Julian Hirniak, an early proponent of periodic chemical reaction

TL;DR

This paper reviews Julian Hirniak's early 20th-century work on periodic chemical reactions, analyzing its scientific validity, relation to thermodynamics, and historical impact, highlighting both its influence and limitations.

Contribution

It clarifies Hirniak's theoretical claims, assesses their thermodynamic consistency, and connects his ideas to modern enzyme kinetics and oscillation models.

Findings

Hiraniak's reaction cycle violates the Second Law of Thermodynamics.

His work influenced Lotka's oscillation models.

Damped oscillations in enzyme reactions are theoretically possible but practically unobservable.

Abstract

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 \textit{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.