Significance of Effects of High Pressure on Kinetics of Electrode Reactions: II . The Nature of Solvent Reorganization in the Activation Process of an Electrochemical Redox Reaction

1978 ◽  
Vol 125 (2) ◽  
pp. 257-264 ◽  
Author(s):  
B. E. Conway ◽  
J. C. Currie
Keyword(s):  
High Pressure ◽  
Redox Reaction ◽  
Activation Process ◽  
Electrode Reactions ◽  
Electrochemical Redox ◽  
Kinetics Of

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

2002 ◽  
Vol 57 (9-10) ◽  
pp. 85-88 ◽  
Author(s):  
S. A. Kuznetsov ◽  
M. Gaune-Escarda
Keyword(s):  
Coordination Sphere ◽  
Rate Constants ◽  
Diffusion Coefficients ◽  
Redox Reaction ◽  
Alkali Halide ◽  
Molten Salts ◽  
Electrode Reactions ◽  
Standard Rate ◽  
Second Coordination Sphere ◽  
Kinetics Of

The influence of the second coordination sphere on the 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 the large caesium cations in the melt reduce the transfer and the diffusion coefficients as well as the heterogeneous rate constants for charge transfer of hafnium complexes. The standard rate constants for the europium redox reaction increase when going from NaCl-KCl to CsCl. The different influence of the second coordination sphere on the electrode reactions is explained by different limitation stages for electron transfer.

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

High-pressure methods as a tool in organometallic syntheses: facilitation of oxidative addition to platinum(II)

1996 ◽  
Vol 74 (11) ◽  
pp. 1998-2001 ◽  
Author(s):  
Andrew R.L. Skauge ◽  
Richard D. Shalders ◽  
Thomas W. Swaddle
Keyword(s):  
High Pressure ◽  
Pressure Dependence ◽  
Pressure Range ◽  
Oxidative Addition ◽  
Activation Process ◽  
Batch Reactors ◽  
Oxidative Additions ◽  
Solvation Of Ions ◽  
Alkyl Iodides ◽  
Kinetics Of

High-pressure (2 GPa) batch reactors now commercially available may offer substantial accelerations of organometallic syntheses, without resort to heating, when the activation process is multicentered or involves the generation and solvation of ions. As an example of the latter class of reactions, the kinetics of the oxidative additions of methyl and ethyl iodides (RI) to dimethyl(2,2′-bipyridine)platinum(II) in acetone have been studied over the pressure range 0–200 MPa. The volumes of activation ΔV1≠, if assumed to be constant over this range, are −11.7 ± 0.3 and −9.7 ± 0.7 cm3 mol−1, respectively, implying an acceleration of ca. 3000-fold for a batch synthesis of this sort at 2 GPa. However, a possible slight pressure dependence of ΔV1≠ may reduce this acceleration to ca. 1 000-fold. The ΔV1≠ data and the 500-fold retardation on going from R = Me to R = Et are consistent with an SN2 attack of Pt11 on the α-carbon in the alkyl iodides, forming I− and [RMe2Pt(bpy)]+. Key words: volumes of activation, high pressure, oxidative addition, platinum(II), organometallic syntheses.

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