An experimental study on the temperature dependence for the gas-phase reactions of NO3 radical with a series of aliphatic aldehydes

被引:24
作者
Cabañas, B [1 ]
Martín, P [1 ]
Salgado, S [1 ]
Ballesteros, B [1 ]
Martínez, E [1 ]
机构
[1] Univ Castilla La Mancha, Fac Quim, E-13071 Ciudad Real, Spain
关键词
D O I
10.1023/A:1010797424283
中图分类号
X [环境科学、安全科学];
学科分类号
08 ; 0830 ;
摘要
The absolute rate constants for the gas-phase reactions of the NO3 radical with a series of aldehydes such as acetaldehyde, propanal, butanal, pentanal, hexanal and, heptanal were measured over the temperature range 298-433 K, using a discharge flow system and monitoring the NO3 radical by Laser Induced Fluorescence (LIF). The measured rate constants at 298 K for the reaction of NO3, in units of 10(-14) cm(3) molecule(-1) s(-1), were as follows: acetaldehyde 0.32 +/- 0.04, propanal 0.60 +/- 0.06, butanal 1.46 +/- 0.16, pentanal 1.75 +/- 0.06, hexanal 1.83 +/- 0.36, and heptanal 2.37 +/- 0.42. The proposed Arrhenius expressions are k(1) = (6.2 +/- 7.5) x 10(-11) exp [-(2826 +/- 866)/T] (cm(3) molecule(-1) s(-1)), k(2) = (1.7 +/- 1.0) x 10(-11) exp [-(2250 +/- 192)/T] (cm(3) molecule(-1) s(1)), k(3) =(7.6 +/- 9.8) x 10(11) exp [-(2466 +/- 505)/T] (cm(3) molecule(-1) s(-1)), k(4) = (2.8 +/- 1.4) x 10(-11) exp [-(2189 +/- 156)/T] (cm(3) molecule(-1) s(-1)), k(5) = (7.0 +/- 1.8) x 10(-11) exp [-(2382 +/- 998)/T] (cm(3) molecule(-1) s(-1)), and k(6) = (7.8 +/- 1.0) x 10(-11) exp [-(2406 +/- 481)/T] (cm(3) molecule(-1) s(-1)). Tropospheric lifetimes for these aldehydes were calculated at night and during the day for typical NO3 and OH average concentrations and showed that both radicals provide an effective tropospheric sink for these compounds and that the night-time reaction with the NO3 radical can be an important, if not dominant, loss process for these emitted organics and for NO3 radicals.
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页码:23 / 39
页数:17
相关论文
共 49 条
[1]   KINETICS OF THE REACTIONS OF THE NITRATE RADICAL WITH A SERIES OF HALOGENOBUTENES - A STUDY OF THE EFFECT OF SUBSTITUENTS ON THE RATE OF ADDITION OF NO3 TO ALKENES [J].
AIRD, RWS ;
CANOSAMAS, CE ;
COOK, DJ ;
MARSTON, G ;
MONKS, PS ;
WAYNE, RP ;
LJUNGSTROM, E .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1992, 88 (08) :1093-1099
[2]   THE EMISSION OF (Z)-3-HEXEN-1-OL, (Z)-3-HEXENYLACETATE AND OTHER OXYGENATED HYDROCARBONS FROM AGRICULTURAL PLANT-SPECIES [J].
AREY, J ;
WINER, AM ;
ATKINSON, R ;
ASCHMANN, SM ;
LONG, WD ;
MORRISON, CL .
ATMOSPHERIC ENVIRONMENT PART A-GENERAL TOPICS, 1991, 25 (5-6) :1063-1075
[3]   KINETICS AND MECHANISMS OF THE GAS-PHASE REACTIONS OF THE NO3 RADICAL WITH ORGANIC-COMPOUNDS [J].
ATKINSON, R .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1991, 20 (03) :459-507
[4]   Evaluated kinetic, photochemical and heterogeneous data for atmospheric chemistry .5. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry [J].
Atkinson, R ;
Baulch, DL ;
Cox, RA ;
Hampson, RF ;
Kerr, JA ;
Rossi, MJ ;
Troe, J .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1997, 26 (03) :521-1011
[5]   RATE CONSTANTS FOR THE GAS-PHASE REACTIONS OF NITRATE RADICALS WITH A SERIES OF ORGANICS IN AIR AT 298 +/- 1-K [J].
ATKINSON, R ;
PLUM, CN ;
CARTER, WPL ;
WINER, AM ;
PITTS, JN .
JOURNAL OF PHYSICAL CHEMISTRY, 1984, 88 (06) :1210-1215
[6]  
ATKINSON R, 1989, J PHYS CHEM REF DATA, V1
[7]  
ATKINSON R, 1994, J PHYS CHEM REF DATA, V2
[8]   STUDY OF THE TEMPERATURE-DEPENDENCE OF THE REACTION OF THE NITRATE RADICAL WITH PROPENE [J].
CANOSAMAS, CE ;
SMITH, SJ ;
WAYGOOD, SJ ;
WAYNE, RP .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1991, 87 (21) :3473-3478
[9]   THE CH3CHO-NO3 REACTION AND POSSIBLE NIGHTTIME PAN GENERATION [J].
CANTRELL, CA ;
DAVIDSON, JA ;
BUSAROW, KL ;
CALVERT, JG .
JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES, 1986, 91 (D5) :5347-5353
[10]   KINETIC-STUDY OF THE NO3-CH2O REACTION AND ITS POSSIBLE ROLE IN NIGHTTIME TROPOSPHERIC CHEMISTRY [J].
CANTRELL, CA ;
STOCKWELL, WR ;
ANDERSON, LG ;
BUSAROW, KL ;
PERNER, D ;
SCHMELTEKOPF, A ;
CALVERT, JG ;
JOHNSTON, HS .
JOURNAL OF PHYSICAL CHEMISTRY, 1985, 89 (01) :139-146