The interrelation between the temperature of solid decompositions and the E parameter of the Arrhenius equation

被引:33
作者
L'vov, BV [1 ]
机构
[1] St Petersburg State Univ, Dept Analyt Chem, St Petersburg 195251, Russia
关键词
kinetics; physical approach; solid decompositions; second-law method; third-law method;
D O I
10.1016/S0040-6031(02)00013-8
中图分类号
O414.1 [热力学];
学科分类号
摘要
A criterion of equilibrium development for the sublimation processes has been for-mutated and theoretically substantiated. It is based on the ratio of sublimation temperature, Tub (which corresponds to the vapor partial pressure of 10(-7) bar), to the enthalpy of sublimation, DeltaH(T)(o). This ratio is in the range 3.6 +/- 0.2 K mol kJ(-1) (S.D.). This criterion has been applied to the free-surface decompositions of 100 different substances including some metalloids and simple binary compounds together with metal salts of inorganic and organic acids, ammonium and hydrated salts. The experimental values of the initial temperature, T-in, and the E parameter, which are equivalent to the theoretical T-sub and DeltaH(T)(o) values, were taken from the literature. The mean value of T-in/E ratio for all reactants is equal to 3.6+/-0.4 (S.D.). This means that the decomposition of all solids proceeds in agreement with the equilibrium laws. A higher deviation of T-in/E ratio from the mean (compared to theory) is connected with random errors in the determination of the E parameter and the uncertainty in the definition of the initial temperature of decomposition. For the first time, the third-law method was used for the purposeful calculation of the E parameters in cases of free-surface solid decompositions. The comparison of results obtained by the second- and third-law methods for 20 different reactants revealed the great advantages of the latter method in precision and accuracy of determinations and also in time spent for the experiment. (C) 2002 Published by Elsevier Science B.V.
引用
收藏
页码:199 / 211
页数:13
相关论文
共 79 条
[1]   THE THERMAL DECOMPOSITION OF SILVER(I) OXIDE [J].
ALLEN, JA .
AUSTRALIAN JOURNAL OF CHEMISTRY, 1960, 13 (04) :431-442
[2]   Thermal stability and desorption of Group III nitrides prepared by metal organic chemical vapor deposition [J].
Ambacher, O ;
Brandt, MS ;
Dimitrov, R ;
Metzger, T ;
Stutzmann, M ;
Fischer, RA ;
Miehr, A ;
Bergmaier, A ;
Dollinger, G .
JOURNAL OF VACUUM SCIENCE & TECHNOLOGY B, 1996, 14 (06) :3532-3542
[3]  
ARKHAROV VI, 1955, ZH FIZ KHIM+, V29, P272
[4]   KINETICS AND THERMODYNAMICS OF DECOMPOSITION OF BARIUM CARBONATE [J].
BASU, TK ;
SEARCY, AW .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1976, 72 :1889-1895
[5]   USE OF LANGMUIR METHOD FOR KINETIC STUDIES OF DECOMPOSITION REACTIONS - CALCITE (CACO3) [J].
BERUTO, D ;
SEARCY, AW .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS I, 1974, 70 :2145-2153
[6]   THE THERMAL DECOMPOSITION OF LEAD OXALATE [J].
BIRCUMSHAW, LL ;
HARRIS, I .
JOURNAL OF THE CHEMICAL SOCIETY, 1948, (NOV) :1898-1902
[7]   RATE OF SUBLIMATION OF MAGNESIUM NITRIDE FROM EFFUSION CELLS AND FROM FREE SURFACES IN VACUO AND IN ARGON AND NITROGEN GASES [J].
BLANK, BAH ;
SEARCY, AW .
JOURNAL OF PHYSICAL CHEMISTRY, 1968, 72 (06) :2241-&
[8]  
BRACH BY, 1972, VESTNIK LGU, V40, P126
[9]   KINETIC-STUDY ON THE THERMAL-DECOMPOSITION OF COPPER(II) OXALATE [J].
BROADBENT, D ;
DOLLIMORE, J ;
DOLLIMORE, D ;
EVANS, TA .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1991, 87 (01) :161-166
[10]   A MECHANISM FOR THE THERMAL-DECOMPOSITION OF POTASSIUM-PERMANGANATE CRYSTALS BASED ON NUCLEATION AND GROWTH [J].
BROWN, ME ;
GALWEY, AK ;
MOHAMED, MA ;
TANAKA, H .
THERMOCHIMICA ACTA, 1994, 235 (02) :255-270