We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
A comparative analysis of empirical equations describing pressure dependence of equilibrium and reaction rate constants.
- Authors
Spooner, Jacob; Weinberg, Noham
- 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.
- Subjects
CHEMICAL kinetics; HIGH pressure chemistry; EQUILIBRIUM constant (Chemistry); ACTIVATION (Chemistry); ERROR analysis in mathematics
- Publication
Canadian Journal of Chemistry, 2017, Vol 95, Issue 2, p149
- ISSN
0008-4042
- Publication type
Article
- DOI
10.1139/cjc-2016-0454