DEUTERIUM KINETIC ISOTOPE EFFECTS. V. TEMPERATURE DEPENDENCE OF /cap beta/- DEUTERIUM EFFECTS IN WATER SOLVOLYSIS OF ISOPROPYL COMPOUNDS

Journal Article · Sun Oct 01 00:00:00 EDT 1961 · Canadian Journal of Chemistry (Canada)

DOI:https://doi.org/10.1139/v61-268· OSTI ID:4834037

Leffek, K T; Robertson, R E; Sugamori, S E

The secondary BETA -deuterium isotope effect (k/sub H//k/sub D/) was measured over a range of temperature for the water solvolysis reactions of isopropyl methanesulfonate, p-toluenesulfonate, 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. (auth)

• Research Organization: National Research Council, Ottawa
• Sponsoring Organization: USDOE
• NSA Number: NSA-16-000164
• OSTI ID: 4834037
• Journal Information: Canadian Journal of Chemistry (Canada), Vol. Vol: 39; Other Information: Orig. Receipt Date: 31-DEC-62
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

CHEMISTRY
ACTIVATION
BROMIDES
DECOMPOSITION
DEUTERIUM
ENTHALPY
HYDROLYSIS
ISOTOPE EFFECTS
MEASURED VALUES
METHANE
METHYL RADICALS
OPTICAL SYSTEMS
ORGANIC COMPOUNDS
PROPYL RADICALS
REACTION KINETICS
SOLVOLYSIS
SULFONIC ACIDS
TEMPERATURE
THERMODYNAMICS
TOLUENE