Summary
-
1.
The thermal decomposition of Ca, Ba, Li, Rb, Ag, and Cu acetates at 473–873°K was analyzed thermodynamically. In all cases apart from Ag and Cu acetates, and regardless of the nature of the acid radical, the decomposition of the salt to the anhydride and the metal oxide was thermodynamically forbidden. The results of the calculations are confirmed by experimental data.
-
2.
The characteristics of the topochemical decomposition of Ca, Ba, Cd, Mg, and Zn acetates were examined: they were the lack of an induction period, the fact thatn in Erofeev's equationα=1−e−kτn is close to unity, the planar form of the reaction nucleus, and the fact that the reaction proceeds in the kinetic region. The decomposition proceeds by the growth of initial centers present in the substance and the activation energy determined experimentally is the activation energy of the growth of the reaction nuclei.
-
3.
In the case of the decomposition of Li, Na, K, and Rb acetates, which occurs in the melt, an interpretation is given for the effect of the nature of the metal on the activation energy and pre-exponent. The effect of thermodynamic factors on the course of the change in activation energy is discussed.
Similar content being viewed by others
Literature cited
A. M. Rubinshtein and V. I. Yakerson, Zh. obshch. khimii,30, 2789 (1960).
A. M. Rubinshtein and V. I. Yakerson, Zh. obshch. khimii,30, 3153 (1960).
A. M. Rubinshtein and V. I. Yakerson, Kinetika i kataliz,2, 118(1961).
V. I. Yakerson and A. M. Rubinshtein, Kinetika i kataliz,2, 172 (1961).
V. I. Yakerson, É. A. Fedorovskaya, and A. M. Rubinshtein, Dokl. AN SSSR,140, 626 (1961).
V. D. Nefedov, M. A. Toropova, and I. A. Skul'skii, Zh. fiz. khimii,29, 2236 (1955).
R. I. Reed, J. Chem. Soc. 4423 (1955).
G. C. Kuriacose and G. C. Jungers, Bull. Soc. chem. belges64, 502 (1955).
M. M. Shemyakin, Izv. AN SSSR. Otd. khim. n. 1515 (1961).
S. G. Kanevskaya, M. M. Shemyakin, and É. M. Bamdas-Shemyakina, Ber.67, 1518 (1934);69, 257 (1936); S. G. Kanevskaya and M. M. Shemyakin, Ber.69, 2152 (1936); É. M. Bamdas and M. M. Shemyakin, Zh. obshch. khimii,18, 324, 629 (1948).
É. M. Bamdas, Study of the thermal decomposition of some salts of carboxylic acids [in Russian], Dissertation, Moscow (1946).
A. M. Rubinshtein and V. I. Yakerson, Dokl. AN SSSR,121, 664 (1958).
M. I. Temkin and L. A. Shvartsman, Uspekhi khimii,17, 259 (1948).
Thermal Constants of Inorganic Substances [in Russian]. Compiled by É. V. Britske et al., Izd. AN SSSR, Moscow (1949).
F. D. Rossini, Selected values of chemical thermodynamic properties, Washington (1952).
M. Kh. Karapet'yants, Chemical Thermodynamics [in Russian], Goskhimizdat (1953).
F. D. Fastmen, J. Amer. Chem. Soc.45, 80 (1923).
R. R. Venner, Thermochemical Calculations [Russian translation], IL, Moscow (1950).
G. Parks and H. Huffman, Free Energies of Organic Compounds [Russian translation], ONTI (1936).
B. V. Erofeev, Dokl. AN SSSR,52, 515 (1946).
P. I. Bel'kevich, Dissertation [in Russian], Minsk (1950).
T. Ichikawa, H. Yamamura, M. Kato, and Y. Komura, J. Sci. Hiroshima Univ., Ser A.16, No. 3, 587 (1953).
V. V. Boldyrev, Methods of Studying the Kinetics of Thermal Decomposition of Solids [in Russian], Tomsk (1958).
K. B. Yatsimirskii, Izv. AN SSSR, Otd. khim. n. 453 (1947).
W. Latimer, Oxidation States of the Elements and Their Potentials in Aqueous Solutions [Russian translation], IL, Moscow (1954).
I. A. Kablukov, Thermochemistry [in Russian], p. 87. Gos. khim.-tekhn. izdat. (1931).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Yakerson, V.I. Mechanism of thermal decomposition of salts of carboxylic acids. Russ Chem Bull 12, 914–921 (1963). https://doi.org/10.1007/BF00845465
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF00845465