Coulometric titration of copper in CuxMo6S8?y(0?y?0.4) with solid Cu-electrolyte Rb4Cu16I7Cl13

In order to determine the copper content x of copper Chevrel compound Cu_xMo₆S_8?y(0?y?0.4) as a function of copper activity a_Cu and sulfur deficit y, a solid state electrochemical cell, Cu/Rb₄Cu₁₆I₇Cl₁₃/Cu_xMo₆S_8?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 Cu_xMo₆S_8?y with varying x and y at 1000°C. The structural change of Cu_xMo₆S_8?y with a change in x and y was studied by the X-ray diffraction method. It was found that x for constant a_Cu decreases with increasing y. The maximum value x_max of x in Cu_xMo₆S_8?y in equilibrium with metallic copper was found to be expressed by $\text{x}{}_{\mathrm{<mtext>max</mtext>}}\text{=-(}\text{10}\text{3}\text{)y+5}$. In the region of y<0.3, x_max exceeded 4, contrary to a presupposition that x_max is less than 4. X-ray analysis revealed that most of the copper Chevrel compounds denoted by Cu_xMo₆S₈ 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.