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

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+.

1991 ◽  
Vol 56 (9) ◽  
pp. 1803-1812 ◽  
Author(s):  
Vijay K. Syal ◽  
Suvarcha Chauhan ◽  
Alok Katoch ◽  
Mohinder S. Chauhan

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.


2004 ◽  
Vol 59 (9) ◽  
pp. 615-620 ◽  
Author(s):  
Dip Singh Gill ◽  
Hardeep Anand ◽  
J. K. Puri

Viscosity and molar conductance of Bu4NBPh4, Bu4NClO4, [Cu(CH3CN)4]ClO4, NaClO4 and NaBPh4 have been measured in the concentration ranges 0.02 - 0.5 mol dm−3 and 0.0005 - 0.0065 mol dm−3 at 298.15 K in AN + DMF mixtures containing 0, 10, 20, 40, 60, 75, 80, 90, and 100 mol % DMF. The viscosity data have been analyzed by the extended form of the Jones-Dole equation in the form: (η/η0) = 1+AC1/2+BC+DC2 to evaluate B and D parameters and the conductance data by the Shedlovsky equation to evaluate Λo and KA values of the salts. Ionic viscosity B-coefficients (B±) and ionic molar conductances (λ◦ i) have been calculated by using Bu4NBPh4 as a reference electrolyte. Solvated radii (ri) for Na+, Cu+ and ClO4 − have been estimated by using Gill’s modification of Stokes’ law. The variation of B± and ri as a function of mol % DMF shows that both Na+ and Cu+ are highly solvated in AN + DMF mixtures over the entire composition region. The solvation passes through a maximum between 40 to 80 mol % DMF. Both Na+ and Cu+ are more strongly solvated between 40 to 80 mol % DMF. Cu+ is relatively more strongly solvated than Na+ in AN + DMF mixtures. ClO4 − shows poor solvation in AN + DMF mixtures.


2021 ◽  
Vol 33 (12) ◽  
pp. 2924-2928
Author(s):  
Suresh Kumar ◽  
Hardeep Anand ◽  
Narender Singh

Densities (ρ) and viscosities (η) of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), potassium thiocyanate (KSCN), tetrabutyl-ammonium thiocyanate (Bu4NSCN), tetrabutylammonium tetraphenylborate (Bu4NBPh4) and tetrabutylammonium perchlorate (Bu4NClO4) were measured in binary mixed solutions of 2-aminoethanol (AE) and N,N-dimethylacetamide (DMA) containing 25, 50, 60, 80 and 100 mol % DMA in the concentration range (3-500) ×10-4 mol kg-1 at 298.15 K and 308.15 K temperatures. The density and viscosity data were analyzed using the Jones-Dole equation in the form ηr = 1 + A(C1/2) + BC for unassociated electrolytes and viscosity A and B-coefficients were obtained from the plots of of ηr – 1/C1/2 versus C1/2. The A-coefficients obtained from the analysis of Jones-Dole equation are positive as well as negative. The positive values indicate the solvation of ions in solutions of binary mixtures (AE + DMA) especially in 50 and 60 mol% DMA. The viscosity B-coefficients of all these electrolytes were positive and large in case of cations and were split into their respective ionic (B±) coefficient values using a method reported by Gill and Sharma. The viscosity B-coefficients values were increasing with the increase increasing DMA composition in the binary mixed solvent system of AE + DMA but decreasing with increasing temperature from 298.15 K to 308.15 K. The obtained results indicate about the preferential solvation of ions i.e. Li+, Na+, K+, Bu4N+ and Ph4B– ions and poor solvation of ClO4 – and SCN– ions. The results also revealed that these interactions get weaker with increase in temperature. The resulting B-coefficients and its dependence of temperature provide useful information regarding changes in the solvent structure.


1992 ◽  
Vol 57 (9) ◽  
pp. 1879-1887 ◽  
Author(s):  
Zdeněk Palatý

The applicability of the equation derived for calculating the dynamic viscosity of ternary non-electrolyte mixtures, to the correlation of viscosity data of the H2O- K2CO3/KHCO3 system is verified in this work. It was found out that the values of dynamic viscosity obtained experimentally are in good agreement with the viscosity values calculated from this equation. The equation constants - interaction coefficients - were determined from the measurements of dynamic viscosity on mixing the basic solutions of K2CO3 and KHCO3 of known concentration. The correlation equation makes it possible to calculate viscosity of the K2CO3/KHCO3 solutions in the K2CO3 and KHCO3 concentration range from 0 to about 2.0 kmol m-3.


1992 ◽  
Vol 57 (10) ◽  
pp. 2078-2088 ◽  
Author(s):  
Mohinder S. Chauhan ◽  
Kishore C. Sharma ◽  
Sanjay Gupta ◽  
Suvarcha Chauhan ◽  
Vijay K. Syal

Molar conductances and viscosities of Bu4NBPh4, NaBPh4 and R4NBr (R ethyl, propyl and butyl) at 35 °C in acetonitrile (AN), dimethylsulfoxide (DMSO) and their binary mixtures have been reported. The conductivity data has been analysed by the Shedlovsky conductance equation and viscosity data by the Jones-Dole equation. Resolution of limiting molar conductivity (Λ0) and viscosity B coefficient of electrolytes into their ionic components have been achieved by the reference salt method. Viscosity A coefficients have been compared with theoretical Aη coefficients. Derived conductance and viscosity parameters have been discussed in terms of the ion-solvent interaction.


1976 ◽  
Vol 54 (18) ◽  
pp. 2953-2966 ◽  
Author(s):  
Douglas E. Goldsack ◽  
Raymond Franchetto ◽  
Arlene (Anttila) Franchetto

The Falkenhagen–Leist–Kelbg equation for the conductivity of electrolyte solutions has been extended to include the effect of solvation on the concentration of the salt. Two equations have been derived, both of which have only two freely adjustable parameters at any temperature: Λ0 the molar conductance of the salt at infinite dilution and H0, a solvation number parameter for the salt. In one of these equations H0 is assumed to be independent of concentration. In the other, H0 is assumed to be dependent on concentration and an explicit concentration dependent formula is derived for H0. Conductance data for the alkali halide salts in the 0.5 to 10 m concentration range and 0 to 60 °C temperature range were found to be adequately reproduced by both these equations, but with the variable hydration parameter equation yielding better fits to the data. The H0 parameters from the fixed hydration parameter equation are found to be similar to those obtained from the analysis of activity coefficient and other data whereas the variable hydration parameter equation yields H0 parameters which are much larger.


1988 ◽  
Vol 66 (7) ◽  
pp. 1720-1727 ◽  
Author(s):  
Auaz Ahmad Ansari ◽  
M. R. Islam

Electrical conductivities of Me4NBr, Et4NBr, Pr4NBr, Bu4NBr, and Bu4PBr have been measured in isopropanol + water (2-PrOH + H2O) mixtures covering the approximate range of dielectric constant (71.40 ≥ D ≥ 19.40) at 25 °C. The conductance data have been analysed by using the Fuoss-1978 (F78) conductance equation and the results compared with those obtained from the Fuoss–Onsager–Skinner (FOS) equation. The values of the limiting equivalent conductance, Λ0, the association constant, KA, and the distance of ion-size parameter [Formula: see text] are computed from these data. A better fit of the conductance data was provided by the F78 equation. Ion–solvent interactions and effective sizes of tetraalkylammonium ions are also discussed in order to understand the magnitude of the ionic association. The overall association behaviour of these salts has been found to increase with decrease in dielectric constant of the medium.


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