A comparative analysis of empirical equations describing pressure dependence of equilibrium and reaction rate constants-Reference-Cited by-同舟云学术

A comparative analysis of empirical equations describing pressure dependence of equilibrium and reaction rate constants

Published:2017-02 Issue:2 Volume:95 Page:149-161
ISSN:0008-4042
Container-title:Canadian Journal of Chemistry
language:en
Short-container-title:Can. J. Chem.

Author:

Spooner Jacob¹,Weinberg Noham¹²

Affiliation:

1. Department of Chemistry, Simon Fraser University, Burnaby, BC V5A 1S6, Canada.

2. Department of Chemistry, University of the Fraser Valley, Abbotsford, BC V2S 7M8, Canada.

Abstract

General properties of the empirical analytical functions used to describe the effect of pressure on rate and equilibrium constants in solution are reviewed, and the effects of experimental errors on the accuracy of activation and reaction volumes predicted by these equations are compared. When the error levels are low (1%–2%) and pressure ranges are small (0–1 kbar), all functions perform well, but when fitting data with high error or extending to higher pressures, special care must be taken to obtain reliable results. Analysis of the results from fitting the equations to simulated data, as well as experimental data for Diels–Alder, Menshutkin, and methanolysis reactions, allows us to propose a set of general recommendations when using these equations as a tool for obtaining accurate activation and reaction volumes.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

Link

http://www.nrcresearchpress.com/doi/pdf/10.1139/cjc-2016-0454

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