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.

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.

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 Experimental and computational kinetics investigations for the reactions of Cl atoms with series of unsaturated ketones in gas phase

2017 ◽  
Author(s):  
Siripina Vijayakumar ◽  
Avinash Kumar ◽  
Balla Rajakuma
Keyword(s):  
Gas Phase ◽  
State Theory ◽  
Rate Coefficients ◽  
Gas Phase Reactions ◽  
Temperature Dependent ◽  
Unsaturated Ketones ◽  
Temperature Range ◽  
Computational Calculations ◽  
Temperature Rate ◽  
Cl Atoms

Abstract. Temperature dependent rate coefficients for the gas phase reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one were measured over the temperature range of 298–363 K relative to 1-pentene, 1,3-butadiene and isoprene. Gas Chromatography (GC) was used to measure the concentrations of the organics. The derived temperature dependent Arrhenius expressions are k4-hexen-3-one+Cl (298–363 K) = (2.82 ± 1.76)×10−12exp [(1556 ± 438)/T] cm3 molecule−1 s−1 and k5-hexen-2-one+Cl (298–363 K) = (4.6 ± 2.4)×10−11exp[(646 ± 171)/T] cm3 molecule−1 s−1. The corresponding room temperature rate coefficients are (5.54 ± 0.41)×10−10 cm3 molecule−1 s−1 and (4.00 ± 0.37)×10−10 cm3 molecule−1 s−1 for the reactions of Cl atoms with 4-hexen-3-one and 5-hexen-2-one respectively. To understand the mechanism of Cl atom reactions with unsaturated ketones, computational calculations were performed for the reactions of Cl atoms with 4-hexen-3-one, 5-hexen-2-one and 3-penten-2-one over the temperature range of 275–400 K using Canonical Variational Transition state theory (CVT) with Small Curvature Tunneling (SCT) in combination with CCSD(T)/6-31+G(d, p)//MP2/6-311++G(d, p) level of theory. Atmospheric implications, reaction mechanism and feasibility of the title reactions are discussed in this manuscript.

Gas-phase ozonolysis of β-ocimene: Temperature dependent rate coefficients and product distribution

2016 ◽  
Vol 147 ◽  
pp. 46-54 ◽  
Author(s):  
Elizabeth Gaona-Colmán ◽  
María B. Blanco ◽  
Ian Barnes ◽  
Mariano A. Teruel
Keyword(s):  
Gas Phase ◽  
Product Distribution ◽  
Rate Coefficients ◽  
Temperature Dependent ◽  
Dependent Rate

Temperature‐dependent rate coefficients for the gas‐phase OH + furan‐2,5‐dione (C 4 H 2 O 3 , maleic anhydride) reaction

2020 ◽  
Vol 52 (10) ◽  
pp. 623-631 ◽  
Author(s):  
Aparajeo Chattopadhyay ◽  
Vassileios C. Papadimitriou ◽  
Paul Marshall ◽  
James B. Burkholder
Keyword(s):  
Maleic Anhydride ◽  
Gas Phase ◽  
Rate Coefficients ◽  
Temperature Dependent ◽  
Dependent Rate

Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes

2018 ◽  
Vol 122 (17) ◽  
pp. 4252-4264 ◽  
Author(s):  
François Bernard ◽  
Dimitrios K. Papanastasiou ◽  
Vassileios C. Papadimitriou ◽  
James B. Burkholder
Keyword(s):  
Gas Phase ◽  
Rate Coefficients ◽  
Phase Reaction ◽  
Oh Radical ◽  
Temperature Dependent ◽  
Gas Phase Reaction ◽  
Dependent Rate

scholarly journals Atmospheric sink of methyl chlorodifluoroacetate and ethyl chlorodifluoroacetate: temperature dependent rate coefficients, product distribution of their reactions with Cl atoms and CF2ClC(O)OH formation

RSC Advances ◽  
2016 ◽  
Vol 6 (57) ◽  
pp. 51834-51844
Author(s):  
María B. Blanco ◽  
Ian Barnes ◽  
Peter Wiesen ◽  
Mariano A. Teruel
Keyword(s):  
Relative Rate ◽  
Product Distribution ◽  
Rate Coefficients ◽  
Gas Phase Reactions ◽  
Temperature Dependent ◽  
Dependent Rate ◽  
P Rate ◽  
Distribution Studies ◽  
First Time ◽  
Cl Atoms

Rate coefficients as a function of temperature and product distribution studies have been performed for the first time for the gas-phase reactions of chlorine atoms with methyl chlorodifluoracetate (k1) and ethyl chlorodifluoroacetate (k2) using the relative rate technique.

Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method

2012 ◽  
Vol 14 (18) ◽  
pp. 6596 ◽  
Author(s):  
Mohamed Ghalaieny ◽  
Asan Bacak ◽  
Max McGillen ◽  
Damien Martin ◽  
Alan V. Knights ◽  
...  
Keyword(s):  
Gas Phase ◽  
Elevated Temperatures ◽  
Relative Rate ◽  
Rate Coefficients ◽  
Rate Method

scholarly journals Temperature dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, <i>α</i>-pinene and Δ-3-carene

2017 ◽  
Author(s):  
Terry J. Dillon ◽  
Katrin Dulitz ◽  
Christoph M. B. Gross ◽  
John N. Crowley
Keyword(s):  
Cross Sections ◽  
Room Temperature ◽  
Relative Rate ◽  
Gas Pressure ◽  
Rate Coefficients ◽  
Absorption Cross ◽  
Temperature Dependent ◽  
Degradation Reactions ◽  
Dependent Rate ◽  
Accuracy And Precision

Abstract. Abstract. Pulsed laser methods for OH generation and detection were used to study atmospheric degradation reactions for three important biogenic gases: OH + isoprene (R1); OH + α-pinene (R2); and OH + Δ-3-carene (R3). Gas-phase rate coefficients were characterised by non-Arrhenius kinetics for all three reactions. For (R1), k1 (241–356 K) = (1.93 ± 0.08) × 10−11 exp (466 ± 12)/T cm3 molecule−1 s−1 was determined, with a room temperature value of k1 (297 K) = (9.3 ± 0.4) × 10−11 cm3 molecule−1 s−1, independent of bath-gas pressure (5–200 Torr) and composition (M = N2 or air). Accuracy and precision were enhanced by online optical monitoring of isoprene, with absolute concentrations obtained via an absorption cross-section, σisoprene = (1.28 ± 0.06) × 10−17 cm2 molecule−1 at λ = 184.95 nm, determined in this work. These results indicate that significant discrepancies between previous absolute and relative rate determinations of k1 result in part from σ values used to derive the isoprene concentration. Similar methods were used to determine rate coefficients (in 10−11 cm3 molecule−1 s−1) for (R2–R3): k2 (238–357 K) = (1.83 ± 0.04) × exp (330 ± 6)/T; and k3 (235–357 K) = (2.48 ± 0.14) × exp (357 ± 17)/T. This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime conditions. Room temperature values of k2 (296 K) = (5.4 ± 0.2) × 10−11 cm3 molecule−1 s−1 and k3 (297 K) = (8.1 ± 0.3) × 10−11 cm3 molecule−1 s−1 were independent of bath-gas pressure (7–200 Torr, N2 or air), and in good agreement with previously reported values. In the course of this work, 184.95 nm absorption cross-sections were determined: σ = (1.54 ± 0.08) × 10−17cm 2 molecule−1 for α-pinene and (2.40 ± 0.12) × 10−17  cm2 molecule−1 for Δ-3-carene.

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