scholarly journals Arrhenius parameters for the OH-initiated degradation of methyl crotonate, methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate over the temperature range of 288–314 K

RSC Advances ◽  
2016 ◽  
Vol 6 (59) ◽  
pp. 53723-53729 ◽  
Author(s):  
Juan P. Colomer ◽  
María B. Blanco ◽  
Alicia B. Peñéñory ◽  
Ian Barnes ◽  
Peter Wiesen ◽  
...  
Keyword(s):  
Relative Rate ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Arrhenius Parameters ◽  
Temperature Range

The relative-rate technique has been employed to obtain rate coefficients for the reactions of OH radicals with methyl crotonate, methyl-3,3-dimethyl acrylate, (E)-ethyl tiglate and methyl-3-butenoate between 288 and 314 K in 760 Torr of air.

scholarly journals Atmospheric Chemistry, Sources, and Sinks of Carbon Suboxide, C<sub>3</sub>O<sub>2</sub>

2017 ◽  
Author(s):  
Stephan Keßel ◽  
David Cabrera-Perez ◽  
Abraham Horowitz ◽  
Patrick R. Veres ◽  
Rolf Sander ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Relative Rate ◽  
Ambient Air ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Carbon Suboxide ◽  
Air Samples ◽  
Sources And Sinks

Abstract. Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere is largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C3O2. Rate coefficients for the reactions of C3O2 with OH radicals and ozone were determined using relative rate techniques as k4 = (2.6 ± 0.5) × 10−12 cm3 molecule−1 s1 at 295 K (independent of pressure between ~ 25 and 1000 mbar) and k6 

scholarly journals Direct and relative rate coefficients for the gas-phase reaction of OH radicals with 2-methyltetrahydrofuran at room temperature

2016 ◽  
Vol 119 (1) ◽  
pp. 5-18
Author(s):  
Ádám Illés ◽  
Mária Farkas ◽  
Gábor László Zügner ◽  
Gyula Novodárszki ◽  
Magdolna Mihályi ◽  
...  
Keyword(s):  
Gas Phase ◽  
Room Temperature ◽  
Relative Rate ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Relative Rate Coefficients

scholarly journals Rate coefficients for the reaction of methylglyoxal (CH<sub>3</sub>COCHO) with OH and NO<sub>3</sub> and glyoxal (HCO)<sub>2</sub> with NO<sub>3</sub>

2011 ◽  
Vol 11 (21) ◽  
pp. 10837-10851 ◽  
Author(s):  
R. K. Talukdar ◽  
L. Zhu ◽  
K. J. Feierabend ◽  
J. B. Burkholder
Keyword(s):  
Relative Rate ◽  
Order Conditions ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Phase Reaction ◽  
First Order ◽  
No3 Radical ◽  
Pseudo First Order ◽  
Arrhenius Expression ◽  
Coefficient Method

Abstract. Rate coefficients, k, for the gas-phase reaction of CH3COCHO (methylglyoxal) with the OH and NO3 radicals and (CHO)2 (glyoxal) with the NO3 radical are reported. Rate coefficients for the OH + CH3COCHO (k1) reaction were measured under pseudo-first-order conditions in OH as a function of temperature (211–373 K) and pressure (100–220 Torr, He and N2 bath gases) using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to measure its temporal profile. k1 was found to be independent of the bath gas pressure with k1(295 K) = (1.29 ± 0.13) × 10−11 cm3 molecule−1 s−1 and a temperature dependence that is well represented by the Arrhenius expression k1(T) = (1.74 ± 0.20) × 10−12 exp[(590 ± 40)/T] cm3 molecule−1 s−1 where the uncertainties are 2σ and include estimated systematic errors. Rate coefficients for the NO3 + (CHO)2 (k3) and NO3 + CH3COCHO (k4) reactions were measured using a relative rate technique to be k3(296 K) = (4.0 ± 1.0) × 10−16 cm3 molecule−1 s−1 and k4(296 K) = (5.1 ± 2.1) × 10−16 cm3 molecule−1 s−1. k3(T) was also measured using an absolute rate coefficient method under pseudo-first-order conditions at 296 and 353 K to be (4.2 ± 0.8) × 10−16 and (7.9 ± 3.6) × 10−16 cm3 molecule−1 s−1, respectively, in agreement with the relative rate result obtained at room temperature. The atmospheric implications of the OH and NO3 reaction rate coefficients measured in this work are discussed.

scholarly journals Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003 ◽  
Vol 3 (6) ◽  
pp. 2233-2307 ◽  
Author(s):  
R. Atkinson
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Relative Rate ◽  
Oh Radicals ◽  
Gas Phase Reactions ◽  
Temperature Dependent ◽  
Temperature Range ◽  
Dependent Rate ◽  
Temperature Ranges ◽  
Kinetics Of

Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented over the entire temperature range for which measurements have been made (~180-2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented. The recommended 298 K rate constants, temperature-dependent parameters, and temperature ranges over which these recommendations are applicable are listed in Table 1.

Shock Tube Studies of the Reactions of Hydrogen Atoms. I. The Reaction H + NH3 → H2 + NH2

1974 ◽  
Vol 52 (7) ◽  
pp. 1171-1180 ◽  
Author(s):  
John E. Dove ◽  
Wing S. Nip
Keyword(s):  
Shock Tube ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
High Concentration ◽  
Hydrogen Atoms ◽  
Elementary Reactions ◽  
Temperature Range ◽  
Reflected Shock ◽  
Branched Chain ◽  
Chain Explosion

The partial equilibrium state following the branched-chain explosion of shock-heated rich H2/O2/diluent mixtures contains a high concentration of H atoms. The conditions under which this state can be used as a source of H atoms for the study of elementary reactions have been investigated. A small amount of NH3 was added to H2/O2/inert gas mixtures in order to measure the rate of the reaction H + NH3 → H2 + NH2. The pseudo-first order decay of NH3 in an approximately ten-fold excess of H atoms was followed by a time-of-flight mass spectrometer which sampled from the reflected shock region in a shock tube. The rate coefficient for this reaction, determined over the temperature range 1500–2150 °K, is 1013.44±0.10 exp −(17 400 ± 1 300 cal mol−1)/RT cm3 mol−1 s−1.It is pointed out that, under certain stated conditions, the method can also be extended to study the rates of elementary reactions involving O atoms and OH radicals. From our experiments, upper limits on the rate coefficients of the reactions OH + NH3 → H2O + NH2 and O + NH3 → OH + NH2 over the temperature range 1620–1920 °K are 8 × 109T0.08 exp (−1100/RT) and 1 × 1013 exp (−6600/RT), respectively.

scholarly journals Kinetics of the gas-phase reactions of OH radicals with alkanes and cycloalkanes

2003 ◽  
Vol 3 (4) ◽  
pp. 4183-4358 ◽  
Author(s):  
R. Atkinson
Keyword(s):  
Gas Phase ◽  
Rate Constants ◽  
Relative Rate ◽  
Oh Radicals ◽  
Reference Compound ◽  
Gas Phase Reactions ◽  
Temperature Dependent ◽  
Temperature Range ◽  
Dependent Rate ◽  
Kinetics Of

Abstract. The available database concerning rate constants for gas-phase reactions of the hydroxyl (OH) radical with alkanes through early 2003 is presented ove the entire temperature range for which measurements have been made (~180–2000 K). Measurements made using relative rate methods are re-evaluated using recent rate data for the reference compound (generally recommendations from this review). In general, whenever more than one study has been carried out over an overlapping temperature range, recommended rate constants or temperature-dependent rate expressions are presented.

scholarly journals Kinetic Study of the Atmospheric Oxidation of a Series of Epoxy Compounds by OH Radicals

2021 ◽  
Author(s):  
Carmen Maria Tovar ◽  
Ian Barnes ◽  
Iustinian Gabriel Bejan ◽  
Peter Wiesen
Keyword(s):  
Kinetic Study ◽  
Relative Rate ◽  
Epoxy Compound ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Cyclohexene Oxide ◽  
Gas Phase Reactions ◽  
Structure Activity ◽  
Temperature Rate ◽  
Kinetics Of

Abstract. The kinetics of the gas-phase reactions of hydroxyl radicals with cyclohexene oxide (CHO), 1,2-epoxyhexane (EHX), 1,2-epoxybutane (12EB), trans-2,3-epoxybutane (tEB) and cis-2,3-epoxybutane (cEB) have been investigated using the relative rate technique. The experiments have been performed at (298 ± 3) K and (760 ± 10) Torr total pressure of synthetic air using different reference compounds in a 1080 l Quartz Reactor (QUAREC) and a 480 l Duran glass chamber. The following room temperature rate coefficients (cm3 molecule−1 s−1) were obtained: k1 (OH+CHO) = (5.93 ± 1.78) × 10−12, k2 (OH+EHX) = (5.77 ± 1.29) × 10−12, k3 (OH+12EB) = (1.98 ± 0.39) × 10−12, k4 (OH+cEB) = (1.50 ± 0.26) × 10−12, k5 (OH+tEB) = (1.81 ± 0.42) × 10−12. With the exception of previous studies for 1,2-epoxybutane and cyclohexene oxide, this is to the best of our knowledge the first kinetic study of the reaction of these compounds with OH radicals. Atmospheric lifetimes, reactivity trends and atmospheric implications are discussed considering the epoxy compound rate coefficients obtained in the present study. In addition to a direct comparison with the literature data where possible, the results from the present study are compared with values estimated from the Structure Activity Relationship method.

scholarly journals Gas-phase degradation of 2-butanethiol initiated by OH radicals and Cl atoms: kinetics, product yields and mechanism at 298 K and atmospheric pressure

RSC Advances ◽  
2019 ◽  
Vol 9 (39) ◽  
pp. 22618-22626
Author(s):  
Alejandro L. Cardona ◽  
Rodrigo G. Gibilisco ◽  
María B. Blanco ◽  
Peter Wiesen ◽  
Mariano Teruel
Keyword(s):  
Gas Phase ◽  
Atmospheric Pressure ◽  
Relative Rate ◽  
Product Distribution ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Product Yields ◽  
Cl Atoms ◽  
Relative Rate Coefficients

Relative rate coefficients and product distribution of the reaction of 2-butanethiol (2butSH) with OH radicals and Cl atoms were obtained at atmospheric pressure and 298 K.

Kinetic study of the thermal isomerization of fulvene

1981 ◽  
Vol 34 (2) ◽  
pp. 449 ◽  
Author(s):  
BJ Gaynor ◽  
RG Gilbert ◽  
KD King ◽  
PJ Harman
Keyword(s):  
High Pressure ◽  
Reaction Mechanism ◽  
Kinetic Study ◽  
Low Pressure ◽  
Thermal Isomerization ◽  
Marcus Theory ◽  
Rate Coefficients ◽  
Arrhenius Parameters ◽  
Temperature Range ◽  
Concerted Reaction

The thermal unimolecular isomerization of fulvene to benzene was studied by the technique of very low-pressure pyrolysis. The observed fall-off regime rate coefficients (obtained over the temperature range of c. 1050-1150 K) were fitted by using RRKM (Rice-Ramsperger-Kassel-Marcus) theory (assuming a concerted reaction mechanism) to give high-pressure Arrhenius parameters in the range E∞ = 268-285 kJ mol-1, log(A/s-1) = 13-14.

scholarly journals OH- and O3-initiated atmospheric degradation of camphene: temperature dependent rate coefficients, product yields and mechanisms

RSC Advances ◽  
2017 ◽  
Vol 7 (5) ◽  
pp. 2733-2744 ◽  
Author(s):  
Elizabeth Gaona-Colmán ◽  
María B. Blanco ◽  
Ian Barnes ◽  
Peter Wiesen ◽  
Mariano A. Teruel
Keyword(s):  
Gas Phase ◽  
Relative Rate ◽  
Rate Coefficients ◽  
Temperature Dependent ◽  
Product Yields ◽  
Temperature Range ◽  
Dependent Rate ◽  
Atmospheric Degradation ◽  
Rate Method

Gas-phase rate coefficients for the reactions of OH and O3 with camphene have been measured over the temperature range 288–311 K using the relative rate method.

Sign in / Sign up

Export Citation Format

Share Document