Pulse radiolysis of solutions of amines of low ionization potential

Kemp, Terence J.; Roberts, J. P.; Salmon, G. Arthur; Thompson, G. F.

doi:10.1021/j100851a012

Cited by 17 publications

(10 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The techniques of sample preparation, saturation with argon or nitrous oxide, and details of the pulse radiolysis apparatus have been described previously (16)(17)(18). Pulse lengths from 10 ns to 0.2 ~s were chosen as appropriate.…”

Section: Methodsmentioning

confidence: 99%

The yield and extinction coefficient of the solvated electron in methanol: pulse radiolysis of nitrobenzene and tetranitromethane solutions

Johnson¹,

Salmon²

1977

Can. J. Chem.

View full text Add to dashboard Cite

. Can. J. Chem. 55.2030Chem. 55. (1977. The radical anion C 6 H 5 N 0 2 -, NB-, which has a strong absorption spectrum from 250-500 nm, is formed by reaction of nitrobenzene with solvated electrons, e,-, and hydroxymethyl radical anions, ' C H 2 0 -, with kl = (1.92 t 0.35) x 10" M -' s-' and k, = (1.03 k 0.02)GE~. is constant for NB-over a wide range of nitrobenzene concentrations in basic solution. By assuming that the yields of scavengeable radicals are the same in neutral and basic solutions we obtain E ( N B -) ,~~, , = (1.66 & 0.02) x lo4 IM-' cm-'. This value is used to evaluate the yield of e,-scavengeable by dilute solutions of solutes as G(e,-),,, = 1.20 1 0.03. Extinction coefficients of es-, hydroxymethyl radicals, 'CH20H, and 'CH,O-and the oscillator strength of the e,-absorption are calculated.The yields of e,-determined by previous workers are discussed in terms of dry, damp, geminate, free, spur, and escaped electrons. A model is constr~~cted in terms of damp, spur, and escaped electrons which compares favourably with experimental scavenging results and direct measurements by optical pulse radiolysis. La valeur de GEI. est constante pour NB' des concentrations de nitrobenzkne trPs diverses lorsque I'on travaille en solution basique. En faisant I'hypothese que les rendements des radicaux qui peuvent Ctre pieges sont les m&mes en solutions neutres et basiques, on obtient la valeur E(NB-),,~ . , = (1.66 i 0.02) x lo4 M -' cm-'. On peut utiliser cette valeur pour evaluer le rendement en e,-piegeable pour des solutions dilutes de solutCs; alors G(e,-),,, =

show abstract

Section: Methodsmentioning

confidence: 99%

The yield and extinction coefficient of the solvated electron in methanol: pulse radiolysis of nitrobenzene and tetranitromethane solutions

Johnson¹,

Salmon²

1977

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…Kemp et al (5) obtained G = 1.7 for the yield of radical cations of TMPD in DMSO which they attribute to the "free ion" yield. Hayon (4) has also recently reported G = 1.62 as the yield of anthracene anions produced from solvated electrons in DMSO.…”

Section: Discussionmentioning

confidence: 99%

“…If the reaction 1 was in competition with [5] then the hydrogen do not affect the gaseous yields of pure DMSO at all (Fig. 3 For personal use only.…”

Section: Discussionmentioning

confidence: 99%

“…Some recent studies on aspects of the radiolysis radiolysis absorption spectroscopy using various solutes to scavenge electrons and cations produced (4,5). The only other report (6) on the radiolysis of DMSO concerns a study of DMSO containing 0.4 M H2S04 where the chemistry seems to be rather different, since neither solvated electrons nor solvent anions can be involved in secondary reactions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Free-ion Yield in the Radiolysis of Dimethylsulfoxide

Cooper¹,

Walker²

1971

Can. J. Chem.

View full text Add to dashboard Cite

Dimethylsulfoxide is a dipolar aprotic solvent of high basicity having a large dielectric constant (E = 48) but very low solvating power for negative ions. The radiation yield of "free ions" in this liquid is in accord with the dielectric constant, G(free ions) = 1.8 f 0.2, but these "free ions" do not resemble the strongly solvated electrons found in other polar media such as water and aliphatic alcohols. Evidence for this conclusion is based principally on competitive reactions involving a wide range of scavengers in competition with nitrous oxide. The radiation yields of gaseous products from pure liquid dimethylsulfoxide are G(H2) = 0.20 f 0.01, G(CH4) = 3.3 + 0.1, and G(C2H6) = 0.49 f 0.03.Le dimCthylsulfonyle est un solvant dipolaire aprotique de haute basicit&, ayant une constante dielectrique BlevCe (E = 48) mais un pouvoir de solvatation tres faible pour les ions negatifs. Le rendement d"ions libres" obtenus par radiation dans ce liquide, G(ions libres) = 1.8 + 0.2, est en accord avec la constante dielectrique mais ces ions libres ne ressemblent pas du tout aux electrons hautement solvatb trouves dans des milieux polaires comme I'eau ou les alcools aliphatiques. Les preuves supportant cette conclusion sont basks principalement sur les reactions competitives impliquant un grand nombre de scavangers en competition avec l'oxyde nitreux. Les rendements de produits gazeux obtenus par radia-

show abstract

“…9 All chemicals were purchased from Aldrich and were used as received. 17 O-enriched oxygen (37% of O-17) was obtained from Icon. If oxygen saturation was needed, the samples were sealed with the small amount of liquid oxygen in quartz ESR tubes and then brought to ambient temperature.…”

Section: Methodsmentioning

confidence: 99%

One-Electron Oxidation and Reduction of Sulfites and Sulfinic Acids in Oxygenated Media: The Formation of Sulfonyl and Sulfuranyl Peroxyl Radicals

Razskazovskii

Sevilla

1996

J. Phys. Chem.

View full text Add to dashboard Cite

Bisulfite anions and sulfinic acids are shown by ESR spectroscopy to undergo reduction with radiolytically produced free electrons and oxidation by hole centers (Cl 2 •-) in a low-temperature aqueous LiCl glass. Electronreduced intermediates display g anisotropy within the 2.010-2.002 range and are considered as neutral or singly deprotonated forms of sulfuranyl radicals (HO) 3 S • , (RO) 2 SOH • , and RS(OH) 2 • . The oxidized species produced by hole trapping are sulfite (SO 3 •-) and sulfonyl (RSO 2 • ) radicals. Dialkyl sulfites scavenge free electrons only and are not oxidized by Cl 2 •-. Both oxidized and reduced intermediates add oxygen on annealing forming peroxyl radicals which are identified by their characteristic oxygen-17 hyperfine couplings. A large 100 G oxygen-17 coupling with the terminal oxygen atom found for oxidized sulfite-oxygen adduct -O 3 SOO • is in accord with its known high reactivity. Sulfuranyl peroxyls formed by the reductive pathway show lower 17 O couplings (e.g., 90 G with terminal oxygens) and are expected to be far less reactive than alkyl peroxyls. Ab initio MO calculations predict stable structures for these sulfuranyl peroxyls, suggesting a trigonal-bipyramid coordination of the central sulfur atom. However, the sulfuranyl intermediates formed through one-electron reduction of dimethyl and methylphenyl sulfoxides are found to be unstable even in low-temperature glass, fragmenting into a methyl radical and sulfenic acid or into a hydroxyl anion and sulfide radical cation, respectively.

show abstract

Pulse radiolysis of solutions of amines of low ionization potential

Cited by 17 publications

References 0 publications

The yield and extinction coefficient of the solvated electron in methanol: pulse radiolysis of nitrobenzene and tetranitromethane solutions

The yield and extinction coefficient of the solvated electron in methanol: pulse radiolysis of nitrobenzene and tetranitromethane solutions

Free-ion Yield in the Radiolysis of Dimethylsulfoxide

One-Electron Oxidation and Reduction of Sulfites and Sulfinic Acids in Oxygenated Media: The Formation of Sulfonyl and Sulfuranyl Peroxyl Radicals

Contact Info

Product

Resources

About