Group additivity determination for enthalpies of formation of carbenium ions

Kathryn R. Bjorkman, Chun Yi Sung, Eric Mondor, Janine C. Cheng, Deng Yang Jan, Linda J. Broadbelt*

*Corresponding author for this work

Research output: Contribution to journalArticle

6 Scopus citations

Abstract

Modeling of acid-catalyzed hydrocarbon conversion processes at the mechanistic level requires rate coefficients for a large number of reactions. The computational demand of finding activation energy barriers for each reaction is substantially reduced by employing structure-reactivity correlations such as the Evans-Polanyi relationship that correlates activation energy with the enthalpy of reaction. However, there are many species for which the enthalpies of formation are unknown. Therefore, group additivity methods to specify enthalpies of formation for each species involved in the reaction network are valuable. Quantum mechanical (QM) calculations and isodesmic reactions were used to calculate enthalpies of formation for a number of acyclic and cyclic carbenium ions, including allylic carbenium ions. These values compare favorably with experimental values, establishing Gaussian-4 as an accurate QM method for these calculations. Using these values, Benson-type group additivity values for enthalpies of formation were then derived through multiple linear regression. Enthalpies of formation values calculated from the group additivity scheme capture experimental and QM enthalpies of formation well and enhance the range of species that can be described by the group additivity approach.

Original languageEnglish (US)
Pages (from-to)19446-19452
Number of pages7
JournalIndustrial and Engineering Chemistry Research
Volume53
Issue number50
DOIs
StatePublished - Dec 17 2014

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

Fingerprint Dive into the research topics of 'Group additivity determination for enthalpies of formation of carbenium ions'. Together they form a unique fingerprint.

  • Cite this