Pulsradiolytische Untersuchung von Dimethylthioäther und Dimethylsulfoxyd in wäßriger Lösung

Meissner, G.; Henglein, A.; Beck, G.

doi:10.1515/znb-1967-0105

Cited by 58 publications

(34 citation statements)

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“…The most studied reactions are those with OH, a key gas phase and aqueous phase atmospheric oxidant. Several studies of the OH + DMSO reaction have been reported (Meissner et al, 1967;Reuvers et al, 1973;Veltwisch et al, 1980;Milne et al, 1989;Bardouki et al, 2002) which are in good agreement, suggesting a room temperature rate coefficient in the range of (6 ± 2) ¥ 10 9 M -1 s -1 . One study of the OH + DMSO2 reaction (Milne et al, 1989) reports a relatively slow rate coefficient of 3.0 ¥ 10 7 M -1 s -1 .…”

Section: Introductionsupporting

confidence: 54%

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Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Zhu

Nicovich

Wine

2003

Aquatic Sciences - Research Across Boundaries

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A laser flash photolysis -long path UV-visible absorption -competitive kinetics technique has been employed to investigate the kinetics of the aqueous phase reactions between the hydroxyl radical (OH) and three organic sulfur species of atmospheric interest, dimethylsulfoxide (DMSO; CH 3 S(O)CH 3 ), dimethylsulfone (DMSO2; CH 3 (O)S(O)CH 3 ), and methanesulfonate (MS; CH 3 (O)S(O)O -). Thiocyanate anion (SCN -) has been employed as the competitor. Temperature dependent rate coefficients for the reactions of interest are reported for the first time. The following Arrhenius expressions adequately summarize the kinetic data obtained over the temperature range 275 -310 K (units are M -1 s -1 ): ln k DMSO = Aquat. Sci. 65 (2003) 425-435 Aquatic Sciences (26.88 ± 0.14) -{(1270 ± 40)/T}; ln k DMSO2 ≤ (22.36 ± 0.17) -{(1690 ± 50)/T}; ln k MS = (25.20 ± 0.13) -{(2630 ± 40)/T}. Uncertainties in the Arrhenius parameters are 2s and represent precision only. The accuracies of individual measured rate coefficient ratios, k X (T)/k SCN -(T) (X = DMSO, DMSO2, or MS), are estimated to be ±5% independent of T and the identity of X. Taking uncertainties in k SCN -(T) into account, we estimate the absolute accuracy of reported rate coefficients to be 16 % at 275 K, 9 % at 295 K, and 12 % at 310 K. The implications of the new kinetics results for understanding the atmospheric sulfur cycle are discussed.

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Section: Introductionsupporting

confidence: 54%

“…Room temperature (295 K) rate coefficients determined in this study are compared with literature values in Table 2. All data summarized in Meissner et al, 1967;2. Reuvers et al, 1973;3.…”

Section: Comparison With Previous Workmentioning

confidence: 99%

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Zhu

Nicovich

Wine

2003

Aquatic Sciences - Research Across Boundaries

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“…The formation of SO, indicates that the addition pathway is not necessarily related only to the formation of CH,SO,H, but could also lead to the production of SO, as well. The same reaction has been studied by Meissner et al (1967) in aqueous solutions of sulfoxides and a YIN, DANIEL GROSJEAN, AND JOHN H. SEINFELD similar reaction rate constant of 1.2 X lo-" cm3 molecule-' s-l has been reported (Gilbert et al, 1975a). While CH,S(O)CH, and CH,S(O),CH, may react with a number of radicals in the atmosphere, their reaction with OH is likely to be the most important chemical loss process, and their reactions with NO, could also be important at nighttime in the atmosphere.…”

Section: Reaction Of Chs(o) Chmentioning

confidence: 97%

Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

1990

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Detailed theoretical (Part I, this article) and experimental (Part II) investigations are presented for the mechanism of the atmospheric photooxidation of dimethyl sulfide (CH,SCH,) and dimethyi disulfide (CH,SSCH,). In this paper, comprehensive mechanisms for the atmospheric chemistry of CH,SCH, and CH,SSCH, are developed based on fundamental considerations of all available kinetic and mechanistic information.

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“…At a mole fraction of 0.017 the rate constant is 2.9 x lo6 M-' s-' but the rate constant seems to be decreasing as the concentration of DMSO decreases. Meissner et al (36) reported a value of 1.7 x lo6 M -I s-' for the reaction of es-with DMSO in alkaline solutions of DMSO slightly more dilute than 0.017 mole fraction.…”

Section: Resultsmentioning

confidence: 98%

The Pulse Radiolysis of Dimethylsulfoxide and Binary Mixtures with Water

Cooper¹,

Walker²,

Gillis³

et al. 1973

Can. J. Chem.

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The simultaneous interaction of solvated electrons with strongly solvating water molecules and weakly solvating dimethylsulfoxide (DMSO) molecules has been studied by pulse radiolysis. In all DMSO/H,O mixtures investigated the solvated electrons have a single absorption band with a maximum intermediate between that of pure DMSO (X,,,> 1500 nm) and that of water (X,,,=720 nm). There is a nearly linear relationship between the photon energy of h,,, and the bulk dielectric constant, indicating that the optical properties of solvated electrons in the mixtures are not dominated by the water. A minimum is observed in the variation of GE,,, with DMSO/H,O composition which may be associated with intermolecular structure. In mixtures containing >0.2 mole fraction DMSO the solvated electrons have half-lives of 11-18 ns.The radiation produced oxidizing species in DMSO has a half-life of 1-4 ps and an absorption band centered at 600 nm. This species seems to be present in all DMSO/H,O mixtures.Pure DMSO gives a free-ion yield in the range 1.2 to 1.8, as determined separately for the oxidizing and reducing species by bromide and anthracene scavenging experiments respectively. This free-ion yield is in keeping with the dielectric constant of DMSO of 46. The yields in fully deuterated D M S O are -30% higher than in the protonated material.L'interaction simultanee des electrons solvates sur des molCcules d'eau fortement solvatantes e t des molecules de dimCthylsulfoxyde (DMSO) faiblement solvatantes a ttC etudide par radiolyse pulsee. Dans tous les melanges DMSO/H,O CtudiCs, les electrons solvates ont une bande d'absorption simple dont le maximum se situe entre celui du DMSO pur (X,,, > 1500 nm) et celui de I'eau (X, , , = 720 nm).Une relation presque lintaire existe entre I'Cnergie du photon du h,,, et la constante dielectrique du melange, montrant ainsi que les proprittes optiques des electrons solvates dans ces melanges ne sont pas masquees par I'eau. On a observe un minimum dans la variation de GE,,, avec la composition DMSO/ H20, ce fait peut Ctre associe a une structure intermolCculaire. Dans les melanges > 0.2 en fractionsmolaire de DMSO, les electrons solvates ont des demi-vies de 11-18 ns. L'espece oxydante produite par la radiation dans le DMSO a une demi-vie de 1-4 ps et une bande d'absorption centree a 600 nm. Cette espece semble Etre presente dans tous les melanges DMSO/H,O. Le DMSO pur donne un rendement en ion libre de 1.2 a 1.8, determine separement sur I'espece oxydante et reductrice par les experiences de piegeage par le bromure et I'anthracene respectivement. Ce rendement en ion libre est en accord avec la constante diklectrique du DMSO de 46. Les rendements dans le DMSO totalement deutkrie sont de -30% plus eleves que pour le DMSO protone.[ Introduction We have previously shown that the solvated electron (e,-) in dimethylsulfoxide (DMSO) is very weakly trapped, as evidenced by an absorption band in the near i.r. similar to that found in hydrocarbons (1). This was attributed to the strictly aprotic nature of...

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Pulsradiolytische Untersuchung von Dimethylthioäther und Dimethylsulfoxyd in wäßriger Lösung

Cited by 58 publications

References 0 publications

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate

Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

The Pulse Radiolysis of Dimethylsulfoxide and Binary Mixtures with Water

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