The explicit analysis of consecutive pseudo-first-order reactions: Application to kinetics of thiolysis of dithiasuccinoyl (Dts) amino acids

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Abstract

An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.

Original languageEnglish (US)
Pages (from-to)114-122
Number of pages9
JournalAnalytical Biochemistry
Volume109
Issue number1
DOIs
StatePublished - Jan 1 1980

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Amino Acids
Kinetics
Disulfides

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title = "The explicit analysis of consecutive pseudo-first-order reactions: Application to kinetics of thiolysis of dithiasuccinoyl (Dts) amino acids",
abstract = "An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100{\%} [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.",
author = "George Barany",
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N2 - An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.

AB - An explicit set of general methods for the experimental determination of the rates k1 and k2 of consecutive pseudo-first-order reactions is described and discussed. These rely on the direct simultaneous analytical quantitation of the starting material, intermediate, and product of the reaction, and thus differ from present techniques based on measurement of coreactant consumption or coproduct appearance. The quantity kenv = k1k2/(k1 + k2) is shown to define a good “envelope” approximation to product formation according to the simple law 100% [1 − exp(−kenvt)]. The theory of envelopes is useful for comparing overall rates of reactions with widely differing values of κ = k2/k1. The kinetic pattern of thiolysis of dithiasuccinoyl amino acids to carbamoyl disulfide intermediates to product free amino acids is analyzed and shown to agree quantitatively with theory.

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