Bimolecular Decomposition Pathways for Carboxylic Acids of Relevance to Biofuels

Jared Clark, David Robichaud, Mark Nimlos

Research output: Contribution to journalArticlepeer-review

17 Scopus Citations


The bimolecular thermal reactions of carboxylic acids were studied using quantum mechanical molecular modeling. Previous work1 investigated the unimolecular decomposition of a variety of organic acids, including saturated, α,β-unsaturated, and β,γ-unsaturated acids, and showed that the type and position of the unsaturation resulted in unique branching ratios between dehydration and decarboxylation, [H2O]/[CO2]. In this work, the effect of bimolecular chemistry (water-acid and acid-acid) is considered with a representative of each acid class. In both cases, the strained 4-centered, unimolecular transition state, typical of most organic acids, is opened up to 6- or 8-centered bimolecular geometries. These larger structures lead to a reduction in the barrier heights (20-45%) of the thermal decomposition pathways for organic acids and an increase in the decomposition kinetics. In some cases, they even cause a shift in the branching ratio of the corresponding product slates.

Original languageAmerican English
Pages (from-to)501-516
Number of pages16
JournalJournal of Physical Chemistry A
Issue number3
StatePublished - 2015

Bibliographical note

Publisher Copyright:
© 2014 American Chemical Society.

NREL Publication Number

  • NREL/JA-5100-63292


  • biofuels production
  • carboxylic acid
  • kinetic modeling
  • molecular modeling
  • thermal decomposition


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