Laser induced fluorescence studies of iodine oxide chemistry. Part II. The reactions of IO with CH3O2, CF3O2 and O3

• Published in: Physical chemistry chemical physics : PCCP Vol. 8; no. 44; p. 5185
• Main Authors: Dillon, Terry J, Tucceri, María E, Crowley, John N
• Format: Journal Article
• Language: English
• Published: England 28-11-2006
• Subjects: Computer Simulation; Iodine Compounds - chemistry; Iodine Compounds - radiation effects; Kinetics; Lasers; Models, Chemical; Models, Molecular; Oxides - chemistry; Oxides - radiation effects; Oxygen - chemistry; Oxygen - radiation effects; Spectrometry, Fluorescence - methods
• ISSN: 1463-9076
• DOI: 10.1039/b611116e

The technique of pulsed laser photolysis was coupled to laser induced fluorescence detection of iodine oxide (IO) to measure rate coefficients, k for the reactions IO + CH(3)O(2)--> products (R1, 30-318 Torr N(2)), IO + CF(3)O(2)--> products (R2, 70-80 Torr N(2)), and IO + O(3)--> OIO + O(2) (R3a). Values of k(1) = (2 +/- 1) x 10(-12) cm(3) molecule(-1) s(-1), k(2) = (3.6 +/- 0.8) x 10(-11) cm(3) molecule(-1) s(-1), and k(3a) <5 x 10(-16) cm(3) molecule(-1) s(-1) were obtained at T = 298 K. In the course of this work, the product yield of IO from the reaction of CH(3)O(2) with I was determined to be close to zero, whereas CH(3)OOI was formed efficiently at 70 Torr N(2). Similarly, no evidence was found for IO formation in the CF(3)O(2) + I reaction. An estimate of the rate coefficients k(CH(3)O(2) + I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) and k(CH(3)OOI + I) = 1.5 x 10(-10) cm(3) molecule(-1) s(-1) was also obtained. The results on k(1)-k(3) are compared to the limited number of previous investigations and the implications for the chemistry of the marine boundary layer are briefly discussed.