The influence of physical conditions on the velocity of decomposition of certain crystalline solids
The influence of physical conditions on the velocity of decomposition of certain crystalline solids
复制标题
物理条件对某些结晶固体分解速度的影响
DOI：
10.1098/rspa.1921.0035
复制
发表时间：
1921
期刊：
影响因子：
--
通讯作者：
E. J. Bowen
中科院分区：
文献类型：
--
作者：
C. Hinshelwood;E. J. Bowen
化学变化速度的研究通常仅限于液态或气态物质。速度的温度系数是特别重要的，因为它可以用来计算反应分子的“临界增量”或“活化热”。在溶液中反应的情况下，速度在很大程度上受溶剂的影响，但由于分子复合物的形成等因素，定量关系不符合任何简单的规律。固态反应的研究不多，虽然在许多方面，由于原子在空间晶格中的固定排列，固态更简单。本文所描述的实验的目的是确定是否可以找到简单的定量关系的情况下，“不可逆”分解的某些结晶固体。结果表明，在这些情况下，温度系数是一个复杂的量，取决于多个物理因素;并且不能从中计算活化热。另一方面，发现高锰酸钾在高氯酸钾中的固溶体中的析氧速率与高锰酸钾在各种固溶体中的活化热之间存在简单的关系。
The study of the velocity of chemical change has usually been confined to substances in the liquid or gaseous state. The temperature coefficient of the velocity is of special importance, since it can be used to calculate the “critical increment” or 'heat of activation” of the reacting molecule. In the case of reactions in solution the velocity is very largely influenced by the solvent, but the quantitative relationships do not conform to any simple law, owing to such factors as the formation of molecular complexes. Reactions in the solid state have not been much studied, although in many respects the solid state is simpler, owing to the fixed arrangement of the atoms in a space lattice. The object of the experiments described in this paper was to ascertain whether simple quantitative relationships could be found for cases of “irreversible” decompositions of certain crystalline solids. The results show that in these cases the temperature coefficient is a complicated quantity, dependent on several physical factors; and that the heat of activation cannot be calculated from it. On the other hand, a simple relation is found connecting the rate of evolution of oxygen from solid solutions of potassium permanganate in potassium perchlorate and the heats of activation of the potassium permanganate in the various solid solutions.