Spectroscopic and thermal behavior of chromium soaps

Abstract

The physicochemical characteristics of chromium soaps (myristate and stearate) were investigated in the solid state (thermal, X-ray, and IR measurements) and in solutions (spectrophotometric measurements). The thermal measurements showed that the decomposition of chromium soaps is a two-step process. The soap decomposed into chromium oxycarboxylate, ketone, and carbon dioxide in the first step and the intermediate oxycarboxylate underwent further decomposition to chromium trioxide in the second step. The results showed that the second step is kinetically of zero order and the values of energy of activation for the first and second steps lie in the ranges 6-7 and 17-18 kcal mol-1, respectively. The X-ray diffraction results showed that these soaps possess double-layer structure with molecular axes slightly inclined to the basal plane. The infrared results revealed that the fatty acids exist with dimeric structure through hydrogen bonding between two molecules of fatty acids whereas the metal-to-oxygen bonds in chromium soaps are not purely ionic but possess considerable covalent character. The results of spectrophotometric measurements also confirmed the somewhat covalent nature of chromium soaps in solutions in dichloromethane. © 1996 Academic Press, Inc.