Reactivity and catalytic activity of copper chlorides. Part 3.—Evidence on defect structure of CuClx(1 ⩽x⩽ 2) from X-ray diffraction, electrical conductivity and magnetic susceptibility

Abstract

Studies of electrical conductivity, lattice parameter by the power method, and magnetic susceptibility of partly-chlorinated CuCl (CuCl_x) all provide evidence for a structural change in the region from x= 1.6 to x= 1.7. For x > 1.7, the observed properties rapidly approach those of normal CuCl and CuCl₂. For x < 1.7, CuCl shows unusual activation energies for conduction, while CuCl₂ shows small changes in lattice parameter consistent with displacement of Cu²⁺ into normally vacant layers of octahedral holes. The magnetic properties also suggest displaced cations in CuCl₂, although the interpretation of these results is by no means clear-cut.

It is suggested that, in the reaction of CuCl with chlorine, the diffusion layer of CuCl₂ is first formed with a spinel-like displacement of cations which creates cation diffusion paths not present in normal CuCl₂.