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Titolo:
Fluorescence excitation spectrum of the 2-butoxyl radical and kinetics of its reactions with NO and NO2
Autore:
Lotz, C; Zellner, R;
Indirizzi:
Univ Essen Gesamthsch, Inst Phys & Theoret Chem, D-45117 Essen, Germany Univ Essen Gesamthsch Essen Germany D-45117 Chem, D-45117 Essen, Germany
Titolo Testata:
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
fascicolo: 13, volume: 3, anno: 2001,
pagine: 2607 - 2613
SICI:
1463-9076(2001)3:13<2607:FESOT2>2.0.ZU;2-V
Fonte:
ISI
Lingua:
ENG
Soggetto:
THERMAL UNIMOLECULAR DECOMPOSITION; PULSE INITIATED OXIDATION; I-PROPOXY RADICALS; RATE CONSTANTS; ALKOXY RADICALS; TERT-BUTOXY; LASER PHOTOLYSIS; ETHOXY RADICALS; SUPERSONIC JET; TOTAL PRESSURE;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
52
Recensione:
Indirizzi per estratti:
Indirizzo: Lotz, C Univ Essen Gesamthsch, Inst Phys & Theoret Chem, D-45117 Essen, Germany Univ Essen Gesamthsch Essen Germany D-45117 45117 Essen, Germany
Citazione:
C. Lotz e R. Zellner, "Fluorescence excitation spectrum of the 2-butoxyl radical and kinetics of its reactions with NO and NO2", PHYS CHEM P, 3(13), 2001, pp. 2607-2613

Abstract

The ((A) over tilde <-- <(X)over tilde>) fluorescence excitation spectrum of the 2-C4H9O((X) over tilde) (2-butoxyl) radical in the wavelength range 345-390 nm was obtained using a combined laser photolysis/laser-induced fluorescence (LIF) technique following the generation of the radicals by excimer laser photolysis of 2-butylnitrite at lambda =351 nm. The fluorescence excitation spectrum shows 5 vibronic bands, where the dominant progression corresponds to the CO-stretching vibration in the first electronically excited state with (v) over tilde ('CO)=(560 +/- 10) cm(-1). The transition origin was assigned at (v) over tilde (00)=(26768 +/- 10) cm(-1) (lambda (00)=(373.58 +/-0.15) nm). The kinetics of the reactions of the 2-butoxyl radicalwith NO and NO2 at temperatures between T=223-305 K and pressures between p=6.5-104 mbar have been determined. The rate coefficients for both reactions were found to be independent of total pressure with k(NO)=(3.9 +/-0.3)x10(-11) cm(3) s(-1) and k(NO2)=(3.6 +/-0.3)x10(-11) cm(3) s(-1) at T=295 K. The Arrhenius expressions have been determined to be k(NO)=(9.1 +/-2.7)x10(-12) exp((3.4 +/-0.6) kJ mol(-1)/RT) cm(3) s(-1) and k(NO2)=(8.6 +/-3.3)x10(-12) exp((3.3 +/-0.8) kJ mol(-1)/RT) cm(3) s(-1). In addition, the radiative lifetime of the 2-C4H9O((A) over tilde) radical after excitation at lambda =365.938 nm in the (0,1) band has been determined to be tau (rad)(2-C4H9O((A) over tilde))=(440 +/- 80) ns. Quenching rate constants of the 2-C4H9O((A) over tilde) radical were measured to be k(q)=(4.7 +/-0.3)x10(-10) cm(3) s(-1) and k(q)=(5.0 +/-0.4)x10(-12) cm(3) s(-1) for 2-butylnitrite and nitrogen, respectively.

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Documento generato il 06/04/20 alle ore 08:47:36