Conductance studies of some 1:1 electrolytes in acetone + dimethylsulphoxide mixtures at 25 °C

1991 ◽  
Vol 56 (9) ◽  
pp. 1803-1812 ◽  
Author(s):  
Vijay K. Syal ◽  
Suvarcha Chauhan ◽  
Alok Katoch ◽  
Mohinder S. Chauhan
Keyword(s):  
Model Evaluation ◽  
Composition Range ◽  
Preferential Solvation ◽  
Solvent Composition ◽  
Rich Region ◽  
Conductance Data ◽  
Ionic Conductances

Precise molar conductances of Bu4NBPh4, Bu4NI, Bu4NNO3, AgNO3, LiNO3, NaBPh4 and KI have been measured in acetone (Ac), dimethylsulphoxide (DMSO) and Ac + DMSO mixtures over the whole solvent composition range at 25°C. The conductance data has been analysed by computer using Shedlovsky conductance equation. Limiting ionic conductances have been calculated by using Gill’s model. Evaluation of solvated radii of Li+, Na+, K+ and Ag+ ions in Ac + DMSO mixtures shows strong preferential solvation for Li+ ion by DMSO. Na+ and Ag+ ions are found to be preferentially solvated by DMSO in Ac-rich region and by Ac in DMSO rich regions. K+, NO3- and I- ions show no preferential solvation in Ac + DMSO mixtures.

Viscometric and Conductometric Studies of Solvation Behaviour of Tetraalkylammonium Salts in the Binary Mixtures of Dimethylsulfoxide and Methanol at 298.15 K

2019 ◽  
Vol 233 (5) ◽  
pp. 737-753 ◽  
Author(s):  
Hardeep Anand ◽  
Renu Verma
Keyword(s):  
Binary Mixtures ◽  
Preferential Solvation ◽  
Molar Conductance ◽  
Viscosity Data ◽  
Tetraalkylammonium Salts ◽  
Rich Region ◽  
Tetraalkylammonium Ions ◽  
Conductance Data ◽  
Ionic Conductances ◽  
Good Agreement

Abstract Molar conductance and viscosity of some tetraalkylammonium perchlorates (R4NClO4 where R = Methyl, Ethyl, Propyl, Butyl) have been measured in the concentration range (30–500) × 10−4 mol kg−1 at 298.15 K in the binary mixtures of dimethylsulfoxide (DMSO) + methanol (MeOH) containing 0, 20, 40, 50, 60, 80 and 100 mol% methanol. Conductance data has been analyzed using the Shedlovsky equation and the viscosity data by Jones-Dole equation. The limiting ionic conductances ($\lambda_{\pm}^{o}$) were used to calculate the solvated radii (ri) of the ions. The A and B coefficients of the Jones-Dole equation are positive in all salts. The A coefficients are in reasonable good agreement with the limiting theoretical values (Aη) calculated using Falkenhagen-Vernon equation. The variation of the ionic B± coefficients as well as the actual solvated radii (ri) with solvent composition in DMSO + MeOH mixtures show the preferential solvation of tetraalkylammonium ions by MeOH and MeOH-rich region of the mixtures. The tetraalkylammonium ions exhibit solvation in the order Me4N+ > Et4N+ > Pr4N+ > Bu4N+.

The Ionization of Picric Acid in Ethanol–Sulfolane and t-Butyl Alcohol – Sulfolane Mixtures at 30 °C

1975 ◽  
Vol 53 (11) ◽  
pp. 1651-1656 ◽  
Author(s):  
Maurizio Castagnolo ◽  
Angelo De Giglio ◽  
Angelo Dell'atti ◽  
Giuseppe Petrella
Keyword(s):  
Association Constant ◽  
Composition Range ◽  
Dissociation Constants ◽  
Picric Acid ◽  
Preferential Solvation ◽  
Butyl Alcohol ◽  
Weak Acid ◽  
Solvent Composition ◽  
Solvent Mixtures ◽  
Simple Dissociation

Dissociation constants at 30 °C of picric acid have been determined by a spectrophotometric method in ethanol–sulfolane and t-butyl alcohol – sulfolane mixtures over the entire solvent composition range. Picric acid behaves as a weak acid in all mixtures. In pure sulfolane, picric acid undergoes simple dissociation for c < 0.08 M (pKHPI = 7.6). At concentrations higher than 0.08 M more complex equilibria have been observed and interpreted assuming Pi(HPi)2− as the principal picrate species in solution. Complex behavior of dependence of association constant on solvent composition was observed; in both solvent mixtures as sociation of picric acid decreases with decrease of dielectric constant. This behavior was discussed in terms of preferential solvation of picric acid by alcohols, the more basic components of the mixtures. A reaction mechanism of four alcohol molecules with one acid molecule accounts for the behavior observed.

Densities and viscosities of binary aqueous mixtures of nonelectrolytes: tert-Butyl alcohol and tert-butylamine

1994 ◽  
Vol 72 (9) ◽  
pp. 1937-1945 ◽  
Author(s):  
Pius K. Kipkemboi ◽  
Allan J. Easteal
Keyword(s):  
Shear Viscosity ◽  
Composition Range ◽  
Excess Molar Volumes ◽  
Butyl Alcohol ◽  
Aqueous Mixtures ◽  
Rich Region ◽  
Molar Volumes ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Tert Butylamine

The density and shear viscosity of mixtures of tert-butyl alcohol (BuOH) and tert-butylamine (TBA) with water have been determined for various temperatures (288 to 318 K for H2O + BuOH and 288 to 308 K for H2O + TBA) over the whole composition range. Excess molar volumes and apparent molar volumes of the components of each system were calculated from the density data. In both systems the apparent molar volume of the organic component passes through a minimum in the water-rich region. Both systems exhibit large negative excess molar volumes which are essentially independent of temperature at all compositions. The two systems show pronounced maxima in their shear viscosity isotherms.

Ultrasonic velocity and volumetric properties of isomeric butanediols plus water systems

1998 ◽  
Vol 76 (4) ◽  
pp. 464-468 ◽  
Author(s):  
Brent Hawrylak ◽  
Kim Gracie ◽  
R Palepu
Keyword(s):  
Ultrasonic Velocity ◽  
Infinite Dilution ◽  
Composition Range ◽  
Transfer Functions ◽  
Adiabatic Compressibility ◽  
Partial Molar Volumes ◽  
Water Systems ◽  
Ultrasonic Velocities ◽  
Rich Region ◽  
Liquid Solutions

Ultrasonic velocities and densities of binary aqueous solutions of isomeric butanediols were measured in the temperature range 298-318 K at 10 degree intervals over the entire composition range, and 5 degree intervals in the water-rich region. The experimental data in the dilute region, with mole fraction of water less than 0.1, was analysed to determine the partial molar volumes and adiabatic compressibilities of water at infinite dilution. The standard thermodynamic transfer functions were calculated to evaluate the environment of water at infinite dilution in these systems. From the compressibility isotherms, as a function of temperature in the water-rich region, the formation and the composition of clathrate-like structures in the liquid solutions was determined, and the nature of these structures was discussed.Key words: ultrasonic velocity, adiabatic compressibility, density, partial molar quantities, standard thermodynamic transfer functions.

Thermodynamic and physical behaviour of some water + polyethyleneglycol mixtures. II. Dielectric properties

1979 ◽  
Vol 57 (6) ◽  
pp. 608-613 ◽  
Author(s):  
Gérard Douhéret ◽  
Maurice Morénas
Keyword(s):  
Dielectric Properties ◽  
Composition Range ◽  
Dipole Moments ◽  
Partial Molar Volumes ◽  
Correlation Factor ◽  
Dielectric Constants ◽  
Treatment Results ◽  
Rich Region ◽  
Physical Behaviour ◽  
Water Lattice

Dielectric constants of water + glycol (mono-, di-, tri-, and tetraethyleneglycol) mixtures have been measured at 298.15 K over the entire composition range. The mixtures involving monoethyleneglycol have also been studied at temperatures from 308.15 to 288.15 K. Calculated deviations from ideality are always positive and show one maximum. Related properties have been computed: polarizability volume and excess polarizability volume, correlation factor of mixtures, and dipole moments of both components using the Mecke–Reuter treatment. Results support conclusions previously deduced from excess and partial molar volumes; they suggest that the addition of glycol molecules gives rise to a slight enhancement of the water-lattice in the water-rich region, followed by a progressive destructuring; the ether functions do not seem to play a prominent role.

THE LIMITING EQUIVALENT CONDUCTANCES OF AMMONIUM CHLORIDE, AMMONIUM BROMIDE, AND AMMONIUM NITRATE AT 35.00 °C.

1958 ◽  
Vol 36 (2) ◽  
pp. 330-338 ◽  
Author(s):  
A. N. Campbell ◽  
E. Bock
Keyword(s):  
Aqueous Solutions ◽  
Ammonium Nitrate ◽  
Ammonium Chloride ◽  
Stokes Equation ◽  
Probable Error ◽  
Ammonium Bromide ◽  
Conductance Data ◽  
Ionic Conductances ◽  
Hydrolysis Of ◽  
Limiting Equivalent Conductances

The limiting equivalent conductances of ammonium chloride, ammonium bromide, and ammonium nitrate as well as the limiting ionic conductances of the ammonium and nitrate ions were determined at 35 °C. with a probable error of 0.05%. The values found were [Formula: see text] 180.97 mhos, [Formula: see text] 182.73 mhos, [Formula: see text] 174.21 mhos, [Formula: see text] 88.73 mhos, and [Formula: see text] 85.48 mhos. These values were obtained by the application of the Shedlovsky method of extrapolation to equivalent conductance data, which had been corrected for the hydrolysis of the ammonium ion.Observed equivalent conductances of aqueous solutions of ammonium nitrate at 35 °C., in the concentration range from 0.0002 N to 10 N, have been compared with those calculated by means of the Wishaw–Stokes and Falkenhagen–Leist equations. The Wishaw–Stokes equation was found to give better agreement with experiment than the Falkenhagen–Leist equation.

Self-Diffusion of Sodium, Chloride and Iodide Ions in Acetonitrile-Water Mixtures

1987 ◽  
Vol 42 (9) ◽  
pp. 1014-1016 ◽  
Author(s):  
E. Hawlicka
Keyword(s):  
Diffusion Coefficient ◽  
Sodium Chloride ◽  
Diffusion Coefficients ◽  
Preferential Solvation ◽  
Solvent Composition ◽  
The Self ◽  
Sodium Ions ◽  
Iodide Ions ◽  
Self Diffusion ◽  
Self Diffusion Coefficient

The self-diffusion coefficient of sodium, chloride and iodide ions in acetonitrile-water mixtures at 25.0 ± 0.05 °C has been measured in dependence on the salt molarity in the range 1.0 ·10-4 1.0 ·10-2 mol/dm3. The ionic self-diffusion coefficients in infinitely diluted solutions have been computed. The influence of the solvent composition on the solvation of the ions is discussed. Preferential solvation of the ions by acetonitrile above 15m ol% of acetonitrile has been found. An effect of the sodium ions on the formation of acetonitrile globules is postulated.

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