Synthesis, identification and thermal decomposition of double sulfites like Cu2SO3 center dot MSO3 center dot 2H(2)O (M = Cu, Fe, Mn or Cd)

Double sulfites with empirical formula Cu2SO3. MSO3. 2H(2)O (where M is Cu, Fe, Mn, or Cd) were obtained by saturation with sulfur dioxide gas of an a queous mixture of M-II sulfate and copper sulfate at room temperature. The salts obtained were identified by infrared spectra, X-ray powder diffractio n and elemental analysis. The compounds studied are isostructural with the Cu-II replacement by Mn-II, Fe-II, and Cd-II in Chevreul's salt (Cu2SO3. Cu SO3. 2H(2)O). The thermal behavior of the double sulfites was evaluated by thermogravimetry analysis (nitrogen and air atmospheres) and differential s canning calorimetry. These salts are thermally stable up to 200 degrees C. The structures of sulfite ion coordination influence strongly the course of the thermal decomposition. The sulfite species coordinated to the metal th rough the oxygen are easier oxidized to sulfate than sulfur-coordinated spe cies, leading to preferential formation of (MSO4)-S-II and Cu2O in the firs t step. The weight gain relative to the second step can be due to oxidation of Cu2O to CuO and/or oxidation of (MSO3)-S-II to (MSO4)-S-II probably by self-generated atmosphere formed by dense volatile products liberated in th e latter step. (C) 2000 Elsevier Science B.V. All rights reserved.