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A two‐phase second‐order reaction: Kinetics of epoxidation of methyl 12,13‐epoxyoleate
Author(s) -
Rothbart H. L.,
Snook M. E.,
Rusling J. F.,
Scott W. E.
Publication year - 1969
Publication title -
journal of the american oil chemists' society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.512
H-Index - 117
eISSN - 1558-9331
pISSN - 0003-021X
DOI - 10.1007/bf02545015
Subject(s) - reaction rate constant , peracetic acid , chemistry , kinetics , thermodynamics , benzene , constant (computer programming) , reaction rate , chloroform , phase (matter) , function (biology) , order of reaction , partition coefficient , analytical chemistry (journal) , organic chemistry , physics , quantum mechanics , evolutionary biology , computer science , catalysis , biology , programming language , hydrogen peroxide
The kinetics of epoxidation of methyl 12,13‐epoxyoleate with peracetic acid have been studied. Chloroform and benzene solvents were used at 25, 30 and 40 C. A second‐order equation was developed to determine the rate constants in this two‐phase system. Variation of the relative phase volumes provides a convenient method for controlling the rate of reaction. Differences in the ΔS° of activation for the formation of the two isomeric diepoxides were greater than 1 eu in all cases. If the usual integrated second‐order equation is used, the rate constant will be in error. The magnitude of the error is related to the partition coefficient of the species distributed between the phases and the volume ratios of the two phases. Other errors in the rate constant were determined by expressing K as a function of time, temperature and the concentration of reactants at any time in the reaction. The total differential of K divided by K, to get the relative error, was evaluated at various reaction times. The choice of best times for the determination of the rate constant was dictated from the error analysis.