DEUTERIUM KINETIC ISOTOPE EFFECTS: V TEMPERATURE DEPENDENCE OF β-DEUTERIUM EFFECTS IN WATER SOLVOLYSIS OF ISOPROPYL COMPOUNDS

Autor:	R. E. Robertson, S. E. Sugamori, K. T. Leffek
Rok vydání:	1961
Předmět:	Chemistry Organic Chemistry Inorganic chemistry Enthalpy General Chemistry Toluene Catalysis Chemical kinetics chemistry.chemical_compound Deuterium Bromide Kinetic isotope effect Solvolysis Isopropyl
Zdroj:	Canadian Journal of Chemistry. 39:1989-1994
ISSN:	1480-3291 0008-4042
DOI:	10.1139/v61-268
Popis:	The secondary β-deuterium isotope effect (kH/kD) has been measured over a range of temperature for the water solvolysis reactions of isopropyl methanesulphonate, p-toluenesulphonate, and bromide. In these cases the isotope effect is due to a difference in entropies of activation of the isotopic analogues rather than a difference in the enthalpies of activation. It is suggested that the observed isotope effect is due to internal rotational effects of the methyl groups in the isopropyl radical, and the lack of an isotope effect on the enthalpy of activation is accounted for by a cancellation of an effect from this source and one from zero-point energy.
Databáze:	OpenAIRE
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