Kinetics of the solvolysis of thetrans-dichlorobis (Diaminoethane)-cobalt(III) ion in aqueous ethylene carbonate and aqueous propylene carbonate

1987 ◽  
Vol 16 (5) ◽  
pp. 399-409 ◽  
Author(s):  
Grahame S. Groves ◽  
Kamal H. Halawani ◽  
Cecil F. Wells
Keyword(s):  
Propylene Carbonate ◽  
Ethylene Carbonate ◽  
Kinetics Of

Voltammetric investigation of the kinetics of alkali metal cation reduction in N,N-dimethylformamide

1975 ◽  
Vol 28 (2) ◽  
pp. 237 ◽  
Author(s):  
JW Diggle ◽  
AJ Parker ◽  
DA Owensby
Keyword(s):  
Electron Transfer ◽  
Alkali Metal ◽  
Propylene Carbonate ◽  
Rate Constant ◽  
Alkali Metal Cation ◽  
Electrode Reaction ◽  
Amalgam Electrode ◽  
Kinetics Of ◽  
Dipolar Aprotic Solvents

The standard electron-transfer heterogeneous rate constant of lithium, potassium, sodium and caesium amalgams in N,N-dimethylformamide was ascertained employing cyclic voltammetry in an effort to relate the presence of a non-equilibrium electrode reaction at the dropping lithium amalgam electrode to the variation of the lithium amalgam electrode potential with amalgam electrode con- figuration, i.e. whether streaming, dropping or stationary. Such variations are not observed at other alkali metal amalgam electrodes. ��� In the dipolar aprotic solvents the standard electron-transfer heterogeneous rate constant for the Li(Hg) electrode increases as the solvating power for Li+ decreases, i.e. dimethyl sulphoxide < di- methylformamide < propylene carbonate. Water is a much stronger solvator of Li+ than is propylene carbonate, but the electron transfer is faster in water than in propylene carbonate; the important role of entropic contributions in ion solvation is discussed as an explanation.

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