Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions

David W. Rothgeb, Ekram Hossain, Angela T. Kuo, Jennifer L. Troyer, Caroline Chick Jarrold, Nicholas J. Mayhall, Krishnan Raghavachari

Research output: Contribution to journalArticle

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Abstract

Addition of H2 O and D2 O to small tungsten suboxide cluster anions Wx Oy - (x=1-4; y3x) was studied using mass spectrometric measurements from a high-pressure fast flow reactor. Within the WO y- mass manifold, which also includes WO4 H-, product masses correspond to the addition of one to three H2 O or D2 O molecules. Within the W2 Oy - cluster series, product distributions suggest that sequential oxidation W2 O y - + H2 O/ D2 O→ W2 O y+1 - + H2 / D2 occurs for y<5, while for W 2 O5-, W2 O6 H2- / W 2 O6 D2- is primarily produced. W2 O6- does not appear reactive. For the W3 O y - cluster series, sequential oxidation with H2 and D2 production occurs for y<6, while W3 O 6- and W3 O7- produce W3 O 7 H2- / W3 O7 D2- and W3 O8 H2- / W3 O8 D 2-, respectively. Lower mass resolution in the W4 O y - mass range prevents definitive product assignments, but intensity patterns suggest that sequential oxidation with H2 / D2 evolution occurs for y<6, while W4 Oy+1 H2- / W4 Oy+1 D2- products result from addition to W4 O6- and W4 O7-. Based on bond energy arguments, the H2 / D2 loss reaction is energetically favored if the new O- Wx Oy - bond energy is greater than 5.1 eV. The relative magnitude of the rate constants for sequential oxidation and H2 O/ D2 O addition for the x=2 series was determined. There are no discernable differences in rate constants for reactions with H2 O or D2 O, suggesting that the H2 and D2 loss from the lower-oxide/hydroxide intermediates is very fast relative to the addition of H2 O or D 2 O.

Original languageEnglish (US)
Article number124314
JournalJournal of Chemical Physics
Volume130
Issue number12
DOIs
StatePublished - 2009
Externally publishedYes

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Gases
vapor phases
Oxidation
products
oxidation
Rate constants
Tungsten
Oxides
Anions
hydroxides
tungsten
Molecules
reactors
anions
oxides
energy
molecules

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Rothgeb, D. W., Hossain, E., Kuo, A. T., Troyer, J. L., Jarrold, C. C., Mayhall, N. J., & Raghavachari, K. (2009). Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions. Journal of Chemical Physics, 130(12), [124314]. https://doi.org/10.1063/1.3096414

Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions. / Rothgeb, David W.; Hossain, Ekram; Kuo, Angela T.; Troyer, Jennifer L.; Jarrold, Caroline Chick; Mayhall, Nicholas J.; Raghavachari, Krishnan.

In: Journal of Chemical Physics, Vol. 130, No. 12, 124314, 2009.

Research output: Contribution to journalArticle

Rothgeb, DW, Hossain, E, Kuo, AT, Troyer, JL, Jarrold, CC, Mayhall, NJ & Raghavachari, K 2009, 'Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions', Journal of Chemical Physics, vol. 130, no. 12, 124314. https://doi.org/10.1063/1.3096414
Rothgeb DW, Hossain E, Kuo AT, Troyer JL, Jarrold CC, Mayhall NJ et al. Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions. Journal of Chemical Physics. 2009;130(12). 124314. https://doi.org/10.1063/1.3096414
Rothgeb, David W. ; Hossain, Ekram ; Kuo, Angela T. ; Troyer, Jennifer L. ; Jarrold, Caroline Chick ; Mayhall, Nicholas J. ; Raghavachari, Krishnan. / Unusual products observed in gas-phase Wx Oy - + H2 O and D2 O reactions. In: Journal of Chemical Physics. 2009 ; Vol. 130, No. 12.
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abstract = "Addition of H2 O and D2 O to small tungsten suboxide cluster anions Wx Oy - (x=1-4; y3x) was studied using mass spectrometric measurements from a high-pressure fast flow reactor. Within the WO y- mass manifold, which also includes WO4 H-, product masses correspond to the addition of one to three H2 O or D2 O molecules. Within the W2 Oy - cluster series, product distributions suggest that sequential oxidation W2 O y - + H2 O/ D2 O→ W2 O y+1 - + H2 / D2 occurs for y<5, while for W 2 O5-, W2 O6 H2- / W 2 O6 D2- is primarily produced. W2 O6- does not appear reactive. For the W3 O y - cluster series, sequential oxidation with H2 and D2 production occurs for y<6, while W3 O 6- and W3 O7- produce W3 O 7 H2- / W3 O7 D2- and W3 O8 H2- / W3 O8 D 2-, respectively. Lower mass resolution in the W4 O y - mass range prevents definitive product assignments, but intensity patterns suggest that sequential oxidation with H2 / D2 evolution occurs for y<6, while W4 Oy+1 H2- / W4 Oy+1 D2- products result from addition to W4 O6- and W4 O7-. Based on bond energy arguments, the H2 / D2 loss reaction is energetically favored if the new O- Wx Oy - bond energy is greater than 5.1 eV. The relative magnitude of the rate constants for sequential oxidation and H2 O/ D2 O addition for the x=2 series was determined. There are no discernable differences in rate constants for reactions with H2 O or D2 O, suggesting that the H2 and D2 loss from the lower-oxide/hydroxide intermediates is very fast relative to the addition of H2 O or D 2 O.",
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