Dissociation constants of some monovalent sulfate ion pairs at 25.deg. from stoichiometric activity coefficients

1975 ◽  
Vol 79 (5) ◽  
pp. 422-425 ◽  
Author(s):  
E. J. Reardon
1987 ◽  
Vol 40 (7) ◽  
pp. 1201 ◽  
Author(s):  
W Mizerski ◽  
MK Kalinowski

An empirical relation describing the effect of solvent on the dissociation constant ( Kd ) of ion pairs is described. An equation of the form pKd = apKso + bD-1 + c ( Kso and D stand for the solubility product of a given salt and for the electric permittivity of a solvent, respectively) has been tested with 13 sets of experimental data for salts containing tetraalkylammonium and alkali-metal cations. A successful correlation was obtained in 100% of the cases considered.


Osmotic coefficient data for the sulphates of Mg, Ca, Zn, Ni and Cu in aqueous solution have been analysed to obtain the dissociation constants (d.c.) of ion pairs, triplets and quadruplets, as well as information on their state of hydration. The d.c.’s of the sulphate ion pairs, though of similar magnitude, show distinct individualities, and the trend is similar to that of the d.c.’s calculated for the nitrates of di-valent ions, though the d.c.’s of the latter are about 200 times larger. The d.c.’s of the ion triplets show no correlations, but their absolute values are similar to those calculated from the theory of Fuoss & Kraus (1933, 1935) based on electrostatic considerations. The hydration parameters of the associated sulphates (both pairs and triplets), as characterized in the linear (statistical) terms of the osmotic coefficients, are only slightly smaller than those of the fully dissociated electrolytes, indicating that there is only little loss of hydration water in the process of association, in spite of the heavy hydration of the divalent cations and the relatively close approach of the sulphate ion. The complete analysis of the osmotic coefficient curves makes it possible to calculate the absolute values of the activity coefficients of the divalent sulphates (previously not known to any accuracy).


1974 ◽  
Vol 78 (13) ◽  
pp. 1287-1294 ◽  
Author(s):  
Frank J. Millero ◽  
William L. Masterton

1968 ◽  
Vol 46 (12) ◽  
pp. 2005-2011 ◽  
Author(s):  
W. A. Adams ◽  
K. J. Laidler

The ion-pair dissociation constants determined from a Shedlovsky analysis of conductivity (see Part I) were used to calculate the enthalpy, the internal energy at constant volume, the entropy, and the volume of dissociation of tetramethylammonium iodide, tetraethylammonium iodide, and tetra-n-propylammonium iodide ion pairs in acetone solution. The sign and magnitude of these parameters over the range of conditions investigated, temperature 25 to 55 °C and atmospheric to 1.1 kbar pressure, indicated that the free ions in acetone solution are extensively solvated and that, depending on the conditions, solvent-shared or solvent-separated ion pairs are formed.


1983 ◽  
Vol 63 (3) ◽  
pp. 479-484 ◽  
Author(s):  
A. ALZUBAIDI ◽  
G. R. WEBSTER

The kinds and concentrations of the major ion pairs were determined in saturation extracts of 141 soil samples collected from a Solonetzic soil treated with various kinds of tillage combined with surface-applied chemical amendments. The correlations between concentrations of ion pairs and EC and pH of saturation extracts were statistically tested. Sulfate ion pairs NaSO4−, MgSO40 and CaSO40 occurred in relatively high concentrations. The other ion pairs were of low concentrations. Of the total soluble Ca, ion pairs ranged from 20.8% in the Ap horizon to 50.5% in the Csk horizon and Mg was approximately the same. The comparable values for Na were 0.8% and 4.6%, respectively. Ion pairs NaSO4−, KSO4−, MgSO40 and CaSO40 were significantly correlated with EC. Only carbonate ion pairs were significantly correlated with pH. Correcting concentrations of Na, Ca and Mg for ion pairs and activities changed considerably the SAR values in the Bnt1 horizon. Key words: Ion pairs, Solonetzic soils, ion activities


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