Pulse radiolysis of solutions of stilbene. 2. Ionic and free radical species in benzene and cyclohexane

Journal Article · Thu Feb 23 00:00:00 EST 1978 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100493a003· OSTI ID:5171254

Robinson, E A; Salmon, G A

The spectra of the radical cation and anion of trans-stilbene in benzene and cyclohexane have been resolved using various electron and positive charge scavengers. The decay of the ions is second order in both solvents. In cyclohexane only part of the yield of solvent cations is scavengeable by trans-stilbene; in benzene the stilbene cation is converted to the dimer in the presence of high stilbene concentrations. The electron scavengers N/sub 2/O and c-C/sub 6/F/sub 12/ compete directly with trans-stilbene for electrons and we deduce rate constants for the reactions of electrons with c-C/sub 6/F/sub 12/ and trans-stilbene of (1.2 +- 0.6) x 10/sup 12/ and (0.72 +- 0.5) x 10/sup 12/ M/sup -1/ s/sup -1/, respectively. SF/sub 6/ reduces the yield of trans-stilbene anion more efficiently than can be attributed solely to electron scavenging and it is shown that electron transfer from trans-stilbene anion to SF/sub 6/ occurs at a rate constant, k/sub 4/ = (3.9 +- 0.4) x 10/sup 9/ M/sup -1/ s/sup -1/. The presence of either aniline or n-butylamine causes enhancement of the yield of stilbene anion, the effect being particularly marked in the case of aniline. Possible explanations of the effect are considered. It is proposed that the UV absorptions are due to radical species, which in cyclohexane solution are most probably formed by the addition of cyclohexyl radicals to the olefinic double bond of the stilbenes.

• Research Organization: Univ. of Leeds, Eng.
• OSTI ID: 5171254
• Journal Information: J. Phys. Chem.; (United States), Vol. 82:4
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
RADICALS
ABSORPTION SPECTRA
STILBENE
RADIOLYSIS
BENZENE
CYCLOHEXANE
PULSED IRRADIATION
ALKANES
AROMATICS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
CYCLOALKANES
DECOMPOSITION
HYDROCARBONS
IRRADIATION
ORGANIC COMPOUNDS
RADIATION CHEMISTRY
RADIATION EFFECTS
SPECTRA
400600* - Radiation Chemistry