Coulometric titration of copper in CuxMo6S8−y(0⩽y⩽0.4) with solid Cu-electrolyte Rb4Cu16I7Cl13 |
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Authors: | Junichiro Mizusaki Shi Yi Han Kazuo Fueki Koichi Kitazawa |
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Affiliation: | 1. Department of Industrial Chemistry, Faculty of Engineering, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113, Japan |
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Abstract: | In order to determine the copper content x of copper Chevrel compound CuxMo6S8?y(0?y?0.4) as a function of copper activity aCu and sulfur deficit y, a solid state electrochemical cell, Cu/Rb4Cu16I7Cl13/CuxMo6S8?y/Pt, was constructed and coulometric titration studies were made at 400 K. For the evaluation of the coulometric titration data, measurements were made on the electronic conductivity of copper-ion conductor Rb4Cu16I7Cl13. Also, a brief investigation was made on the condition of formation of single phase Chevrel CuxMo6S8?y with varying x and y at 1000°C. The structural change of CuxMo6S8?y with a change in x and y was studied by the X-ray diffraction method. It was found that x for constant aCu decreases with increasing y. The maximum value xmax of x in CuxMo6S8?y in equilibrium with metallic copper was found to be expressed by . In the region of y<0.3, xmax exceeded 4, contrary to a presupposition that xmax is less than 4. X-ray analysis revealed that most of the copper Chevrel compounds denoted by CuxMo6S8 so far were sulfur deficient ones with y?0.4. The importance of sulfur deficit on the properties of the copper Chevrel compound was emphasized. |
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