SOLVOLYSIS IN LIGHT AND HEAVY WATER: VI. THE ROLE OF INITIAL STATE STRUCTURE

1965 ◽  
Vol 43 (1) ◽  
pp. 154-158 ◽  
Author(s):  
P. M. Laughton ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Heavy Water ◽  
Solubility Data ◽  
State Structure ◽  
Solvent Isotope Effect ◽  
Initial State ◽  
Solvent Isotope

The solubility data in light and heavy water of Swain and Thornton and of Taft and coworkers are reinterpreted to show that they support primarily the initial state origin for the kinetic solvent isotope effect. Other recent data, including the effect for t-butyl and α-phenethyl fluorides, are also shown to be compatible with the same hypothesis.

Solvolysis of sulphonyl halides. V. Hydrolysis and deuterolysis of methanesulphonyl chloride

1970 ◽  
Vol 23 (12) ◽  
pp. 2427
Author(s):  
ML Tonnet ◽  
AN Hambly
Keyword(s):  
Transition State ◽  
Thermodynamic Parameters ◽  
Isotope Effect ◽  
Large Reduction ◽  
Butyl Chloride ◽  
Solvent Isotope Effect ◽  
Initial State ◽  
Solvent Isotope ◽  
Hydrolysis Of

The values of the thermodynamic parameters of activation have been determined for the solvolysis of methanesulphonyl chloride in H2O and D2O and their mixtures with moderate amounts of dioxan. Some of the data are not in agreement with the postulate that the kinetic solvent isotope effect and the maximum in the rate of solvolysis produced by the addition of dioxan are due to changes in the initial state of the reacting system rather than to changes in the transition state. The addition of dioxan does not produce a large reduction in the solvent isotope effect as reported for the hydrolysis of t-butyl chloride and predicted to be general. The relative rates of solvolysis in mixtures of H2O and D2O are not in agreement with the analysis of such reactions by Swain and Thornton.

Solvent Isotope Effect on the Viscosity Coefficient B for Monovalent Ions in Water at 25 and 40°C

1991 ◽  
Vol 46 (1-2) ◽  
pp. 127-130
Author(s):  
K. Ibuki ◽  
M. Nakahara
Keyword(s):  
Isotope Effect ◽  
Heavy Water ◽  
Viscosity Coefficient ◽  
Solvent Isotope Effect ◽  
B Values ◽  
Light Water ◽  
Temperature Coefficients ◽  
Monovalent Ions ◽  
Ion Size ◽  
Solvent Isotope

AbstractFor heavy water solutions of LiCl, NaCl, KCl and CsCl at 25 and 40 C and KI at 25 °C the values of B(M + ) and B(X-) in the equation ]η/η0= 1 + A √c + [B(M + ) + B(X- )] c were determined under the conventional assumption B(K + ) = ß(Cl-). Here η0 is the viscosity of the solvent and c the molarity. The solvent isotope effect on the B values was found to be small. The B values for the medium-sized ions K + , Cs + , Br-, and I- were systematically more negative in heavy water than in light water. This is consistent with the idea that negative B values indicate the ability of the ion to break the structure of the water, the structure of heavy water being more developed than that of light water. For the tetraalkylammonium ions, Me4N + , Pr4N+ , and Bu4N + , on the other hand, the solvent isotope effect was small and random irrespective of the ion size. The temperature coefficients of B for the monatomic ions in heavy water were the same as for those in light water.

SOLVOLYSIS IN LIGHT AND HEAVY WATER: V. EFFECT OF DIOXANE ON THE SOLVENT ISOTOPE EFFECT WITH t-BUTYL CHLORIDE

1963 ◽  
Vol 41 (8) ◽  
pp. 2118-2120 ◽  
Author(s):  
Wm. G. Craig ◽  
Leo Hakka ◽  
P. M. Laughton ◽  
R. E. Robertson
Keyword(s):  
Isotope Effect ◽  
Heavy Water ◽  
Butyl Chloride ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

not available

Understanding the Role of the Essential Asp251 in Cytochrome P450cam Using Site-Directed Mutagenesis, Crystallography, and Kinetic Solvent Isotope Effect†

Biochemistry ◽  
1998 ◽  
Vol 37 (26) ◽  
pp. 9211-9219 ◽  
Author(s):  
Momcilo Vidakovic ◽  
Stephen G. Sligar ◽  
Huiying Li ◽  
Thomas L. Poulos
Keyword(s):  
Isotope Effect ◽  
Site Directed Mutagenesis ◽  
Directed Mutagenesis ◽  
Cytochrome P450cam ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

THE SOLVENT ISOTOPE EFFECT AND THE PARTIAL MOLAR VOLUME OF IONS

1966 ◽  
Vol 44 (4) ◽  
pp. 487-494 ◽  
Author(s):  
R. E. Robertson ◽  
S. E. Sugamori ◽  
R. Tse ◽  
C.-Y. Wu
Keyword(s):  
Molar Volume ◽  
Isotope Effect ◽  
Partial Molar Volume ◽  
Heavy Water ◽  
Solvent Isotope Effect ◽  
Precise Information ◽  
Ionic Solvation ◽  
Solvent Isotope

The partial molar volume of ions in water furnishes an indication, if not precise information, about the nature of ionic solvation (1–5). Accordingly, it was hoped that differences in this term and particularly the effect of temperatures on the differences in the apparent partial molar volume for a series of ions in light and heavy water would provide a basis for decisions on the nature of solvation of the benzenesulfonic ion. This ion is of considerable interest in the study of solvolysis, but very little is known about the characteristics of solvation.

The nature of the structure difference between light and heavy water and the origin of the solvent isotope effect—I

Tetrahedron ◽  
1960 ◽  
Vol 10 (3-4) ◽  
pp. 182-199 ◽  
Author(s):  
C. Gardner Swain ◽  
Richard F. W. Bader
Keyword(s):  
Isotope Effect ◽  
Heavy Water ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

Kinetic solvent isotope effect studies on the methanolysis of 1-phenylethyl chlorides

1993 ◽  
Vol 6 (6) ◽  
pp. 361-366 ◽  
Author(s):  
Ikchoon Lee ◽  
Won Heui Lee ◽  
Hai Whang Lee
Keyword(s):  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Solvent Isotope

Neutral Solvolysis of Acyl Carbon and the Temperature Dependence of the Kinetic Solvent Isotope Effect

1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson
Keyword(s):  
Temperature Dependence ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Acyl Carbon ◽  
Rate Of Hydrolysis ◽  
Solvent Isotope ◽  
Neutral Conditions ◽  
Hydrolysis Of

The temperature dependence of the rate of hydrolysis of benzoic, phthalic, and succinic anhydrides have been determined in H2O and D2O under "neutral" conditions. Corresponding data have been obtained for methyl trifluoroacetate. While both series supposedly react by the same BAc2 mechanism, remarkable differences are made obvious by this investigation. Possible sources of such differences are proposed.

Proton-coupled electron transfer between [Ru(bpy)2(py)OH2]2+ and [Ru(bpy)2(py)O]2+. A solvent isotope effect (kH2O/kD2O) of 16.1

1981 ◽  
Vol 103 (10) ◽  
pp. 2897-2899 ◽  
Author(s):  
Robert A. Binstead ◽  
Bruce A. Moyer ◽  
George J. Samuels ◽  
Thomas J. Meyer
Keyword(s):  
Electron Transfer ◽  
Isotope Effect ◽  
Solvent Isotope Effect ◽  
Proton Coupled Electron Transfer ◽  
Solvent Isotope
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