Isoparametricity paradox in the pyridine-catalyzed reaction of phenyloxirane with 3-nitrobenzoic acid

Autor:	I. V. Shpan’ko, I. V. Sadovaya
Rok vydání:	2013
Předmět:	chemistry.chemical_compound chemistry Computational chemistry Pyridine Enthalpy Substituent Physical chemistry Activation energy Physical and Theoretical Chemistry Constant (mathematics) Acetonitrile 3-nitrobenzoic acid Catalysis
Zdroj:	Russian Journal of Physical Chemistry A. 87:1955-1959
ISSN:	1531-863X 0036-0244
DOI:	10.1134/s0036024413120224
Popis:	The combined effect of structure and temperature on rate and activation energy of the X-substituted pyridine-catalyzed reaction between phenyloxirane and 3-nitrobenzoic acid in acetonitrile is studied. It is found that the intense interaction (nonadditivity) of effects of X substituents and temperature manifests itself in cross-reaction series; experimental evidence of isoparametricity in its enthalpy-entropy compensation aspect is obtained. It is determined that at the isoparametric temperature point (the isokinetic temperature), the rate (activation energy) of the catalytic process does not depend on structure of X substituents and a reversal of the order of effect of X on catalytic activity of pyridines is observed upon the transition of this isoparametric point (the isoparametricity paradox). It is shown that at the isoparametric point on the constant of the X substituent, temperature has almost no effect on the rate of the process since the value of the activation enthalpy is close to zero.
Databáze:	OpenAIRE
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