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Reaction Schemes That Are Easily Confused with a Reversible First–Order Reaction
Author(s) -
Balogh Ágnes,
Lente Gábor,
Kalmár József,
Fábián István
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20960
Subject(s) - chemistry , kinetic energy , taylor series , exponential function , order of reaction , reversible reaction , series (stratigraphy) , thermodynamics , reagent , reaction rate , order (exchange) , reaction rate constant , statistical physics , kinetics , first order , computational chemistry , mathematics , mathematical analysis , organic chemistry , quantum mechanics , physics , catalysis , finance , economics , paleontology , biology
ABSTRACT A detailed kinetic analysis of two schemes, one involving coupled consecutive processes and another featuring the simultaneous association reaction and decay of a component, is presented here using Taylor series expansion. It is shown that both of these schemes are easily confused with the reversible second–order reaction in a routine kinetic study. The kinetic traces predicted by both schemes are sufficiently close to pseudo–first–order curves so that it is practically impossible to identify the deviations based on data with the usual experimental errors, which was also demonstrated by fitting simulated theoretical curves to exponential functions. The dependence of the pseudo–first–order rate constants on the concentration of the excess reagent features the same trend as in the case of a reversible reaction: A straight line with an intercept is observed. This analysis emphasizes that the reversible nature of reactions should be demonstrated by direct equilibrium studies when elements of reversibility are implied by kinetic results.