OH-Initiated Photooxidations of 1-Pentene and 2-Methyl-2-propen-1-ol: Mechanism and Yields of the Primary Carbonyl Products

被引：3
作者：
Peirone, Silvina A. [1 ,2 ]
Cometto, Pablo M. [1 ,2 ]
Lane, Silvia I. [1 ,2 ]
机构：
[1] Univ Nacl Cordoba, Inst Invest Fisicoquim Cordoba INFIQC, CONICET, RA-5000 Cordoba, Argentina
[2] Univ Nacl Cordoba, Ctr Laser Ciencias Mol, Dept Fisicoquim, Fac Ciencias Quim, RA-5000 Cordoba, Argentina
来源：
CHEMPHYSCHEM | 2014年 / 15卷 / 17期
关键词：
1-pentene; photooxidation; product yields; radicals; solid-phase micro extraction; GAS-PHASE REACTIONS; UNSATURATED ALCOHOLS; RATE CONSTANTS; ATMOSPHERIC CHEMISTRY; RATE COEFFICIENTS; METHYL NITRITE; RADICALS; 2-METHYL-3-BUTEN-2-OL; NITRATE; SERIES;
D O I：
10.1002/cphc.201402159
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：
The products of the gas-phase reactions of OH radicals with 1-pentene and 2-methyl-2-propen-1-ol (221MPO) at T=298 +/- 2 K and atmospheric pressure were investigated by using a 4500 L atmospheric simulation chamber that was built especially for this work. The molar yield of butyraldehyde was 0.74 +/- 0.12 mol for the reaction of 1-pentene. This work provides the first product molar yield determination of formaldehyde (0.82 +/- 0.12 mol), 1-hydroxypropan-2-one (0.84 +/- 0.13 mol), and methacrolein (0.078 +/- 0.012 mol) from the reaction of 221MPO with OH radicals. The mechanism of this reaction is discussed in relation to the experimental results. Additionally, taking into consideration the complex mechanism, the rate coefficients of the reactions of OH with formaldehyde, 1-hydroxypropan-2-one, and methacrolein were derived at atmospheric pressure and T=298 +/- 2 K.; the obtained values were (8.9 +/- 1.6)x10(-12), (2.4 +/- 1.4)x10(-12), and (22.9 +/- 2.3)x10(-12) cm(3) molecule(-1) s(-1), respectively.
引用
收藏
页码：3848 / 3854
页数：7
相关论文
共 31 条
  • [1] Products and mechanisms of the gas-phase reactions of OH radicals and O3 with 2-methyl-3-buten-2-ol
    Alvarado, A
    Tuazon, EC
    Aschmann, SM
    Arey, J
    Atkinson, R
    [J]. ATMOSPHERIC ENVIRONMENT, 1999, 33 (18) : 2893 - 2905
  • [2] Alvarez E. G., 2007, TALANTA, V72, P1757
  • [3] Products of the gas-phase reactions of cis-3-hexen-1-ol with OH radicals and O-3
    Aschmann, SM
    Shu, YH
    Arey, J
    Atkinson, R
    [J]. ATMOSPHERIC ENVIRONMENT, 1997, 31 (21) : 3551 - 3560
  • [4] Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II - gas phase reactions of organic species
    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.
    [J]. ATMOSPHERIC CHEMISTRY AND PHYSICS, 2006, 6 : 3625 - 4055
  • [5] ALKYL NITRATE FORMATION FROM THE NOX-AIR PHOTOOXIDATIONS OF C2-C8 N-ALKANES
    ATKINSON, R
    ASCHMANN, SM
    CARTER, WPL
    WINER, AM
    PITTS, JN
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1982, 86 (23) : 4563 - 4569
  • [6] PRODUCTS OF THE GAS-PHASE REACTIONS OF A SERIES OF 1-ALKENES AND 1-METHYLCYCLOHEXENE WITH THE OH RADICAL IN THE PRESENCE OF NO
    ATKINSON, R
    TUAZON, EC
    ASCHMANN, SM
    [J]. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 1995, 29 (06) : 1674 - 1680
  • [7] AN EXPERIMENTAL PROTOCOL FOR THE DETERMINATION OF OH RADICAL RATE CONSTANTS WITH ORGANICS USING METHYL NITRITE PHOTOLYSIS AS AN OH RADICAL SOURCE
    ATKINSON, R
    CARTER, WPL
    WINER, AM
    PITTS, JN
    [J]. JOURNAL OF THE AIR POLLUTION CONTROL ASSOCIATION, 1981, 31 (10): : 1090 - 1092
  • [8] Formation and reaction of hydroxycarbonyls from the reaction of OH radicals with 1,3-butadiene and isoprene
    Baker, J
    Arey, J
    Atkinson, R
    [J]. ENVIRONMENTAL SCIENCE & TECHNOLOGY, 2005, 39 (11) : 4091 - 4099
  • [9] Rate constants for the gas-phase reactions of OH radicals with a series of hydroxyaldehydes at 296 ± 2 K
    Baker, J
    Arey, J
    Atkinson, R
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2004, 108 (34) : 7032 - 7037
  • [10] Calvert J.G., 2011, MECH ATMOSPHERIC OXI
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