Reactant solvation and kinetics of simple charge-transfer electrode reactions in mixed solvents

1991 ◽  
Vol 312 (1-2) ◽  
pp. 27-41 ◽  
Author(s):  
Waldemar Górski ◽  
Zbigniew Galus
Keyword(s):  
Charge Transfer ◽  
Mixed Solvents ◽  
Electrode Reactions ◽  
Kinetics Of

Influence of Second Coordination Sphere on the Kinetics of Electrode Reactions in Molten Salts

2002 ◽  
Vol 57 (1-2) ◽  
pp. 85-88
Author(s):  
S. A. Kuznetsov ◽  
M. Gaune-Escarda
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Coordination Sphere ◽  
Diffusion Coefficients ◽  
Redox Reaction ◽  
Alkali Halide ◽  
Molten Salts ◽  
Electrode Reactions ◽  
Second Coordination Sphere ◽  
Kinetics Of

The influence of the second coordination sphere on die electroreduction of hafnium complexes to hafnium metal and the redox reaction Eu(III)+e-⇔ Eu(II) in alkali halide melts was studied. It is shown that die large caesium cations in the melt reduce the transfer and the diffusion coefficients as well as the heterogeneous rate constants for charge transfer of harnitcn complexes. The standard rare constants for the europium redox reaction increase when going from NaCl-KCl to CsCl. The different influence of die second coordination sphere on the electrode reactions is explained by different limitation stages for electron transfer

Lifetime of Singlet Oxygen and Quenching by NaN3 in Mixed Solvents

1982 ◽  
Vol 37 (5) ◽  
pp. 649-652 ◽  
Author(s):  
N. Miyoshi ◽  
M. Ueda ◽  
K. Fuke ◽  
Y. Tanimoto ◽  
M. Itoh ◽  
...  
Keyword(s):  
Activation Energy ◽  
Charge Transfer ◽  
Singlet Oxygen ◽  
Mixed Solvents ◽  
Solvent Polarity ◽  
Thermal Lensing ◽  
Partial Charge ◽  
Partial Charge Transfer ◽  
Quenching Rate ◽  
Quenching Rate Constant

Singlet oxygen was generated by the photosensitization of erythrosine. The lifetime of singlet oxygen and the quenching rate constant for singlet oxygen by NaN3 were measured by a thermal lensing method in MeOH-H2O mixed solvents. The reciprocal of the lifetime increased linearly with the increase of the H2O mole fraction. Semi-log plot of the quenching constant against the reciprocal of the solvent polarity exhibited a linear relation. The quenching of the singlet oxygen by NaN3 may proceed through a partial charge-transfer intermediate. The activation energy for the quenching reaction of N3- + 1O2 →[N3·1O2-] increased with the increase of the solvent polarity. The lifetime was also measured in MeOH-ethyleneglycol mixed solvents, and its relation with viscosity was obtained

Time-Resolved Kinetics of Electrode Reactions

2019 ◽  
Vol 1 (6) ◽  
pp. 3-15
Author(s):  
Eliezer Gileadi
Keyword(s):  
Time Resolved ◽  
Electrode Reactions ◽  
Kinetics Of

Kinetic medium effects. IV. Transition state activity coefficients in mixed solvents

1972 ◽  
Vol 25 (4) ◽  
pp. 777 ◽  
Author(s):  
PT McTigue ◽  
AR Watkins
Keyword(s):  
Transition State ◽  
Activity Coefficients ◽  
Mixed Solvents ◽  
State Theory ◽  
Medium Effects ◽  
State Activity ◽  
Medium Activity ◽  
Solvent Systems ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of acid hydrolysis of a number of aliphatic acetals have been studied in dimethyl sulphoxide-water and dioxan-water mixtures. Where possible, experimentally measured medium activity coefficients for the acetals in the solvent systems have been used in order to calculate the transition state activity coefficients as a function of solvent composition. These activity coefficients are compared with those calculated for the transition states of other hydrolytic reactions, and with the known activity coefficients of some stable ions. The results show no features inconsistent with the assumptions of transition state theory.

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