Revised structure activity parameters derived from new rate coefficient determinations for the reactions of chlorine atoms with a series of seven ketones at 290 K and 1 atm

被引：14

作者：

Farrugia, L. N. ^{[1
]}

Bejan, I. ^{[1
,2
,3
]}

Smith, S. C. ^{[1
]}

Medeiros, D. J. ^{[1
]}

Seakins, P. W. ^{[1
,4
]}

机构：

[1] Univ Leeds, Sch Chem, Leeds LS2 9JT, W Yorkshire, England

[2] Alexandru Ioan Cuza Univ, Fac Chem, Iasi, Romania

[3] Alexandru Ioan Cuza Univ, Integrated Ctr Environm Sci Studies North East De, Iasi, Romania

[4] Univ Leeds, Natl Ctr Atmospher Sci, Leeds LS2 9JT, W Yorkshire, England

来源：

CHEMICAL PHYSICS LETTERS | 2015年 / 640卷

关键词：

GAS-PHASE REACTIONS; HIGHLY INSTRUMENTED REACTOR; ATMOSPHERIC CHEMISTRY; RATE CONSTANTS; CL-ATOMS; PHOTOCHEMICAL DATA; ORGANIC-COMPOUNDS; KINETICS; OH; PHOTOLYSIS;

D O I：

10.1016/j.cplett.2015.09.055

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Rate coefficients of Cl atom reactions with several ketones have been investigated at 298K and 1 atm using relative rate methods, monitoring substrates with both GC and FTIR and with two reference compounds. The following rate coefficients (1010 k/cm(3) molecule(-1) s(-1)) were obtained: k((2-pentanone)) (1.08 +/- 0.05), k((3-pentanone)) (0.89 +/- 0.12), k((3-methyl-2-butanone)) =(0.68 +/- 0.06), k((4-methyl-2-pentanone)) = (1.10 +/- 0.10), k((5-methyl-2-hexanone)) = (1.65 +/- 0.14), k((3-methyl-2-pentanone)) = (0.94 +/- 0.10) and k((3,3-chmethyl-2-butanone)) (0.48 +/- 0.05). The results are discussed in terms of Cl reactivity trends and existing literature. k((3-methyl-2-pentanone)) and k((3,3-chmethyl-2-butanone)) are poorly predicted with current structure activity relationships and revised parameters are proposed. In regions of high [Cl], these reactions can significantly reduce the fraction of ketones reaching the free troposphere. (C) 2015 Elsevier B.V. All rights reserved.

引用

页码：87 / 93

页数：7

共 47 条

[1] Gas-phase chemistry of atmospheric Cl atoms:: a PLP-RF kinetic study with a series of ketones [J].

Albaladejo, J ;

Notario, A ;

Cuevas, CA ;

Jiménez, E ;

Cabañas, B ;

Martínez, E .

ATMOSPHERIC ENVIRONMENT, 2003, 37 (04) :455-463

[2] Effects of using renewable fuels on vehicle emissions [J].

Anderson, Larry G. .

RENEWABLE & SUSTAINABLE ENERGY REVIEWS, 2015, 47 :162-172

[3] Kinetic study of the gas-phase reactions of Cl radicals with 3-pentanone and 3-hexanone [J].

Aranda, A ;

de Mera, YD ;

Rodríguez, A ;

Morales, L ;

Martínez, E .

JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (34) :7027-7031

[4] Photodissociation of acetone: Atmospheric implications of temperature-dependent quantum yields [J].

Arnold, SR ;

Chipperfield, MP ;

Blitz, MA ;

Heard, DE ;

Pilling, MJ .

GEOPHYSICAL RESEARCH LETTERS, 2004, 31 (07) :L071101-4

[5] 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

[6] Evaluated kinetic and photochemical data for atmospheric chemistry:: Volume I -: gas phase reactions of Ox, HOx, NOx and SOx species [J].

Atkinson, R ;

Baulch, DL ;

Cox, RA ;

Crowley, JN ;

Hampson, RF ;

Hynes, RG ;

Jenkin, ME ;

Rossi, MJ ;

Troe, J .

ATMOSPHERIC CHEMISTRY AND PHYSICS, 2004, 4 :1461-1738

[7] Atmospheric degradation of volatile organic compounds [J].

Atkinson, R ;

Arey, J .

CHEMICAL REVIEWS, 2003, 103 (12) :4605-4638

[8] Kinetic Investigation of the OH Radical and Cl Atom Initiated Degradation of Unsaturated Ketones at Atmospheric Pressure and 298 K [J].

Banco, Maria B. ;

Barnes, Ian ;

Wiesen, Peter .

JOURNAL OF PHYSICAL CHEMISTRY A, 2012, 116 (24) :6033-6040

[9]

Brauers T, 1997, INT J CHEM KINET, V29, P665, DOI 10.1002/(SICI)1097-4601(1997)29:9<665::AID-KIN3>3.0.CO

[10]

2-S

← 1 2 3 4 5 →