Influence of electric field in the double layer on rate constants determined with electrochemical relaxation techniques for fast homogeneous proton transfer reactions in solution

1965 ◽  
Vol 39 (0) ◽  
pp. 136-148 ◽  
Author(s):  
Hans Wolfgang Nürnberg
Keyword(s):  
Electric Field ◽  
Proton Transfer ◽  
Double Layer ◽  
Rate Constants ◽  
Transfer Reactions ◽  
Relaxation Techniques ◽  
Proton Transfer Reactions

Gas-phase proton-transfer reactions of the hydronium ion at 298 K

1979 ◽  
Vol 57 (12) ◽  
pp. 1518-1523 ◽  
Author(s):  
Gervase I. Mackay ◽  
Scott D. Tanner ◽  
Alan C. Hopkinson ◽  
Diethard K. Bohme
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Transfer Reactions ◽  
Flowing Afterglow ◽  
Hydronium Ion ◽  
Proton Transfer Reactions

Rate constants measured with the flowing afterglow technique at 298 ± 2 K are reported for the proton-transfer reactions of H3O+ with CH2O, CH3CHO, (CH3)2CO, HCOOH, CH3COOH, HCOOCH3, CH3OH, C2H5OH, (CH3)2O, and CH2CO. Dissociative proton-transfer was observed only with CH3COOH. The rate constants are compared with the predictions of various theories for ion–molecule collisions. The protonation is discussed in terms of the energetics and mechanisms of various modes of dissociation.

An experimental study of the reactivity and relative basicity of the methoxide anion in the gas phase at room temperature, and their perturbation by methanol solvation

1982 ◽  
Vol 60 (20) ◽  
pp. 2594-2605 ◽  
Author(s):  
Gervase I. Mackay ◽  
Asit B. Rakshit ◽  
Diethard K. Bohme
Keyword(s):  
Proton Transfer ◽  
Gas Phase ◽  
Rate Constants ◽  
Solvent Free ◽  
Transfer Reactions ◽  
Free Proton ◽  
Proton Transfer Reactions ◽  
Intrinsic Reactivity ◽  
Relative Acidity ◽  
Methoxide Anion

Flowing afterglow measurements at 296 ± 2 K are reported which explore three aspects of the gas-phase acid–base chemistry of the methoxide anion. Firstly, the intrinsic reactivity of this ion has been determined from measurements of rate constants for solvent-free proton-transfer reactions with molecules more acidic than methanol including CH2=C=CH2, C6H5CH3, C2H5OH, C2H2, CH3CN, CH3COCH3, CH3CHO, CH3NO2, and HCN. Secondly, equilibrium constant measurements have been performed for solvent-free proton-transfer reactions which provide a gas-phase scale of acidities for these molecules relative to the acidity of methanol. Finally, rate constants were measured for the reactions of these acids with methoxide ions solvated with up to three molecules of methanol. The results establish trends in reactivity as a function of step–wise solvation when relative acidity is preserved and when a reversal occurs in the relative acidity upon solvation.

Kinetics of Proton Transfer Reactions of Carbon Acids. II. Reaction of Di-(4-nitrophenyl)methane with Alkoxide Bases

1972 ◽  
Vol 50 (1) ◽  
pp. 24-30 ◽  
Author(s):  
A. Jarczewski ◽  
K. T. Leffek
Keyword(s):  
Proton Transfer ◽  
Transition State ◽  
Rate Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Activation Process ◽  
Proton Transfers ◽  
Proton Transfer Reactions ◽  
Carbon Acids ◽  
Kinetics Of

The second-order rate constants have been measured over a range of temperatures for the proton-transter reactions from di-(4-nitrophenyl)methane to ethoxide, isopropoxide, and t-butoxide ions in solvents consisting of the corresponding alcohols containing 10% toluene by volume. The activation parameters ΔH≠ and ΔS≠ have been calculated and an interpretation of them is given in terms of solvation effects during the activation process. A comparison between the activation parameters for proton transfers and E2 olefin-forming β-elimination reactions is made and discussed with respect to transition state character of the latter reactions.

Study of the dissociation of the products of some proton transfer reactions in acetonitrile solvent

1992 ◽  
Vol 70 (3) ◽  
pp. 935-942 ◽  
Author(s):  
Wlodzimierz Galezowski ◽  
Arnold Jarczewski
Keyword(s):  
Proton Transfer ◽  
Rate Constants ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Ion Pair ◽  
Transfer Reactions ◽  
Side Reactions ◽  
First Order ◽  
Kinetic Isotope ◽  
Proton Transfer Reactions

The conductometric study of the products of the proton transfer reactions of C-acids (nitriles, nitroalkanes, and 2,4,6-trinitrotoluene) with the strong amine bases (1,1,3,3-tetramethylguanidine (TMG), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,8-bis(dimethylamino)naphthalene (DMAN), and piperidine) in acetonitrile shows their large degree of dissociation into free ions. The dissociation constant values have been estimated at 25 °C to be larger than 1 × 10−4 M. This weakens the formalism commonly accepted in spectrophotometric kinetic studies of these systems of reactions, based on the assumption that the product is an ion pair. Spectrophotometric equilibrium and kinetic measurements provided evidence that reverse reaction is a second-order process (pseudo-first order because cation concentration is controlled by side reactions). The influence of the common cation (TMGH+) on the equilibria of the proton abstraction from 2-methyl-1-(4-nitrophenyl)-1-nitropropane and 4-nitrophenylcyanomethane with TMG base in acetonitrile at 25 °C was examined and was found to be compatible with the assumption of large dissociation of the reaction product for free ions. "Equilibrium constants" estimated by the Benesi and Hildebrand method (which assumes an ion-pair product) decreased with increasing concentration of added TMGH+ cation, but these "equilibrium constants" multiplied by [TMGH+] are constant. The observed pseudo-first-order rate constants of the proton transfer reaction, measured at large excess of the base over C-acid, grow with the cation concentration due to the increase of the backward reaction rate. The concentration of added common cation shows a negligible influence on the observed rate constants of deuteron transfer reaction. Thus, as a result of side reactions, in which extra amounts of cation are formed, some second-order rate constants [Formula: see text] and also kinetic isotope effects (KIEs) [Formula: see text] that have been measured in acetonitrile can be substantially overestimated. Keywords: ion-pair dissociation, proton transfer reactions, kinetic isotope effects.

Proton transfer reactions between ortho-methyl substituted derivatives of 4-nitrophenylphenylcyanomethane and nitrogen bases in acetonitrile solvent

1988 ◽  
Vol 66 (6) ◽  
pp. 1454-1458 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Przemyslaw Pruszynski
Keyword(s):  
Proton Transfer ◽  
Isotope Effect ◽  
Rate Constants ◽  
Isotope Effects ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Methyl Groups ◽  
Methyl Group ◽  
Proton Transfer Reactions

Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters have been measured for the proton transfer reactions in acetonitrile solvent of 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenyl-cyanomethane with tetramethylguanidine base and for the reactions of 2-methyl-4-nitrophenylphenylcyanomethane and 2,6-di-methyl-4-nitrophenylphenylcyanomethane with 1,5-diazabicyclo[5.4.0]undec-7-ene base. Introduction of the ortho-methyl groups in the substrate molecule caused significant reductions in the equilibrium and rate constants. The expected rise in the kinetic primary deuterium isotope effect was not observed when the first ortho-methyl group was introduced, but a 20% increase did accompany the introduction of the second ortho-methyl group. Enthalpy of activation measurements indicated that there was no increase in the proton tunnelling contribution to the isotope effect when the amount of steric hindrance is increased with ortho-methyl groups.

scholarly journals Proton Transfer Reactions of Carbon Acids. III. Effect of Solvent Change on the Equilibrium and Kinetic Parameters of the Reaction of Di-(4-nitrophenyl)methane with Alkoxide Bases

1973 ◽  
Vol 51 (17) ◽  
pp. 2805-2809 ◽  
Author(s):  
Jae-Hang Kim ◽  
Kenneth T. Leffek
Keyword(s):  
Proton Transfer ◽  
Kinetic Parameters ◽  
Rate Constants ◽  
Equilibrium Constants ◽  
Mixed Solvents ◽  
Activation Parameters ◽  
Transfer Reactions ◽  
Effect Of Solvent ◽  
Proton Transfer Reactions ◽  
Carbon Acids

The equilibrium constants, the second-order rate constants, and the activation parameters have been determined for the proton transfer from di-(4-nitrophenyl)methane to ethoxide ion in a series of mixed solvents containing various amounts of acetonitrile in ethanol. The quantities have been interpreted in terms of the general postulates of the Miller–Parker theory of solvation effects.

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