Reactions of gaseous pollutants with solids. II. Infrared study of sorption of sulfur dioxide on magnesium oxide

Goodsel, A. J.; Low, M. J. D.; Takezawa, Nobutsune

doi:10.1021/es60062a001

Cited by 52 publications

(45 citation statements)

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“…As mentioned in the Introduction, the absorption bands for δ ip (COH) of H 2 CO 3 , V as (COO -) of bidentate and bridged carbonates are very close to the band around 1273 cm -1 , and SO 4 2-may also contribute to the band at 1250 cm -1 . 21 Therefore, the assignment for the bands at 1578, 1333, and around 1273 cm -1 need be further carefully confirmed.…”

Section: Surface Species For the Heterogeneous Reaction Of Cos On Mgomentioning

confidence: 97%

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Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

2009

J. Phys. Chem. A

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In situ diffuse reflectance infrared Fourier transform spectroscopy combined with derivative spectroscopy analysis, two-dimensional correlation spectroscopy analysis, and quantum chemical calculations were used to investigate the infrared absorbance assignment and the molecular structure of hydrogen thiocarbonate on magnesium oxide. The bands at 1283 and 1257 cm -1 , which had the typical characteristic of intermediate, were observed in experiments for the heterogeneous reaction of COS on MgO. On the basis of two-dimensional correlation spectroscopy analysis and quantum chemical calculations, the band at 1283 cm -1 was assigned to the V s band of bridged thiocarbonate which formed on the two neighboring Mg atoms in the (100) face of MgO crystal, and the band at 1257 cm -1 was the V s band of monodentate thiocarbonate on MgO. The V as (OCO) band of thiocarbonates was invisible in the experiment due to their weak absorbance and the interruption of surface carbonate. The formation mechanism of thiocarbonates is proposed, which occurred through a nucleophilic attack of preadsorbed COS by surface -OH groups followed by hydrogen atom transfer from the -OH group to the sulfur atom of preadsorbed COS. The activation energy for the intramolecular protontransfer reaction of bridged thiocarbonate was calculated to be 18.52 kcal · mol -1 at the B3LYP/6-31+G(d,p) level of theory.

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Section: Surface Species For the Heterogeneous Reaction Of Cos On Mgomentioning

confidence: 97%

“…For example, the absorption bands for δ ip . 21 The bands at 1574 and 1327 cm -1 may also originate from surface carbonate 22 and physisorbed SO 2 , 23,24 respectively. Therefore, the assignment of infrared absorbance and molecular structure of HTC on mineral oxides need to be further carefully confirmed.…”

Section: Introductionmentioning

confidence: 98%

Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

2009

J. Phys. Chem. A

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“…3. Peaks were counted if they were more than three times the noise at the peak position (Goldstein et al, 1981), and an approximate height was measured by overlaying a grid as shown in the figure. The known composition of the dust (Hanisch and Crowley, 2003) was used to determine relative sensitivity factors (RSF) for the different elements based on the EDX measurements on unreacted dust grains.…”

Section: Sem Analysismentioning

confidence: 99%

“…This study will only consider irreversible uptake, which can account for >98 % of uptake at low SO 2 concentrations (Adams et al, 2005;Goodman et al, 2001). The initial uptake coefficient on Sahara dust, γ = 4 × 10 −5 , is not dependent on RH, [SO 2 ] or O 3 (Crowley et al, 2010) which suggests SO 2 adsorption is the rate-limiting step, rather than subsequent reactions and oxidation (Ullerstam et al, 2002).…”

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confidence: 99%

“…NO 2 (g) and surface nitrate have been observed to oxidise surface sulfite (Ullerstam et al, 2003), and oxidation to CaSO 4 occurs when calcite is exposed to SO 2 and O 2 (Al-Hosney and Grassian, 2005). Sulfate production has even been observed on MgO in the absence of O 2 and O 3 , and was attributed to the highly basic character of four-coordinated O anions on steps and corners (Pacchioni et al, 1994;Goodman et al, 2001). In this study, SO 2 will always be exposed to dust in synthetic air, and the reaction time will be very long, so the oxidation of adsorbed sulfite to sulfate should be close to completion (Ullerstam et al, 2002).…”

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confidence: 99%

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Sulfur isotope fractionation during heterogeneous oxidation of SO<sub>2</sub> on mineral dust

Harris

Sinha

Foley³

et al. 2012

Atmos. Chem. Phys.

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Abstract. Mineral dust is a major fraction of global atmospheric aerosol, and the oxidation of SO 2 on mineral dust has implications for cloud formation, climate and the sulfur cycle. Stable sulfur isotopes can be used to understand the different oxidation processes occurring on mineral dust. This study presents measurements of the 34 S/ 32 S fractionation factor α 34 for oxidation of SO 2 on mineral dust surfaces and in the aqueous phase in mineral dust leachate. Sahara dust, which accounts for ∼60 % of global dust emissions and loading, was used for the experiments.The fractionation factor for aqueous oxidation in dust leachate is α leachate = 0.9917±0.0046, which is in agreement with previous measurements of aqueous SO 2 oxidation by iron solutions. This fractionation factor is representative of a radical chain reaction oxidation pathway initiated by transition metal ions. Oxidation on the dust surface at subsaturated relative humidity (RH) had an overall fractionation factor of α het = 1.0096 ± 0.0036 and was found to be almost an order of magnitude faster when the dust was simultaneously exposed to ozone, light and RH of ∼40 %. However, the presence of ozone, light and humidity did not influence isotope fractionation during oxidation on dust surfaces at subsaturated relative humidity. All the investigated reactions showed mass-dependent fractionation of 33 S relative to 34 S.A positive matrix factorization model was used to investigate surface oxidation on the different components of dust. Ilmenite, rutile and iron oxide were found to be the most reactive components, accounting for 85 % of sulfate production with a fractionation factor of α 34 = 1.012±0.010. This overlaps within the analytical uncertainty with the fractionation of other major atmospheric oxidation pathways such as the oxidation of SO 2 by H 2 O 2 and O 3 in the aqueous phase and OH in the gas phase. Clay minerals accounted for roughly 12 % of the sulfate production, and oxidation on clay minerals resulted in a very distinct fractionation factor of α 34 = 1.085±0.013. The fractionation factors measured in this study will be particularly useful in combination with field and modelling studies to understand the role of surface oxidation on clay minerals and aqueous oxidation by mineral dust and its leachate in global and regional sulfur cycles.

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Infrarotspektroskopische Untersuchungen der Adsorption von Schwefeldioxid an Zeolithen vom Typ A

Förster

Seelemann

1976

Ber Bunsenges Phys Chem

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Die Sorption von Schwefeldioxid wurde an im UHV entgasten Zeolithen NaA und NaCaA infrarotspektroskopisch untersucht. Aus der Lage der beobachteten Banden, ihrer Veränderung mit der Zeit und dern Belegungsgrad auch hinsichtlich ihrer Intensitätsverhältnisse und dem Verhalten bei Desorption wird auf zwei unterschiedliche Sorptionszustände geschlossen: physisorbierte Spezies mit ν3‐Banden bei 131520 cm−1 (NaA) bzw. 131530 cm−1 (NaCaA) und einer fester gebundenen Spezies bei 1300 cm−1 (NaA) bzw. 1280 cm−1 (NaCaA), für die eine gleichzeitige Bindung des Adsorpts an ein Kation und ein Sauerstoffion der Hohlraumwand angenommen wird. In Überein‐stimmung mit anderen gewinkelten dreiatomigen Molekülen sind die Banden der Kombinations‐ und der asymmetrischen Valenzschwingungen gegenüber der Gasphase nach niedrigeren Wellenzahlen verschoben, wobei eine stärkere Wechselwirkung mit einer größeren Frequenzverschiebung verbunden ist. Einige Ergebnisse der Koadsorption von Schwefeldioxid mit Wasserstoff bzw. Kohlendioxid werden diskutiert.

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Reactions of gaseous pollutants with solids. II. Infrared study of sorption of sulfur dioxide on magnesium oxide

Cited by 52 publications

References 10 publications

Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

Sulfur isotope fractionation during heterogeneous oxidation of SO<sub>2</sub> on mineral dust

Infrarotspektroskopische Untersuchungen der Adsorption von Schwefeldioxid an Zeolithen vom Typ A

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Reactions of gaseous pollutants with solids. II. Infrared study of sorption of sulfur dioxide on magnesium oxide

Cited by 52 publications

References 10 publications

Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

Experimental and Theoretical Study of Hydrogen Thiocarbonate for Heterogeneous Reaction of Carbonyl Sulfide on Magnesium Oxide

Sulfur isotope fractionation during heterogeneous oxidation of SO&lt;sub&gt;2&lt;/sub&gt; on mineral dust

Infrarotspektroskopische Untersuchungen der Adsorption von Schwefeldioxid an Zeolithen vom Typ A

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Sulfur isotope fractionation during heterogeneous oxidation of SO<sub>2</sub> on mineral dust