Theoretical study of the reaction of hydrogen with nitric acid

Ab initio MO and TST/RRKM calculations

J. W. Boughton, S. Kristyán, M. C. Lin

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

The kinetics and mechanism of the H + HNO3 reaction have been elucidated with ab initio molecular orbital and statistical theory calculations. Our room temperature reaction rate results accord well with available experimental data. The reaction is dominated by an indirect metathetical process taking place via vibrationally excited dihydroxyl nitroxide, ON(OH)2, producing OH + cis-HONO. The excited ON(OH)2 also undergoes molecular elimination, yielding H2O + NO2 as a minor competing reaction. The direct H abstraction reaction forming H2 + NO3 was found to be the least important one. At atmospheric pressure, we recommend the following expressions for the three rate constants, in units of cm3/molecule s, from the 300-3000 K temperature range for H + HNO3 collision yielding the products H2 + NO3 by direct mechanism ka = (9.24 × 10-16)T1.53e-8253/T based on CTST calculations, OH + cis-HONO by indirect mechanism kb = (6.35 × 10-19)T2.30e-3511/T, and H2O + NO2 by indirect mechanism kc = (1.01 × 10-22)T3.29e-3163/T, the latter two are based on Arrhenius fits to the solution of the master equation which includes RRKM microscopic rate constants and tunneling corrections.

Original languageEnglish
Pages (from-to)219-227
Number of pages9
JournalChemical Physics
Volume214
Issue number2-3
Publication statusPublished - Jan 15 1997

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Nitric Acid
nitric acid
Hydrogen
Rate constants
Molecular orbitals
hydrogen
Atmospheric pressure
Reaction rates
Temperature
Molecules
Kinetics
elimination
atmospheric pressure
molecular orbitals
reaction kinetics
collisions
kinetics
room temperature
products
molecules

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Theoretical study of the reaction of hydrogen with nitric acid : Ab initio MO and TST/RRKM calculations. / Boughton, J. W.; Kristyán, S.; Lin, M. C.

In: Chemical Physics, Vol. 214, No. 2-3, 15.01.1997, p. 219-227.

Research output: Contribution to journalArticle

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