Heterogeneous Catalysis

Deuterium Exchange Reactions of Hydrogen and Methane

Anne Mirich, Trisha Hoette Miller, Elsbeth Klotz, Bruce M. Mattson

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H2 + D2, which proceeds at temperatures as low as 77 K yielding a mixture that includes HD. Products are analyzed by 1H NMR spectrometry. At low temperatures, this reaction requires a catalyst, but it proceeds without a catalyst at high temperature of a gentle flame. The second deuterium/hydrogen exchange reaction involves CH4 + D2 producing a series of isotopologues, methane-dx, x = 0-4, with product analysis by GC-MS and 1H NMR spectrometry. This reaction only takes place in the presence of a catalyst at elevated temperatures due to the large energy of activation of the sp3-carbon-to-hydrogen bond. Two outcomes have been observed in the literature regarding D/H exchange and methane. Some catalysts and temperature conditions yield a single-exchange result, methane-d1. Others yield multiple exchange results, such as we observe with our catalyst. The single exchange outcome is associated with lower temperatures. Two mechanisms, one by Kemball (1959) and one by Frennet (1974), have been put forth to explain single and multiple exchange outcomes. We discuss our results in the context of these mechanisms. Interested readers could develop a research experience for undergraduate chemistry students based on the open-ended experiments presented here.

Original languageEnglish
Pages (from-to)2087-2093
Number of pages7
JournalJournal of Chemical Education
Volume92
Issue number12
DOIs
StatePublished - Sep 30 2015

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Deuterium
Methane
Catalysis
Hydrogen
Ion exchange
Catalysts
Temperature
Spectrometry
Nuclear magnetic resonance
Aluminum Oxide
activation
Gas mixtures
chemistry
Hydrogen bonds
energy
Carbon
Gases
Chemical activation
Students
experiment

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Education

Cite this

Heterogeneous Catalysis : Deuterium Exchange Reactions of Hydrogen and Methane. / Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce M.

In: Journal of Chemical Education, Vol. 92, No. 12, 30.09.2015, p. 2087-2093.

Research output: Contribution to journalArticle

Mirich, Anne ; Miller, Trisha Hoette ; Klotz, Elsbeth ; Mattson, Bruce M. / Heterogeneous Catalysis : Deuterium Exchange Reactions of Hydrogen and Methane. In: Journal of Chemical Education. 2015 ; Vol. 92, No. 12. pp. 2087-2093.
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