Local polymer and solvent dynamics in Aroclor solutions: implications for solvent modification

1992 ◽  
Vol 25 (4) ◽  
pp. 1284-1293 ◽  
Author(s):  
Daniel J. Gisser ◽  
M. D. Ediger
Keyword(s):  
Solvent Dynamics ◽  
Solvent Modification

Hole Transfer Processes in meta- and para-Conjugated Mixed Valence Compounds: Unforeseen Effects of Bridge Substituents and Solvent Dynamics

2017 ◽  
Vol 139 (17) ◽  
pp. 6200-6209 ◽  
Author(s):  
Julian Schäfer ◽  
Marco Holzapfel ◽  
Boryana Mladenova ◽  
Daniel Kattnig ◽  
Ivo Krummenacher ◽  
...  
Keyword(s):  
Mixed Valence ◽  
Hole Transfer ◽  
Transfer Processes ◽  
Solvent Dynamics ◽  
Mixed Valence Compounds

Volumes of activation for electrode processes of various charge-types in nonaqueous solvents

2001 ◽  
Vol 79 (12) ◽  
pp. 1864-1869 ◽  
Author(s):  
Mitsuru Matsumoto ◽  
Delanie Lamprecht ◽  
Michael R North ◽  
Thomas W Swaddle
Keyword(s):  
Electron Transfer ◽  
Reaction Rate ◽  
Electrode Reaction ◽  
State Theory ◽  
Exchange Reactions ◽  
Pt Electrode ◽  
Electrode Processes ◽  
Solvent Dynamics ◽  
The Mean ◽  
Dynamical Control

Volumes of activation (ΔV‡el) are reported for electron transfer at a Pt electrode of Mn(CN-cyclo-C6H11)62+/+ in acetonitrile, acetone, methanol, and propylene carbonate, and of Fe(phen)33+/2+ in acetonitrile. In all cases, ΔV‡el is markedly positive, whereas for the homogeneous self-exchange reactions of these couples in the same solvents the corresponding parameter is known to be strongly negative. The rate constants for the electrode reactions correlate loosely with the mean reactant diffusion coefficients (i.e., with solvent fluidity) and the ΔV‡el values with the volumes of activation for diffusion (i.e., for viscous flow), consistent with solvent dynamical control of the electrode reaction rate in organic solvents. A detailed analysis of ΔV‡el values of the kind presented for a couple with an uncharged member (Zhou and Swaddle, Can. J. Chem. 79, 841 (2001)) fails, however, either because of ion-pairing effects with these more highly charged couples or because of breakdown of transition-state theory in predicting the contribution of the activational barrier. Attempts to measure ΔV‡el for the oxidation of the uncharged molecule ferrocene at various electrodes in acetonitrile were unsuccessful, although ΔV‡el was again seen to be clearly positive.Key words: electrode kinetics, volumes of activation, nonaqueous electron transfer, solvent dynamics.

Diffusion of Small Solute Particles in Viscous Liquids: Cage Diffusion, a Result of Decoupling of Solute–Solvent Dynamics, Leads to Amplification of Solute Diffusion

2015 ◽  
Vol 119 (34) ◽  
pp. 11169-11175 ◽  
Author(s):  
Sayantan Acharya ◽  
Manoj K. Nandi ◽  
Arkajit Mandal ◽  
Sucharita Sarkar ◽  
Sarika Maitra Bhattacharyya
Keyword(s):  
Solute Diffusion ◽  
Viscous Liquids ◽  
Solvent Dynamics ◽  
Cage Diffusion ◽  
Small Solute
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