Absolute and relative-rate techniques have been used to obtain rate coefficients for the reactions: NO3+CH3C(O)CHCH2--> products (1), NO3+CH2C(CH3)CHO --> products (2), NO3+CH2CHCHO --> products (3), and NO3+CH2CHC(O)OCH3--> products (4). The reaction NO3+CH2C(CH3)C(O)OCH3--> products (5), has been investigated by a relative-rate method only. The rate coefficients obtained by the relative-rate method at T=296 +/- 2 K and P=760 Torr are k(1)=(4.7 +/- 1.7)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(3.7 +/- 1.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(1.1 +/- 0.4)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.0 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1) and k(5)=(3.6 +/- 1.3)x10(-15) cm(3) molecule(-1) s(-1). The rate coefficients determined by the discharge-flow technique at low pressure (P=1-10 Torr) and at T=293-303 K are k(1)=(3.2 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(9.6 +/- 2.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(8.9 +/- 2.8)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.9 +/- 0.4)x10(-16) cm(3) molecule(-1) s(-1). The discrepancy between the values obtained from the relative-rate technique and the absolute technique are discussed and explained in terms of interference in the absolute study caused by secondary chemistry and fast-reacting impurities. Product studies reveal that methyl glyoxal is a product of reactions (1) and (2) along with peroxymethacryloyl nitrate (MPAN) for reaction (2) in air. A diurnally varying boundary-layer model suggests that reaction (2) is an important loss process for methacrolein and that it can lead to the generation of OH at night.
%0 Journal Article
%1 CanosaMas:1999p4009
%A Canosa-Mas, CE
%A Carr, S
%A King, MD
%A Shallcross, DE
%A Thompson, KC
%A Wayne, RP
%D 1999
%J Physical Chemistry Chemical Physics
%K Alkanes, Atmosphere, Chemistry, Constants Forest, Isoprene Organic-Compounds, Oxidation-Products, Ozone Phase Production, Rate Reaction, Temperature-Dependence, Volatile
%N 18
%P 4195--4202
%T A kinetic study of the reactions of NO3 with methyl vinyl ketone, methacrolein, acrolein, methyl acrylate and methyl methacrylate
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%V 1
%X Absolute and relative-rate techniques have been used to obtain rate coefficients for the reactions: NO3+CH3C(O)CHCH2--> products (1), NO3+CH2C(CH3)CHO --> products (2), NO3+CH2CHCHO --> products (3), and NO3+CH2CHC(O)OCH3--> products (4). The reaction NO3+CH2C(CH3)C(O)OCH3--> products (5), has been investigated by a relative-rate method only. The rate coefficients obtained by the relative-rate method at T=296 +/- 2 K and P=760 Torr are k(1)=(4.7 +/- 1.7)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(3.7 +/- 1.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(1.1 +/- 0.4)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.0 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1) and k(5)=(3.6 +/- 1.3)x10(-15) cm(3) molecule(-1) s(-1). The rate coefficients determined by the discharge-flow technique at low pressure (P=1-10 Torr) and at T=293-303 K are k(1)=(3.2 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(9.6 +/- 2.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(8.9 +/- 2.8)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.9 +/- 0.4)x10(-16) cm(3) molecule(-1) s(-1). The discrepancy between the values obtained from the relative-rate technique and the absolute technique are discussed and explained in terms of interference in the absolute study caused by secondary chemistry and fast-reacting impurities. Product studies reveal that methyl glyoxal is a product of reactions (1) and (2) along with peroxymethacryloyl nitrate (MPAN) for reaction (2) in air. A diurnally varying boundary-layer model suggests that reaction (2) is an important loss process for methacrolein and that it can lead to the generation of OH at night.
@article{CanosaMas:1999p4009,
abstract = {Absolute and relative-rate techniques have been used to obtain rate coefficients for the reactions: NO3+CH3C(O)CHCH2--> products (1), NO3+CH2C(CH3)CHO --> products (2), NO3+CH2CHCHO --> products (3), and NO3+CH2CHC(O)OCH3--> products (4). The reaction NO3+CH2C(CH3)C(O)OCH3--> products (5), has been investigated by a relative-rate method only. The rate coefficients obtained by the relative-rate method at T=296 +/- 2 K and P=760 Torr are k(1)=(4.7 +/- 1.7)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(3.7 +/- 1.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(1.1 +/- 0.4)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.0 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1) and k(5)=(3.6 +/- 1.3)x10(-15) cm(3) molecule(-1) s(-1). The rate coefficients determined by the discharge-flow technique at low pressure (P=1-10 Torr) and at T=293-303 K are k(1)=(3.2 +/- 0.6)x10(-16) cm(3) molecule(-1) s(-1), k(2)=(9.6 +/- 2.0)x10(-15) cm(3) molecule(-1) s(-1), k(3)=(8.9 +/- 2.8)x10(-15) cm(3) molecule(-1) s(-1), k(4)=(1.9 +/- 0.4)x10(-16) cm(3) molecule(-1) s(-1). The discrepancy between the values obtained from the relative-rate technique and the absolute technique are discussed and explained in terms of interference in the absolute study caused by secondary chemistry and fast-reacting impurities. Product studies reveal that methyl glyoxal is a product of reactions (1) and (2) along with peroxymethacryloyl nitrate (MPAN) for reaction (2) in air. A diurnally varying boundary-layer model suggests that reaction (2) is an important loss process for methacrolein and that it can lead to the generation of OH at night.},
added-at = {2010-06-22T19:38:37.000+0200},
affiliation = {Phys {\&} Theoret Chem Dept, Oxford OX1 3QZ, England},
author = {Canosa-Mas, CE and Carr, S and King, MD and Shallcross, DE and Thompson, KC and Wayne, RP},
biburl = {https://www.bibsonomy.org/bibtex/2cc5f51ede786cbfcb3ee077a55c6dacf/gsmith},
date-added = {2010-05-21 12:25:00 -0400},
date-modified = {2010-05-21 12:26:51 -0400},
interhash = {a1509428af49e13451b3e20f4ae2fb74},
intrahash = {cc5f51ede786cbfcb3ee077a55c6dacf},
journal = {Physical Chemistry Chemical Physics},
keywords = {Alkanes, Atmosphere, Chemistry, Constants Forest, Isoprene Organic-Compounds, Oxidation-Products, Ozone Phase Production, Rate Reaction, Temperature-Dependence, Volatile},
language = {English},
local-url = {file://localhost/Users/geoffreysmith/Documents/Papers/Physical%20Chemistry%20Chemical%20Physics/1999/Physical%20Chemistry%20Chemical%20Physics,%201,%204195-4202%201999.pdf},
month = Jan,
number = 18,
pages = {4195--4202},
pmid = {000082601000009},
rating = {0},
timestamp = {2010-06-22T19:39:10.000+0200},
title = {A kinetic study of the reactions of NO3 with methyl vinyl ketone, methacrolein, acrolein, methyl acrylate and methyl methacrylate},
uri = {papers://E88B624E-D406-46FF-9D95-BB9C1AAE3FDC/Paper/p4009},
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volume = 1,
year = 1999
}