Reactions for chemical systems far from equilibrium
Reactions for chemical systems far from equilibrium
复制标题
远离平衡的化学系统的反应
DOI：
10.1039/f19837900075
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发表时间：
1983
期刊：
影响因子：
--
通讯作者：
G. King
中科院分区：
文献类型：
--
作者：
G. King
反应制定系统远离平衡运行可能会产生误导性的结论，如果他们包含一个隐含的假设稳定状态。这种假设最常见的是通过从一对基元反应中消除一个中间产物，将它们浓缩成一个单一的汇总反应。使用这种不充分的反应的后果说明通过两个众所周知的模型系统，洛特卡振荡器和振荡器。该反应器包括一个三分子反应，它可以通过总结几组基元反应中的任何一组来产生。当用初等集代替三分子反应时，修正的自振子不能显示其特征极限环。在催化循环中，同样的物质既作为反应物又作为产物，通过消除某些中间产物而形成。包括即使是短寿命的中间体改变所示的洛特卡计划的稳定性，使行为在相平面的变化从一个保守的循环到一个不断扩大的螺旋。
Reactions formulated for systems operating far from equilibrium may generate misleading conclusions if they contain an implied assumption of steady state. This assumption is introduced most commonly by eliminating an intermediate product from a pair of elementary reactions, condensing them into a single summary reaction. The consequences of using such inadequate reactions are illustrated through two well known model systems, the Lotka oscillator and the Brusselator. The Brusselator includes a termolecular reaction which could be generated by summarizing any of several sets of elementary reactions. When an elementary set is used in place of the termolecular reaction, the revised Brusselator fails to show its characteristic limit cycle. Both the Brusselator and the Lotka scheme have reactions in which the same substance appears both as reactant and as product, formed by eliminating some intermediate in a catalytic cycle. Including even short-lived intermediates alters the stability shown by the Lotka scheme, so that behaviour in the phase plane changes from a conservative cycle into an expanding spiral.