Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions

Lauren D. Dellon, Chun Yi Sung, David J. Robichaud, Linda J. Broadbelt*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked group additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involving the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.

Original languageEnglish (US)
Pages (from-to)10259-10270
Number of pages12
JournalIndustrial and Engineering Chemistry Research
Volume56
Issue number37
DOIs
StatePublished - Sep 20 2017

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions'. Together they form a unique fingerprint.

Cite this