{"title":"朱利安-希尔尼亚克,周期性化学反应的早期倡导者","authors":"Niklas Manz, Yurij Holovatch, John Tyson","doi":"10.1007/s11144-024-02700-3","DOIUrl":null,"url":null,"abstract":"<div><p>In this article we present and discuss the work and scientific legacy of <span>Julian Hirniak</span>, 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 <span>Alfred Lotka</span>’s theoretical model of an oscillating reaction system. Other authors have pointed out thermodynamic problems in <span>Hirniak</span>’s reaction scheme. Based on English translations of his 1908 Ukrainian and 1911 German articles, we show that <span>Hirniak</span>’s claim (that a cycle of inter-conversions of three chemical isomers in a closed reaction vessel can show damped periodic behavior) violates the <i>Principle of Detailed Balance</i> (i.e., the Second Law of Thermodynamics), and that <span>Hirniak</span> was aware of this Principle. We also discuss his results in relation to <span>Lotka</span>’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 <span>Hirniak</span> and <span>Lotka</span>, we show that the mundane case of a kinase enzyme catalyzing the phosphorylation of a sugar can satisfy <span>Hirniak</span>’s conditions for damped oscillations to its steady state flux (i.e., the <span>Michaelis–Menten</span> rate law), but that the oscillations are so highly damped as to be unobservable. Finally, we examine historical and factual misunderstandings related to <span>Julian Hirniak</span> and his publications.</p></div>","PeriodicalId":750,"journal":{"name":"Reaction Kinetics, Mechanisms and Catalysis","volume":null,"pages":null},"PeriodicalIF":1.7000,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s11144-024-02700-3.pdf","citationCount":"0","resultStr":"{\"title\":\"Julian Hirniak, an early proponent of periodic chemical reactions\",\"authors\":\"Niklas Manz, Yurij Holovatch, John Tyson\",\"doi\":\"10.1007/s11144-024-02700-3\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>In this article we present and discuss the work and scientific legacy of <span>Julian Hirniak</span>, 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 <span>Alfred Lotka</span>’s theoretical model of an oscillating reaction system. Other authors have pointed out thermodynamic problems in <span>Hirniak</span>’s reaction scheme. Based on English translations of his 1908 Ukrainian and 1911 German articles, we show that <span>Hirniak</span>’s claim (that a cycle of inter-conversions of three chemical isomers in a closed reaction vessel can show damped periodic behavior) violates the <i>Principle of Detailed Balance</i> (i.e., the Second Law of Thermodynamics), and that <span>Hirniak</span> was aware of this Principle. We also discuss his results in relation to <span>Lotka</span>’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 <span>Hirniak</span> and <span>Lotka</span>, we show that the mundane case of a kinase enzyme catalyzing the phosphorylation of a sugar can satisfy <span>Hirniak</span>’s conditions for damped oscillations to its steady state flux (i.e., the <span>Michaelis–Menten</span> rate law), but that the oscillations are so highly damped as to be unobservable. Finally, we examine historical and factual misunderstandings related to <span>Julian Hirniak</span> and his publications.</p></div>\",\"PeriodicalId\":750,\"journal\":{\"name\":\"Reaction Kinetics, Mechanisms and Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.7000,\"publicationDate\":\"2024-09-12\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://link.springer.com/content/pdf/10.1007/s11144-024-02700-3.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reaction Kinetics, Mechanisms and Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11144-024-02700-3\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reaction Kinetics, Mechanisms and Catalysis","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11144-024-02700-3","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
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.
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.