Rate constants for the reactions of NO3•, SO4•- and Cl• radicals with formate and acetate esters in aqueous solution

Buxton, George V.; Wang, Jiaqiang; Salmon, G. Arthur

doi:10.1039/b101932p

Cited by 22 publications

(22 citation statements)

References 17 publications

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“…45,[58][59][60][61][62] The only explanation of this behaviour is slightly differing electron densities occurring at the CQC double bond due to electron-withdrawing properties of the deprotonated group. Other studies confirm this trend regardless of whether H abstraction, addition or electron transfer reactions of OH, NO 3 or SO 4 À with saturated, unsaturated or aromatic compounds were considered.…”

Section: Resultsmentioning

confidence: 99%

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies

Schöne

Schindelka

Szeremeta

et al. 2014

Phys. Chem. Chem. Phys.

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Kinetic and mechanistic studies were conducted on the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic and acrylic acid reacting with hydroxyl and nitrate radicals and sulfate radical anions in aqueous solution by use of the laser flash photolysis technique and a reversed-rate method for kinetics. High-performance liquid chromatography/mass spectrometry was applied for product analysis. The kinetic investigations show the highest reactivity of the hydroxyl radical followed by sulfate and nitrate radicals. For methacrolein and methyl vinyl ketone the following rate constants have been determined at 298 K: k(OH+methacrolein) = (9.4 ± 0.7) × 10(9) M(-1) s(-1), k(OH+methyl vinyl ketone) = (7.3 ± 0.5) × 10(9) M(-1) s(-1), k(NO3+methacrolein) = (4.0 ± 1.0) × 10(7) M(-1) s(-1), k(NO3+methyl vinyl ketone) = (9.7 ± 3.4) × 10(6) M(-1) s(-1), k(SO4(-)+methacrolein) = (9.9 ± 4.9) × 10(7) M(-1) s(-1) and k(SO4(-)+methyl vinyl ketone) = (1.0 ± 0.2) × 10(8) M(-1) s(-1). Temperature and pH dependencies of the reactions of OH, NO3 and SO4(-) with methacrolein, methyl vinyl ketone, methacrylic and acrylic acid as well as Arrhenius parameters have been obtained and discussed. Product studies were performed on the OH radical induced oxidation of methacrolein and methyl vinyl ketone. In the reaction of methacrolein + OH methylglyoxal and hydroxyacetone were identified as first oxidation products with yields of 0.099 and 0.162. Methylglyoxal was primarily produced in the oxidation of methyl vinyl ketone with a yield of 0.052. For both precursor compounds the formation of glycolaldehyde was observed for the first time with yields of 0.051 and 0.111 in the oxidation of methacrolein and methyl vinyl ketone, respectively. Furthermore, highly functionalised C4 compounds were determined from the oxidation of both precursor compounds, but for the first time for methyl vinyl ketone. Reaction schemes were developed based on known peroxyl radical reaction mechanisms. The aqueous phase conversion of the first generation isoprene oxidation products can potentially contribute to tropospheric aqueous phase budgets of important carbonyl and dicarbonyl components which are expected to be conducive to the formation of aqSOA.

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Section: Resultsmentioning

confidence: 99%

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies

Schöne

Schindelka

Szeremeta

et al. 2014

Phys. Chem. Chem. Phys.

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“…It has also been shown that small esters are present in the interstellar space [1]. The significance of ethyl acetate is in its wide use in industry as a solvent, as well as in production of printing ink, glue or paint [2]. Its presence was also detected in the atmosphere of forests in Central Europe due to biogenic sources emissions [3].…”

Section: Introductionmentioning

confidence: 87%

“…22 [2] on ethyl acetate in aqueous phase that is of importance for acid rain chemistry. All these cases prove that not only is radical attack the main mechanism for the ester removal from the atmosphere, but also that the order of the reactivities of ethyl acetate with such species would be as follows: Cl ≈ OH NO 3 ≈ SO − 4 .…”

Section: Absolute Photoabsorption Cross Sections and Atmospheric Photmentioning

confidence: 99%

“…The proposed Rydberg transitions, labeled in Figures 5 and 6 and presented in Tables 4 and 5, originate mainly from the HOMO (19a ) according to our calculations. The positions of the peaks, E n , have been predicted using the well-known Rydberg formula: 2 , where E i is the ionisation energy, R is the Rydberg constant 13.61 eV, n is the principal quantum number of the Rydberg orbital of energy E n , and δ is the quantum defect. Quantum defects are expected to be in range of 1.0−0.9, 0.6−0.3 and <0.25 for ns, np and nd series, respectively.…”

Section: Rydberg Seriesmentioning

confidence: 99%

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Electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations of ethyl acetate

et al. 2016

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Abstract. The high-resolution vacuum ultraviolet photoabsorption spectrum of ethyl acetate, C4H8O2, is presented over the energy range 4.5−10.7 eV (275.5−116.0 nm). Valence and Rydberg transitions and their associated vibronic series observed in the photoabsorption spectrum, have been assigned in accordance with new ab initio calculations of the vertical excitation energies and oscillator strengths. Also, the photoabsorption cross sections have been used to calculate the photolysis lifetime of this ester in the upper stratosphere (20−50 km). Calculations have also been carried out to determine the ionisation energies and fine structure of the lowest ionic state of ethyl acetate and are compared with a newly recorded photoelectron spectrum (from 9.5 to 16.7 eV). Vibrational structure is observed in the first photoelectron band of this molecule for the first time.

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“…The rate constant for this reaction (1.3 9 10 4 M -1 s -1 ) [17] is 1,000 times lower than that of OH radicals with acetic acid (1.6 9 10 7 M -1 s -1 ). Therefore, in our system, the main reaction involved in acetic acid decomposition is considered to be an OH radical oxidation reaction.…”

Section: Acetic Acid Decompositionmentioning

confidence: 94%

Acetic Acid Decomposition in a Coaxial Dielectric Barrier Discharge Tube with Mist Flow

Shibata

Nishiyama

2014

Plasma Chem Plasma Process

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Non-thermal plasmas can be used for water treatment system because they allow free radical generation without heating. Advanced oxidation processes using nonthermal plasmas have been developed to decompose persistent organic pollutants. In this study, a water treatment method that involves spraying a solution into a coaxial dielectric barrier discharge (DBD) tube using an air, argon or oxygen carrier gas was investigated. The alumina DBD tube had an inner high-voltage electrode and an outer ground electrode. Acetic acid was used as the decomposition target because acetic acid is a known persistent organic material. An acetic acid solution, diluted 10,000 times in purified water, was atomized by an ultrasonic atomizer unit and introduced into the DBD tube. The residence time of the droplets sprayed into the discharge area was almost 7 ms. Acetic acid was effectively decomposed and the decomposition ratio reached almost 80 % when Ar was employed as the carrier gas. This is due to the very fine droplets in the sprayed mist having a large specific surface area and OH radicals being able to react directly in solution. Furthermore, the results suggest that the chemical processes involved in acetic acid decomposition can be controlled by varying the carrier gas composition.

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Rate constants for the reactions of NO3•, SO4•- and Cl• radicals with formate and acetate esters in aqueous solution

Cited by 22 publications

References 17 publications

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies

Atmospheric aqueous phase radical chemistry of the isoprene oxidation products methacrolein, methyl vinyl ketone, methacrylic acid and acrylic acid – kinetics and product studies

Electronic state spectroscopy by high-resolution vacuum ultraviolet photoabsorption, He(I) photoelectron spectroscopy and ab initio calculations of ethyl acetate

Acetic Acid Decomposition in a Coaxial Dielectric Barrier Discharge Tube with Mist Flow

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