Chemistry of radical ions: the absolute rate constant of dimerization of radical anions of 1 ,1-diphenyl ethylene

The combination of the labile radical ions, (Ph 2 C:CH 2 )7~, Na+, into dimeric dianions Na + , C - (Ph) 2 .CH 2 .CH 2 .C(Ph) - 2, Na+ was investigated by a flow and a stopflow technique. The bimolecular rate constant of combination was found to be 2 to 3 x 106 1. mole-1 s-1. The reaction was initiated by an electron transfer naphthalene^ + (P/*,2C:CH2) naphthalene+ (P/*,2C:CH^) or terphenylener + (P7fc2C:CH2) ⇔ terphenylene + (Pfe2C:CH^). The equilibrium constant of the first electron transfer process was found to be 20 and of the second about 16. These results are consistent with recent determinations of electron affinities of aromatic hydrocarbons.

1957 ◽  
Vol 35 (10) ◽  
pp. 1225-1236 ◽  
Author(s):  
David J. McEwen ◽  
Thomas De Vries

The uranium(VI) and (V) polarographic waves were studied in chloride and perchlorate supporting electrolytes of 0.1 M to almost neutral acidities and containing 0 to 100 fold excess of fluoride. The concentrations of the uranium(VI)–fluoride species (UO2Fn+2−n, n = 1 − 4) were calculated and it is shown that the first two species, UO2F+ and UO2F2, are either reduced reversibly at the D.M.E., or dissociate rapidly to the uncomplexed ion, UO2++, which is known to reduce reversibly. The UO2F4− species, and possibly also UO2F3− is reduced irreversibly, and the rate constant of the electron transfer process, kf°, and the transfer coefficient, α, were calculated by two methods. The electrode reaction is proposed as UO2Fn+2−n+e− = UO2++nF−. The rate of disproportionation of uranium(V) was found to depend upon the F/U ratio, and the rate constants for the reaction were calculated.


1989 ◽  
Vol 67 (10) ◽  
pp. 1628-1631 ◽  
Author(s):  
Glen W. Dillow ◽  
P. Kebarle

Electron affinities for aza-substituted polycyclic aromatics were determined from measurements of electron transfer equilibria in the dilute gas phase with a pulsed electron high pressure mass spectrometer (PHPMS). These are (in kcal/mol): quinazoline (12.7), quinoxaline (15.8), cinnoline (16.0), acridine (20.3), benzo[c]cinnoline (20.6), pyrido[2,3-b]pyrazine (22.5), phenazine (29.5). Solvation energies of the corresponding radical anions in acetonitrile and dimethylformamide are derived from the gas phase data and literature on electron reduction potentials in solution. An observed linear relationship between the electron affinities and the reduction potentials allows estimates of electron affinities to be made for 12 aza compounds whose EA's are too low to be measured with the present method. Keywords: aza-substituted aromatic hydrocarbons, electron affinities, electron transfer, radical anions, reduction potentials, solvation energies of radical anions, stabilities of radical anions.


2017 ◽  
Vol 19 (22) ◽  
pp. 14412-14423 ◽  
Author(s):  
Ewelina Krzyszkowska ◽  
Justyna Walkowiak-Kulikowska ◽  
Sven Stienen ◽  
Aleksandra Wojcik

Quenching of the thionine singlet excited state in covalently functionalized graphene oxide with an efficient back electron transfer process.


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