Kinetics of electron-transfer and in tetrahydrofuran

Fisher, M.; Rämme, Göran; Claesson, Stig; Szwarc, M.

doi:10.1016/0009-2614(71)80226-9

Cited by 20 publications

(18 citation statements)

References 12 publications

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“…Reaction 23 representing the collapse of sodium ion-pairs into sodium atoms, NaO, was proposed by Fisher et al (8,9) If we exclude this process the computed yield of N a continues to increase slightly rather than level off with time as depicted in Fig. 10.…”

Section: Solutions Of Thf Contairling Naalhmentioning

confidence: 85%

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Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

Salmon¹,

Seddon²,

Fletcher³

1974

Can. J. Chem.

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. Can. 9. Chem. 52.3259(1974). Pulse radiolysis of solutions of alkali metal cations in tetrahydrofuran (THFj demonstrates the formation of solvated electrons e,-, alkali metal cation -ion pairs (M', e,-), and alkali metal anions M -. This paper describes the spectra, extinction coefficients, and radiolytic yields of es-, iithium, sodium, potassium, and cesium species in TFIF. The reaction kinetics are colnplex but largely involve reactions A and B with the concomitant disappearance of all three species by reaction with radiolytically produced radicals. Rate constants and ion-pair dissociation constants for e,-and the sodium and potassium species are presented and compared with data established from studies of blue solutions of alkali metals dissolved in THF. e,-+ M + (M+, e,-)

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Section: Solutions Of Thf Contairling Naalhmentioning

confidence: 85%

“…10. Using k,, = 4 x lo3 s P 1 (8,9) causes Na-to contiiuouslv decrease. Reactions 24 and 25 assume that NaO would react in an analogous manner to (Na', e,- FIG.…”

Section: Solutions Of Thf Contairling Naalhmentioning

confidence: 99%

Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

Salmon¹,

Seddon²,

Fletcher³

1974

Can. J. Chem.

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“…(Na22+, es-) + es--Na-+ Na+ (13) (Na22+, es-) + (Na+, es-) -Na-+ 2Na+ (14) (Na22+, es-) + (Na22+, es-) -Na-+ 3Na+ (15) At low methylamide concentrations and/or high doses per pulse, additional refinements are necessary to account for the reaction of es-and metal-electron species with radiolytically produced radicals. For example es-+ R -product (16) (Na+, es-) or (Na22+, es-) or Na-+ R ->-product (17) For a given dose per pulse this effect decreases with increasing concentrations of methylamide, suggesting that the solvent base differs from other solute anions in that the radicals (or geminate and parent positive ions) are converted into a less reactive basic form.…”

Section: Reactionmentioning

confidence: 99%

“…(Na+, es-) + es--» Na-2.0 X 109 M~' sec-1 (-9) Na--* (Na+, es-) + es-8.0 X 102 sec" (8) (Na+, es-) + (Na+, es-)-> Na' " + Na+ 2.0 X 109 M-1 sec-1 (12) (Na+, es-) + Na+ -» (Naj+, e " ") 5.0 X 10 7M-1 sec-1 (-12) (Na, , e -) -> (Na+, es-) + Na 4 1.2 X 10s sec" (13) (Na, , e-) + es--* Na -+ Na+ 6.7 X 109 M~' sec-1 (14) (Na2+,e-) + (Na+,es-)->Na-4 2Na+ 6.7 X 109 M~' sec-1 (15) (Na2+, e-) + (Na2+, e-) -* Na' " 4 3Na+ 2.0 X 109 M~' sec-1 (16) es-+ R -> product 6.6 X 1010 M~1 sec-: I [ (Na+, es-) + R -* product 6.6 X 1010 M~1 sec-! (17) In general the overall rate of formation of Nais not significantly different from that expected in solutions containing just Na+. In the second, or "alkaline earth" category, the situation is much different.…”

Section: Reactionmentioning

confidence: 99%

Alkali metal species in liquid amines, ammonia, and ethers. Formation by pulse radiolysis

Fletcher¹,

Seddon²

1975

J. Phys. Chem.

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“…Electron photoejection from solutions of radical anions was first observed in rigid media by Hoytink and others (Hoytink & Zandstra i960;van Voorst & Hoytink 1965 and later in fluid phases by Eloranta & Linschitz (1963) and by Giling Kloosterboer, Rettschnick & van Voorst (1971). The electron photoejection from sodium pyrenide (tt7, Na+) in tetrahydrofuran (THF) was reported by us in a preliminary communication (Fisher, Ramme, Claesson & Szwarc 1971).…”

Section: Electron Transfer Processesmentioning

confidence: 88%

Kinetics of electron transfer processes involving free ions and ion pairs studied by flash photolysis

Rämme

Fisher

Claesson

et al. 1972

Proc. R. Soc. Lond. A

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Photoejection of electrons from pyrenide ions (π. - ) or sodium pyrenide ion pairs (π. - , Na + ) was effected in tetrahydrofuran (THF) or tetrahydropyran (THP) solution by flash of light (λ > 420 nm). As the reaction was performed in the presence of a large excess of biphenyl (B) the ejected electrons were captured preferentially by that hydrocarbon reducing it to biphenylide radical ion (B. - or B. - , Na + ). Due to the low concentration of pyrene (π) the subsequent reactions between biphenylide and pyrene, namely B. - + π ( k 1 →) B + π. - (1) and B. - , Na + + π ( k 2 →) B + π. - , Na + , (2) could be easily monitored after the flash. By varying the ratio of [B. - ]/[B. - , Na + ] it was possible to make either (1) or (2) dominant, and hence to determine the rate constants k 1 and k 2 . Thus, k 1 = (4.8 ± 0.5) x 10 10 1 mol -1 s -1 and k 2 = 0.6 x 10 10 1 mol -1 s -1 for the electron transfer in THF, and k 2 = 0.5 x 10 10 1 mol -1 s -1 for the reaction in THP, all the constants referring to ≈ 20 °C.

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Kinetics of electron-transfer and in tetrahydrofuran

Cited by 20 publications

References 12 publications

Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

Alkali metal species in liquid amines, ammonia, and ethers. Formation by pulse radiolysis

Kinetics of electron transfer processes involving free ions and ion pairs studied by flash photolysis

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