Studies on metal hydroxy compounds. XII. Thermal analyses, decomposition kinetics, and infrared spectra of copper basic oxysalts

Abstract

The thermal analyses of copper basic oxysalts of the type Cu2(OH)2XOy, where X = S, C, Cl, Br, I, N, HC and y = 4, 3, or 2 reveal that decomposition occurs, in most cases, by dehydroxylation with concomitant disproportionation of the oxysalt. An outstanding exception to this pattern of decomposition is the basic sulfate. Calorimetric measurements along with related enthalpic values for the decomposition reaction are given.The kinetics of thermal decomposition of the compounds are classified into three main categories: (i) three-dimensional contracting sphere model, (ii) first-order rate, and (iii) nucleation controlled rate processes.The infrared spectral data of nine copper basic oxycompounds in the frequency region 4000–250 cm−1 are presented with their assignments. The fundamental infrared inactive modes of the anionic species SO42−, NO3−, etc. become active by the presence of the copper hydroxide ligand indicating a lowering of symmetry in the anion.