Kinetics and mechanism of formation and hydrolysis of acid methyl sulfate in aqueous solutions of sulfuric acid

Винник, М. И.; Кислина, И. С.; Kitaigorodskii, A. N.; Nikitaev, A. T.

doi:10.1007/bf01474195

Cited by 9 publications

(17 citation statements)

References 9 publications

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“…This reaction mechanism is in good agreement with the chemistry previously observed. [16][17][18][19][20] As discussed in Experimental Methods, the fractional change in the methanol signal can be used to determine the uptake coefficient for methanol on sulfuric acid (eqs 1-3). For acid concentrations >65 wt %, all uptake can be considered irreversible.…”

Section: Resultsmentioning

confidence: 99%

Uptake of Methanol Vapor in Sulfuric Acid Solutions

Leu

Kane

2000

J. Phys. Chem. A

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The uptake of gas-phase methanol by liquid sulfuric acid has been investigated over the composition range of 40-85 wt % H 2 SO 4 and the temperature range of 210-235 K. Laboratory studies were performed with a flow-tube reactor coupled to an electron-impact ionization mass spectrometer to detect trace gases. While reversible uptake was the primary mechanism at low acid concentrations, an irreversible reaction between methanol and sulfuric acid at low temperatures, forming methyl hydrogen sulfate and dimethyl sulfate, was observed at all concentrations. At compositions >65 wt % H 2 SO 4 , more than 90% of uptake was found to be reactive. On the basis of the uptake data and the calculated liquid-phase diffusion coefficients, the product of the effective Henry's law constant (H*) and the square root of the overall liquid-phase reaction rate (k l ) was calculated as a function of acid concentration and temperature. The results suggest that the reaction with sulfuric acid forming methyl hydrogen sulfate and dimethyl sulfate is the dominant loss mechanism of methanol and that the oxidation of methanol is only a minor source of hydroxyl radicals in the upper troposphere. † Part of the special issue "Harold Johnston Festschrift". Dedicate to Professor Harold Johnston for his contributions to atmospheric chemistry.

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Section: Resultsmentioning

confidence: 99%

Uptake of Methanol Vapor in Sulfuric Acid Solutions

Leu

Kane

2000

J. Phys. Chem. A

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“…20 Viscosities were calculated from Williams and Long. 21 The rate coefficient, k, for methanol reaction with H 2 SO 4 has been measured at room temperature 22,23 and can be estimated to be on the order of 10 -10 s -1 for our experimental conditions. Values as small as this exerted no discernible influence on the values of H* obtained, thus the results reported here were obtained by setting k ) 0.…”

Section: Experimental Techniquesmentioning

confidence: 95%

“…It has long been known that primary alcohols will react with concentrated H 2 SO 4 to form mono-and dialkyl sulfates, 22,[27][28][29] so it is necessary to consider reaction as a parallel uptake process which may influence our solubility measurements at low temperatures. Few quantitative reports exist for methanolsulfate "esterification," but the available data 22,23 are summarized in the Appendix. In this section we show that our data suggest k e 3 × 10 -5 s -1 .…”

Section: Slow Reaction Between Methanol and H 2 Somentioning

confidence: 99%

Solubility of Methanol in Low-Temperature Aqueous Sulfuric Acid and Implications for Atmospheric Particle Composition

2002

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“…Lastly, alcohols may react with sulfuric acid to form sulfate esters ( Deno and Newman, 1950 ; Iraci et al, 2002 ; Michelsen et al, 2006 ; Minerath et al, 2008 ; Van Loon and Allen, 2004 , 2008 ; Vinnik et al, 1986 ), so alcohol species including the diol formed by hydration of propanal and/or (hemi-)acetals ( Surratt et al, 2008 ) formed from propanal ( Fig. 1c ) could react directly with sulfuric acid to form organosulfates similar to those formed by reaction of glyoxal on sulfuric acid aerosols ( Liggio et al, 2005 ).…”

Section: Introductionmentioning

confidence: 99%

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

et al. 2015

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Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

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Kinetics and mechanism of formation and hydrolysis of acid methyl sulfate in aqueous solutions of sulfuric acid

Cited by 9 publications

References 9 publications

Uptake of Methanol Vapor in Sulfuric Acid Solutions

Uptake of Methanol Vapor in Sulfuric Acid Solutions

Solubility of Methanol in Low-Temperature Aqueous Sulfuric Acid and Implications for Atmospheric Particle Composition

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

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