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Solvent Extraction and Ion Exchange

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THERMOCHEMISTRY STUDY ON THE EXTRACTION OF Co(II) AND Ni(II) WITH CYANEX 272 IN KEROSENE
X. Yu , G. Gu , X. Fu , B. Su & H. Zhang
a b c a b c b a

Dept. of Chemistry, Qufu Normal University, Qufu, 273165, China Qingdao Institute of Chem. Tech., Qingdao, 266042, P. R. China

Qingdao Institute of Chem. Tech., Qingdao, 266042, P. R. China Version of record first published: 15 Feb 2007.

To cite this article: X. Yu , G. Gu , X. Fu , B. Su & H. Zhang (2001): THERMOCHEMISTRY STUDY ON THE EXTRACTION OF Co(II) AND Ni(II) WITH CYANEX 272 IN KEROSENE , Solvent Extraction and Ion Exchange, 19:5, 939-943 To link to this article: http://dx.doi.org/10.1081/SEI-100107031
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SOLVENT EXTRACTION AND ION EXCHANGE, 19(5), 939943 (2001)

RESEARCH NOTE
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THERMOCHEMISTRY STUDY ON THE EXTRACTION OF Co(II) AND Ni(II) WITH CYANEX 272 IN KEROSENE*
X. Yu,1 G. Gu,2 X. Fu,2,{ B. Su,2 and H. Zhang1 Dept. of Chemistry, Qufu Normal University, Qufu 273165, China 2 Qingdao Institute of Chem. Tech., Qingdao 266042, P. R. China
1

ABSTRACT The extraction of Co(II) and Ni(II) from sulfate solution with Cyanex 272 in kerosene has been studied by titration microcalorimetry. The heats produced in the reaction processes were determined by the powertime curves and the DrHy m values at 298 K were identied. The extraction equilibrium constants and thermodynamic functions at different temperatures were calculated. Key Words: Microcalorimetry; Cyanex 272; Co(II); Ni(II). Extraction; Reaction heat;

This study is supported by the National Natural Science Foundation of China (29971020) and the Natural Science Foundation of Shandong Province (L2000B01). {Corresponding author. 939
Copyright # 2001 by Marcel Dekker, Inc. www.dekker.com

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INTRODUCTION The 2277 thermal activity monitor (Sweden) has been widely used in the measurement of the heat effect in chemical and biochemical systems (1,2). This instrument is very sensitive. Its detection limit is 0.15 mW and the baseline stability over a period of 24 h is 0.2 mW. It can be maintained at a given temperature in the range of 10 $ 80 C, for example 298 K, very accurately. In a previous paper (3) we studied the extraction of Co(II) and Ni(II) from sulfate solution with Cyanex 272 in kerosene. The extraction reactions were determined as
Co2 a 2H2 A2 o CoA2 2HAo 2Ha Ni2 a 3H2 A2 o NiA2 4HAo 2Ha

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1 2

With the obtained equilibrium constants at different temperatures of 298, 308, 318 and 313 K, respectively, their reaction heats were calculated from the slope of logK vs. 1/T to be Dr Hy mCo 51:18 kJ=mol and Dr Hy mNi 9:58 kJ=mol 4 3

In this paper, the titration microcalorimetry has been used to measure the reaction heats again for above processes under the same experimental conditions. Using the newly obtained more accurate data of reaction heats and the reported equilibrium constants at 298 K (logK(Co), 298 7.58 and logK(Ni), 298 9.72) from reference (3), we calculated the extraction y equilibrium constants and thermodynamic functions (DrGy m and DrS m) at different temperatures.

EXPERIMENTAL Materials Solution 1: 0.0100 mol/L CoSO4, 0.2 mol/L Na2SO4, pH 4.35 (at equilibrium); Solution 2: 0.0100 mol/L NiSO4, 0.2 mol/L Na2SO4, pH 5.50 (at equilibrium); Solution 3: 0.350 mol/L Cyanex272 in kerosene (based on the monomer).

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Equipment and Method The 2277 thermal activity monitor contains 23 liters of isothermally thermostatic water, which can hold up to 4 independent calorimetric units. 4 ml stainless steel perfusion/titration ampoules are inserted in the thermostats. The perfusion/titration units come with two stirrer shafts, a hollow one for perfusion and the other plugged for titration. They are equipped with a stirrer and a stirrer motor to rotate the shaft at desired speed (usually between 60 $ 120 rpm). A kalf turbine is used for a 4 ml system to be lled with 2.5 $ 3 ml solution. In the experiment, two 4 ml ampoule-units were used. One of them contained the reaction sample and the other the reference solution. The sample normally occupied position A and the reference occupied position B in the monitor. The solutions of the extraction system were: 1.5 ml solution 1 or 2 and 1.5 ml solution 3, the reference contained 1.5 ml solution 1 or 2 and 1.5 ml kerosene. All measurements were carried out at 298 K and the amplier of the monitor was set at 100 mW. Before the monitor began to record the powertime curve, the stirrer shaft was set at the desired speed of 120 rpm. RESULTS AND DISCUSSION The powertime curves reect the solvent extraction process and the area under the curve represents the reaction heat. The powertime curves of the extraction of cobalt and nickel with Cyanex 272 in kerosene have been determined at 298 K, see Figures 1 and 2 respectively. Based on the data of pt and t in the curves, the reaction heats Q were obtained from three experiments. Then the reaction enthalpy changes were calculated by DrHy m Q/n, where n represented the reacted amounts of metal ions at equilibrium. The values of n were calculated from logKex reported in reference (3). Both the reactions are exothermic reaction as for reaction (1), Dr Hy mCo 53:60:43 kJ=mol; for reaction (2), Dr Hy mNi 10:00:13 kJ=mol; Comparing them with the data of the reaction enthalpy changes at the same experimental conditions reported in reference (3), we can see that the data obtained by the two methods are very near. The relative errors of the results in reference (3) are 4.51% and 4.20% for cobalt and nickel respectively, if the new data are considered to be more accurate. Based on the determined enthalpy changes here and the extraction equilibrium constants reported in reference (3) at 298 K, we can calculate the

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y thermodynamic functions (DrGy m, DrS m) and the equilibrium constants at y different temperatures with GibbsHelmholtz equation, DrGy m RTlnK and y y y DrG m DrH m 7 TDrS m, when DCp % 0 over the range of studied temperatures was regularly assumed. The obtained data are listed on the left side of Table 1 (for extraction of cobalt) and Table 2 (for extraction of nickel) respectively. The right side of both the tables shows the data reported in reference (3) for comparison.

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Table 1. Equilibrium Constants and Thermodynamic Functions at Different Temperatures for the Extraction of Cobalt, Reaction (1) Data of This Paper (Microcalorimetric Method) Dr Hy m kJ/mol 53.6 Dr Sy m J/K.mol 34.6 D r Gy m kJ/mol 43.5 43.3 43.1 42.9 42.8 42.6 42.1 logKy 7.75 7.58* 7.43 7.28 7.16 7.00 6.60 Data from Reference (3) (Equilibrium Method) Dr Hy m kJ/mol 51.18 Dr Sy m J/K.mol 26.6 27.2 26.7 26.5 Dr Gy m kJ/mol 43.3 42.8 42.7 42.3 logKy 7.58 7.26 7.01 6.63

T/K 293 298 303 308 313 318 333

* Taken from (3).

Table 2. Equilibrium Constants and Thermodynamics Functions at Different Temperatures for the Extraction of Nickel, Reaction (2) Data of This Paper (Microcalorimetric Method) Dr Hy m kJ/mol 10.0 Dr Sy m J/Kmol 153 Dr Gy m kJ/mol 54.8 55.5 56.4 57.1 57.9 58.7 60.9
y

Data from Reference [3] (Equilibrium Method) Dr Hy m kJ/mol 9.58 Dr Sy m J/Kmol 154 153 154 154 Dr Gy m kJ/mol 55.5 56.7 58.4 60.8 logKy 9.72 9.61 9.60 9.53

T/K 293 298 303 308 313 318 333

logK

9.77 9.72 9.72 9.68 9.66 9.64 9.55

* Taken from (3).

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The uncertainty of enthalpies determined by calorimetry comes mainly from the data of log Kex but not from the heat measurement. The heats measured y here are accurate to within 1.3%. The error propagations of DrGy m and DrS m are also from the uncertainty of log Kex taken from reference (3) where the original distribution data are not available. The comparison indicates that the two series data are very similar and that the results obtained by the two methods can be conrmed. The higher value of DrGy m and the negative entropy make the extraction of nickel more difcult.

CONCLUSION The microcalorimetric method can also be used in the measurement of reaction heat for two-phase extraction systems. Combining the equilibrium constant, one can get much information about the thermodynamic functions. These data are very useful in studies of the thermokinetic properties of solvent extraction (4).

REFERENCES 1. Lu, C.; Yu, X.; Zhang, H. Determination of the reaction heat and studies of thermodynamic functions Hydrolytic polymerization of chromium(III) at relatively high concentrations by microcalorimetry. J. of Thermal Analysis 1997, 48, 327. Zhang, H.; Sun, H.; Liu, Y.; Nan, Z.; Xu, L.; Shan, Q.; Su, X.; Zhang, G. Determination of power-time curves of bacterial growth and study of optimum allowable concentration of a synthetic medicine. J. of Thermal Analysis 1995, 45, 87. Fu, X.; Golding, J.A. Solvent extraction of cobalt and nickel in bis(2,4,4trimethylpentyl) phosphinic acid, Cyanex 272. Solvent Extraction and Ion Exchange 1987, 5 (2), 205. Zhang, H.; Sun, S. Determination of reaction heat and thermokinetic study on the extraction of Co(II) with HEH[EHP] in kerosene from sulfate solution. Chinese J. of Appl. Chem. 2000, 17 (6), 666.

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Received January 5, 2001

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