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首页> 外文期刊>Thermochimica Acta: An International Journal Concerned with the Broader Aspects of Thermochemistry and Its Applications to Chemical Problems >The interrelation between the temperature of solid decompositions and the E parameter of the Arrhenius equation
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The interrelation between the temperature of solid decompositions and the E parameter of the Arrhenius equation

机译：固体分解温度与Arrhenius方程的E参数之间的相互关系

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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. [References: 79]
机译：升华过程平衡发展的标准已经过突变并在理论上得到证实。它基于升华温度Tub（对应于10（-7）bar的蒸气分压）与升华焓DeltaH（T）（o）之比。该比率在3.6 +/- 0.2Kmol kJ（-1）（S.D。）范围内。此标准已应用于100种不同物质的自由表面分解，包括一些准金属和简单的二元化合物，以及无机和有机酸的金属盐，铵和水合盐。初始温度，T-in和E参数的实验值等于理论上的T-sub和DeltaH（T）（o）值，均取自文献。所有反应物的T-in / E比的平均值等于3.6 +/- 0.4（标准偏差）。这意味着所有固体的分解均按照平衡定律进行。 T-in / E比值相对于平均值的较高偏差（与理论相比）与E参数确定中的随机误差以及分解初始温度定义中的不确定性有关。在自由表面固体分解的情况下，首次使用第三定律方法有目的地计算E参数。通过第二定律和第三定律方法对20种不同的反应物进行的结果比较表明，后一种方法在测定的精确度和准确性以及实验所花费的时间上具有很大的优势。 （C）2002由Elsevier Science B.V.出版[参考号：79]

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