Gas-Phase Reactions of Chlorine Atoms and ClO Radicals with Dimethyl Sulfide. Rate Coefficients and Temperature Dependences

Abstract. We present a digital, freely available, searchable and evaluated compilation of rate coefficients for the gas-phase reactions of organic compounds with OH, Cl and NO3 radicals and with O3 (McGillen et al., 2019). Although other compilations of much of these data exist, many are out-of-date, most have limited scope, and all are difficult to search and to load completely into a digitized form. This compilation uses results of previous reviews, though many recommendations are updated to incorporate new or omitted data or address errors, and includes recommendations on many reactions that have not been reviewed previously. The database, which incorporates over 50 years of measurements, consists of a total of 2765 recommended bimolecular rate coefficients for the reactions of 1357 organic substances with OH, 709 with Cl, 310 with O3, and 389 with NO3, and is much larger than previous compilations. A large variety of functional groups is present in this database, including naturally occurring chemicals formed in or emitted to the atmosphere and anthropogenic compounds such as halocarbons and their degradation products. Recommendations were made for rate coefficients at 298 K and, where possible, the temperature dependences over the entire range of the available data. The primary motivation behind this project has been to provide a large and thoroughly evaluated training dataset for the development of structure-activity relationships (SARs), whose reliability depends fundamentally upon the availability of high-quality experimental data. However, there are other potential applications of this work, such as research related to atmospheric lifetimes and fates of organic compounds, or modelling gas-phase reactions of organics in various environments. This database is freely accessible at https://doi.org/10.25326/36 (McGillen et al., 2019).

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Database for the kinetics of the gas-phase atmospheric reactions of organic compounds

Earth System Science Data ◽

10.5194/essd-12-1203-2020 ◽

2020 ◽

Vol 12 (2) ◽

pp. 1203-1216 ◽

Cited By ~ 3

Author(s):

Max R. McGillen ◽

William P. L. Carter ◽

Abdelwahid Mellouki ◽

John J. Orlando ◽

Bénédicte Picquet-Varrault ◽

...

Keyword(s):

Gas Phase ◽

Organic Compounds ◽

Degradation Products ◽

Rate Coefficients ◽

Training Dataset ◽

Gas Phase Reactions ◽

Atmospheric Reactions ◽

Temperature Dependences ◽

Potential Applications ◽

Kinetics Of

Abstract. We present a digital, freely available, searchable, and evaluated compilation of rate coefficients for the gas-phase reactions of organic compounds with OH, Cl, and NO3 radicals and with O3. Although other compilations of many of these data exist, many are out of date, most have limited scope, and all are difficult to search and to load completely into a digitized form. This compilation uses results of previous reviews, though many recommendations are updated to incorporate new or omitted data or address errors, and includes recommendations on many reactions that have not been reviewed previously. The database, which incorporates over 50 years of measurements, consists of a total of 2765 recommended bimolecular rate coefficients for the reactions of 1357 organic substances with OH, 709 with Cl, 310 with O3, and 389 with NO3, and is much larger than previous compilations. Many compound types are present in this database, including naturally occurring chemicals formed in or emitted to the atmosphere and anthropogenic compounds such as halocarbons and their degradation products. Recommendations are made for rate coefficients at 298 K and, where possible, the temperature dependences over the entire range of the available data. The primary motivation behind this project has been to provide a large and thoroughly evaluated training dataset for the development of structure–activity relationships (SARs), whose reliability depends fundamentally upon the availability of high-quality experimental data. However, there are other potential applications of this work, such as research related to atmospheric lifetimes and fates of organic compounds, or modelling gas-phase reactions of organics in various environments. This database is freely accessible at https://doi.org/10.25326/36 (McGillen et al., 2019).

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Rate Coefficients for the Gas-Phase Reactions of Chlorine Atoms with Cyclic Ethers at 298 K

International Journal of Chemical Kinetics ◽

10.1002/kin.20765 ◽

2013 ◽

Vol 45 (5) ◽

pp. 295-305 ◽

Cited By ~ 12

Author(s):

H. D. Alwe ◽

M. Walawalkar ◽

A. Sharma ◽

K. K. Pushpa ◽

S. Dhanya ◽

...

Keyword(s):

Gas Phase ◽

Rate Coefficients ◽

Cyclic Ethers ◽

Gas Phase Reactions ◽

Chlorine Atoms

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Gas-Phase Reactions in the ISM: Rate Coefficients, Temperature Dependences, and Reaction Products

Proceedings of the International Astronomical Union ◽

10.1017/s1743921311025117 ◽

2011 ◽

Vol 7 (S280) ◽

pp. 361-371 ◽

Cited By ~ 1

Author(s):

Ian W. M. Smith

Keyword(s):

Interstellar Medium ◽

Gas Phase ◽

Rate Coefficients ◽

Reaction Products ◽

Empirical Methods ◽

Gas Phase Reactions ◽

Rich Variety ◽

Temperature Dependences ◽

The Rich ◽

Semi Empirical

AbstractInformation about the rate coefficients and products of processes that occur in the interstellar medium are required as input to computer models that seek to reproduce the abundances of the rich variety of molecules that have been observed in different regions of the interstellar medium. In this brief review, I seek to identify the different kinds of gas-phase processes for which information is required and to consider the experimental, theoretical, and semi-empirical methods which are employed to measure or predict rate coefficients, k(T), and how they depend on temperature (T) – and also how the products of reactions can, in favourable cases, be observed.

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

10.5194/acp-2017-163 ◽

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.

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