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- W2289095377 abstract "The primary deuterium isotope effect has been measured for the proton transfer reaction from di(4-nitropheny1)methane to t-butoxide ion in a solvent consisting of 10% v/v toluene in 1-butanol at a series of temperatures between 20 and 45 C. The isotopic rate ratio, kH/kD, is 7.3 at 25 C. The activation parameters showed an enthalpy of activation difference (AHD* -AHH*) of only ra. ) kcal mol-' and an entropy isotope effect (ASD* -ASH*) of -2.4 cal mol-' deg-I. The latter indicates, according to the theory of Bell, that tunnelling of the proton through the energy barrier is unimportant in this reaction. This result is compared to other reactions in the literature, in which tunnelling has been postulated to occur. L'effet isotopique primairedu deuterium a kt6 mesure pour la reaction de transfert du proton du di(nitro4 phtnyl) methane a I'ion t-butoxide, dans un solvant constitut de 10z v/v de toluene dans le I-butanol et pour des temperatures variant entre 20 et 45 C. Le rapport des vitesses isotopiques, k,/k, est de 7.3 a 25 C. Les parametres d'activation montrent une difference d'enthalpie d'activation de seulement ca. 9 kcal mol-' pour (AHD* - AHH*) et un effet isotopique d'entropie, (ASD* - AS1,*) de -2.4cal mol-' deg-I. Ce dernier rtsuItat indique, selon la thtorie de Bell, que I'effet tunnel du proton a travers la barriere tnergdtique n'est pas important dans cette reaction. Ces resultats sont compares a ceux d'autres riactions de la litttrature, oh I'effet tunnel est suppose present. [Traduit par le journal]" @default.
- W2289095377 created "2016-06-24" @default.
- W2289095377 creator A5026177962 @default.
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- W2289095377 date "1974-02-15" @default.
- W2289095377 modified "2023-09-27" @default.
- W2289095377 title "Kinetics of proton transfer reactions of carbon acids. 4. Primary deuterium isotope effect in the reaction of di-(4-nitrophenyl)-methane-d$sub 2$ with t-butoxide" @default.
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