Pulse radiolysis of dimethyl sulphoxide

Koulkès-Pujo, A. M.; Gilles, L.; Lesigne, B.; Sutton, J.

doi:10.1039/c29710000749

Cited by 14 publications

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“…The situation with respect to solvated electron yields when high concentration of base is added is as follows. In the normal spur theory, the recombination between e"-+ -' + H20 (5) eai" + -OH -OH" (6) OH" + Haq+ -> H20 (7) and H90 eaq-+ ß"--H2 + 20 H" (8) will explain the higher initial yields of products. When OHis added as a scavenger of Haq+ in the spur, a higher yield is expected.…”

Section: Introductionmentioning

confidence: 99%

Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

Wolff¹,

Aldrich²,

Penner³

et al. 1975

J. Phys. Chem.

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Publication costs assisted by the Ontario Cancer InstituteThe stroboscopic pulse radiolysis, spr, system has been used to determine the yield of electrons in aqueous solution 30 psec after irradiation in the presence of high concentrations of scavenger. Using Cd2+ and cystamine as efficient electron scavengers a yield, G (product), of at least 4.8 molecules/100 eV is found for electrons compared to ag(eaq-)30psec of 4.0. The yield of eaq_ has also been investigated in high concentration of base. There is found to be very little, if any, increase in initial yield at concentrations up to 1 M NaOH. Small increases (~13%) are noted in initial yield at concentrations up to 5 M which are attributed to recombination of species in the radiation "spurs" or to hole reactions. Very little increase in yield was noted when high concentrations (5 M) of NaCl were used (~3%). By taking into account both the fast electron addition to scavengers observed in this paper and assuming the spur yield can be given by a simple equation, g (eaq"")t = 2.7 + 1.3 exp(-108f), excellent agreement was obtained between these pulse radiolysis studies and steady-state yields. The total yield of electrons can be described by the equation, G (product) = 4.8(1 -exp(-[S]/C37) + exp(-[S]/C37)(2.7 + 1.3/z [S])/(108 + k [S])), again in agreement with other product yield studies.

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Section: Introductionmentioning

confidence: 99%

Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

Wolff¹,

Aldrich²,

Penner³

et al. 1975

J. Phys. Chem.

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“…The length of the chain reaction is limited by biradical termination reactions that include reactions (11), (14), (15), (16), (17), and (18). The products of these reactions are reasonable but unknown and were not measured.…”

Section: Resultsmentioning

confidence: 99%

“…The products of these reactions are reasonable but unknown and were not measured. (18) To check this suggestion, irradiation was repeated with a γ source having a lower dose rate ( Table 1). As expected, the chain length in this experiment is considerably longer (G t = 111).…”

Section: Resultsmentioning

confidence: 99%

BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution

Yanus

Yardeni²,

Maimon

et al. 2016

Eur J Inorg Chem

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“…Our observation that e,-in DMSO/H,O mixtures have single absorption bands intermediate between that in pure water and that in pure DMSO leads us to the different conclusion that the absorption band at low DMSO concentrations, though very similar to that in water, is due to e,-and not simply to e,,-. Koulkes-Pujo et al (37) have reported increasing values of (rate of decay of e,-)/G(e,-) with increasing DMSO concentration up to 0.08 mole fraction DMSO. Their observation is consistent with an increased decay rate and/or a lower yield of e,-with increased concentration of DMSO.…”

Section: Resultsmentioning

confidence: 99%

“…On the other hand, DMSO has a high dielectric constant (D, = 46 at 25 "C), a large dipole moment (4. yield of reducing species was measured by the use of N,O at 0.08 M to be 1.8 f 0.2 (2). Anthracene (A) has been used as a n electron scavenger in pulse radiolysis studies by KoulkesPujo et al (3) and Hayon (4) to give-yields of G(A-) of 0.64 and 1.62 respectively. These results will be discussed later in relation to our data using A as an electron scavenger and Br-as a scavenger for the oxidizing species.…”

Section: Introductionmentioning

confidence: 99%

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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Pulse radiolysis of dimethyl sulphoxide

Cited by 14 publications

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Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution

The Pulse Radiolysis of Dimethylsulfoxide and Binary Mixtures with Water

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Pulse radiolysis of dimethyl sulphoxide

Cited by 14 publications

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Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

Picosecond pulse radiolysis. V. Yield of electrons in irradiated aqueous solution with high concentrations of scavenger

BH4–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH3)2SO by N2O in Aqueous Solution

The Pulse Radiolysis of Dimethylsulfoxide and Binary Mixtures with Water

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BH₄^–‐Promoted, Radical‐Initiated, Catalytic Oxidation of (CH₃)₂SO by N₂O in Aqueous Solution