Correlating temperature dependence to free-energy dependence of intramolecular long-range electron transfers

1989 ◽  
Vol 111 (23) ◽  
pp. 8740-8741 ◽  
Author(s):  
N. Liang ◽  
J. R. Miller ◽  
G. L. Closs
Keyword(s):  
Free Energy ◽  
Temperature Dependence ◽  
Long Range ◽  
Energy Dependence ◽  
Electron Transfers

Free energy-dependence of the electronic factor in biological long-range electron transfer

1989 ◽  
Vol 111 (4) ◽  
pp. 1315-1319 ◽  
Author(s):  
Kurt V. Mikkelsen ◽  
Jens Ulstrup ◽  
Merab G. Zakaraya
Keyword(s):  
Electron Transfer ◽  
Free Energy ◽  
Long Range ◽  
Energy Dependence ◽  
Electronic Factor

Insights into the Free-Energy Dependence of Intramolecular Dissociative Electron Transfers

2002 ◽  
Vol 124 (38) ◽  
pp. 11503-11513 ◽  
Author(s):  
Sabrina Antonello ◽  
Marco Crisma ◽  
Fernando Formaggio ◽  
Alessandro Moretto ◽  
Ferdinando Taddei ◽  
...  
Keyword(s):  
Free Energy ◽  
Energy Dependence ◽  
Electron Transfers

Heat capacity of activation for the hydrolysis of methanesulfonyl chloride and benzenesulfonyl chloride in light and heavy water

1969 ◽  
Vol 47 (22) ◽  
pp. 4199-4206 ◽  
Author(s):  
R. E. Robertson ◽  
B. Rossall ◽  
S. E. Sugamori ◽  
L. Treindl
Keyword(s):  
Heat Capacity ◽  
Free Energy ◽  
Temperature Dependence ◽  
Heavy Water ◽  
Bond Formation ◽  
Sulfonyl Chlorides ◽  
Benzenesulfonyl Chloride ◽  
Methanesulfonyl Chloride ◽  
Hydrolysis Of ◽  
Parameter Temperature Dependence

Rates of solvolysis of methanesulfonyl chloride and benzenesulfonyl chloride have been determined in H2O and D2O. The free energy, enthalpy, entropy, and heat capacity of activation were calculated. The exceptional accuracy of the data permitted an estimation of dΔCp≠/dT from a four parameter temperature dependence of the kinetic rates.From these data we conclude that both sulfonyl chlorides hydrolyse by the same mechanism (Sn2) The change in R from CH3 to C6H5 in RSO2Cl did not alter ΔCp≠ but ΔS≠ (20°) was changed from −8.32 to −13.25 cal deg−1 mole−1, respectively. The significance of this difference is attributed to the probability of bond formation rather than to differences in solvent reorganization.

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