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Titolo:
PRESSURE AND TEMPERATURE-DEPENDENCE OF THE RATE CONSTANTS FOR THE ASSOCIATION REACTION OF OH RADICALS WITH NO BETWEEN 301-K AND 23-K
Autore:
SHARKEY P; SIMS IR; SMITH IWM; BOCHEREL P; ROWE BR;
Indirizzi:
UNIV BIRMINGHAM,DEPT CHEM,POB 363 BIRMINGHAM B15 2TT W MIDLANDS ENGLAND UNIV RENNES 1,DEPT PHYS ATOM & MOLEC,CNRS,UA 1203 F-35042 RENNES FRANCE
Titolo Testata:
Journal of the Chemical Society. Faraday transactions
fascicolo: 24, volume: 90, anno: 1994,
pagine: 3609 - 3616
SICI:
0956-5000(1994)90:24<3609:PATOTR>2.0.ZU;2-P
Fonte:
ISI
Lingua:
ENG
Soggetto:
KINETIC DATA EVALUATION; CODATA TASK GROUP; ATMOSPHERIC CHEMISTRY; PHOTOCHEMICAL DATA; RADIATIVE ASSOCIATION; IUPAC SUBCOMMITTEE; CHEMICAL-KINETICS; + O2; CN; RECOMBINATION;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Science Citation Index Expanded
Citazioni:
39
Recensione:
Indirizzi per estratti:
Citazione:
P. Sharkey et al., "PRESSURE AND TEMPERATURE-DEPENDENCE OF THE RATE CONSTANTS FOR THE ASSOCIATION REACTION OF OH RADICALS WITH NO BETWEEN 301-K AND 23-K", Journal of the Chemical Society. Faraday transactions, 90(24), 1994, pp. 3609-3616

Abstract

The pulsed laser photolysis (PLP), time-resolved laser-induced fluorescence (LIF) technique has been used to study the association reactionOH + NO(+M) --> HONO(+M) at low and ultra-low temperatures. Using a cryogenically cooled cell, rate constants have been determined at temperatures down to 80 K and with M = N-2 over a range of total gas densities. The PLP-LIF method has also been implemented in the ultra-cold environment provided by the gas flow in a CRESU (Cinetique de Reaction en Ecoulement Supersonique Uniforme) apparatus yielding rate constants at temperatures as low as 23 K. At 52 K, rate constants have been measured at total gas densities from 5.1 x 10(16) to 8.2 x 10(17) moleculecm(-3). The results reported here are the first for any neutral-neutral radical recombination at such low temperatures. The pressure and temperature dependence of the rate constants observed in the cryogenically cooled cell are fitted to obtain rate constants in the limits of low and high pressure given by the expressions: k degrees(T)[N-2] = 8.9 x 10(-31)(T/298)(-2.1)[N-2] cm(3) molecule(-1) s(-1) k infinity(T) approximate to 5.4 x 10(-11)(T/298)(-0.1) cm(3) molecule(-1) s(-1) The rate constants determined at ultra-low temperatures in the CRESU apparatus are used to derive values of limiting low-pressure rate constants for the combinations of temperature and third-body gas (Ar, N-2 and He)employed in these experiments. The rate constants for M = Ar at temperatures between 295 and 23 K are fitted well by the following expression for the limiting low-pressure rate constant: k degrees(T)[Ar] = 4.5x 10(-31)(T/298)(-2.6)[Ar] cm(3) molecule(-1) s(-1) The limiting low-pressure rate constants deduced from the experiments are compared withvalues calculated using the methodology of Tree (J. Chem. Phys., 1977, 66, 4758). The results are in fair agreement.

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Documento generato il 30/11/20 alle ore 18:36:26