European Journal of Applied Sciences 8 (1): 28-40, 2016ISSN 2079-2077© IDOSI Publications, 2016DOI: 10.5829/idosi.ejas.2016.8.1.22849

Corresponding Author: H.F. Aly, Hot Labs. And Waste Management Center, Atomic Energy Authority, P.O. Box: 13759, Cairo, Egypt. E-mail-nessem.abdel@yahoo.com.

28

Separation and Speciation of Ruthenium from Nitrate Medium byIra-410 Anion Exchangers Kinetic, Thermodynamics and Reaction Mechanism

H.F. Aly, N. EL-said and A.T. Kassem

Hot Labs. And Waste Management Center, Atomic Energy Authority, P.O. Box: 13759, Cairo, Egypt

Abstract: The kinetics of exchange of Ru(III) at extremely low concentration on the strongly basic anionexchanger IRA-410 has been studied by means of finite volume method. The rate of exchange of Ru(III)studied as function of different parameters, the concentration, the particle size of the exchanger andtemperature. The apparent activation energy obtained is 48.75±0.07 and 16.8 kJmol for IRA-410. The1

adsorption of ruthenium goes through a chemical reaction mechanism IRA-410 and a particle diffusionmechanism in the case of macroreticular resin. The free energy of activation and the entropy of activation werefound to be, -17.71Kjmol and 143.40 Jkmol respectively. In order to understand the exchange behavior of1 1

IRA-410, The distribution coefficient was studied as a function of pH and temperature. The equilibrium studyof Ru(III) ions with the two exchangers has been studied at 25, 35, 45, 55 and 65°C. The extraction ofRu(III)depends strongly on the change of pH rather than on the temperature.

Key words: Kinetic Separation Adsorption of ruthenium IRA-410 and Anion Exchangers

INTRODUCTION Pt(IV), amongst which nitro complexes are well known,

The occurrence of the relatively long-lived isotopes has partly arisen from the tetra nitro complex havingof ruthenium, Ru and Ru, amongst the fission hitherto been regarded as a penta nitro complex of Ru(III)103 106

products, Ruthenium has seven naturally occurring [9-13]. The particular nitrosylruthenium compoundsisotopes: Ru, Ru, Ru, Ru, Ru, Ru and Ru prepared are formulated on the assumption that, as in the96 98 99 100 101 102 104

with the relative abundance of 5.5, 1.9, 12.7, 12.6, 17.0, 31.6 amino-nitrosylruthenium complexes, the ruthenium atomand 18.7 % respectively. Additionally, 34 radioactive has a co-ordination number of 6, one position beingisotopes have been discovered. Of these radioisotopes, occupied by the nitrosyl group: thus the mononuclearthe most stable ones are Ru, Ru and Ru with half- nitrato complexes are represented by the general formula106 103 97

lives of 373.6, 39.3 and 2.9 days respectively. Ru, which [RuNO(NO ) (OH) (H O) ]. Their identity as106

is a soft beta emitter (Ebmax = 39 keV) is used for nitrosylruthenium complexes has been established bytreatment of eye cancerand hence their presence in their conversion to nitrosyl-ruthenium hydroxide orsolutions of irradiated fissile material dissolved in nitric hydrosulphide, in both of which the ratio [N]: [Ru] isacid, has drawn attention to extensive gaps in the unity. Among many other fission products, Ru andknowledge of ruthenium chemistry.Such solutions contain Ru also are found after nuclear fission. On dissolvingtetra valent nitrosyl ruthenium complexes in which the the fuel elements in HNO , numerous neutral, anionic andligands are nitrato, nitro, hydroxo and aquo groups [1-8]. particularly, cationic ruthenium nitrosyl nitrato complexesAlthough a large number of RuNO complexes (containing are formed which are converted into one another morethe ligands NH , halide ions, OH , SO , C O and in a few or less quickly, depending on the external conditions.3 4 2 4

- 2- 2-

cases NO ) have been identified, the aquo-nitrato During the PUREX process, Ru is distributed2

complexes have been neglected since Joly (1) prepared uncontrollably between the organic and the aqueousthem in solution; furthermore, in spite of the general phases and interferes with the decontamination during thesimilarity of RuNO complexes to those of Ru(III) and process [14]. A important way of treatment of radioactive

no nitro complex of RuNO has hitherto been formulated;

3 4 2-4 2 2

103

106

3

/od

C C VK x ml gC m−=

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

29

waste solutions is to know the knowledge and give and filled with 7.5 gm of either IRA-410 or IRA-900 anionichighlights on the kinetics and thermodynamics of one of exchangers to give ~22 cm bed length. Before use, thethe interested fission products which is the ruthenium column was preconditioned by 300ml of the loadingisotopes. In context the starting complexes and the solution and in all cases the follow rate of the mobilebehavior of the ruthenium during the single steps of the phase was 2 ml/min.process are of interest. Till now there have been only fewreliable results on the kinetics and thermodynamics and Analytical Procedure: For Ruthenium loading, 300 ml ofseparation of ruthenium nitrosyl complexes and the the simulated waste solution containing the studieddetermination of their composition [15]. In dilute nitric elements in 0.1N NaNO at pH~ 1 was run down thesolutions different mononuclear complexes are present column where ruthenium was loaded as a brown zone at[16, 17]. For the isolation of the ruthenium nitrosyl the top of the column. complexes on a preparative scale, column chromatographyis suitable. It allows on the one hand the clear separation Separation of Ruthenium by the Batch Technique: In thisof the complexes, on the other hand their elution as in concern, 1 gm of the anionic exchanger; IRA-410 waschromatography. This advantage plays an important role preconditioned with 100 ml 0.1N NaNO , 40 ml of thein the elucidation of the extraction behavior of the simulated waste solution containing the ions undercomplexes [1-10]. investigation in 0.1N NaNO were adjusted to pH~ 1 and

MATERIALS AND METHODS equilibration (1-2h), filtraction was carried out. Filtrate

Materials: Two strongly basic anion exchangers namely; (III). These separations of ruthenium from wereIRA-410 (16-50 mesh) was used. The two resins are of experimented as follows: A solution of 0.1N NaNO (40 ml)Amberlyte type in Cl-form and obtained from Aldrich. of pH~ 1, shaken equilibrated together with the usedSodium nitrate, nitric acid and all other elements used resin. However, filtrate analysis showes rutheniumwere from Merck. Formic acid was obtained from GEB presence.Laborchemi Apolda. Other chemicals and reagents wereof analytical reagent grade. Were obtained from Merck. RESULTS AND DISCUSSION

Preparation of Mother Solution (Simulated Waste Adsorption Behavior of Ruthenium Ions on the IRA-410:Solution): The pure nitric ruthenium solutions was In order to discuss the distribution data experimentallyprepared by dissolving Ru N O in 100ml of 0.15 M obtained for the ruthenium ions studied in the present2 6 15

HNO The solution was adjusted to prepare aqueous work, the exchange process is considered. It has been3.

solutions of ruthenium (~10 M Ru) of the nitrato found experimentally for organic ion exchangers and-3

complexes. An inductively Coupled Plasma-Optical organic resins that:Emission Spectrometry (ICP-OES) of ARL type model3520, was used for element analysis where argon is used The adsorption of a given cation with decrease as theand the power was 1.5 kilo watt and the temperature of the concentration of foreign cations is increased at anyplasma was about 6000°C. given pH.

Batch Investigation: For batch investigations, ten species in true solution takes place. samples from the mother solution, each of 40 ml were The affinity of a cation for the adsorption increasesadjusted to different pH’s (1-11). These samples were with its increasing valence. shaken for half hour with one grame of the exchange. The The affinity of ions having the same charge for thedistribution coefficient was calculated as: adsorption tends to decrease as the size of the

(1) exchangers the exchange process involves mainly,

Column Application: A chromatographic double jaket by the cationic species in solution. If a metal ion Mcolumn was used in connection with a Julabo circulator and the proton H are competing for the exchanger,which control the temperature with an a quracy of ± the equilibrium encountered can be represented by0.01°C. The column was of 1 cm diameter and 25 cm long the following:

3

3

3

shaked in contact with the applied resin. After

analysis (by ICP) showed the fraction of uptake of Ru

3

No significant adsorption of anions or neutral

hydrated ion increases. In case of organic

replacement of the hydrogen ions in the exchangern+

+

( ) [ ]( )( ) [ ] ( )

n

n n

n nNR M N n Mn n n

MR N N NR

a a f NR aKa a N a+ += =

n[NR ].............. /[ ]d nK ml gN +=

M( )( )

nN

nN MH

f aKa +=

log tan logd HK cons t n a= −

.nn NK K K=

,.................. H Rd

HR

a aHR H R K

a+ −= + =

.,............( )

nNRn N n

R n

anR N NR K

a a− ++ = =

( )nnm HR nH M R+ + ↔ +

[ ] [ ]

[ ] [ ]

nm nH n n

H MRKRH M +

=

[ ][ ]

nn

MRDM +=

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

30

where a denote the activity, R , the matrix anion of the conditions satisfies the assumption for deducing Eq, 6.-

exchanger, f, the activity coefficient of the N ion in the This contradiction compels us to consider that K on then+

exchanger and the y , the activity coefficient of the N in pH. The uptake of Ru(III) was found to be from 30-80% inNn+

the solution.The distribution coefficient, K of the N the pH(1-11) at 25°C while at 65°C was found to be fromd,n+

ions is expressed by this. 60-80%in range of pH (1-11). If the solution is acidic

(2) sites with lowest apparent pK value in the ion exchange

Eq. 2 is a combination of the following two reactions.

(3) of the exchanger and Eq. 8, the variation of the anionic

by combining Eqs. 3 and 4, we obtain: similar conflict between the Eq. 6 and the experimental

contradiction was attributable to the gradual decrease in(4) the acid dissociation constant.K of the ion exchanger

(5) constant, but a certain average value. If this discussion

when the amount of N is negligible as compared with the between Ru (III) metal ions in an alkaline medium. Wheren+

that of M , a , f are regard as constant. Moreover, yN is the acid dissociation can be ignored. In a dilute aqueous+MR N

also constant if the ionic strength is kept constant. solution, i.e. solution of activity coefficient 1,Under such conditions, the following equation holds bytaking logarithum of Eq. 5: That is, if the logarithum of the (6)distribution coefficint of N is plotted against pH or then+

D against hydrogen ion concentration on log-log scale, astraight line possessing the slope of -n should be (7)obtained.

Adsorption Behavior of Ru (III) (8)The Effect of pH: The results of the uptake behavior of Ru(III) by zirconium phosphate in HNO acids are shown3

graphically in Fig. 1 as D vs acid concentration on log-log (9)scale. From the plot in this figure it could be seen that theadsorption behavior of Ru (III) in HNO has D-values are where m is the cation to be exchanged in the solution3

low at low acid concentration, then it slightly increases and the superscript bar denotes the exchanger phase.with increasing acid concentration and finally decreases In the reaction the ion hydration is omitted for simplicity.at higher acid concentration, It is, however, noticed here For metal ion-proton the equilibrium constant K is giventhat Ru (III) in aqueous solution of dilute acid is present by:mainly as the hexa-aquo ion. So the low distribution ratioat low acid concentration may be related to hydrolysis in (10)acidic medium. From nitric acid medium the log D vs acidconcentration r elation gives a negative slope of -2.65 Experimentally, the metal ion concentration used is(0.1-2.0M acid range). This indicates that Ru(III) is the generally less than the hydrogen ion and the [RH] can bemain cation from nitric acid, Fig. (1) [11-20]. considered constant in equation (10). On the other hand,

From Figs. (2-6) it is obvious that, in the acidic range the distribution ratio at equilibrium is given by:lower than 0.1M the results cannot be explained by thisargument because the slopes are about half of the valency (11)of the exchanging cation, N . Since the experimentaln+

equ

enough to permit the participation of only ion exchangea

reaction. And if the cation to be exchanged is present ashydrated ions, it can regarded that the reaction of the H+

Equation:

Accordingly, equation. 7 represents the acid dissociation

form of the exchanger with the exchanging cations, N , an+

results of the ion examined., it was considered that the

H

with pH. Accordingly, it is considered that the pKa is not

holds true, the ralation of Eq. 6 should in the ion exchange

n+

HM

n

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

31

Fig. 1: Adsorption behaviour of Ru(III)on IRA-410 from different acid solutions

Fig. 2: Effect of pH on the uptake of Ru(III) using IRA-410 anion exchanger (0.02g) from 0.1M NaNO3 solution atdifferent concentrations

Fig. 3: Plot of the diffusition coefficient D x10 VS 1/r for Co(III) at 25°C onIRA-4108 2

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

32

Fig. 4: Kinetics of the uptakeof Ru(III) using IRA-410 anion exchanger (0.02g) from 0.1M NaNO solution at different pH3

media at 25°C

Fig. 5: Kinitics of the uptakeof Ru(III) onto IRA-410 exchanger (0.02g) from 0.1M NaNO solution at different pH media3

at 35°C

Fig. 6: Kinitics of the uptakeof Ru(III) onto IRA_410 anion exchanger (0.05g) from 0.1M NaNO solution at different pH3

media at 45°C

/[ ][ ] [ ]

nmH n n

M R KD KH H+ += = =

/log log log[ ]D K n H += −

% ( )100o t

o

A AuptakeA−

=

1 ......... /dF VK X ml gmF

−=

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

33

Substituting equation (10) into equation (11) it becomes: where,

(12) A = Activity at time t in ml solution.

In logarithmic form, equation (12) becomes, A quantity of 10 mg of the IRA-410 ion-exchanger to

(13) containing the radioactive isotope of suitable activity for

Thus, if the law of mass action is obeyed, a plot of D determined for Ru(III) from a separate experiment carriedvs H on log-log scale for a certain metal cation of charge out specifically for this purpose. The distribution ratio in+

n should give a straight line of a slope (-n). In this work all the series of the measurement was calculated according+

the adsorption behaviour of Ru(III) in nitric acid solutions to the following equation:is studied. The study was carried out by the batchtechnique in duplicate and the main value of the final (15)results is taken. Deviation of singlets from the main valueis found not to exceed 3%. where,

Adsorption and Speciation: Prior to evaluate the F : The residual activity after equilibrium (counts/sec.).possibility of studying the effect of pH concentration on V : The volume of the aqueous phase (ml.).the adsorption of different Ru (III) on IRA-410, the m : The weight of the ion exchanger (g).kinetics of ion exchange process is studied. Our aim is tostudy the mechanism of ion exchange process (film and/or The value of the distribution ratio in each study is theparticle diffusion or chemical reaction), not only to mean value obtained from the experiments carried out fordetermine the equilibrium time. The rate of adsorption of each. The effect of pH is clear in Fig. 7. Which that Kthe activity is followed by contacting 0.01g of the increase as the pH increase in the pH range (3-7) while atexchanger with 10 ml of the spiked investigated ruthenium 7<pH<3 it remains constant. Fig. 2. depict the effect ofions solution. The solution is then shaken at a fixed rate pH at different temperature on the exchange in rangeand samples are removed periodically for analysis. The (25-65°C) on the K was value and outlined in Fig. 7. It ispercentage uptake of ruthenium ions at different intervals obvious that as the temperature increases, the K

increases from 25 to 35°C. While the K remains constant

(14) strictly of Ru(III) in the solution was as follows:

A = Initial activity in ml solution. o

t

be studied was shaken with 10 ml of the aqueous solution

a sufficient time to attain equilibrium. This time was

I : The initial activity (counts/sec.).

d

d

d

of time is calculated from the following equation: d

at temperatures higher than 55°C. The expected chemical

Fig. 7: Kinitics of the uptakeof Ru(III) using IRA-410 exchanger (0.02g) from 0.1M NaNO solution at different pH media3

at 55°C

2 2 2 2

3 3 3 3

2 2 2 2

3 3 3 3

2 1 1 2 35 4 3 2 2 3 1 4 5

2 1 14 3 3 2 2 2

[ ] [ ] [ ] [ ] [ ] [ ]

[ ] [ ] [ ] [ 2 ] [

H O H O H O H ONO NO NO NO

H O H O H O H ONO NO NO NO

AB AB C AB C AB C AB C AC

AB D AB CD AB D AB CD AB CD

− − − −

− − − −

+ + + +− − + + +− − − −

+ + + +− − +− − − −

→ → → →

↓

→ → → →

2 2 2

3 3 3

2 2

3 3

2

3

23

2 1 13 2 2 2 2 2 3 2

2 12 3 3 3 2

2 14 4

]

[ ] [ ] [ ] [ ]

[ ] [ ] [ ]

[ ] [ ]

H O H O H ONO NO NO

H O H ONO NO

H ONO

AB D AB D C AB C D AC D

AB D AB D C AC D

ABD AD C

− − −

− −

−

+

+ + +− − +− − −

+ +− −− −

+− −−

↓

→ → →

↓

→ →

↓

→

3 32 2

3 5 3 52 2

3 4 3 42 2

3 3 2 3 3 22 2

3 2 3 3 2 3

[ ( ) ] [ ( ) ] 2

[ ( ) ] [ ( ) ] 2

[ ( ) ( ) ] [ ( ) ( ) ] 2

[ ( ) ( ) ] [ ( ) ( ) ] 2

[

HNO H NO

RCl RuNO NO R RuNO NO Cl

RCl RuNO NO O H R RuNO NO OH Cl

RCl RuNO NO OH R RuNO NO OH Cl

RCl RuNO NO OH R RuNO NO OH Cl

RCl RuN

+ −

− − −

− − −

− − −

− − −

→ +

+ → +

+ → +

+ → +

+ → +

+ 2 23 4 3 2

1 13 4 2 3 4 2

1 13 3 2 3 2

1 13 2 2 2 3 2 2 2

( ) ( ) ] [ ( ) ] 2

[ ( ) ( )] [ ( ) ( )]

[ ( ) ( )] [ ( ) ( )]

[ ( ) ( ) ( )] [ ( ) ( ) ( )]

[ (

O NO OH R RuNO NO Cl

RCl RuNO NO H O R RuNO NO H O Cl

RCl RuNO NO OH H O R Ru NO OH H O Cl

RCl RuNO NO OH H O R RuNO NO OH H O Cl

RCl RuNO

− − −

− − −

− − −

− − −

→ +

+ → +

+ → +

+ → +

+ 1 13 3 2 3 3 2 2

1 14 2 4 2 2

3 3 2 2 3 3 2 2

3 2 2 2 3 2 2 2

) ( ) ( )] [ ( )( ) ( ) ]

[ ( ) ( )] [ ( ) ( ) ]

3 3[ ( ) ( ) ] 3 [ ( ) ( ) ] 3

2 3[ ( ) ( ) ] 2 [ ( ) ( ) ] 2

NO OH H O R RuNO NO OH H O Cl

RCl RuNO OH H O R RuNO OH H O Cl

RCl RuNO NO H O R RuNO NO H O Cl

RCl RuNO NO OH H O R RuNO NO OH H O Cl

RC

− − −

− − −

−

−

→ +

+ → +

+ → +

+ → +

3 2 2 2 3 2 2 2

3 2 2 3 2 2

3[ ( ) ( ) ( ) ] [ ( ) ( ) ( ) ]

[ ( ) ( ) ] [ ( ) ( ) ]

l RuNO NO OH H O R RuNO NO OH H O Cl

RCl RuNO OH H O R RuNO OH H O Cl

−+ → +

+ →

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

34

Speciation:

(16)

(17)

(18)-NO-

3

(19)OH,-

(20)

where A = RuNO, B = NO , C = H O, D = OH , Reactions in equations [16-20].3 2- -

While the reaction mechanism can be described as below and thaexchange speces positive and neutral species andthe reaction species in the solution was shown below.

Mechanism and Chemical Reaction: The expected species in aqueous nitrate medium evaluated by soft ware programmeMintque. A series of nitratoaquo nitrosylruthenium complexes of general formula [RuNO (NO ) (OH) (H O) ] has been2 3 2-3 2 2 5

identified. In aqueous solution they give rice to anionic and cationic ruthenium apecies; the higher nitrato complexesare hydrolysed at room temperature at a rapid but measurable rate to lower nitrato complexes; condensation topolynuclear species accompanies these reactions. The trinitrato complex has been.

1 13 2 2 3 3 2 2 3

1 13 2 3 3 2 3

1 12 2 3 2 2 3

2 23 2 4 3 2 4

2 2[ ( ) ( ) ] [ ( ) ( ) ] 2

[ ( ) ( ) ] [ ( ) ( ) ]

[ ( ) ( ) ] [ ( ) ( ) ]

2 2[ ( )( ) ] 2[ ( )( ) ] 2

RCl RuNO NO H O R RuNO NO H O Cl

RCl RuNO NO OH H O R Ru NO OH H O Cl

RCl RuNO OH H O R RuNO OH H O Cl

RCl RuNO NO H O RuNO NO H O Cl

+ + −

+ + −

+ +

+ + −

+ → +

+ → +

+ →

+ → +2 2

2 4 2 43 3

2 5 2 2 3

2 2[ ( )( ) ] 2[ ( )( ) ] 2

3 3[ ( ) ] 3 [ ( ) ( ) ] 3

RCl RuNO OH H O RuNO OH H O Cl

RCl RuNO H O R RuNO OH H O Cl

+ +

+ +

+ → +

+ → +

2

21

2 exp( )( ) 13 (1 /(9 (1 )nn

nSU tw S w w

∞

=

−= − + + ∑

0

6( )( )

oQ DtU tr Q Q

= − ∞

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

35

It has long been established the ion exchange proportional to the square root of the time, and inverselyreaction in anion exchange resin is controlled either by proportionally to the particle radius Similarly for particlefilm or by particle diffusion [18-22]. In this work, an diffusion controlled exchange with a finite volumeattempt was made to establish the kinetic behavior of condition, the kinetic equation. Where w=CV. /CV, Qstrongly basic anion exchangers IRA-410 resin as =Dl/r , S is the roots of equation S cot S =1+(S /3w).exchanger to elucidate which type of the reaction Under the experimental conditions, the volume of themechanism for separation of Ru (III) is going on. Since the solution is significntly higher than that of the resist sinceconcentration of the adsorbing ion is extremely low; the this system may be taken as semi-finite. Equation (2) canchanges of the composition of the resin and external be approximated by [21, 22]: Where Q is the amount of thesolution remains insignificant. In such a system the reaction group in the reaction, Q is the amount of theconventional rate low for an Ru (III) isotope exchange exchange at equilibrium. The deviation from linearity

(21) exceed 0.5. For the exchange reaction controlled by a

reaction is valid, The kinetic equation [21-29] for an Eqs. (21, 22) and (18) drived from Fick diffusion law.exchange reaction controlled by film diffusion under thecondition of finite volume is given by the Patersonequation; [10] where C is the initial metal concentration,o

C(t) the metal concentration at time (t) and C is theequilibrium metal concentration. Paterson equation forsolid diffusion process was applied to the experimentaldata. Paterson ‘s approximation is widely applied to theion exchange between spherical beds of exchangercontaining the counter ion A and a well stirred solution+

of B when the diffusion coefficient may be supposed+

constant (isotopic exchange) and the concentration ofA entering the solution is not necessary negligible+

thought the process. Equation. (21), predicts that, if therate determining step is film diffusion, Log [1-U(t)] isdirectly proportional to the reaction time and inversely tothe particle radius and film thickness.

(22)

The film thickness decreases with an increase of the ionicradius. Thus the rate of exchange reaction increases withincrease the ionic strength, [22, 23]. From Eq. (24), we seethat U(t) in the reaction controlled by particle diffusion is

2 2n n n n

between U(t) and t is less than 2.5%if U(t) doesn’t1/2

chemical reaction, the rate is expressed by a conventionalrate equation for chemical instead of such equation as

Taking in to consideration the fact that the amount offunctional group in the reaction system is significantlylarger than that of exchanging ion, this reaction can beregarded as first-order with respect to the exchanging ion[23, 24]. The rate equation is where Q is the initial amount1

of exchanging ion. Q is amount of exchange at time t andt

k is the rate constant was assumed that the reaction in thechelating resin was controlled either by diffusion (film orparticle) or by a pseudo-first-order chemical reaction.The kinetics of exchange of Ru(III) in the solution forH in the resin was studied and the results were given+

in Fig. (10). It can be seen that the relationshipbetween log[Q /(Q –Q )] or –log[1-U(t) and t is linear1 1 t

corresponding to Eq. (16-18), no linearity being obtainedin U(t)-t relation. Each value of log [Q /( Q –Q )] at1 1 t

corresponding time does not so much differ from that of–log[1-U(t), Fig. (8-11). This makes it difficult to determinewhich mechanism is operating as the rate determiningstep. For sake of clarification, the effects of ionic strength(0.05-0.001) and the particle radius [0.15-0.2mm) on the rateof exchange reaction were examined. The effect of particlesize seems to have a marked effect on the ion exchangerate. Aplot of D vs.1/r . Fig. 3. Shows a reciprocial2

proportionality between the rate of exchange and square

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

36

Fig. 8: Kinitics of the uptakeof Ru(III) using IRA-410 exchanger(0.02g) from 0.1M NaNO solution at different pH media3

at 65°C

Fig. 9: Linear plot of Arhenious and Eyring plots for ln k,min vs 1000/T for extraction of Ru(III) from 0.1M HNO13

Fig. 10: 3D-Optimization

/aE RToD D e−=

( )22.72 exp( /oKTD d S Rh

= ∆

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

37

Fig. 11: Contour plot of exchange Ru(III) on IRA-410 where X=pH, Y=T,C° Z=Kd

of the particle size which again verifies that the diffusion activation energy of exchange controlled by diffusion isexchanger particles is the rate govering step. The rate of supposed to be distinctly lower than that for the chelateexchange is independent of the above parameters. formation reaction. This is certainly the case with suchThus, it might be concluded that the rate of exchange of metal ion where the apparent activation energy is aboutRu(III) in the resin should be controlled by insignificant 27.51 kJ mol The results support the view that the rateparticle diffusion mechanism and controlled by film determining step of this reaction is particle diffusiondiffusion mechanism. mechsanism. Fig. 9 shows that the plot of ln D vs 1000/T

Thermodynamics: The effect of temperature on the rate of reactions is thus endothermic. However it should beexchange should be expected to afford a criterion of the noted that values of S/R were obtained from equationmechanism, the Arhenious plot between ln D vs 100/T, (25) the temperature dependence of the equilibrium-

Fig. 8., Equ. (25), Table (1). where D is the pre-exponential constant nevetheless, it is interesing to note that S iso

constant and R is the gas constant, a straight line is positive values and G is negative values confirm that theobtained and the activation energy is calculated from reaction goes spontaneously in the forward directionsthe slope of this line. The activation energy is calculated negative Table (2). An appreciable decrease in G and anfrom Arhenious and Erying equations shows more increase in S values. From these facts as well as thecloseness in Erying to the higher values than Aerhenious. magnitude of S we conclude that G for the exchangeThe pre-exponential constants D are obtained from the reaction is not governed by enthalpy term which increaseo

intercepts of the lines were usesd for calculated of the in a positive direction which reflect the energy required toentropy of activation ( S*) is obtained the D in distort the IRA-400 and IRA-900 for entry Ru(III) ions.o

calculated from the following equation. For studing cations in the mixture of the, Pd , Rh , Ru ,,

(25) IRA-410, the behaviors of the studied ions were different

(26) 0.1, 0.3 and 0.5N. In this concern, the distribution values

where k and h the Boltzman and Plank constants, d is the and are, also, different of the same order of magnetude.ionic jump distance taken [25-28] as 0.5mm, R is the gas The only element which has high distributions in this caseconstants and T is taken as 273°K Equation (25). Since the is palladium where its K ’s are maximum at lower pH’s and

1

is linear over a wide range of temperature the exchange

3+ 3+ 3+

Fe , Cr , Ni , Al , Ca Ru . With the two resins studied3+ 3+ 2+ 3+ 2+ 3+

the nitrate media employed in different concentrations,

of the studied cations are low at all the pH’s experimented

d

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

38

Table 1: Kinetics of the uptake of Ru(III) using IRA-410 exchanger(0.05g)from 0.1N NaNO solution of different pH media and temperature.3

is the activation energy, D is the effective diffusion coefficienta

Dx10 , m Sec8 2 1

Temperature,°C 25 35 45 55 65pH 0.5 3.12 4.75 6.87 6.871 1 4.72 5.22 7.5 7.53 1.5 4.83 5.51 8.12 8.125 2 4.91 5.70 8.50 8.507 2.5 4.99 5.98 8.70 8.709 3 5.07 6.46 9.37 9.3711 3 5.07 6.46 9.37 9.37

Table 2: Thermodynamic functions for extraction of Ru (III) by stronglybasic anion exchangers IRA-410 from nitrate medium

T, °C H G S

KJmol IRA-410 IRA-410 IRA-4101

25 14.19±0.01 -78.55±0.01 192.89±0.0135 14.11±0.02 -81.83±0.05 187.91±0.1545 14.21±0.05 -84.93±0.04 183.26±0.0955 14.49±0.03 -87.85±0.06 178.89±0.165 14.86±0.06 -90.68±0.07 174.8±0.21

decreased by increasing the pH values. The distributionbehaviors of the studied ions in presence of nitric acidcan be explained on the bases of the nitrate salt formationwhich is bulky and can hinder the exchange process ofthe formed negatively charged nitric acid complexes withthe anionic resins employed. The distribution behavior ofruthenium can be explained by considering the formationof ruthenium nitrate complexes which are positively andnutral charged and can be exchanged with the anionicresins investigated. Ruthenium can form also hydrolyticspecies where the stability constant log K ford1

ruthenium to hydrolysis. Therefore, Ru can form both3+

nitrate complex [29] and hydrolytic species under theexperimental conditions applied which can be exchangedwith the anionic resins used.

Separation of Ruthenium: Separation of ruthenium was achivied by advanced reduction process. From theaforementioned batch experiments carried out, ruthenium-III showed a unique behavior rather than the other twelveelements studied. In this concern, ruthenium had thehigher distribution values at relatively high hydrogen ionconcentrations from all the media experimented with theresin used; IRA-410. Therefore, it was of interest to carryout certain experiments for its separation from the otherelements representing [ILLW] studied using the twoinvestigated resins.

Characterization of Ruthenium (III) Aqua nitratoSpecies: From the literature it is evident that the bulk ofresearch on ruthenium and especially ruthenium (III) wasdone in the 1950’s and 60’s. This was due to the fact thatruthenium was a by-product of nuclear processes andneeded to be removed. Its chemistry needed to beunderstood before efficient removal could be achieved.Renewed interest in ruthenium was generated by its usein catalysis in the 1980’s. The series of ruthenium(III)species in aqueous hydrochloric acid medium can besummarized as [RuCl (H O) ] and was first separated6-n 2 n

n-3

and characterized by various people before research couldbe done on the kinetics of the series. The focus was onthe separation and characterization in the early stages.

Separation of Ruthenium by Column Technique: In thisconcern, 1 gm of the anionic exchanger; IRA-410 wasfirstly preconditioned with 100 ml 0.1N NaNO . 40 ml of3

the simulated waste solution containing the ions underinvestigation together in 0.1N NaNO was adjusted to3

pH~ 1 and shaked in contact with the applied resin.After equilibration (0.5 or1.5 h), filtration was carried out.Filtrate analysis (by ICP) showed that all the experimentedelements are found exept ruthenium [23-29].

The Separation of Ruthenium from the Resin WasExperimented as Follows: A solution of 0.1N NaNO3

(40ml) of pH~ 1, was equilibrated together with the usedresin. However, filtrate analysis did not show rutheniumpresence. This process was experimented using thedifferent media studied with the concentrations and pH’sat which ruthenium had low K ’s. However, in all cases,d

negative results were obtained i.e the filtrate had noruthenium. Other media of strongly complexing agentswere used such as sodium thiocyanate and sodium iodidewith different concentrations and pH’s. Negative resultswere, also, obtained. The difficulty of getting rutheniumfrom the solid phase was suggested to be due to thecomplexation of ruthenium with NO ions of the resin.3

-2

Therefore, reduction and dissolution processes weresuggested to get the complexed ruthenium from the resin.In this respect, concentrated formic (40 ml) was added tothe solid phase and shaked for 20 min. After filtration, theused resin (IRA-410) was washed and a concentratednitric acid solution (14N) was added (40ml) and shakedwith the resin to dissolve ruthenium. After filtration, theanalysis (by ICP) showed that the nitric acid solutioncontains ruthenium.

Europ. J. Appl. Sci., 8 (1): 28-40, 2016

39

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