Salt-like behaviour of covalent halides. Part IV. Electrolytic conductance of solutions of thionyl chloride, and its reactions with silver salts and Lewis acids in acetone

Abstract

Thionyl chloride behaves as a weak electrolyte in acetone solution; values for its molar conductance are given. The mode of ionisation is envisaged as formation of chlorothionyl and thionyl cations. Metathetic exchanges of thionyl chloride with silver(I) nitrate and perchlorate produce thionyl dinitrate, SO(NO₃)₂, and chlorothionyl and thionyl perchlorates. ClSO(ClO₄) and SO(ClO₄)₂, respectively, in acetone solutions. Its reactions with Lewis acids give series of chlorothionyl and thionyl salts of complex chloro-anions, ClSO⁺(MCl_x+1^–), SO²⁺(MCl_x+1^–)₂, (M = Fe^III, P^III, P^V, OP^V, As^III, Sb^III, Sb^V, Ti^IV, and Sn^IV), and (SO²⁺)₃(MCl_x+3^3–)₂(M = Fe^III, P^III, OP^V, As^III, Sb^III, Sb^V, Ti^IV; x= 3–5), which have been identified by conductimetric evidence in acetone solutions.