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

not available


1970 ◽  
Vol 23 (12) ◽  
pp. 2427
Author(s):  
ML Tonnet ◽  
AN Hambly

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.



1991 ◽  
Vol 46 (1-2) ◽  
pp. 127-130
Author(s):  
K. Ibuki ◽  
M. Nakahara

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.



1966 ◽  
Vol 44 (4) ◽  
pp. 487-494 ◽  
Author(s):  
R. E. Robertson ◽  
S. E. Sugamori ◽  
R. Tse ◽  
C.-Y. Wu

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.



1965 ◽  
Vol 43 (1) ◽  
pp. 154-158 ◽  
Author(s):  
P. M. Laughton ◽  
R. E. Robertson

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.







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


1975 ◽  
Vol 53 (6) ◽  
pp. 869-877 ◽  
Author(s):  
B. Rossall ◽  
R. E. Robertson

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.



1981 ◽  
Vol 103 (10) ◽  
pp. 2897-2899 ◽  
Author(s):  
Robert A. Binstead ◽  
Bruce A. Moyer ◽  
George J. Samuels ◽  
Thomas J. Meyer


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