Solvent isotope effect on ion mobility in water at high pressure. Conductance and transference number of potassium chloride in compressed heavy water

1985 ◽  
Vol 83 (1) ◽  
pp. 280-287 ◽  
Author(s):  
M. Nakahara ◽  
M. Zenke ◽  
M. Ueno ◽  
K. Shimizu
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.


1963 ◽  
Vol 41 (8) ◽  
pp. 2118-2120 ◽  
Author(s):  
Wm. G. Craig ◽  
Leo Hakka ◽  
P. M. Laughton ◽  
R. E. Robertson

not available


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.


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.


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