Near-UV absorption cross sections and trans/cis equilibrium of nitrous acid

The A {sup 1}A{double prime} {l arrow} X {sup 1}A{prime} absorption spectrum of gaseous nitrous acid has been measured in the 300-400-nm range. Absolute cross sections were determined by a combination of gas-phase and wet chemical analysis. The cross sections of prominent bands are 25% larger than t...

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Bibliographic Details
Published in:Journal of physical chemistry (1952) 1991-02, Vol.95 (3), p.1076-1082
Main Authors: Bongartz, A, Kames, J, Welter, F, Schurath, U
Format: Article
Language:English
Subjects:
400102 - Chemical & Spectral Procedures
540120 - Environment, Atmospheric- Chemicals Monitoring & Transport- (1990-)
ABSORPTION SPECTRA
ATMOSPHERIC CHEMISTRY
Atomic and molecular physics
CHEMISTRY
CROSS SECTIONS
DATA
DIFFERENTIAL CROSS SECTIONS
ENVIRONMENTAL SCIENCES
Exact sciences and technology
EXPERIMENTAL DATA
GAS ANALYSIS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
Molecular properties and interactions with photons
NITROUS ACID
NUMERICAL DATA
Physics
SPECTRA
SPECTRAL RESPONSE
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Summary:The A {sup 1}A{double prime} {l arrow} X {sup 1}A{prime} absorption spectrum of gaseous nitrous acid has been measured in the 300-400-nm range. Absolute cross sections were determined by a combination of gas-phase and wet chemical analysis. The cross sections of prominent bands are 25% larger than the recommended values of Stockwell and Calvert. The influence of spectral resolution on absolute and differential absorption cross sections was also investigated. The integrated band area of the n{pi}* transition yields an oscillator strength f = (8.90 {plus minus} 0.36) {times} 10{sup {minus}4}, less than the reported liquid phase value of 2 {times} 10{sup {minus}3}. The equilibrium constant K = p{sub trans}/p{sub cis}, based on the assumption that the oscillator strength of the n{pi}* transition is the same for both rotamers, was found to be 3.25 {plus minus} 0.30 at 277 K. This yields an energy difference {Delta}E between trans- and cis-HONO of -2,700 J mol{sup {minus}1} in the electronic ground state, and -6,000 J mol{sup {minus}1} in the excited state.
ISSN:0022-3654
1541-5740
DOI:10.1021/j100156a012