THE THERMAL DECOMPOSITION OF DIETHYL ETHER .1. RATE-PRESSURE RELATIONS
THE THERMAL DECOMPOSITION OF DIETHYL ETHER .1. RATE-PRESSURE RELATIONS
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DOI：
10.1098/rspa.1958.0063
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发表时间：
1958-01-01
影响因子：
--
通讯作者：
HINSHELWOOD, C
中科院分区：
文献类型：
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作者：
FREEMAN, GR;DANBY, CJ;HINSHELWOOD, C
在乙醚的热分解过程中，一级速率常数(K)随乙醚本身的压力(P)、氢气的压力或各种化学惰性气体的压力(P)而变化，其规律比迄今所认为的更为复杂。一般而言，在一定范围内，k与pX近似线性增加：然后曲线的斜率减小，就好像接近极限一样。当X指的是乙醚、氢气或某些其他气体时，实际上没有达到极限，但仍在以相当低的速度继续增加。然而，对于某些气体，曲线的斜率变得非常小或为零。墨水的变化不能用产品化学成分的变化来解释。对于无抑制反应(很大程度上是一个链式反应)和对于一氧化氮抑制反应(假设的分子反应)，k-p曲线的形式在定性上是相似的，但在数量上却有很大的不同。分子反应的k-式符合最近建立的烷烃和一氧化二氮分解的k-式，并可能用为这些例子提出的扩展的单分子反应理论来解释。链式反应的关系要复杂得多，但解释中可能包含了类似于上述的考虑因素，适用于链条开始的初始分子过程。
In the thermal decomposition of diethyl ether the first-order rate constant (k) varies with the pressure (p) of the ether itself, or that of added hydrogen, or that of various chemically inert gases according to a more complex pattern than has hitherto been supposed. In general,kincreases approximately linearly with pXover a certain range: the slope of the curve then decreases as though a limit were being approached. WhenXrefers to ether, hydrogen or certain other gases no limit is in fact reached, butkcontinues to increase at a considerably reduced rate. With certain gases, however, the slope of the curve becomes very small or zero. Changes inkare not explicable by variations in the chemical composition of the products. The forms of thek-pcurves are qualitatively similar for the uninhibited reaction (largely a chain process) and for the nitric oxide-inhibited reaction (hypothetical molecular reaction), but the effects are quantitatively quite different. Thek-prelations for the molecular reaction conform to those recently established for the decomposition of paraffins and of nitrous oxide, and may possibly be interpreted by the extended theory of unimolecular reactions proposed for these examples. The relations for the chain reactions are more complicated but the interpretation probably includes considerations similar to the above, applied to the initial molecular process by which the chains start.