CHEM-5151_S05_L13

CHEM-5151_S05_L13 - Lecture 13 Gas Phase OrganicNOx UV...

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1 Required Reading: FP&P Chapter 6 (except as noted next) Additional Reading: S&P Chapter 5 Catching-Up Reading: Jacob Chapters 11 & 12 (free online) Atmospheric Chemistry CHEM-5151 / ATOC-5151 Spring 2005 Prof. Jose-Luis Jimenez Lecture 13: Gas Phase Organic- NO x + UV Reactions II All figures from F-P&P Outline of Lecture The big picture of atmospheric oxidation A. Oxidants B. Lifetimes of Organics C. Reactions of Alkanes D. of R, RO, and RO 2 Radicals E. of Alkenes & Biogenics F. of Alkynes G. of Aromatics H. of O-Containing Organics I. of N-Containing Organics J. Chemistry of Remote Regions K. Atm. Chem. & Biomass Burning Today Last Lecture
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2 Summary of Alkane Oxidation D . . . . . . . “Chemistry is all about electrons” • Species with unpaired electrons (radical) doing most of the work 1 st generation stable products VOC+oxidant chemistry Peroxy (RO 2 ) chemistry Alkoxy (RO) chemistry NO 3 , (RO 2 ) O 2 H O 2 , N ( R ) Parent (primary) species O 3 h ν OH NO 3 NO D e c o m p . I s CO 2 2 nd generation stable products VOC+oxidant chemistry Peroxy (RO 2 ) chemistry Alkoxy (RO) chemistry NO 3 , (RO 2 ) O 2 O 3 h ν OH NO 3 NO VOC+oxidant chemistry Peroxy (RO 2 ) chemistry Alkoxy (RO) chemistry NO 3 , (RO 2 ) O 3 h ν OH NO 3 NO Big Picture of Organic Oxidation Aumont , Laval, and Madronich, accepted in ACPD, 2004 D
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3 k = 1.1 × 10 -11 e -1440/T k(298 K) = 1.0 × 10 -13 cm 3 /#/s [Cl] max = 10 4 #/cm 3 τ CH4 =(k[Cl]) -1 = 32 years k = 2.45 × 10 -12 e -1775/T k(298 K) = 6.3 × 10 -15 cm 3 /#/s [OH] max = 10 6 #/cm 3 τ CH4 =(k[OH]) -1 = 5 years CH 4 CH 3 · + Cl· - HCl + OH -H 2 O + O 2 M CH 3 O 2 ·C H 3 + NO -NO 2 + O 2 -HO 2 CH 2 O hv HCO· + or H 2 + CO + O 2 M HO 2 + O 2 HO
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CHEM-5151_S05_L13 - Lecture 13 Gas Phase OrganicNOx UV...

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