✦ LIBER ✦

Evaluation of the protonation thermochemistry obtained by the extended kinetic method

✍ Scribed by Guy Bouchoux

Publisher: John Wiley and Sons
Year: 2006
Tongue: English
Weight: 196 KB
Volume: 41
Category: Article
ISSN: 1076-5174
DOI: 10.1002/jms.1055

No coin nor oath required. For personal study only.

✦ Synopsis

Abstract

An evaluation of the results obtained by the extended kinetic method for a series of representative bases is presented here. Analysis of the original experimental data is conducted using the orthogonal distance regression (ODR) statistical treatment. A comparison with the proton affinities and protonation entropies obtained from variable temperature equilibrium constant measurements demonstrate deviations, which may be ascribed to random and systematic errors. Considerable random errors are associated with the extended kinetic method if the number of reference bases and the range of effective temperatures are too low. It is also confirmed that large systematic errors on proton affinities and protonation entropies are obtained when large protonation entropy is associated with the considered system. It is, however, encouraging to note that the gas phase basicities obtained by the extended kinetic method are generally comparable to that obtained by other methods within a few kJ/mol. Copyright © 2006 John Wiley & Sons, Ltd.

📜 SIMILAR VOLUMES

Obtaining thermochemical data by the ext

Obtaining thermochemical data by the extended kinetic method

✍ Guy Bouchoux; Michel Sablier; Florence Berruyer-Penaud 📂 Article 📅 2004 🏛 John Wiley and Sons 🌐 English ⚖ 246 KB

## Abstract A microcanonical analysis of the extended kinetic method is performed using statistical rate calculations based on orbiting transition state theory. The model systems simulate polydentate bases M which exhibit losses of entropy upon protonation of up to 35 kJ mol^−1^ K^−1^. It is shown

Thermochemistry of Multiply Charged Meli

Thermochemistry of Multiply Charged Melittin in the Gas Phase Determined by the Modified Kinetic Method

✍ Igor A. Kaltashov; Catherine Fenselau 📂 Article 📅 1996 🏛 John Wiley and Sons 🌐 English ⚖ 444 KB 👁 2 views

The modified kinetic method was expanded to measuring gas-phase basicities of biopolymers carrying two or more charges. Relative rates of the unimolecular dissociation of metastable multiply charged proton-bound dimers formed by melittin and reference bases provided the values of 'apparent' gas-phas

Kinetics of proton transfer in ice via t

Kinetics of proton transfer in ice via the pH-jump method: Evaluation of the proton diffusion rate in polycrystalline doped ice

✍ E. Pines; D. Huppert 📂 Article 📅 1985 🏛 Elsevier Science 🌐 English ⚖ 594 KB

The value of-the proton diffusion coefficient D He in ice was extracted from the diffusion-controlled rate k, of the proton recombination reaction RO-+H30i + \*,ROH + Hz0 in polycrystalhte doped ice. At -10°C. DH+ was estimated to lie between 3.5 x10-" and 1.3~10-~ cm' s-l, well below the correspond

Improving the accuracy of the spatial di

Improving the accuracy of the spatial discretization in finite-difference electrochemical kinetic simulations, by means of the extended Numerov method

✍ Lesław K. Bieniasz 📂 Article 📅 2004 🏛 John Wiley and Sons 🌐 English ⚖ 122 KB 👁 1 views

## Abstract The fourth‐order accurate, three‐point finite‐difference Numerov spatial discretization provides accurate and efficient solutions to the time‐dependent governing differential equations of electrochemical kinetics in one‐dimensional space geometry, when the equations contain first time d

Proton mobilities obtained by the moving

Proton mobilities obtained by the moving boundary method and an empirical equation in capillary electrophoresis

✍ Cao, Cheng-Xi 📂 Article 📅 1997 🏛 John Wiley and Sons 🌐 English ⚖ 221 KB

A simple method for extending the range

A simple method for extending the range of pseudo-order kinetic measurements

✍ James L. Jensen; Richard C. Kanner; Gregory R. Shaw 📂 Article 📅 1990 🏛 John Wiley and Sons 🌐 English ⚖ 376 KB

Data are presented demonstrating the validity of a new method of measuring pseudo-order rate constants, based on an iterative computational procedure long in use for kinetic conditions where the "infinity" value is not experimentally accessible. This new method requires that the kinetic order be kno