Deuterium kinetic isotopic study for hydrogenolysis of ethyl butyrate

Muthu Kumaran Gnanamani, Gary Jacobs, Robert A. Keogh, Burtron H. Davis

Research output: Contribution to journalArticlepeer-review

19 Scopus citations

Abstract

The hydrogenation of ethyl butyrate, n-butyric acid, and n-butyraldehyde to their corresponding alcohol(s) has been studied over a γ-Al 2O3-supported cobalt catalyst using a high-pressure fixed-bed reactor in the temperature range of 473-493 K. H2-D 2-H2 switching experiments show that ethyl butyrate and n-butyric acid follow an inverse kinetic isotope effect (KIE) (i.e. r H/rD = 0.50-0.54), whereas n-butyraldehyde did not display any KIE (i.e. rH/rD = 0.98). DRIFTS experiments were performed over the support and catalyst to monitor the surface species formed during the adsorption of ethyl butyrate and n-butyric acid at atmospheric pressure and the desired temperature. Butanoate and butanoyl species are the stable surface intermediates formed during hydrogenation of ethyl butyrate. Hydrogenation of butanoate to a partially hydrogenated intermediate is likely involved in the rate-determining step of ethyl butyrate and butyric acid hydrogenation.

Original languageEnglish
Pages (from-to)27-35
Number of pages9
JournalJournal of Catalysis
Volume277
Issue number1
DOIs
StatePublished - Jan 3 2011

Keywords

  • Deuterium isotope effect
  • DRIFTS
  • Ethyl butyrate
  • Hydrogenolysis
  • n-Butyraldehyde
  • n-Butyric acid

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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