Electrochemistry of CeCl3 in Molten LiCl-KCl Eutectic

doi:10.1007/s40242-014-3399-1

Chemical Research in Chinese Universities ›› 2014, Vol. 30 ›› Issue (3): 489-494.doi: 10.1007/s40242-014-3399-1

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Electrochemistry of CeCl₃ in Molten LiCl-KCl Eutectic

ZHANG Meng¹, HAN Wei², ZHANG Milin², LI Yunna², ZHU Fengyan², XUE Yun¹

1. Fundamental Science on Nuclear Safety and Simulation Technology Laboratory, Harbin Engineering University, Harbin 150001, P. R. China;
2. Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, Harbin Engineering University, Harbin 150001, P. R. China

Received:2013-09-24 Revised:2014-01-28 Online:2014-06-01 Published:2014-03-05
Contact: HAN Wei E-mail:weih@hrbeu.edu.cn
Supported by:
Supported by the High Technology Research and Development Program of China(No.2011AA03A409), the National Natural Science Foundation of China(Nos.51104050, 91326113, 21271054, 21173060), the China Postdoctoral Science Foundation(No.20110491029), the Heilongjiang Postdoctoral Fund, China(No.LBH-Z10208), the Heilongjiang Educational Commission Foundation, China(No.12513045), the Fundamental Research Funds for the Central Universities, China(No.HEUCF141502), the Project of the Scientific Technology Bureau of Harbin, China(No.2012RFQXS102) and the Basic Research Foundation of Harbin Engineering University, China(No.HEUFT08031).

Abstract

Abstract:

The electrochemical properties of CeCl₃, dissolved in LiCl-KCl eutectic melt, were investigated by electrochemical techniques, such as cyclic voltammetry and square wave voltammetry on Mo electrode. It was shown that Ce(Ⅲ) is reduced to Ce(0) based on a three-step mechanism. In a temperature range of 833―923 K, the diffusion coefficient of Ce(Ⅲ) is lgD_Ce(Ⅲ)=-2.49-1704/T determined by means of the Berzins-Delahay equation with two different expressions under reversible and irreversible conditions. The apparent standard potential of a Ce(Ⅲ)/Ce(0) red- ox system is E_{Ce³⁺/Ce⁰}^0*=3.551+0.0006132T(K) vs. Cl₂/Cl^-. Some thermochemical properties of CeCl₃ solutions were also derived from the electrochemical measurements, such as the enthalpy, entropy, Gibbs free energies and the activity coefficients of Ce(Ⅲ). The Gibbs free energy of a dilute solution of CeCl₃ in this system was determined to be ΔGCeCl₃^0*(kJ·mol^-1)=-1027.9+0.178T(K) And the activity coefficients,γCeCl₃, range between (7.78―9.14)×10^-3. Furthermore, the standard rate constant of kinetic reaction was calculated to be (4.94―9.72)×10^-3 cm²/s and the reaction was regarded as a quasi-reversible reaction under the present experimental conditions at 833 K.

Key words: LiCl-KCl eutectic melt, CeCl₃, Standard rate constant, Standard apparent potential, Activity coefficient

ZHANG Meng, HAN Wei, ZHANG Milin, LI Yunna, ZHU Fengyan, XUE Yun. Electrochemistry of CeCl₃ in Molten LiCl-KCl Eutectic[J]. Chemical Research in Chinese Universities, 2014, 30(3): 489-494.

References

[1] Gibilaro M., Massot L., Chamelot P., Taxil P., J. Nucl. Mater., 2008, 382, 39
[2] Gibilaro M., Massot L., Chamelot P., Cassayre L., Taxil P., Electrochim. Acta, 2009, 54, 5300
[3] Yan Y. D., Xu Y. L., Zhang M. L., Xue Y., Han W., Huang Y., Chen Q., Zhang Z. J., J. Nucl. Mater., 2013, 433, 152
[4] Sun Y., Zhang M. L., Han W., Li M., Yang Y. S., Chem. Res. Chinese Universities, 2013, 29(2), 324
[5] Iizuka M., J. Electrochem. Soc., 1998, 145, 84
[6] Chen L. J., Zhang M. L., Han W., Yan Y. D., Cao P., Chem. J. Chinese Universities, 2012, 33(2), 327
[7] Castrillejo Y., Hernández P., Rodriguez J. A., Vega M., Barrado E., Electrochim. Acta, 2012, 71, 166
[8] Tang H., Yan Y. D., Zhang M. L., Xue Y., Zhang Z. J., Du W. C., He H., Acta Phys. Chim. Sin., 2013, 29, 1698
[9] Marsden K. C., Pesic B., J. Electrochem. Soc., 2011, 158, 111
[10] Betancourtt R., Nattland D., Chem. Phys., 2005, 7, 173
[11] Castrillejo Y., Bermejo M., Millan R., Martínez A., Barrado E., Caravaca C., Arocas P., Progress in Molten Salt Chemistry, Elsevier, New York, 2000
[12] Castrillejo Y., Bermejo M. R., Pardo R., Martínez A. M., J. Electroanal. Chem., 2002, 552, 124
[13] Castrillejo Y., Bermejo M. R., Barrado E., Martínez A. M., Díaz Arocas P., J. Electroanal. Chem., 2003, 545, 141
[14] Fusselman S. P., Roy J. J., Grimmett D. L., Grantham L. F., Krueger C. L., Nabelek C. R., Storvick T. S., Inoue T., Hijikata T., Kinoshita K., Sakamura Y., Uozumi K., Kawai T., Takahashi N., J. Electrochem. Soc., 1999, 146, 2573
[15] Lantelme F., Cartailler T., Berghoute Y., Hamdani M., J. Electrochem. Soc., 2001, 148, C604
[16] Kim T., Ahn D. H., Paek S. W., Jung Y., J. Electrochem. Sci., 2013, 8, 9180
[17] Zhang M., Han W., Zhang M. L., Zhu F. Y., Xue Y., Zhang Z. J., J. Rare Earths, 2013, 31, 609
[18] Han W., Zhang Y., Ye K., Yan Y., Zhang M., Mater. Trans. B, 2010, 41, 1123
[19] Matsuda H., Ayabe Y. Z., Fur Elektrochem., 1955, 59, 494
[20] Ogura T., Sasaki K., Takao K., Arai T., Ikeda Y., Sci. China Chem., 2012, 55, 1699
[21] Pletcher D., Greef R., Peat R., Peter L. M., Robinson J., Instrumental Methods in Electrochemistry, Horwood Publish Ltd., London, 2001
[22] Bard A. J., Faulkner L. R., Electrochemical Methods: Fundamentals and Applications, John Wiley & Sons, New York, 2001, 201
[23] Osteryoung J., Osteryoung R. A., Anal. Chem., 1985, 57, 101
[24] Ramaley L., Krasue M. S., Anal. Chem., 1969, 41, 1362
[25] Berzins T., Delahay P., J. Am. Chem. Soc., 1953, 75, 555
[26] Delahay P., New Instrumental Methods in Electrochemistry: Theory, Instrumentation, and Application to Analytical and Physical Chemistry, Interscience, New York, 1954
[27] Masset P., Bottomley D., Konings R., Malmbeck R., Rodrigues A., Serp J., Glatz J. P., J. Electrochem. Soc., 2005, 152 A1109
[28] Yang L., Hudson R. G., J. Electrochem. Soc., 1959, 106, 986
[29] Pankratz L. B., Thermodynamic Properties of Halides, Bureau of Mines, Bulletin, 1984, 674
[30] Nicholson R. S., Anal. Chem., 1965, 37, 1351
[31] Kuznetsov S. A., Kuznetsova S. V., Stangrit P. T., Soviet Electrochem., 1990, 26, 55

Electrochemistry of CeCl₃ in Molten LiCl-KCl Eutectic

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