Rate constants for hydrogen abstraction reactions of the sulfate radical, SO<sub>4</sub><sup>−</sup>. Alkanes and ethers

Huie, Robert E.; Clifton, Carol L.

doi:10.1002/kin.550210802

Cited by 135 publications

(58 citation statements)

References 9 publications

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“…The reason for that difference is not clear, but in that study, in opposition to the other investigations, it was not a direct determination but the kinetics that were obtained relative to 1,3,5-trimethoxybenzene, which is very reactive compared to alcohols. So, we believe that for the same reason as described previously, our work is in agreement with the results reported by Huie and Clifton [22].…”

Section: ؉ Alcoholssupporting

confidence: 95%

“…All the results are summarized in Table III . When compared to literature data (see Table III), the values for diethyl ether and tert-butyl methyl ether appear to be 20 -30% higher than the two other determinations [20,22] which have been conducted at room temperature (i.e., at a temperature 5 -10 K lower than in our study). This difference may certainly be the reason for this apparent difference.…”

Section: ؉ Alcoholscontrasting

confidence: 46%

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Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

George

El-Rassy

Chovelon

2001

Int J of Chemical Kinetics

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Rate constants for a series of alcohols, ethers, and esters toward the sulfate radical (SO 4 Ϫ ) have been directly determined using a laser photolysis set-up in which the radical was produced by the photodissociation of peroxodisulfate anions. The sulfate radical concentration was monitored by following its optical absorption by means of time resolved spectroscopy techniques. At room temperature the following rate constants were derived: methanol ((1.); and dimethyl succinate (CH 3 OC(O)CH 2 CH 2 C(O)OCH 3 ) ((1.37 Ϯ 0.08) ϫ 10 6 M Ϫ1 s Ϫ1 ) where the errors represent 2. For the two latter species, we also measured the temperature dependence of the corresponding rate constants. A correlation of these kinetics with the bond dissociation energy is also presented and discussed.

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Section: ؉ Alcoholssupporting

confidence: 95%

Section: ؉ Alcoholscontrasting

confidence: 46%

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

George

El-Rassy

Chovelon

2001

Int J of Chemical Kinetics

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“…Also, we found that the rate constant for the reaction of SO,-with p-dioxane is lower than for the reaction with tetrahydrofuran [7]. Assuming the C -H bonds a to the ether linkage are weaker than normal secondary C -H bonds, the reverse order of reactivity would be expected.…”

Section: Introductionmentioning

confidence: 77%

Rate constants for Hydrogen abstraction reactions of NO₃ in aqueous solution

Shastri

Huie

1990

Int J of Chemical Kinetics

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Rate constants have been measured by pulse radiolysis for the reactions of the NO, radical with five cyclic ethers and a series of alcohols. Rate constants ranged from 3.5 x lo4 M-' 5 -l for deuterated methanol to 1.1 x lo7 M-' 5-l for tetrahydrofuran. The rate constants for the reactions of NO3 with the alcohols 1-propanol to 1-heptanol were found to be linearly dependent on the number of CH2 groups with a group reactivity of 6.4 x lo5 M-' s-'.

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“…The sulfate radical anion is a strong oxidant in aqueous phase. For example, Huie and Clifton (1989) have reported that hydrogen abstraction by sulfate radical anions on the alkane can result in the formation of bisulfate ions. They also reported that the hydrogen 20 abstraction rate is the highest on the tertiary carbon, and the rate is one order of magnitude smaller for the secondary carbon, and even smaller for the primary carbon.…”

Section: Formation and Reaction Of Sulfate Radical Anion In The Oh Rementioning

confidence: 99%

Importance of Sulfate Radical Anion Formation and Chemistry in Heterogeneous OH Oxidation of Sodium Methyl Sulfate, the Smallest Organosulfate

Kwong¹,

Chim²,

Davies³

et al. 2017

Preprint

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Abstract.Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, 10 composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH 3 SO 4 Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source 15 (Direct Analysis in Real Time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO 4 − ) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH 2 O) and a sulfate radical anion (SO 4•− ) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from 20 neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10 -13 cm 3 molecule -1 s -1 with an effective OH uptake coefficient, γ eff , of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 10 12 molecule cm −3 s), only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that 25 the heterogeneous OH oxidation of an organosulfate can lead to the formation of sulfate radical anion and produce inorganic sulfate. Fragmentation processes and sulfate radical anion chemistry play a key role in determining the compositional evolution of sodium methyl sulfate during heterogeneous OH oxidation. 35Atmos. Chem. Phys. Discuss., https://doi

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Rate constants for hydrogen abstraction reactions of the sulfate radical, SO₄⁻. Alkanes and ethers

Abstract: Rate constants have been determined for the reactions of SO4-with a series of alkanes and ethers. The SO, radical was produced by the laser-flash photolysis of persulfate, SZO: -.

Cited by 135 publications

References 9 publications

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

Rate constants for Hydrogen abstraction reactions of NO₃ in aqueous solution

Importance of Sulfate Radical Anion Formation and Chemistry in Heterogeneous OH Oxidation of Sodium Methyl Sulfate, the Smallest Organosulfate

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Rate constants for hydrogen abstraction reactions of the sulfate radical, SO4−. Alkanes and ethers

Abstract: Rate constants have been determined for the reactions of SO4-with a series of alkanes and ethers. The SO, radical was produced by the laser-flash photolysis of persulfate, SZO: -.

Cited by 135 publications

References 9 publications

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO4−)

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO4−)

Rate constants for Hydrogen abstraction reactions of NO3 in aqueous solution

Importance of Sulfate Radical Anion Formation and Chemistry in Heterogeneous OH Oxidation of Sodium Methyl Sulfate, the Smallest Organosulfate

Contact Info

Product

Resources

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Rate constants for hydrogen abstraction reactions of the sulfate radical, SO₄⁻. Alkanes and ethers

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

Reactivity of selected volatile organic compounds (VOCs) toward the sulfate radical (SO₄⁻)

Rate constants for Hydrogen abstraction reactions of NO₃ in aqueous solution