Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Anne Schou Hansen; Henrik Grum Kjærgaard

doi:10.1021/acs.jpca.7b06102

Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Anne Schou Hansen, Henrik Grum Kjærgaard

Department of Chemistry

4 Citations (Scopus)

Abstract

Dimethyl sulfoxide (DMSO) is an important intermediate in the atmospheric oxidation of dimethyl sulfide (DMS). DMS, emitted from the ocean, is the main natural sulfur source, and its oxidation products are essential in the formation of sulfate aerosols. The high atmospheric concentration of water makes hydrogen bonding with DMS and its oxidation products likely. Through hydrogen bonding, water can potentially catalyze and affect the steps of the oxidation. We investigate binary hydrogen-bound complexes involving DMSO. Both water·DMSO and methanol·DMSO complexes are identified in an Ar matrix, and at room temperature, a Gibbs free energy of 0.7 kJ/mol for the formation of the methanol·DMSO complex is determined. Assuming a similar Gibbs free energy of the hydrate, it would suggest a relatively high abundance of the DMSO hydrate relative to the monomer in the atmosphere. The effect of changing the atom divalently bound to the hydrogen bond accepting oxygen, from S to C (DMSO to acetone), is found to significantly decrease the equilibrium constant of complex formation.

Original language	English
Journal	The Journal of Physical Chemistry Part A
Volume	121
Issue number	32
Pages (from-to)	6046-6053
Number of pages	8
ISSN	1089-5639
DOIs	https://doi.org/10.1021/acs.jpca.7b06102
Publication status	Published - 17 Aug 2017

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title = "Dimethyl Sulfoxide Complexes Detected at Ambient Conditions",

abstract = "Dimethyl sulfoxide (DMSO) is an important intermediate in the atmospheric oxidation of dimethyl sulfide (DMS). DMS, emitted from the ocean, is the main natural sulfur source, and its oxidation products are essential in the formation of sulfate aerosols. The high atmospheric concentration of water makes hydrogen bonding with DMS and its oxidation products likely. Through hydrogen bonding, water can potentially catalyze and affect the steps of the oxidation. We investigate binary hydrogen-bound complexes involving DMSO. Both water·DMSO and methanol·DMSO complexes are identified in an Ar matrix, and at room temperature, a Gibbs free energy of 0.7 kJ/mol for the formation of the methanol·DMSO complex is determined. Assuming a similar Gibbs free energy of the hydrate, it would suggest a relatively high abundance of the DMSO hydrate relative to the monomer in the atmosphere. The effect of changing the atom divalently bound to the hydrogen bond accepting oxygen, from S to C (DMSO to acetone), is found to significantly decrease the equilibrium constant of complex formation.",

author = "Hansen, {Anne Schou} and Kj{\ae}rgaard, {Henrik Grum}",

year = "2017",

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doi = "10.1021/acs.jpca.7b06102",

language = "English",

volume = "121",

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journal = "Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory",

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TY - JOUR

T1 - Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

AU - Hansen, Anne Schou

AU - Kjærgaard, Henrik Grum

PY - 2017/8/17

Y1 - 2017/8/17

N2 - Dimethyl sulfoxide (DMSO) is an important intermediate in the atmospheric oxidation of dimethyl sulfide (DMS). DMS, emitted from the ocean, is the main natural sulfur source, and its oxidation products are essential in the formation of sulfate aerosols. The high atmospheric concentration of water makes hydrogen bonding with DMS and its oxidation products likely. Through hydrogen bonding, water can potentially catalyze and affect the steps of the oxidation. We investigate binary hydrogen-bound complexes involving DMSO. Both water·DMSO and methanol·DMSO complexes are identified in an Ar matrix, and at room temperature, a Gibbs free energy of 0.7 kJ/mol for the formation of the methanol·DMSO complex is determined. Assuming a similar Gibbs free energy of the hydrate, it would suggest a relatively high abundance of the DMSO hydrate relative to the monomer in the atmosphere. The effect of changing the atom divalently bound to the hydrogen bond accepting oxygen, from S to C (DMSO to acetone), is found to significantly decrease the equilibrium constant of complex formation.

AB - Dimethyl sulfoxide (DMSO) is an important intermediate in the atmospheric oxidation of dimethyl sulfide (DMS). DMS, emitted from the ocean, is the main natural sulfur source, and its oxidation products are essential in the formation of sulfate aerosols. The high atmospheric concentration of water makes hydrogen bonding with DMS and its oxidation products likely. Through hydrogen bonding, water can potentially catalyze and affect the steps of the oxidation. We investigate binary hydrogen-bound complexes involving DMSO. Both water·DMSO and methanol·DMSO complexes are identified in an Ar matrix, and at room temperature, a Gibbs free energy of 0.7 kJ/mol for the formation of the methanol·DMSO complex is determined. Assuming a similar Gibbs free energy of the hydrate, it would suggest a relatively high abundance of the DMSO hydrate relative to the monomer in the atmosphere. The effect of changing the atom divalently bound to the hydrogen bond accepting oxygen, from S to C (DMSO to acetone), is found to significantly decrease the equilibrium constant of complex formation.

U2 - 10.1021/acs.jpca.7b06102

DO - 10.1021/acs.jpca.7b06102

M3 - Journal article

C2 - 28715183

SN - 1089-5639

VL - 121

SP - 6046

EP - 6053

JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 32

ER -

Dimethyl Sulfoxide Complexes Detected at Ambient Conditions

Abstract

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