Julian Hirniak, an early proponent of periodic chemical reactions

Author:

Manz NiklasORCID,Holovatch YurijORCID,Tyson JohnORCID

Abstract

AbstractIn 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.

Funder

Hamburger Collaborative Project Fund at The College of Wooster

Publisher

Springer Science and Business Media LLC

Reference90 articles.

1. Hirniak J (1911) Zur Frage der periodischen Reaktionen (On the question of periodic reactions). Z Phys Chem 75U:675–680

2. Lotka AJ (1910) Zur Theorie der periodischen Reaktionen (On the theory of periodic reactions). Z Phys Chem 72U:508–511, [Note: Reprinted in [15]]

3. Hirniak J (1908) Hirniak, J. Про перiодичнi хемiчнi реакциï, (Über periodische chemischen Reactionen) (About periodic chemical reactions). Збiрник Математично-Природописно-Лïкарськоï Секциï Наукового Товариства iмени Шевченка, (Sammelschrift der Mathematisch-Naturwissenschaftlich-Ärztlichen Section der Ševčenko-Gesellschaft der Wissenschaften in Lemberg) (Proceedings of the Mathematical-Natural Sciences-Medical Section of the Shevchenko Scientific Society in Lviv) 12, 1–8, [Note: Original author name: Юлiян Гiрняк]

4. Bray WC (1921) A Periodic Reaction in Homogeneous Solution and Its Relation to Catalysis. J Am Chem Soc 43:1262–1267

5. Henry W Account of a Series of Experiments, Undertaken with the View of Decomposing the Muriatic Acid. J Natl Philos, Chem Arts (Nicholson’s Journal) 1800, IV, 209–214, 245–249

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