Photo-Tautomerization of Acetaldehyde to Vinyl Alcohol: A Potential Route to Tropospheric Acids

被引：88

作者：

Andrews, Duncan U. ^{[1
]}

Heazlewood, Brianna R. ^{[1
]}

Maccarone, Alan T. ^{[1
]}

Conroy, Trent ^{[1
]}

Payne, Richard J. ^{[1
]}

Jordan, Meredith J. T. ^{[1
]}

Kable, Scott H. ^{[1
]}

机构：

[1] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia

来源：

SCIENCE | 2012年 / 337卷 / 6099期

基金：

澳大利亚研究理事会;

关键词：

GAS-PHASE; DEPENDENCE; ALDEHYDES; ENERGY; AIR;

D O I：

10.1126/science.1220712

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Current atmospheric models underestimate the production of organic acids in the troposphere. We report a detailed kinetic model of the photochemistry of acetaldehyde (ethanal) under tropospheric conditions. The rate constants are benchmarked to collision-free experiments, where extensive photo-isomerization is observed upon irradiation with actinic ultraviolet radiation (310 to 330 nanometers). The model quantitatively reproduces the experiments and shows unequivocally that keto-enol photo-tautomerization, forming vinyl alcohol (ethenol), is the crucial first step. When collisions at atmospheric pressure are included, the model quantitatively reproduces previously reported quantum yields for photodissociation at all pressures and wavelengths. The model also predicts that 21 +/- 4% of the initially excited acetaldehyde forms stable vinyl alcohol, a known precursor to organic acid formation, which may help to account for the production of organic acids in the troposphere.

引用

页码：1203 / 1206

页数：4

共 21 条

[1] Atmospheric transformation of enols: A potential secondary source of carboxylic acids in the urban troposphere [J].

Archibald, Alex T. ;

McGillen, Max R. ;

Taatjes, Craig A. ;

Percival, Carl J. ;

Shallcross, Dudley E. .

GEOPHYSICAL RESEARCH LETTERS, 2007, 34 (21)

[2] Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II - gas phase reactions of organic species [J].

Atkinson, R. ;

Baulch, D. L. ;

Cox, R. A. ;

Crowley, J. N. ;

Hampson, R. F. ;

Hynes, R. G. ;

Jenkin, M. E. ;

Rossi, M. J. ;

Troe, J. .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2006, 6 :3625-4055

[3] Energy Transfer in Master Equation Simulations: A New Approach [J].

Barker, John R. .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2009, 41 (12) :748-763

[4]

Barker John R, 2012, MULTIWELL 2012 1 SOF

[5] Multiple-well, multiple-path unimolecular reaction systems. I. MultiWell computer program suite [J].

Barker, JR .

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 2001, 33 (04) :232-245

[6] Carboxylic Acid Catalyzed Keto-Enol Tautomerizations in the Gas Phase [J].

da Silva, Gabriel .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (41) :7523-7525

[7]

Finlayson-Pitts B.J., 2000, Chemistry of the Upper and Lower Atmosphere: Theory, Experiments, and Applications, Vfirst

[8] Known and unexplored organic constituents in the earth's atmosphere [J].

Goldstein, Allen H. ;

Galbally, Ian E. .

ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2007, 41 (05) :1514-1521

[9] RADIATIVE AND NONRADIATIVE-TRANSITIONS IN 1ST EXCITED SINGLET-STATE OF SIMPLE LINEAR ALDEHYDES [J].

HANSEN, DA ;

LEE, EKC .

JOURNAL OF CHEMICAL PHYSICS, 1975, 63 (08) :3272-3277

[10] Roaming Radical Kinetics in the Decomposition of Acetaldehyde [J].

Harding, Lawrence B. ;

Georgievskii, Yuri ;

Klippenstein, Stephen J. .

JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (02) :765-777

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