KINETIC AND MECHANISTIC STUDY OF THE NONISOTHERMAL DECOMPOSITION OF MANGANESE(II) ACETATE TETRAHYDRATE

Citation
Ma. Mohamed et Sa. Halawy, KINETIC AND MECHANISTIC STUDY OF THE NONISOTHERMAL DECOMPOSITION OF MANGANESE(II) ACETATE TETRAHYDRATE, Thermochimica acta, 242, 1994, pp. 173-186
Citations number
26
Categorie Soggetti
Chemistry Analytical
Journal title
ISSN journal
00406031
Volume
242
Year of publication
1994
Pages
173 - 186
Database
ISI
SICI code
0040-6031(1994)242:<173:KAMSOT>2.0.ZU;2-7
Abstract
The non-isothermal decomposition of manganese(II) acetate tetrahydrate was studied between ambient temperature and 500 degrees C by means of thermogravimetry (TG), derivative thermogravimetry (DTG), differentia l thermal analysis (DTA) and differential scanning calorimetry (DSC). The dehydration process was found to take place in two consecutive ste ps. The first step commences early (approximate to 20 degrees C) while the second step is accompanied by melting (at 120 degrees C) with the evolution of acetic acid. Careful investigation of the course of the decomposition revealed that two reaction intermediates are formed. The first was identified as acetyl manganese acetate, Mn(CH3COO)(2) . COC H3, at approximate to 120 degrees C, which is believed to form during the second dehydration step. The second intermediate compound was iden tified as manganese acetate hydroxide, Mn(CH3COO)(2) . OH, formed near 155 degrees C in an exothermic process. This is followed by the decom position of the hydroxide intermediate to form MnO as a solid product, with possible melting. Then, catalytic decomposition of the anion tak es place, with the formation of initial gaseous products on the surfac e of MnO. In air, however, Mn3O4 is formed as a residual solid product . IR spectroscopy, X-ray diffractometry and scanning electron microsco py (SEM) were used to identify and investigate the solid decomposition products. Gas chromatography (GC) was used to identify the volatile g aseous products as acetone, acetic acid, CO, CO2 and trace amounts of acetaldehyde. Methane and isobutene were formed at high temperatures, i.e. at 290 degrees C. The kinetic parameters (activation energy Delta E, and frequency factor ln A), and the thermodynamic parameters (enth alpy change Delta H, heat capacity C-p, and the entropy change Delta S ), were calculated for the dehydration and the decomposition processes .