朱利安-希尔尼亚克,周期性化学反应的早期倡导者

IF 1.7 4区 化学 Q4 CHEMISTRY, PHYSICAL
Niklas Manz, Yurij Holovatch, John Tyson
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引用次数: 0

摘要

在本文中,我们将介绍和讨论乌克兰化学家和物理学家朱利安-希尔尼亚克(Julian Hirniak)的工作和科学遗产,他于 1908 年和 1911 年发表了两篇关于周期性化学反应的文章。在过去的 110 多年里,他的理论工作经常被引用到阿尔弗雷德-洛特卡(Alfred Lotka)的振荡反应系统理论模型中,并获得好评。其他作者指出了希尔尼亚克反应方案中的热力学问题。根据希尔尼亚克 1908 年乌克兰文和 1911 年德文文章的英译本,我们证明希尔尼亚克的主张(即在封闭的反应容器中三种化学异构体的相互转化循环可以表现出阻尼周期性行为)违反了详细平衡原理(即热力学第二定律),而且希尔尼亚克意识到了这一原理。我们还结合洛特卡关于开放式化学反应系统中阻尼振荡的第一个模型,讨论了他的研究结果,该模型涉及一个远离平衡状态运行的自催化反应。根据希尔尼亚克和洛特卡的提示,我们表明,催化糖的磷酸化的激酶的普通情况可以满足希尔尼亚克对其稳态通量(即米迦勒-门顿速率定律)的阻尼振荡的条件,但振荡的阻尼程度非常高,以至于无法观测。最后,我们探讨了与朱利安-希尔尼亚克及其出版物有关的历史和事实误解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Julian Hirniak, an early proponent of periodic chemical reactions

Julian Hirniak, an early proponent of periodic chemical reactions

In this article we present and discuss the work and scientific legacy of Julian Hirniak, the Ukrainian chemist and physicist who published two articles in 1908 and 1911 about periodic chemical reactions. Over the last 110+ years, his theoretical work has often been cited favorably in connection with Alfred Lotka’s theoretical model of an oscillating reaction system. Other authors have pointed out thermodynamic problems in Hirniak’s reaction scheme. Based on English translations of his 1908 Ukrainian and 1911 German articles, we show that Hirniak’s claim (that a cycle of inter-conversions of three chemical isomers in a closed reaction vessel can show damped periodic behavior) violates the Principle of Detailed Balance (i.e., the Second Law of Thermodynamics), and that Hirniak was aware of this Principle. We also discuss his results in relation to Lotka’s first model of damped oscillations in an open system of chemical reactions involving an auto-catalytic reaction operating far from equilibrium. Taking hints from both Hirniak and Lotka, we show that the mundane case of a kinase enzyme catalyzing the phosphorylation of a sugar can satisfy Hirniak’s conditions for damped oscillations to its steady state flux (i.e., the Michaelis–Menten rate law), but that the oscillations are so highly damped as to be unobservable. Finally, we examine historical and factual misunderstandings related to Julian Hirniak and his publications.

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来源期刊
CiteScore
3.30
自引率
5.60%
发文量
201
审稿时长
2.8 months
期刊介绍: Reaction Kinetics, Mechanisms and Catalysis is a medium for original contributions in the following fields: -kinetics of homogeneous reactions in gas, liquid and solid phase; -Homogeneous catalysis; -Heterogeneous catalysis; -Adsorption in heterogeneous catalysis; -Transport processes related to reaction kinetics and catalysis; -Preparation and study of catalysts; -Reactors and apparatus. Reaction Kinetics, Mechanisms and Catalysis was formerly published under the title Reaction Kinetics and Catalysis Letters.
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