L: i_· :: . . l-tlj i·H·I··. ·•-ti, 1·- ····I! I ·1-1 -·1·11- J+1 !1' 'j' -/i :1-1-: ,il. 1·l·i. 1111-1 .;.!ii o.o I I I. - 1-11J ! .i:rµJJ:lL_~.L .:. .. Jtl i .LL_t _LLLL - .. L. l L! :L!...t !:! I lJ_j :.J 1 J:!..' '..J...l..'..:.. j l t 1 i .! .

0 10 . .20 ' · 30 uO SO 60 70 80 "·· .- · Concentration of benzoyl peroxide

· 1

· ( rg/ml) · . 2 ml. of bf'nzoyl peroxide in benzene and 2 ml. of reagent solution (0~3%) with O.l ml of lN H2$04 added 5 min. after ·mixing vs. reagent' blank.

FIGURE 11. BEER'S LAW CURVE - REACTION STABILIZED WITH ACID AT 555 NANOMETERS

I. I I

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0 4 8 12 16 20 25 30 Time (mjnutes) after mix.i.ng.

Benzoyl peroxide in benzene (601"' g/ml) and reagent solution (0.3%) vs. methanol.

35 I,

FIGURE 12. ABSOhBi•NCE VERSUS TINE WJTH AND WITHOUT ACID

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Time after mixing (minutes) 2 ml~· of benzoyl peroxide in benzene (BO;n g/ml) a~d 2 ml. of reagent solution (0.)%) plus 0.25 mJ. of tris-buff er. Scan vs ... methanol.

FIGUI<E 13. ABSORBAN:E VEBSUS Tii"iE. AT 555, 465, 4ND 670 NANOMETEWi

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FIGURE 14. BEER'S LAW CUfiVE FOR A TRIS-BUFFERED SOLUTION

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. 2 .4

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f-t- t- 1--'-- '-'--- -1---J---- - -j-- ·1 l I I ,_ j-- . '--'--- · -t----- -•-+-+-+--t--11--+-1--- - -1T~- ::::::::H=i~ ~r~1~1=; -:--:'_;_,_ -1--t-- --1--1-- - - ----- _ru ~ij_-~[!~r~s~.l--+._+_-t_+ ___ H-__ +'--t-1--H---t-----t-i-,-t-'t'tt111 1-t-t- t-- t--+---1+ - - _________ i·:J- jLhrc. __ --b -- -- -- -- -j---j---- -~-+- - -1-- -i--

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0.3

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o.o -- L--- - _ ___.____..~-' 400 450 500 --- - 550 600 650 100 __ LJ

Wavelength nm ) Benzoyl peroxide in benzene (Borg/ml) and reag~nt solution (o.J% ,with 0.25 ml or tris-buffer solution added 5 min. after mixing vs. methanol.

FIGURE 15 • COLO.Ii DEVMOP.MENT WITH TIME IN A SLIGHTLY BASIC SOLUTION

7So

,__,___,___ . ._.___,_.__,_~-•--+-+_,__, _ _.__,___, __ ._, __ _.,._, _ _,___,_,__,__, __ , _ _,_ -•-+-+--+-.--•- - -i---1 - --t--f- - -r----H- --t-t-t-i-- --H-t-1 -•->-+-+--+-• --t-+-i·--+-+-+--t--+-+-•-->-+--r-r-•-i-+--+-t--1H-t-t-+-I-- -I-+-'- - --t- - - --t---t--t--t- 1 l--t--t--t-- -- -t-H-1- t--t--__,___,__,___.__,_,__,_1---+--•->-<-t-t--t--t--+--+-'~-~,.---t---t-->--+-+-+--•--•-+-+-+-·•-- -t--t--t-t-1 -i--1--i---1--r -i--1--1- - t--i- 1-t-t--t-~-- - t--+-+--t-·

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11 •-4---+-<--+- -+--+--+·-+--·l-+--+--+--t--l-t-t--+-'---'-~lt--+--t--l-+-+-f·-t-1--t--t- --t-- --~t--t- t-t-t- t-t-t- -- -t--t--t-t- --t-t--t--t-- -t-t-t-- - - -+-I- --~ 1. 2 1---l-- -t-+ --1-t---t-t--1--+-++- --t-+--+-- H--+-t--t--t--t- r-1-·+--t- -+-t---t-- t--r--r---t--t---·- t- --r-+-t- t--r- --r---r+l--'ll :i ... :> n :i (

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o.o l--++-l-t-+-t-i-t-t--t--1h-t--t-t--t--t---t-t

·1

400 450 soo sso 600 650 7<XJ 750 ; Wavelength nm

Benzoyl peroxide in pyridine (60r-g/ml) and reagent solution (0.3%) vs. methanol

. FIGU.HE · 16. EARLY COLOR DEVELOPMENT WITrt TIME IN A SLIGHTLY BASIC SOLUTIOlJ

t--t-t-1-++-1,-+- -t-- -t-- - - -t-t-++-t-l-i-·i-1--t-1- t--t- -H-t-t- t-+-- -1--t- -t-t-t--t-10-t-+-+-t-- -+-1H--r-T--r-t-l- t-, - - f-H- - -t-t-H - -· t-t-t-t- ! -t-t-t-· - '

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l-l-1-H __ ,_,__,__,-+- l-t-t-t-1-- -+-+--t-t-H-t--l-t-1--1--t--r -+-t-+-t-t--i----t--fM-1-r--t-t-r i-t--t-+-+--t---H-H- --J-H-H t-++-1 _,._,r-r-..- --+-+-•~1-J-t-r· - -1--t-t-t-1-r-t-t-+-

1--t--t-1-+-l-1-+-._,~ ... _,_-1_-1-j-- t-t--t--- -t-t-t--t- H--t-+-i---t-l -+-t-+-t-l-,-+-l-t-+-l--t-'!-T--t-1-t---t- · r-t-1-f-2 .1 --+-+-+-+-t--+-1-+ I- - -- -t-+t- +- ---t-HL - t--t-t-+-'.

+--f-t--t-1---+-t-i 1-t- H-1--f-+-1-t--+-1-+--•-1-t--t--t-1-+--+-t---+-t--t-t-t--+---1-.-,.....,--.-._,__,_t-o--•-1---.--r-;-1-t-t--t-i--i t-+-+---1-"--t--+---+-r-r-,-,~-+-t-+H t-i-t-r--t-1-t-t-t-i-t-+-+-t--+- -t-t--t-t--t-t-t--t-i'-1-H-rl-·•-.-..,._,._,_, 1-+--+-1-t-+-+-l-+--+-l-1--t--t-f--t---+-+-+-+---l-+-+-+-+-1--t--+-t-+11-0--t-t-r-t-~4~1--1-T-r--t-1-r--i-r-r-1-r-t-r-r--t-t--+--+-1--t -l-t-f--!-J-f-f-f-f-f--t-j-j--i-1--J-+-t-ll-l---·<-4---4-1-- -t--+·+-t-l-l-t--t-i-·l--+-t-t-'-·f-l-t-i-+-t--1-t-~_,_,

1-+-t-t- -l-+-f-+-t-1--+-I•-+--+- 1- t-t--t-t-· - -t-'!-T--t-1-0--t-t-"-t- t--+---t-<-i--•--+-r--+-+-. -+-1_,__,_,_,_.__....._._,1-+--J-~-1-- - t-t-t- -·1-H- - -1--!H-t- r-i -.-1--,-,i-,--.-,-.-..-r_,_,

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- S~MCjJmfu~J 1& ~~e:rimroc:tru-H ·rt-•-+--+-<-+--+-+-t-t-r-•~-t--~-l-+-t--t--•-•-+-4--+-+-+-+~-t-..-•-+--+-<-+--•-+-+--J---4--

1-+--+-1-t-+-+-+-+-t-t-+-+-11--t-+-+-+-l-+-t-H-t--- -r---l-t-t-'l-t--+-l-if--l-f·-+-+--+-l-1--t--+-t-1-t-t- -t-1-+-t-+-+-t-r-t---+-t­t---t--t-·t---t--t--11--t--1~~--'-!-t---t-l-t-·f--f-t-t-f-·+-t--+-t- >-+-r-+-t--t-+-r+-t>-<---+-+-+-1-H-t- -t-t-t- -r- -+-+-t-+-~-+-t-+-t--1

} . 5 1-t-+-1---+-l-+-I- - -H--t-, t--t--t--t- -- t- -H-i- t-t- t--1-·

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t---+-1-+-+-1-+-l-l-+--l-l-+---+-+-+---+-l-t--+-~-t-+-+-t-+--+-l-•,,..t-t-+--t--t--+-f-l--t-i-t--1-~--t-t-t--r-1

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lL D lJ,_. -+-T-+-t•·•-.--r-1·-.+- -,--r-r-i--.-r-i-·.-,--,

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o.6 .........,_.._ ......... _. -

O.J

o.o uOO - -450 500

Wavelength run 550 600

Benzoy1 peroxide in pyri.dine (60 l"'g/ml)- and reagent solution (O.J%) vs. methanol

FIGURE 17. EARLY COlOR DEVEIOPNENT WITH TIME IN A SLIGHTLY BASIC SOI.UTION

1;6,....,...,...........,~ I ' ·-r "

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·.: .. ·.

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Q. h o-+-1--1-+--l-+-l-+-+-l-l--+-f--f-+-l-l---+-1f--l-H--, -->--•-1-...._.__,_ --l---!-t-t--l-f-l---HLl--i-1-+-\--H--l-

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-1--1 -- --- ~

o.o - -:-450 · .-, --=. . 500 • 550 WO 650

: · .Wavelength nm N,N-Dil!'et~yl-p-phenylenediRmine sulfate in methanol

700

{0.1%,) vs. methanol

750

FIGURE 16• COLOR-· DEVElOPMENT OF THE AMINE IN METHANOL

..

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500 • 550 600 650 700 750 Wavelcn~th nm ·

Benzoyl peroxide in benzene (60./f\-g/ml) and N,N-dimethyl-p-phenylenediamine sulfate in methanol (0.1%) vs. methanol.

FIGURE 19. COLOR DEVELOPMENT IN A SOLUTION WiTHOUT WATER

Q) 0

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L

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I

45-0 500 550 600 650 700 750

Benzoyl peroxide in benzene dia111ine sulfate in methanol

Wav-elength nm (60~g/ml) and 24-hr-old N,N-dimethyl-p-phenylene-(O.}.%) vs. methanol. · ·

FIGURE 20. THt: EFFEI; T OF PEROXIDE ON THE AIR-OXIDIZED AMINE IN METHANOL

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450 500 550 600 650 100 1-So Wavelength nm

24-Hr -old solution of N,N-dimethyl-p-phenylenediamine sulfate in methanol (o.1%) vs. methanol.

FIGUftE 21. 'lHE EFi:<'ECT OF AC ID At\D BAS~ ON 'I'!i.E r.:.1-0XIDIZED MllNE IN. N.I!;THl>!'lOL

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500 550 6oO 650 700 750 Wavelength nm

Benzoyl peroxide in benzene (501"-g/ml) and N,~-dimethyl-p-phenylenediamine · sulfate (0.1%) in methanol vs. methanol.

FIGURE 24. THE EFFF.CT OF EXCESS ACID

•

CV u c

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Wavelength run N,N~Pimethyl-p-phenylenediamine sulfate in water (0.1%) vs. methanol.

FIGURE 25. COLOR DEVELOP,\IENT WI TH TIME OF THE AHINE IN WATER

:750

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Wave~ength run 24-Hr-old solution or N,N .. dimethyl-p-phenylenediamine sulfate in water1 (0.1$)

ve. methanol.

· FIGURE 26. THE !,1FECT OF BASE ON THE AIR-OXIDIZED AMINE lN WATER -,

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0 • 11-1-+-+--l-f-+--lf--l----l--l-t--l-l-f--+---l--l--l--l--l--l-+-t-l-+--l---t-+ r-1-t-l---l--l'-l-+---H

l-t-l-+-f---t--l--lli-+---!-,1--t-l--+-+--+--l-+-+--l--l-+-+-+-+--l--l-+--+-l~l-i-t---t-+--+-+­l-+-t-+--l-+-+--ll-+-+-ll-t--+-+-+--+-t--+-+--t-t-t-+--l-l--+--l--t-+--l~~~-r-+-+-t-~-1-l--.-~~t-+--l--l-l-+-+-+-l-l'--l----l--l--l--l--l-+-1-1-1---1--l--'1-t-t- -- d

0 • 0 _._.._._.._._..._,__.......__.__._._,_._~~_._.__._.___._,~.__._._._..L-'--'-'--'-'---'-'-' ·-400 450 500 550 600

Wavelength run N,N-Dimethyl-p-phenylenediamine sulfate in water plus

2 hrs. after addition of Scan vs. methnnol ..

650 700

l drop cone. NH4oH. Scan made base.

FIGURE 27. 'IHE EF.F'ECT OF BASE ON TIIE COIOR DEVELOP1'1ENT OF THE Ju'1INE rn· WATER

t-

750

r-+--+--+-+-·l-+-+-1-+-- -t--+-H--t-t--- -t-' - -- - -- - -- +-H-1-Ll- --!- -+-t-i -H-t-t-t-+-t-rl-t-1- -+-+--1-1~ t--1- -t-H -H-t-t+1-r-H-H-H-f---t--1 -t-t- -- -t-i-1-+-H-+-+- --H-t-+ -t-t-t---t--i

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0.2

o.o 450 500 550 600 650 700 750

Benzoyl peroxide Wnvel"ngth nm

in pyridine (60,.,..._g/ml) with th~ reagent in water · trs. methanol •

.. FIGURE 28. COLOR DEVELOPMENT IN A BASIC SOIUTION. CONTAINING NO METHANOL

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1.2

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Wavelength nm Benzoyl peroxide in benz~ne (50/>'g/ml) and N,N-dirnethyl-p-phenylenediandne

sulfate in water (O.)%). Water layer vs. methanol.

COLOR DEVELOPJvJ.ENT IN A T~lO-LAYER SYSTEM THE EFFECT OF BASE ON THE PINK WATER IAYER

FIGURE JO. COLOR DEVEIOPHENT IN A T.'10-1.AYER SYSTEM

THE EFFECT OF TRIS-BUFFER ON THE YELLOW BENZENE LAYER

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400 h50 500 550 600 650 700 Wavelength nm.

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1.6

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1-+--t-·1-t--+-<1-+-1-+--+->--+- -+--+-1-l-- • --'-+-+-+- t- -+-+-+-+- -11-+-t-1-t--1-1- t--~ -1-1-H- - +--+- -l-1 -i - t-t -t- 1-t-+-1 +-+-+--+-•·-+-•-I-- --l-l-t-t-1-1-1- -!- -- --t-+-t-1 - - -1-H- --t-t- -H-t-+-t---r-i

t-+-+-+-+-1-+-+-+-+- -1-1-+-1---•--+-+-<--+- l-t-H-+ - H-+-t-H-H-+-1 1-1 - -H-+-H -t-t--t--t-!-+-+--+-<--.J t-+-+-t-+-t-+-+-+-+- l-+--11-t- -l-+-1- - I- - t--1-1 - - I -t-++-1 - - --+-t--t- jl-t--1--1-+-t-+-t-+-+-IJ

t-+-t-+-+-+-+-+-+-+-H- -1-t-t-t·-+-+--+-f-t-+ --1-t•-+--+-1r- -f-t-t- -1-1-1-1-t-+- l-t--f-1--1-t-H-' - -1-t--t--1--1 t-t--+-·+-<-+--+--l-+--+-1-1--1-+-+-I--+-+->-+- -t-t-t- -1-;-h H -1-t- -f- -1-t-: -1-1-· -j-l-t--+--+-+-

'--'-1-t--t-rt-+--t-t-t- -f-t-++-· -!-!-I-· - -1--t--i-j-· -t-t-1-- -1-f-t- · 1-t-J-t- --t-+-t-t--'-->-+--+-+--l·-+-+--+->-+-+--+-+-<-+-+--+-,_f--+--+-t-1- -1-1-- - - -1-11-H- -+-t-+-l- - -t-t- -t-t-t--1

t-i-1 ·-t-+-t-t--t-t--t-+-r-j- -1-1--1-; - -t-+·-1-1-1·-1--1-+-l-l -/-+-t-+ 11-t--t-+-t- -t-t-l-+-l--t-·H--1-t-+-+-+--+-t--t-+-< --t-t-1-1-1--t-l-l--.---t-t-+-t-l-t--t-l-t--1-t-t-t-j-t--t--lt-t--l­

l-+-+-t-+--t-H--+-11-1-+-1-l-H---t-+- -- -- t-t-+--+-ll-l--1--1-+-l-t--+-I t-- ·-+-<~t--+-1·-+--+--+- 1-1 -+--•--+-t- -t-+--+-<--.1

>-+--+-+--'·-+-H-t-1- -1-1-+--+-•--t-t-- t- -l-t-1- ·l-+-H-11- -1-1-H--•-+--+-+--+- -+-·•-t-+-t-+-+-+-+-j

'-+-+-t-+--t-+-+-t-+-1-1-1-+--t-11-+-t--11-t- -t-+-t--1-t-t·-+-1-1-1 -1-t-++ H-1-+ -1--1-H- H-H-1- - -1-t-H--+-+--+--+--<J

[.-+--+--<-+--+-<-+--<-I- - 1-1-H-t--<--t--+-+-+---+·- -1--1-1 -t--t--t- -H-1 - - -1-t-l-!-t-< H--!-t--t-t-t--t-11- ---'--1-+-t-t--t--t-1-+-1 -H-l- -1-H+I r -H-t-H 1-t-t-i-t- - -t- - -1- -t-t- ·-1-+-t--'-'

HHt--t-Ht----H--1-1-Ht-- - t-t--t--1-1-t--t-- t-t--J-t-t-l-t--t-1-- --Ht-H-1-H

Ht-i- --t-t--+- 1--t-I ·t-- - -- -t--1-t-- -t--+--1- - -1-- -!-·!-! -t---H- -!- · - -Ht-H r-r--1-l-+-H-hl- - - I- - -1-t-t-+- --!- -t-- -H- -- - - -t- -t- --t- -t- -1-+-·-H-H -H- -1-+-+....-. f-t--1- t-- - - -1-- -1-t~- --t-1 -H-t-1- ·-!-H- --!-+-·- -1-11-H - -- --·!-+-,-- -H-- - -t--t--- -!- -t-1-· --1 - -t-H t-- -1-t-t-H- 1-t-- - ·-t--H-1- --H- -+ -t- -1+1- -t--t-H-l-t-1- -t- -t-t-+ - ·t-++ - - -H - -H-· - - -1-hH-

t-+-+-1-+-1-t-t-1--1-1-t-1-H- --1-t-·-t-H -H -H--+H-· --· - -t-- - · H-+--1-1- -t-t- - -H-+-t-l-t-t-H-H-1-1-t--1 1-+---+--1--+-.-+-+-t-+-1-;-...-+-+--•-+-<--<--1- -- · 1-1- -H · H -1-+·-+-+--+-1--+--+-+--+-< '--'--+-t-+-+-+-+-+-·t-l-t-t-+-+-lt-t--1-l-+- -+-+-1--+-t-t--+-·t-+- -t- -t-+- - I - ++-+- -1-t-H - 1-t-t-t-- -+-+-t--'-'

§0.8 1--+-+-+--+-+--+-+-t---+--+-+--+--+-+--+-<-+--I·-+- -t--1- -t-- ·+-+-!- -Ht- I H -H

..a F-t 0 (/)

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o.6

1--+-+-•~--+-~-+--+--+-+--+--+-+--+--tf--+- -t-1--+-+-+--+--+--·t-+-t-+-+-+--l-l-t--+-<>-t-1-1--t-+-1--+--t-i-+--t-•--+--+-<-t-t-t-+-1 ~-+-t-+-+-+-+-+-+-t-t-+-1--+-+-+-+-+-+-+-l--l--l--il-+-t-1-+-l--+-<-+--+-•-+-•-1--+-1-+-~-+-+-t--l--t-t--/-lt-H-++-it-+--t-~-.

.-1--+-t-+-t-+-+-+--+-t-t-+-+-t-+--+-+-+--+- t-t·-+--t-i-1! ~ - l-+-i-il·-+-l-l-+- l-t--1-l--t- l-l--+-+-1--t-+-l-+--+- I- t- -t-+-•-+--+--+-+-1---+--+-<-+--+--+-+-H!- --1-l-1-4-1-l--+-lf-+--l-t-t--+--t- -H -+-+- l-+-t-1--1-+--+-t-1--+-rt--+--+-<--+-t-+--+-+--+-·•--+--+-+ +-l-+-+-11-+-I

HI- -t--1-1 -1t-t-t-1-+-+-t-+-t-+-+-t-+-l--+-·+-1-t--+-1- t--t-t-I t-t--H-1-H-+-I- -t-t-t--1 -'--+--+-+-+--+--+--+--+--1-1-1--~t--.--t-1--+--+- •--+->-+--+-1-~ -1-1-+-1-1_.- H-t-+-•-+--+-<-+-+ -t-- -t-+-1 -1--1--+-+-t-+-4-lf-L--'

1-+-1-~-t-+-+-+-t---+-1-+--+-11-t-+-11-+-1-t--t-+-+-1-+-t--+-+-1-1-+-+- H-1-1-t-1-1-+-t-·t-t-t--t-1-+--l- -t-1--1-t-1--t-+-+

t-+-t-t-t--t-1-t--t-1""'1C::J,o"H...C.~-+-1--+-~-+--+-1-+-+-it-t--t-1-+-+-l-t--H-t-~-1-1-+-1t-t--+-+-+--t--l-+--t--11-+-+--H-H-1I-

-+-4-1-1-41"'1-F--+-+-l--H-l-+-l-t--t-l--t--t-t-~l'S-t-+-+-t-+-l---t-+-f-t--+-l-l--t--"f-t--+--+-l--+-l-l-~t-t--+-+-l--t-t-+-t-+-t->-•-+--+-t

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0.4 /1-++-+-1-+-+-r-++.o-;-+-+++-+-+-+++-H-+-F~~t:-+-+++-~-H-+-+-++-+-+-+-+++-H"++-++-!-H 1-+-t-+-+-ll-+-+-t-+-1--1-+-+--t--t--t-+- -t--t--t-H- t-t-H""'_-~ !'h< -+-+-t-·H-f--1-l-l--1-l --t--t-t--t-1·4-•-+-+-+--t--+-<

t-+-+-F?""'-'J-1-t-+-t!-t--1Hf-t--t-t-+,-t-l-l-+-t-+4-lt-t--t-.-. ..,..._'111,;:i--j~t--t-H·-t-t-r-t-t-t-t--t-hht-·H·-+-+-+-1

bi

0.2 N

..-.-+--t--t--Hf-+--t-l-t-+-t-t-t-t-t-t-t-t-t-t--t-t-t--Ht-t--1Ht-f-+-t-t-+-t-+-t-t-+-t-t-+-t-t-t-t-t-t-t-1--+~~-.... ~T'-t---t-t--+-~, 1-+-+-+-+-t--+-+-ll-+-l-+-+--+--+-1--+-+-+--+-•-+-+-+---<--I-+--+--+--+- -1-;-1-+--J-ll-+-+-l-l-t-+-+-+-+-+-+--1'--f-·--+-t-+-t-~•r-~t .... --t-. 1-+-t-+-1--t-+-1--t--t-1-4-ll-+-+-ll--+--+-t--1--l-·l--+--l-lt-l--1-l-t-·I- ~--+--+-t-+---+-1-+-+-1-l--H-t--t-1-+-t--+-l~-t-+-l-f--f-f--t=~

t-+--t-+-1--+-+-+-t-·t- -1-t-+--+--11-/--t-t-- - - --H-f- --1-1·-t-I--+- ·-l---t-l-/--l-l-l--l-l-1-+-t--+--+-- -l--+-·+--H--t-l-+-1--1 t-+-+-t-+--t--t-t-t--t-l-4-l-t--t-11-1--1--11--1--1-t--t-H- -- -l-+-+-+-·i-+-+-t--1- -1--H-t--Hl-+-t-I- -11-t--+-11-t--+-1-+--t-1

1--t--t-1--t--+-11-t-l-t--t-+-+-l-+-l-l-+-1-ll-+-+-+-+-t-+-+-t-~--+-+-+-t--H--t--+-l~~-+-t-+-+-t-+-+-+-+-l-+-l-+-l--t--+-l-1 o.o 400 450 500 550

Wave1enp,th nm 600 650

(0.3%) plus

'700

Benzoyl peroxide in benzene (60ft.'- ~/ml) and reagent solution excess NH4~H. Methanol layer vs methanol.

·FIGURE 34. THE METHANOL iAYEH AFTER ADDITION OF EXCESS BASE TO. THE ilEACTION MIXTURE

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~

Wavelength nm :N,N-Dimethyl-p-phenylenediamine sulfate 1n <11cetone vs. methanol

FIGURE J.5. COIOR DEVELOPMENT OF THE AMINE IN ACETONE

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± 400 450 500 550 600 650 100

Wavelenvth run Benzoyl peroxide in benzene and rearent in water. 6N H2so4 added to benzen~ layer to give red suJ fate. Scan vs. metta nol.

FIGURE 36. THE RED .SALT EXTRACTED FROM BENZENE INTO WATER

750

(49)

tris-buffer. No.scans were made of this solution. No further··

tests with a~dehydes were made. •

D. N,N-Dimethyl-p-phenylenediamine ·Sulfate in Acetone

The behavior of the amine sulfate in a solvent less polar ··

than water or methanol was investigated. The amine sulfate was

insoluble in benzene. It was only slightly soluble in acetone,

forming a yellow solution with maximum absorbance at less than

400 nanometers, as shown in Figure 35. Combining this solutiqn

with an equal amount of benzene containing peroxide caused no

change in the spectrum but showed only the effect of dilution.

No attempt to change the pH of this solution was made.

E. Separation of the Colored Reaction Product

When an acid solution was added to the yellow benzene layer

described in section C, the color was e~tracted almost complete­

ly out of this layer into the polar layer, which turned a bright

red. This occurred upon the addition of either sulfuric acid in

water or in methanol, or an aqueous solution of hydrochlor~c ~ct

acid. This color was apparently due to a reaction product. Its

behavior is characteristic of an Sl)line and its salt.

Figure 36 shows that a scan of the red aqueous layer gives a

very inteqse peak at 510 nanometers, similar to Scan a in Figure

23. Addition of base to this solution caused precipitation.

Figure 37 shows scans made of the red acidic methanol layer,

with Scan a having the same intense peak at 510 nanometers as in

Figure 36 and a slight peak near 640 nanometers. (Compare with

Soans a and bin Figure 23.) Addition of one drop of ammonium

1.6

1.4

ll )

1.2

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Benzoyl peroxide benzene layer to

soo sso 600 650 700 Wavelenp,th run

in benzene and reap,ent in water. 6N H2S04 in methanol added to giv~ red sulfate. Scans vs. methanol ..

FIGURE 37. THE RED SALT EXTRACTED FROM BENZENE INTO HETHANOL THE EFFECT OF BASE

' 750'

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400 450 500 sso 600 650 700 Wavelenp:th run

Benzoyl peroxide in-b~nzene plus tris-buffered rear,ent in water. Benzene layer plus'g1acial acetic acid. Scan vs. metranol.

FIGURE 38. 'rt-IE F.lf'FECT OF ACETIC ACID ON THE YELLOW BENZENE LAYER

i'-..

750

~--

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400 450 500 550 Wavelenp:th run

a) rted anti ne hydrochloride (reaction product) yeJlow-?reen solution.

b) So1uti.on from (a') plus acid. Both scans vs. methanol.

~

600 650 700

dissolved in water, giving a

FIGUhE _39. THE RED SALT DISSOLVED IN WATER

LOO LSo

Red amine sulfate

5CXJ 550 600 Wavelength nm

(reaction product) dissolved in methanol, scanned vs. methanol.

650 700

~I

. ......o 750

giving a blue solutio~,

FIGURE l!O. THE RED SALT DISSOLVED LN &'!ETHANOL

Q.J 0 c

"' ..0 H 0 en

~

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coo h50 500 550 650 700 750 Wavelength nm Red amine sulfate (reaction product) dissolved in ethanol, giving a green solution. _Two concentrations scanned vs. methanol.

FIGURE 41. THE RED SALT DISSOLVED IN ETHANOL

4~00 3000 2000 1500 r1 ~..L...L.l...l. .L ..l. ..l. ..l. ..L.l..L.l ..L J ..l. .l .J.. l ..l. .l .l. l.

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0 3 4 5 6 7 8 9 10 11 12

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FIGURE 42 •. INFRARED SPECTRUM OF THE SECONp_REACTION PRODUCT

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400 450 soo 550 600 650 700 750 Wavelenr.th run

a) Ped amine sulfate. (reaction product) dissolved in methanol", giving a b) Solution from (a) plus 6N H2so4 in metllanol, giving a red solution. Both scans vs. methanol. ·

blue solution.

FIGURE 43. TrlE RED SACT DISSOLVED IN !•!ETHANOL

FIGURE Uh. THE REACTION OF BH01'1INE WITH

N,N-DIMETHYL-P-PHENYlENEDIAMINE SUIFATE IN WATER

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t-+-+-+-+- t--t-t-+-+-·t-+-+-t-+-1-++-t-+ •-+-+-· - - •-+--<--+-+-t-+-t-11-t--t-+-+-t H-1-1-+-+-I- - -f-1-t-+-4 ·--t--t-+-+-l-+-t--t-t--l-+-+-+-<--11

t-+-+--t-•-+-+-+--+-l-1-1-t-+-l--t-1-H-t-1-+-++--1-11-1-+- -1-+-+--1r-t--t-t-+-1-~-.-+-t-+-t--+-t-+-t-t--+-++-l-t-+-+-t-t-l--t-+-l-+-+--H-t-H --.-..-+-<-•-t-t--t-1-1-+--+-•-+-·r-t- ;-1--1-1-+-+ +-+-1-1-+-t-+- t -+-1- -t- -1-t-+-+-~t-t-+-t--++-+-+-+- --t-1--1--1--1--1-t-+-+-t--+-1-1-1-0-+-+-+--1--1

t-+-+-l-+-t-l-++-f-1-f.-t-t- - -+-+- -1-1-1-._,__,_,_,__1-1-+-+-1- - f- --·1-+-H-+t-f-+-t-t-i-· -1--t--+-+-l-t-l--+-i-+-·+-+--+-l~1-t-+-1-+--l-+-i-l'-h

t-t-+-+-+-l-+-+-+-t-1-t-t-i-t- . H-1- -1-+-1--1-1-f-l-+-1-1-t-+-+--t-·1-t-+-+-+-t-t--+-t-+-+-l-·4--l-t-+-t-·-t-1-+-+- -i--+-+-+-t-+-+-1-t--t-+-+-ir-+­l-+--+--+-+-0--1-+-+-+-ll-t-+-t- - - _._,t--·t-l-1--'-'-l-l-l~l-!-t-1-l-+-H-1-+-++-1H-+-+-l-l-t-1-1--+-+-i-l-t--l-f-1-+--t-+-+-1-l-+-+-+-l-l--l-t-+-+­

l-+-~--+-~--'-+·~l-~-+-+-t-+-~-+--+-+-~

1-t--+-l-+-t-+-+-11-+-t-+--t-r--t- -l-+-+·4-11 -+-t-t- -1-+-+-+-+-,_,~t--t-·t-t-1- 1-1-t- -+-+-+- -t--1-t--+-~-1-11--1-·i-t-l-+-l-+-l-t-·+-4-+-+-

-+-+-+-+-1-.-._,,_..-1-J-+-t-- -r- t-1-t-- -l-+-+-+-+-t--1-+--l-lt-t-+-+-t-1-t--+-t-l '-+-+-+-+-l-+-+-+-+-1-1-+--l-+-i-l-t-+- - -t-H-+-1 l-l--+--.-~~t---l-lf--J-l-+-·+-+-l-+-+-+-+-1-t-+--t-+-t-+-+-1--+-~-+_,_.._,_

-t-+-++-t-+-+-+-t--1·-t-+-t--+- - +-1-1- -4-+-+-·+-+---t-1-+-+-t---1-1-+--1-1-1-1-t-+-1--<-•-1-+- -t-H-1-l--l-+-H-t--++-HH-+-+-t-H--+-t-t-t--t-++-1-1~-t-+-+-+-t-+--t-f--+-~- L-~-"--'--1-\-f--~+~-H-+-~-l-l-+-+-t-l--!-+-H-J-+-+~~- l-t-l-t---+-~-+-t-+-+-+--+-+-+-1-1-+-++-t-+-+-+-+-t-

1-t---1-t-+-+-+--+-+-+-t-t-t-+--l-i-+-+-l-l-++-HH-+-+~-f-l--+-t-l-+-t-+-1-l-t-J.+-1H-+-t-+-t-++-t-t-+-+-l-lt-t-+-+-+-+-t-t-i -i--t-+-t- -.__,_-~--+-+-+-f--l-J~l--l-+-+-l-~-l-+-t-.L...L...L.-J-.+-++-+-~f-l--+-t-+-H-++-t-t-t--t-l-t-t-t--t-i-t-t-T-t-1

H--1--t--1-t-J-t-t-+-+-+-+--t--1-t-r~+++--1-1-+-1--+-1~

t-+--+--+-1-+-~·-+--+->-•-1-.v~-t-r-r-t-t-i-+-1-1-+-+-+-1-1-~•--+--t--+-~-t-t-t-V ~ l-l---t-1-t-+-+--1-11--t- 1-+-t-i- -1-1-1--h-.--ri-+..jf-+-l-+-+-H-+-t-+-H-++-+-H---H-t-H-·+-+--l-l-l

l-+--1-t-1-4t--t-+-+--+- .,'J."+-t--+-j~t!\ t-t-+- ·-1- -1-+-+--+-<<-+-+-+-•-·t--t-+-+-t-t-+--+-t--l-t--l-l-+-+-+-J-+-+- l-+--+-+-+-+-+--1-1-+--l-+--1-t--1-+-+-1-t-+­-+--<-+-~t--1-t--t-OFl-+-l---l-li-+L~- +-+- - l·-~-l---t-1-t--t-+-i-lf-l-+-+-+-t-t---1-t-+-+-~+-i-+--t-l - - -1-t-t-+--r-t-+-.,.-t-+-+-+-t-t--+--t-t-+-+--t-i-t-t

-I ll

sso 600 6.50 100 75 Wavelength nm

Benzoyl ti~roxide in benzene and reagent solution (0.3%) to which 0.25 ml or trie­buffer had been added. Scans made 15 min. after mixing vs. reagent blank.

FIGURE 47. SPY.CTR.A REPRESENTING STANDAHD CUHVE lt"OR BENZOYL FEROXIDE IN A TRIS-BU1''FE.RED SOLUTION

1.6 -· ~-+-+-+-4-+-l-f-l--+-+-l--t--l-t-1-t--+-4-1-1-+--+-+-+-IH-+-t- l-t--t-t-t-1--1-+-+-t- t-·t--+-1-!H-+-t--;-t- --;---;--+---;-1--+-t-t--.-..-rlH--+-t--t-t-t-t-,_,__,__._,_ .......... _._,_.._.._._ 1-t_ -+-+--+-t-+--1--+-+-t--+--l--+-+--•-+-·t-t--t--1--t-~--l-t--+--t-· -1-t-t-1-........ ·1--t--t-t-t-+--i-+-,.._,1-t-.,.......,...-1-t--+-<1-+-+--+4->-+-.....

1-+--+-1-+-~-+-!--+-l-+--+-+-+-f-+-+-+-+-l-+--t-+-l-+-+-+-1-1-- -++++ . -t-t--t- - l-t--t-t-1

1-1-+-+·-+-l-+-+-1-+-t-1--+-1--t--1-+-+-1-t-1-+--t-t-+-+- H--t-t- 1-1- - -'r-'-f-+-+.-1-1--1-1-+-+-+--1-1-+-~_,__.-+-.._....._,__._.._1-+--1--+-+-+-+--+-<-+-•-+--1--+-+-,_~-1--+-+-•-+--+-+-+-•-t-t--t-t- r-t-t--t-t-H-f-~-!·--+-''-'--'--+-+-1-1--t-t--;--t-

l. 4 1-1--+-+-+-1-+-+-H-+-+-t--+-+--t-+-1-H-1-1-+--+-+-t-t-t-H +++++- -H-1-1-H-~ ·t-t-t-H-t-t-t--t- - -t-

t--H - -•.....,1-+-+-•-l-t-t- - -1-H- - -+-t-+-+-1-t-f-+ H-1-t-+-+-+-+-t-1-1-- t-t- - -t-- - t-+-H- 1--t-t--r-r-+-+·-+-11-1---1-+--1-1- 1-t- - -t--t-t- -H-H- -+-t-t--,-,-,.-1-t--t-t-+--t-t--t-

l-+-+-f-+-11-1--+-+- -t-+--+-+--t-t-+·++-t--l-+++-t--lrl-1-t-t-t-+--t--1-+- ·t--t--t-t--t-t-+- -t-t-+---t-+-+-·l--t--+-t--t--1-·t-t-+-t-f-t--t-+-+-t-t-+-t-t-

l-+--1-1-+-·+-+--l-1-+-t-+-l-j'-t-+-+--l-lf-+- -l--l--t--1--1--1-!l-t--!- t-+-~-l--IH-+-t--1-+ -l-t--+-1--+-t-+--lH-t- - j-j- f-H-J- -•-+-->--+--+-<l-+-........... 4-ll-l-t-J-I-• -t-+·-t-t- \·--j-•--+-~--+-;-

L-l...+-l-f-1-1--1-1-1-l-+-t-+-+-· - I- - f-t-+- - -+--H--'--'---'-l-+-t-1---1-t-+-t-J. 2 -- -t-1-·-•-t-1----t-l-f-t--,-t-i-t--r-- -t-t--t---1-- -t---t-1··--t-+-- -· r-- ·1---t- H-t-1-+-t-- +-

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1-+-t-- t-+-+-· -t--t-+-- -1-t-·f-f- -1-t--t-t-t-t-+- -+-- -t-1 -H ·t--t- t-t- r" 1"1- -'-'--i I- -H- +- 1-1-1- ·!--- t--r-t-1 '-, 1--f-H--,-t-t- -1-- - · v -r--i- -t°"~

1.0 t-1--t-1-1--+---+-.--t--t-1- - t--+-i 1-t-- t--t--t-1 1--t-t--t- - -1__,-V-l1~trt.l::c.E::Lmlih:I t-1-t-- - 1-t-- - ... ·t--t- - ! y ± ---- · 1-t-t-!I..

r-rl-1- - -I-+--+- ... +--- - ·-t- '"' -+-t-t--l .. J..._,..~-t-t-t--+-t-+-t-- -t-t-"-t-t-lf- - - - -t-+- - - r-+-- t-r·t-i-r-1;,1-t-- -~ -M +-+-I\~'1 1-+-+-1-+-+-+--1---1-+J

-+-1-+-+-1--lJ-+-I- - --1-t--1- -1-t-1---1--t-t--i- - -r---1-t- -t-- +- Y-t~!:iiD. _, ,1rn--~,~~h!l-t---1--11\•-+-+-+--+-'1--+-+--;--+--1

0.2

j_ .._,_...._,__ ..... _ -0 • 0 L-J....J'-L..-1~-1....1-........_......_ ........... __.__, _ _ I

400 450 500 550 600 650 700

Benzoyl peroxide in pyridine and Wavelength nm

reagent solution (O.J%). mixing vs. reagent blank

Scans made 1$ min. after

" FIGURE 48. ('

SPEC TH.A REPRESENTING STANDARD. CURVE FOR BENZOYL PEROXIDE IN A PYRIDINE-WA'Th.R-&THANOL SOLUTION

750

; 1 ••

10

Benzoyl peroxide

·FIGURE u9. BEJ:t:R' S 11'.W CURVE FOR A PYRIDI.NE-METHANOL-WATER SOLUTION

o.a r-r- - . ,-,- - r.- -,---,-- - - r-;

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o.6

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o.5 ,_ H-+-1-1- i 1~1-t---1-t-t-t-ll- '1 '--U 1J 11 , l-+-+-+-+-1--f-f-t-+--f--t-i--Hf-f-f-t- __ j\ I j --r--t-r-·t-t·--t--<'-t-·t- ,__,_,__,J,..,..._._,_r--t--~- .,_..,..._,__,_--t--<-i--t-T-·f->-·.._,_-,1- >-->-->--+---<

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L'l L t-+-H ~ ~-~-~~--t-f-t-+--t-t-t-t-t-+-t-1'-t--i-t--t--t-+-t---t--t-r-t-IM

t-+-t--t-t-l-+--f-+-t-l-+-+-+-+-+--+-1-+-+-l[H~~+-t-t-+IS:'ol--f-l+-f-t-+-+-t-tH ~ - ~l-t--+-t-+-t--t-t-t-t--f-+-+-11-t-+-+--t--t-t---l-f-Hl_\\l-J--4-!-t-l-f"'t--++-l---t-JH-t-1--f-f--+_y:l-t-+-t---t--l:-tr-t-t-+-1- - -tr--+-t-+--+-"1\-\ HH

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0.3

0.2

-- t-+-t-+-HH-+-+-+---l-+--1-++-+--HH-++-+-l-+--l-+++-+--l--t-l-+-t-t-l-+-+-+--Hf-+-4-+-HH-4-+-+---l-t--1-+-++--+-l-++-f--H-+-t-++-t-t-f-

0.1 rt-t-t--t-l-t-t-+-t--+-+-il-l-+++-t-t-'-'--"--t-t-H--H-+-t-t-+-t--t-t--t-t-+-++·+-1H--t-+-t-i-t-~t-+-+-t-HH-++-t--l-t-t-t--t-t-t-t-t-+1

H-+-f--t-i-t-t-t--t-t-t-H--t-t--HH-+++-t-t-t-t--t-t-l-H---t-+-t-1H-++-t-i-t-t-t--t-t-t-H-i

-+-1-+-++++--l-IU-t--+-1-+-t-+--1-+-+-l-+-+-+-Hl-l-t-+-t-f-t-t-t--H--t-H-+-f--H-l--H-+-t-t-t+-t-t--t-H-++-t-1-~+-+-t-t-t-t-t-+-t-!,

o.o 1H--t-+-t-l-t-t-+-+4--h--'~~-I-~~

. l!OO 450

Bonzoyl peroxide in benzene buffer has been added. Each

500 550 600 650 700 Wavelength run

(601'-g/ml) and reap,en~ eolution to which 0.25 ml or aolut.ion scanned againet its own reagent blank~

FIGURE 50. THE EFFEDT OF CHANGJNG THE REAGENT CONCENTHATION IN A TRIS-BUFFERED SOLUTION

75C

tris-

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t-1-+-t-+-+H-1--t-t-t-l-t--~-t-t-r+-t-f-+-t-t-t-+-1-t--l-t--t--·t-+-+-+-~~-+-+-+-+- t-J-+-t-t-t-+-+-+-1-t-t-+-l-I -t-t- t-- - 1-+-t-+- - - +-+-+-- - t-' ,.,

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l ,I..

Wavelength nm Benzoyl peroxide in pyridine (60 .Ag/ml) and reagent sol_ution. Each solution ..

scanned against its own reagent blank.

FIGURE 51. Th.E t.FFJ!:C T OF CHA?\GING 'ffiE REAGENT CONCE.N TBA TlON LN A PYRIDINE-WATER-METHANOL SOLUTI~

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1-+-+-+-1-1-t--1-+--1-1-+-1-1-+-t--1-1-1-.r--1--1-+-+-1-t-+-+-1-1-1-+-+--+-t-+-1-1-+-t-1-t-t-t-·-1-r-.-,_,- ··t-r-i--r-r-i-r--r--i-- -+-1-1-+-+-t-1-t-t--J

1-1-+-+-+-+1-+-1-+--+-1-<-1-1-+-+-+-+-+-+--1--+-J-t-+-1-+-+--+-+-.-1i-t--+-+-f-+-+-r-•--•-+--+-+--f-!1--.-..-.-_,_, _,_11-+-t-1-+-+-t-+-•--t--t--+-1r-F-·1-+--f-+-1 t-+-+-+-t-ll-t-+--t--+-l-+-1-t-+-t--t-+--+-1-t--+-t--+-t-+--t-+-+-+- --+-l--t-1-t-+-+-t-1-l-+-+--+-t-+-t-t--t-+-f-!l-t-t--t--l-l-+-l-++-+-t-1-t-l-+-1-1--t-1 t-+-+-t-t--t-t-t-t--t-t-+-r-+-+-+-t-1-t-.._._-'--t--f-l-l--t-+-t--t-1-t-t--+-t-t-t-t--+-t-t-+--t-+-+-"1--r-·r-t--t-1-t-t-t--t--H-t-1-t-t-t-t-r-+-l--+-l-l-l

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l-l--l->--+-+-+-+-+--+-1-+-1-t-+-+-H --1-1-1-+-l·-+-+-+-1-t- -+-1-t-+-l·-t-l-t--1-.-.,_.,.._,_,_~f-t-t-t-· -t-t-+-+--r--r--+-t--r--'- -+--+-1-t-H-+-t-H

l-l-+-+-+-+-+-t-+--+-1-+-t-+-·t-t-t-+-+-t-t--+-t-+-l-l--l-t--+-t-1-.-·-t-<-+-ll-+-..-r-t-1-t--r--+--t-+-T--1--t--t--tl--t-t--t- ·l-l-l­l-+--l-t-+-+l--+-+-+--t-l-+--l-+-+-t-+-t-t-+-t--t-t-1-1-1-+-+-+-l-t-+-+-+-+-t-t-t-1- -t-1-1-+-1- t--r--i-i--r---,1-H-t- - t- - t-t-'. -1- -H-+·f-- -1-+-H H-+-+-+-t--i-t-t-·t- !-1-t--+-+-+-t-t-+-'-~-• - -+-r-+-·-t-t--1-•-rt-t--t-+-+-l-l-+-+-+-l-t-f-t-- - j- -t-H-1--t-H-1-+--1-1--1-+-+-<

1. 0 1--1--1-1-+-+--+-+-+-+--l -+-+-l-+-t-1--i--i H-t-1-H-t---- 1-t----t-- - 1---i-r-- - - - - - I-+++-

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+-+-+-+·-+-+-+-t--t-1-1-+-r-l-+~+-H-+-+-l---1f-t-+.++.~--l--W--1---l---HH-+-l·-H--t-t-t-t-i--t-H

o.o L-1-'-'

' 400 450 500 ._.__.___.__._._,_.._.__.__._._._._.._...~._._.._.__,__~_.LJ_L.LLL.L_LJLJ,_LL.LJ__t__LI-.J.-J.--'-''-'-~--;-:

550 600 . 650 700 750 Wavelength nm

Benzoyl peroxide in pyridine (60r g/ml/ and vs. reagent bl.an.le. .

reagent solution (O.J%)

·yrGUhE $2. .. -. COIOR DEVELOPMENT WITH TIME IN A PYRIDINE-WATER-METHANOL

$01.UTION

l.·6 r.

t-t-t-t-rt-+-+-+-+-+-+-+-+-+-t-HH-t-t--+++-+-H-H-1-1-+-+-++-+·-+-~-+-tH-1-+-.+-1-1--1-·1-1-t-t-rr-+-+-+-•1-1-1-+-++-+-~-+-+~~ t-t-<r-.-t-•->-+-+-+-·•--+--+->-+-+ .... - H-t- -t-+-+-t-l-l-t-t-+-l -+-t-l-t-+--+-+-+-1--'-'--l-l-+-t-+---1-1-+- l--+-+-l--l- J

1. 4 1-+-+-+-t-l--1-+-+-+-l--+-+--+-t--........ -<-t--I- I -t-1-1-1 -1-+-J l-l-+-t--+-++-+--1-1--1-+-+- t-+-+-+-t- --t-+-t-l'-+--•--+-r-/j

l-+-'l-l-l-l--+-t-+-11-1-1- f-J-1-l-t--t-+-l-f-l-+-l-+-l-+-lf-t-l-t-l-l-t-t-+-f-l-+-t-+-t--l-t-l-t-+--f-1-1-+-+-+->-1-+-<-+-+--•-+-+-+-+-<>-+-<-+-·<-t

0.2

50 600 -· 100 •I,,

Wavelenp,th nm Benzoyl·peroxide in pyridine (60Jl-"g/ml) and reagen:t solution (0.3%) ·(3 hrs. after

preparation) vs. reagent blank.

.,. FIGURE 53. COIOR DEVELOPMENT WITH TIME AFTER AIR-OXIDATION OF THE REAGENT SOLUTION

75C

Q) 0

1.6

1.4

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0.6

0.4

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; 1-t--1-1--1-1-- +--1-+-t-1-t---J-l--1-1---t--1--1·-J,-tl-t-H-- -· -H - H -1-t-t- - -i--t--t---r-;- 1-t-t- -t-t--t-1·--t-t-1- -t-r--t-t-t-1- t-t-- -+--1-t-+.-1---t--1--1-1--1 •--+--+-4_,_l-.__._.____._.__.__,_,_+-•-+--+->-+--f- - j---t-t- --f--1-f-- -r-t-t-r-- "-t-1-f-t- -+--t-t-+-t--t-1-+---t--1 I- - i-+- - -f-+-+-' · <-f--+-1~ r--·t- - 1--r--r--1--t--t---t-r---,-1-1--t-'-~'-t---t-t- 1--+- - t--t-t-'-1--+--+-+--+--+-+--+r-t--+-t--+-+-t-+-+--t-t-++ -+~ -1- -- -+--t- t--t-t- t-r-1-- 1.:1" ~ M ~ ~ -~j n1~ 11 f-"'tj_r- mt~~ ngl-+-+--+->--+--< 1--i-+--l- --t--+-+-+-1~-f-t--l-1-1-l-t-· +- t-t-t- t-1-1- - --1--r--t-: - - '' --t-+-l- -l-+-+---1--l-< l-+---l-l--1--1--1---+---1--1-1-f--+-t- -- - -- t-t-t-#~-t--t-t- ·t-f-t-- -+---lf-+-+--+--+-+--1-t-< t--+-+-+-l--1 ·+-+_,,_.-•H-t-t- -+-"-1-H- -r-+++- t--t-~¥'t°" -~-+-->-+-+-+·-+ 1--1--+--t-t-t--11-+-1-+-H-+- -t--+--+-t-+---1-- --t-t-+-+-t--1-+---t--+- - - JL y~"" --t-t--1--t-1·-t-·t-f--t-1--t--t-t--+--1

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Be-nzoyl peroxide in pyridine (60ft g/ml) and reagent solution (0.3%) vs. methanol.

750

FIGURE 54. COLOR DE'lEl.OPl•lliNT WITH TIME USING METHANOL AS REFERENCE

() • 8 ..-.--,-,- -r-r-r-- - -,-,.-,-.,-r...,-r-.-..-r~.-.-...,-,, --H-t- --H--1-- -1--- --l-+-++-l-+-~j--l- t-+-+--l--l--11-- -t-+--t--l-t-H-1--1-1-+-- - i*ll 1

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400 - 450 500 550 700

Wavelength nm Benzoyl peroxide in pyridine (60 fig/ml) and reagent solution

. hla~.

(0.3%) vs. reagent

·FIGURE 55. EAHLY COIOR DEVELOPi-IBNT WITH TIME IN A PYRIDINE-WATER-.ME'IHANOL I.. SOI.UTIOJW

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Benzoyl peroxide in pyridine

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700

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-t-+-+-t-·1---1---1--1-+-~ --H--+--t- --t-+--+-f-l---+-1-1--1---f--+--+-Hf----I--+-+---+--+- --1-1- - - -1- --!-+--1 >-l-+---+--+-•--t--H-1--- -+- -++-1---t---+-f-I-- f-t-t- - +- -+-<-<-__._,

f-H- t-+-+-+-+-f--+--t--1-1----1--J--!---f-1-1---l----i-l-f- --+-<f-+--+- l--+-t-+---f-l-+-4-+-4--- -- f--t-H--C-1--+-'--1-L I-+-'--~--' "-'--+-+-~-~--+-+-1-->---•---1-__,__._.._, t-H- --\--+++- - -i--+-+-1-- +- -H--++-

1-l-l- - -1--1-+-W--+--+-1-- -- -1- - - 1-t-+- -!-+--+- -- -I-- -- ~-t-t-+--+-+_._, - -+---1--t-+- , __ _,__.__,_._, __ +-++- - --+-+-+-i----i-+-+_,f-+- -f-1-+--+-·l--t-t-

_,_ -1-t-l-

t-+l -+-t-+--l-~---l---1-1---+-i--1--L t-+--l---+--+--t-+-t-t---t--l-t-+-t--l--+-t--H---Hl-4---1-i-t-11--<--'-'-'---•-+--+-+---+- -+--+-+-+-+--+-1---1--~ I 1-+-1-I --+-•---<--'- t-4-4--1-'- t-+--+-+--+- ,__,_..__,____,_,-+-<~I-+- -f-+--1-+-l-+-+-t--~- -1'-+-+--1-l-+-t--+-+-I--1- - - -+-+-+--+--<

+ I --H---Jl-+--+-~+H---H+.J-+-J-1---1---J--j~l---W-l--LJ_ __j_ -f-f-1---J-jl-l--+-1-4-- -H- _,_,_,_ _ __,__, J: +--+--+--+--1- t-+-4-+-1---1---t-I- -+- -+-+-+--1---t-+--1--+-1-1-1-t-t-t-t--+--t-+-t-l--H--l--l-+-t--L--l-..j-1-+-t- -- t- -+-t--+--+--1

-l--+-i-+---'--+-+--->->--l--J-+--+--l- \ -- f-l- -- \---I-\-+--

r--r-+-f---+--l-f-l--~H--1-++-+-t-l-l-++-l-1--+-+-l-4- -t-t--+-t-t---+-+-t-----1----+-l--l--l--l-l-+--l-.l----I- -H-+-· ---1--+-+-+-t-1

+--+--+--+

t-r-t-t-+~-f-\----l--l-l---+--1--l---1-41---t-t--t---' --1--+-+- -1----1---f-4--l--l--1--i!-t--+-1-l--+-l-+-+-l·--+---+-+---+-l---+-l---+-l-- -t--+--+--+-1-- +-+--+-1--1

-t-t--t---t-H·--t-t-+--Hl-+----H-+--+-t-+--+-+-1----1-+-1-1-+--+-l-l---l-·l-+--+-,1-J-t---1--+- +- - -1-t-~-t-t-

-r---r-t-rt-t--+-+-t-t--t--+-t-f-++-1-+--+-1-+---+-l--+-•__,___,__,__,_t-1---+-•-+--•~---l-+---l---l---4-J rr-t-H---t-H---l--1-+--H-l--l---l---+----1--1-+---W-+--W_J___W_j___Ll-LLlJ- -t-++--1- ---<-<-~-+---1-t-+-' -1---1-+---+-+--+-l-4-+-+-­t-t--t-t-++-f-l----l--l---1-+-1---+-i-1--t-r-t-t-t--H--+--+-t--+--+-+--+-~-+--+-+-+-l---J-+--t--+--1--1-1---t-1-t-+--1-+-+-t -1---f-t--+-t--t ~ 11-r-t-t---t-H--f--ll-+-H+-H-+--H-+ l-t+-W-!--W-l--1--1--1--W--l--H t--++-: -H --1----l--\ -+-1-+--+-l

I -·--1-H---l---lf---4-1---f- --l--+---+-L-1-1 _.__._.__,__,_t-+-f-t-t-+--+---,,_._ -f-+-1--t-I- H--t- -I-- - -I- - --1---+-l----t- ---+-1---1--4---l t-T-f-~-l---l-l---L-l-1-1--+--+-4-t-1-+---i-+-._-+-->----~-1-~-f-!- l--+-+-4-+-+-4-l--l----I-- -- -t-- -+- - -f-l- - -->-'--'----+--'

-l--+--+-+-~-++-l-+---t-1--+++ -l-l-+--t-11-1--+-t--l- -+-+--+---+--+-+---1---1>--+- -!--+-+- -1- -!---+-1--1--+-- -f-L-1---f- -t-+-~-1---l---l----1----L-1----l----l-4-1--1----1-1---l-H---t--11-1----l---l'-l----l--1-l----1-4--l--l---f-4-4-1-11- --~-+- --t--H-1--1--+--t--l-+-+--+-t-4

H+-H---l--l----\----1--jW---H-l -t-1-·+--+-1-1---1----1---t-+---+--+-t-+-t-+-+-+--+--l--+--+--l---l---1-1----1---~---1--1-t-I---' - -1-+-+---1---11-+-+-+--t r.--t-r-+--+-f-l----l--il-~--l---l--l---l-l---l---l-+-+--1-+-+-1-+---+--1---1----1---11--1---1---1---1--+-1---1---l--l--+-1-._._--+--1-~-r+--Ht--~-+-1-+-+-t-+---l--+---r-.

'-'----t--;t--~-+-ll-f---H-~.J-t++-f+l-++J--+---1--W-l-W--1--i-l-l---l---l---1---l---l---l-1--1--1--1----1----1--;_+-1--+---+-1-+--+--+--+-t---+--+-+-'-~ 0.2 i---t~1-t--t--l-~-t-l-+-+-+-+-l-t-+-+-+--+--~-\--t-l--\-l----l----!--ll-J--1-+--1----l----l--t--+-l-l--+--+-+-1>-~--i-4---+---~-,___._,_+---f-I-

0.1

~ I

i-t-H-t-t-H--1--1-1---+-~~'l"'-k++-H.-rf:-J7++-PK11---1-++-++--1--1-u+-.1j.-:1.,2t-lfJ~:r~_.. - i ~ rJT. in: r.ar. m !l •. ,_._.__,__,__,_, ,__._t-t-+t--H----1--J-jVWVi4--+--+--~~~~~~--1--l--l---~-l---l----l----W--W---l---l--l---l--l--.W-:l!-]-~~i;i-.~~t-+--+-+-t-1-+-+--~•--t-+----t--4---'--'

-l----1-4-4--1----+-+------4--+-~-1-I--~~ -~

I-+- J. ~ i- I - -

- -~

J:

::r o.o ,___,_

450 500 550 600 650 7:00 Wave)ength nm

Benzoyl peroxide· in pyridine (10rg/m1) and reagent solution (0.3%_} vs. reagent blank.

7SO

FIGURE_ 57 • COLOR DEVELOfi·lENT WITH TINE WITH A WW CONCENTRATION OF PEROXIDE

2 4. 6 8 10 20 30 Time after mixing (minutes)

Benzoyl peroxide iri pyridine and reagent solution (0.3%) vs. reagf>nt blank.

FIGURE 58. ABSOHBANCE VERSUS TINE FOR A PY.i:UDINE-HETllA~OL-WAT~tt SOJ.UTION

o.o 0 10 20 30

-: ~--; _i •. i -t ~

i_jj_ ±il i' ~ - ;. f 1 -t-t-l ; ~ - ; 1

:-.lLL 40 50

Concentration of benzoyl peroxide Benzoyl peroxide in pyridine and reapent solution (0.3%)

60 70 80 (re/m1) vs. reagent blank.

FIGURE 59. BEER'S UW CURVE FOR A PYRIDJ NE-i"lETHAl\OL-WA TER SOLUTION AT 67D NAN01•iETEhS

•

·<'----700 500 ~co· 300

i -1¢ i ! l i

1

~ wircH,1, I ~ .,

--~---- c, 1":~.v --+-----j------ sxi .\.

I /\/0 11 I : •

. 17V I I l C !i~ICH,J,! I £

I I 'J J ·- ' I '

-;::~ I ---1. \ --&- 6H,i, --11· .---n .. 10

v I ' . \/ ......... ~ ... J,~, N~liH - r -! --r l - ·... (') ].]Q'

'0' ! !H \y I y \" j ; f \ \ NICH,i, •

NICHJ, \ I I I : I l: . HNICHJ,

I , C . ! i ! ¢H.'llCH,J1 ¢ '.TO' ""'"' - I - : . A -- . : - " T- ' ~ "' /11

\ ! t }:"'-..._~"'\~: ~ I -~11 I I \ I i I\ y-:. "·.II I ~ ¢ I \ :t\A ,v:. y' 1" I \ f I I '\\ I: - ~

II ~I- I ,.:/ \ I \ NICH;i, ~L.:.ICH;l1 I i . \ ·. //

1.10'

, . I .. ./.. .., · ... /I \[ ··-.( .. " ! ·, / .

l---l~-L~..i--..:.._.:._-1...~~~~-"~---~~-----:~ 0 20 25 30 3SXi1 .. 10 15

--------'>-i> in cm-t

Fig. 1. A bforpt.ionsspcklmm des p, p' -Eis-dimelhylarnino-a.zobenzols (Charaktcristischc Datcn in Tabc!le S. 0000)

FIGURE 60.

Llisungs111ittel: ---·-···-· ~: Fcinsprit . --- ,-Fcinsprit/0,3:--: Salzsaurc (Vo!.-Vcrh. 9:1)

Feiasprit/konz. Salzsaurc (Vol.-Vcrh. 9:1) Feinsprit/Eiscssi0 (Vol.-Verh. 1: 9)

Ti::·: c:::.i:m~ Ii\ ABSOE3.C..l\CE WITH I-H i.''03. P, P ' - 21.s (:.:iL:1T::. YL.:-..::•"n;o )-AZOB!:..l•:ZEhE

Gerson£'. and~. EeiJ.oronrlcr: Fl~ysik2lisch-chcmjsc~it:· iigenshaft.rn unr. r:lck­tr·on'=nstruktu:~ dn· ""zo-".!eroir~curir:cn, Teil XI): Be;;-:.:::rkunp: zur :3-~.::--c.:-::tc::· d .. S ·~zon-iU'".:_Y..,+-ionc- ·c.,.. 1 ->=<~.,..- 1 ~ c •• 1·i»-i -~ o'oQ 7 ' - ' '-·''' ci...~~· '· '· • - ... n"'-v- •• .., C .;J p,-;J ..;J..;; G-:ll<>TOY~o•T.~::10 ~z '-n ... o_,::;, •·'-'-'-'• ·--····~ .;~eta, hS, 54 (1962).

( 132)

:. \

•

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Addenda

Gerson, F. and E. Heilbronner: Physikalisch-chemische Eigen­schaften und Elektronenstruktur der Azo-Verbindungen, XI: Bemerkung zur Struktur des Azonium-Kations des p,p'-Bis­dimethyla'llino-azobenzols, Helv. Chim. Acta, !t2 ( 7-8), 51-9 { 1962).

Green, H~ V. and F. H. Yorston: Identification of Unbleached Sulfite Pulps in Mixtures, Pulp Paper Mag. Can., 2.1 (6),

.133-4 (1952); C. A., ~, 6832 (1957).

Horner, Leopold and Juergen Dehnert: Azoaryls and Phenazines from Primary Arylarnine Anions by Autoxidation, Ber., 96, 786-97 (1963); C. A., 2§_, 13948 (1963). ~

HUnig, Siegfried and Gunter Pielstocker: Substituent Effects, III. Reactivity Sequence of Compounds Containing Active Methylene Groups When Attacked b·1 Radicals, Ann., 2.2Q., 105-22 (1956); C. A., .iQ, 14599 (1959}.

Morrison, Robert Thorton and Robert Neilson Boyd: "Organic Chemistry," p. 745. Allyn and Bacon, Inc., Bos ton, 1966. 2 ed.

Roberts, John D. and Marjorie· c. Casario: "Basic Principles of Organic Chemistry," p. 692. W. A. Benjamin, Inc., New York, 1964.

ibid, p. 1032.

ibid, p. 1042.

1•1969 Sadtler Spec-Finder for Standard Spectra, u p. 304. Sadtler Research Laboratories, Inc., Philadelphia, Pa., 1969.

(138)

AUTOBIOGRAPHY

I, Bertha Brauer Cosby King, was born on May 9, 1931 in

Richmond, Virginia. I attended Richmond and Henrico County pub­

lic schools, graduating in 1948 from Thomas Jefferson High

School. I then enter~d Westhampton College where I was elected

a member of Phi Beta Kappa, Gamma Sigma Epsilon, and Pi Mu Epsi­

lon. In June 1952, I was graduated with the degree of Bachelor

of Science and received the Garnett Ryland Award in Chemistry.

In July 1952, I was employed as an analytical chemist by E.

I. duPont deNemours and Company, Incorporated at' Richmond, Vir­

ginia. From June 1953 until November 1954, I resided at Johnson

Air Force Base, Japan, where my husband wqs stationed as a pilot.

While there I taught mathematics at. the Information and Education

Center. In the spring of 1955, I worked in the admissions of-·

fice at Virginia Polytechnic Institute and State University in

Blacksburg, Virginia. After my husband's graduation in June of

1958, we moved to Georgetown, South Carolina, and to Franklin,

Virginia in February of 1959. From September 1966 until January

1968, I taught science and mathematics at Franklin High School at

which time we moved to Richmond, Virginia. I entered the gradu­

ate school of the University of Richmond in September 1968, and

plan to become a candidate for the aegree of Master of Science

in chemistry in June 1972. I am married to Henry Hobson King.

(139)

We have two daughters and a son. At the present time, we are

living in Charleston, South 6arolina.