Rate Coefficients and Mechanisms for the Atmospheric Oxidation of the Ketones

2011 ◽  
Author(s):  
Jack Calvert ◽  
Abdelwahid Mellouki ◽  
John Orlando ◽  
Michael Pilling ◽  
Timothy Wallington
Keyword(s):  
First Generation ◽  
Rate Coefficient ◽  
Negative Temperature ◽  
Tropospheric Chemistry ◽  
Rate Coefficients ◽  
Anthropogenic Emissions ◽  
Unsaturated Ketones ◽  
Temperature Dependences ◽  
Oh Reactions ◽  
Temperature Ranges

Ketones are emitted directly to the atmosphere, and their sources were discussed in detail in chapter I. In the U.K. acetone and butanone comprise about 7% and 5%, respectively, of the total anthropogenic emissions of oxygenated compounds, and 1.6% and 1.1%, respectively, of the total anthropogenic emissions of nonmethane volatile organic compounds. Ketone emissions from solvents (both industrial and personal) are substantial; emissions from both gasoline- and diesel-fueled vehicles also contribute. Ketones are also formed extensively in the atmosphere in the oxidation of other compounds. Acetone, for example is formed in the OH-initiated oxidation of propane, iso-butane, iso-pentane, and neopentane and from a number of higher hydrocarbons. It is also formed in the oxidation of terpenes. The distribution, sources, and sinks of acetone in the atmosphere have been analyzed by Simpson et al. (1994). Methyl vinyl ketone is an important first generation product in the OH-initiated oxidation of isoprene. In this chapter, we discuss the rate coefficients and the mechanisms of oxidation of ketones. The classes covered include alkanones, hydroxyketones, diketones, unsaturated ketones, ketenes, cyclic ketones, ketones derived from biogenic compounds, and halogen-substituted ketones. Photolysis is a major atmospheric process for many ketones, and will be discussed in chapter IX. The major bimolecular reactions removing ketones from the atmosphere are with OH. Although less important than the OH reactions, reactions with Cl have been studied quite extensively. Other than for unsaturated ketones, reactions with NO3 and O3 are unimportant in tropospheric chemistry and have been studied little. The carbonyl group deactivates the α-position with respect to reaction with OH, but activates the β-position, and possibly more distant sites as well. The net result is that the overall rate coefficient of an alkanone generally exceeds that of the equivalent alkane. The temperature dependences of the rate coefficients can be quite complex, with acetone and possibly butanone showing a minimum in the rate coefficient at ∼250 K, while the higher alkanones show negative temperature dependences across the more limited temperature ranges that have been investigated. The most likely explanation of this behavior is the formation of a pre-reaction, hydrogen-bonded complex.

scholarly journals Rate coefficients for the gas-phase reaction of OH with <i>Z</i>-3-hexen-1-ol, 1-penten-3-ol, <i>E</i>-2-penten-1-ol, and <i>E</i>-2-hexen-1-ol between 243 and 404 K

2011 ◽  
Vol 11 (1) ◽  
pp. 2377-2405 ◽  
Author(s):  
M. E. Davis ◽  
J. B. Burkholder
Keyword(s):  
Gas Phase ◽  
Negative Temperature ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Oh Radical ◽  
Gas Phase Reaction ◽  
First Order ◽  
Unsaturated Alcohols ◽  
Temperature Dependences

Abstract. Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-3-hexen-1-ol ((Z)-CH3CH2CH=CHCH2CH2OH). (k1), 1-penten-3-ol (CH3CH2CH(OH)CH=CH2) (k2), (E)-2-penten-1-ol ((E)-CH3CH2CH=CHCH2OH) (k3), and (E)-2-hexen-1-ol ((E)-CH3CH2CH2CH=CHCH2OH) (k4), unsaturated alcohols that are emitted into the atmosphere following vegetation wounding, are reported. Rate coefficients were measured under pseudo-first-order conditions in OH over the temperature range 243–404 K at pressures between 20 and 100 Torr (He) using pulsed laser photolysis (PLP) to produce OH radicals and laser induced fluorescence (LIF) to monitor the OH temporal profile. The obtained rate coefficients were independent of pressure with negative temperature dependences that are well described by the Arrhenius expressions k1(T) = (1.3 ± 0.1) × 10−11 exp[(580 ± 10)/T]; k1(297K) = (1.06 ± 0.12) × 10−10 k2(T) = (6.8 ± 0.7) × 10−12 exp[(690 ± 20)/T]; k2(297K) = (7.12 ± 0.73) × 10−11 k3(T) = (6.8 ± 0.8) × 10−12 exp[(680 ± 20)/T]; k3(297K) = (6.76 ± 0.70) × 10−11 k4(T) = (5.4 ± 0.6) × 10−12 exp[(690 ± 20)/T]; k4(297K) = (6.15 ± 0.75) × 10−11 (in units of cm3 molecule−1 s−1). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. The rate coefficients obtained in this study are compared with literature values where possible.

Theoretical Prediction of CH3O and CH2OH Gas-Phase Decomposition Rate Coefficients

1986 ◽  
Vol 39 (12) ◽  
pp. 1929 ◽  
Author(s):  
PG Greenhill ◽  
BV Ogrady ◽  
RG Gilbert
Keyword(s):  
High Pressure ◽  
Theoretical Prediction ◽  
Gas Phase ◽  
Decomposition Rate ◽  
Rate Coefficient ◽  
Rate Coefficients ◽  
Phase Decomposition ◽  
Kinetic Schemes ◽  
Theoretical Predictions ◽  
Temperature Dependences

Theoretical predictions are made for the pressure and temperature dependences of two reactions involved in methanol combustion: (A) CH3O → CH2O + H and (B) CH2OH → CH2O + H. The calculations are carried out by using RRKM theory with a Gorin model for the activated complexes, with fall-off effects being taken into account by using the master equation. Results for the high-pressure rate coefficients (s-1) are (A) 3×1014 exp(-108 kJ mol-1 /RT), (B) 7×1014 exp(-124 kJ mol-1 /RT) at 1000 K. For the low-pressure limiting rate coefficient (cm3 s-1) over the range 600- 1000 K (A) 8×10-9 exp(-90 kJ mol-1 /RT); (B) 2×10-8 exp(-108 kJ mol-1 /RT). At 1000 K, the pressure at which the fall-off rate coefficients are one-half of their limiting high-pressure values are 3x108 Pa for both reactions. Formulae for inclusion of these reactions (including fall- off effects) over the range 300-2000 K and 10-2-106 Pa in modelling complex kinetic schemes are presented.

scholarly journals Rate coefficients for the gas-phase reaction of OH with (<i>Z</i>)-3-hexen-1-ol, 1-penten-3-ol, (<i>E</i>)-2-penten-1-ol, and (<i>E</i>)-2-hexen-1-ol between 243 and 404 K

2011 ◽  
Vol 11 (7) ◽  
pp. 3347-3358 ◽  
Author(s):  
M. E. Davis ◽  
J. B. Burkholder
Keyword(s):  
Gas Phase ◽  
Negative Temperature ◽  
Rate Coefficients ◽  
Oh Radicals ◽  
Phase Reaction ◽  
Oh Radical ◽  
Gas Phase Reaction ◽  
First Order ◽  
Unsaturated Alcohols ◽  
Temperature Dependences

Abstract. Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-3-hexen-1-ol (Z)-CH3CH2CH = CHCH2CH2OH) (k1), 1-penten-3-ol (CH3CH2CH(OH)CH = CH2) (k2), (E)-2-penten-1-ol ((E)-CH3CH2CH = CHCH2OH) (k3), and (E)-2-hexen-1-ol ((E)-CH3CH2CH2CH = CHCH2OH) (k4), unsaturated alcohols that are emitted into the atmosphere following vegetation wounding, are reported. Rate coefficients were measured under pseudo-first-order conditions in OH over the temperature range 243–404 K at pressures between 20 and 100 Torr (He) using pulsed laser photolysis (PLP) to produce OH radicals and laser induced fluorescence (LIF) to monitor the OH temporal profile. The obtained rate coefficients were independent of pressure with negative temperature dependences that are well described by the Arrhenius expressions k1(T) = (1.3 ± 0.1) × 10−11 exp[(580 ± 10)/T]; k1(297 K) = (1.06 ± 0.12) × 10−10 k2(T) = (6.8 ± 0.7) × 10−12 exp[(690 ± 20)/T]; k2(297 K) = (7.12 ± 0.73) × 10−11 k3(T) = (6.8 ± 0.8) × 10−12 exp[(680 ± 20)/T]; k3(297 K) = (6.76 ± 0.70) × 10−11 k4(T) = (5.4 − 0.6) × 10−12 exp[(690 ± 20)/T]; k4(297 K) = (6.15 ± 0.75) × 10−11 (in units of cm3 molecule−1 s−1). The quoted uncertainties are at the 2σ (95% confidence) level and include estimated systematic errors. The rate coefficients obtained in this study are compared with literature values where possible.

scholarly journals A self-consistent, multi-variate method for the determination of gas phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

2017 ◽  
Author(s):  
Jacob T. Shaw ◽  
Richard T. Lidster ◽  
Danny R. Cryer ◽  
Noelia Ramirez ◽  
Graham A. Boustead ◽  
...  
Keyword(s):  
Gas Phase ◽  
Atmospheric Chemistry ◽  
Rate Coefficient ◽  
Relative Rate ◽  
Ambient Air ◽  
Rate Coefficients ◽  
Oxidation Reactions ◽  
Oh Reactions ◽  
Simultaneous Study ◽  
Good Agreement

Abstract. Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of nineteen VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (&amp;pm;0.3) × 10–11–cm3 molecule−1 s−1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for twelve aromatic, five alkane, five alkene and three monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. 19 OH rate coefficients were derived from these ambient air samples, including ten reactions for which data was previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

scholarly journals Reaction of NH+, NH2+, and NH3+ ions with H2 at low temperatures

2019 ◽  
Vol 625 ◽  
pp. A74 ◽  
Author(s):  
S. Rednyk ◽  
Š. Roučka ◽  
A. Kovalenko ◽  
T. D. Tran ◽  
P. Dohnal ◽  
...  
Keyword(s):  
Ion Trap ◽  
Rate Coefficient ◽  
Variable Temperature ◽  
Rate Coefficients ◽  
Interstellar Clouds ◽  
Exothermic Reactions ◽  
Measured Rate ◽  
Reaction Proceeds ◽  
Temperature Dependences ◽  
Increasing Temperature

Aims. We present an experimental investigation of the exothermic reactions of NH+, NH2+, and NH3+ ions with H2 at temperatures relevant for interstellar clouds. Methods. The reactions were studied using a variable-temperature 22-pole radio frequency ion trap instrument. Results. The temperature dependences of rate coefficients of these reactions have been obtained at temperatures from 15 up to 300 K. The reaction of NH+ with H2 has two channels, which lead to NH2+ ( ∼ 97%) and H+3 ( ∼ 3%) with nearly constant reaction rate coefficients (kaNH+(17 K) = 1.0 × 10−9 cm3 s−1 and kbNH+(17 K) = 4.0 × 10−11 cm3 s−1, respectively). The reaction of NH2+ with H2 produces only NH3+ ions. The measured rate coefficient monotonically decreases with increasing temperature from kNH2+(17 K) = 6 × 10−10 cm3 s−1 to kNH2+(300 K) = 2 × 10−10 cm3 s−1. The measured rate coefficient of the reaction of NH3+ with H2, producing NH+4, increases with decreasing temperature from 80 K down to 15 K, confirming that the reaction proceeds by tunnelling through a potential barrier.

scholarly journals Effect of ammonia and water molecule on OH + CH3OH reaction under tropospheric condition

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Mohamad Akbar Ali ◽  
M. Balaganesh ◽  
Faisal A. Al-Odail ◽  
K. C. Lin
Keyword(s):  
Water Molecule ◽  
Energy Surface ◽  
Rate Coefficient ◽  
Water Concentration ◽  
State Theory ◽  
Rate Coefficients ◽  
Hydrogen Atoms ◽  
Experimental And Theoretical Studies ◽  
Effective Reaction ◽  
Effective Reaction Rate

AbstractThe rate coefficients for OH + CH3OH and OH + CH3OH (+ X) (X = NH3, H2O) reactions were calculated using microcanonical, and canonical variational transition state theory (CVT) between 200 and 400 K based on potential energy surface constructed using CCSD(T)//M06-2X/6-311++G(3df,3pd). The results show that OH + CH3OH is dominated by the hydrogen atoms abstraction from CH3 position in both free and ammonia/water catalyzed ones. This result is in consistent with previous experimental and theoretical studies. The calculated rate coefficient for the OH + CH3OH (8.8 × 10−13 cm3 molecule−1 s−1), for OH + CH3OH (+ NH3) [1.9 × 10−21 cm3 molecule−1 s−1] and for OH + CH3OH (+ H2O) [8.1 × 10−16 cm3 molecule−1 s−1] at 300 K. The rate coefficient is at least 8 order magnitude [for OH + CH3OH(+ NH3) reaction] and 3 orders magnitude [OH + CH3OH (+ H2O)] are smaller than free OH + CH3OH reaction. Our calculations predict that the catalytic effect of single ammonia and water molecule on OH + CH3OH reaction has no effect under tropospheric conditions because the dominated ammonia and water-assisted reaction depends on ammonia and water concentration, respectively. As a result, the total effective reaction rate coefficients are smaller. The current study provides a comprehensive example of how basic and neutral catalysts effect the most important atmospheric prototype alcohol reactions.

Rapid relaxation NMR measurements to predict rate coefficients in ionic liquid mixtures. An examination of reaction outcome changes in a homologous series of ionic liquids

2021 ◽  
Author(s):  
Daniel C Morris ◽  
Stuart W Prescott ◽  
Jason B Harper
Keyword(s):  
Ionic Liquid ◽  
Ionic Liquids ◽  
Homologous Series ◽  
Rate Coefficient ◽  
Liquid Mixtures ◽  
Solvent Mixture ◽  
Rate Coefficients ◽  
Substitution Process

A series of ionic liquids based on the 1-alkyl-3-methylimidazolium cations were examined as components of the solvent mixture for a bimolecular substitution process. The effects on both the rate coefficient...

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.

scholarly journals On apparent barrier-free reactions

2020 ◽  
Vol 3 (1) ◽  
pp. 3-8
Author(s):  
Maikel Ballester
Keyword(s):  
Low Temperature ◽  
Chemical Reactions ◽  
Rate Constant ◽  
Kinetic Models ◽  
Rate Coefficient ◽  
Minimum Energy ◽  
Temperature Limit ◽  
Rate Coefficients ◽  
Minimum Energy Path ◽  
Full Dimension

Rate coefficients of bi-molecular chemical reactions are fundamental for kinetic models. The rate coefficient dependence on temperature is commonly extracted from the analyses of the reaction minimum energy path. However, a full dimension study of the same reaction may suggest a different asymptotic low-temperature limit in the rate constant than the obtained from the energetic profile.

scholarly journals The Formation of Interstellar Molecules via Radiative Association Reactions

1980 ◽  
Vol 87 ◽  
pp. 323-324
Author(s):  
David Smith ◽  
Nigel G. Adams
Keyword(s):  
Rate Coefficients ◽  
Rate Data ◽  
Association Rate ◽  
Interstellar Molecules ◽  
Ion Molecule Reactions ◽  
Radiative Association ◽  
Temperature Dependences ◽  
Association Reaction

The radiative association rate coefficients and their temperature dependences have been estimated for several likely interstellar ion-molecule reactions from laboratory collisional association rate data. They include the CH3+ + H2 and CH3+ + H2O reactions, which we suggest lead to CH4 and CH3OH respectively, and the critical association reaction C+ + H2.

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