Activation Parameters Of Viscous Flow Research Articles

Effect of sodium acetate on the rheological behaviour of some mono-, di-, and tri-saccharides in aqueous solutions over the temperature range (288.15 to 318.15) K

The Jones–Dole viscosity B-coefficients for various mono-, di-, and tri-saccharides in water and in (0.5, 1.0, 2.0, and 3.0) mol · kg −1 aqueous solutions of sodium acetate have been determined at different temperatures, T = (288.15, 298.15, 308.15, and 318.15) K from viscosity data. Densities used to determine viscosities have been reported earlier. The viscosity B-coefficients of transfer, Δ t B, has been estimated for the transfer of saccharides from water to aqueous sodium acetate solutions. The positive Δ t B values were obtained in all cases and their magnitudes increase with the increase in concentration of sodium acetate. Pair, η AB and higher order, η ABB viscometric interaction coefficients (using McMillan–Mayer theory), and dB/ dT coefficients have also been determined. Activation Gibbs free energies and other related thermodynamic activation parameters of viscous flow have been determined using Feakin’s transition-state theory. These parameters have been discussed in terms of solute–solute and solute–solvent interactions occurring in these solutions.

Studies on molecular interactions of oxalic acid and its salts in co-aqueous solutions of 1,3-dioxolane by volumetric and viscometric measurements at T = (298.15, 308.15, and 318.15) K

The densities and viscosities of oxalic acid and its salts, viz. ammonium oxalate, sodium oxalate and potassium oxalate, have been determined in w 1 = (0.05, 0.10, and 0.15) mass fraction of 1,3-dioxolane (1) + water (2) mixtures at T = (298.15, 308.15, and 318.15) K and p = 0.1 MPa. Apparent molar volumes ( V ϕ), viscosity B-coefficients of these electrolytes were obtained from their densities, viscosities. The limiting apparent molar volumes ( V ϕ 0) and experimental slopes (S v ⁎) derived from the Masson equation and the obtained parameters have been interpreted in terms of ion–solvent and ion–ion interactions, respectively. The viscosity data were evaluated by using the Jones–Dole equation. The structure-making/-breaking capacities of the electrolytes have been inferred from the sign of ( δ 2 V ϕ 0 δ T 2 ) P and dB/ dT. The activation parameters of viscous flow for the ternary solutions studied were also calculated and explained by the application of transition state theory.

Investigation on molecular interactions of nicotinamide in aqueous citric acid monohydrate solutions with reference to manifestation of partial molar volume and viscosity B-coefficient measurements

Apparent molar volumes ( V ϕ), viscosity B-coefficients for nicotinamide in 0.03, 0.05, 0.07 and 0.10 mol dm −3 aqueous citric acid monohydrate solutions have been determined from solution density and viscosity measurements at 298.15, 308.15 and 318.15 K as function of concentration of nicotinamide. The apparent molar volumes have been extrapolated to zero concentration to obtain the limiting values at infinite dilution using Masson equation. The infinite dilution partial molar expansibilities have also been calculated from the temperature dependence of the limiting apparent molar volumes. This results have, in conjunction with the results obtained in pure water, been used to calculate the standard volumes of transfer Δ V ϕ 0 and viscosity B-coefficients of transfer for nicotinamide from water to aqueous citric acid monohydrate solutions for rationalizing various interactions in the ternary solutions. The structure making or breaking ability of nicotinamide has been discussed in terms of the sign of ∂ 2 V ϕ 0 / ∂ T 2 p and dB/ dT. An increase in the transfer volume of nicotinamide with increasing citric acid monohydrate concentration has been explained by Friedman–Krishnan co-sphere model. The activation parameters of viscous flow for the ternary solutions studied have also been calculated and explained by the application of transition state theory.

Volumetric and viscometric studies of glucose in binary aqueous solutions of urea at different temperatures

Densities and viscosities of glucose in (1.0, 2.5, and 5.0) mass% aqueous urea solutions have been measured at T = (298.15, 303.15, 308.15, and 313.15) K, respectively. Apparent molar volumes, limiting partial molar volume, and relative viscosity have been obtained from the density and viscosity results. Limiting partial molar expansibilities have also been calculated from the temperature dependence of limiting partial molar volumes. The viscosity data have been analyzed by using the modified Jones–Dole equation. The results are used to establish the nature of solute–solute and solute–solvent interactions. Transition state treatment of the relative viscosity was also used for the calculation of activation parameters of viscous flow. Pour findings show that the solute acts as a water structure former and provides strong solute–solvent interaction.

Apparent molar volume, viscosity B-coefficient, and adiabatic compressibility of tetrabutylammonium bromide in aqueous ascorbic acid solutions at T = 298.15, 308.15, and 318.15 K

Apparent molar volumes ϕν and viscosity B-coefficients for tetrabutyl ammonium bromide (TBAB) in (0.00, 0.05, 0.10, and 0.15) mol dm−3 aqueous ascorbic acid solutions have been determined from solution density and viscosity measurements at temperatures over the range 298.15 to 318.15 K as function of concentration of ascorbic acid solutions. In the investigated temperature range, the relation: ϕν0 = a0 + a1T + a2T2, have been used to describe the partial molar volume ϕν0. These results, in conjunction with the results obtained in pure water, have been used to calculate the standard volumes of transfer Δϕν0 and viscosity B-coefficients of transfer for TBAB from water to aqueous ascorbic acid solutions for rationalizing various interactions in the ternary solutions. The structure making or breaking ability of TBAB has been discussed in terms of the sign of (δ2ϕν0/δT2)P. An increase in the transfer volume of TBAB with increasing ascorbic acid concentration has been explained by Friedman-Krishnan co-sphere model. The activation parameters of viscous flow for the ternary solutions studied have also been calculated and explained by the application of transition state theory.

Solute–solvent and solvent–solvent interactions of menthol in isopropyl alcohol and its binary mixtures with methyl salicylate by volumetric, viscometric, interferometric and refractive index techniques

The apparent molar volume ( V ∅ ), viscosity B-coefficient, isoentropic compressibility ( ϕ K ) of menthol have been determined in binary solution of isopropyl alcohol and methyl salicylate (at 303.15, 313.15 and 323.15 K) from density ( ρ), viscosity ( η) and sound speed respectively. The apparent molar volumes have been extrapolated to zero concentration to obtain the limiting values at infinite dilution using Masson equation. The infinite dilution partial molar expansibilities have also been calculated from the temperature dependence of the limiting apparent molar volumes. Viscosity B-coefficients has been calculated using Jones–Dole equation. The structure-making or breaking capacity of the solute under investigation has been discussed in terms of sign of ( δ 2 V Ø o / δ T 2 ) P . The activation parameters of viscous flow were determined and discussed by application of transition state theory.

Density, Viscosity, and Electric Conductance of a Ternary Solution of (Nicotinic Acid + Polyethanol + Water)

In this work, the density, viscosity, and electrical conductance of the ternary solution of {nicotinic acid + polyethanol + water} were determined experimentally; polyethanol is commonly known as poly(vinyl alcohol) given the acronym PVA. The degree of dissociation, the partial molar volume of nicotinic acid in PVA aqueous solution, and the B-coefficient of viscous flow were evaluated. The effect of PVA on these parameters was discussed. Using Eyring’s transition state treatment, the activation parameters of viscous flow, which reflects the effect of the concentration of PVA on the motion of nicotinic acid, have been obtained. The result shows that PVA increases the viscosity, decreases the degree of dissociation, and impedes the motion of nicotinic acid at lower concentrations but promotes the solubility and molecular diffusion of nicotinic acid at higher concentrations.

Study of Thermodynamic and Transport Properties of Glycine, Diglycine, and Triglycine in Aqueous Tartrazine at Different Temperatures

The densities (ρ), viscosities (η), and refractive indices (nD) of (0.01, 0.05, 0.10, 0.15, and 0.20 m) amino acid, glycine, and peptides, diglycine and triglycine in 0.01 m aqueous tartrazine solution were determined at 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K. The density data were utilized to evaluate apparent molar volumes (φv) which, in turn, were used to determine partial molar volumes (φv ◦) using Masson’s equation. The transfer volumes were also calculated. The viscosity data were analyzed using the Jones-Dole equation to determine the viscosity coefficients and the activation parameters. The activation parameters of viscous flow were obtained to throw light on the mechanism of viscous flow. The molar refraction was calculated using the refractive index data. The results were interpreted in the light of ion-ion, ion-nonpolar, and nonpolar-nonpolar interactions and the effect of increasing hydrophobicity as we move from glycine to triglycine on these interactions in presence of the dye tartrazine was also investigated.

Apparent molar volumes and viscosity B-coefficients of caffeine in aqueous thorium nitrate solutions at T = (298.15, 308.15, and 318.15) K

Apparent molar volumes ϕ V and viscosity B-coefficients for caffeine in (0.00, 0.03, 0.05, and 0.07) mol · dm −3 aqueous thorium nitrate, Th(NO 3) 4, solutions were determined from solution density and viscosity measurements over the temperature range (298.15 to 318.15) K as function of concentration of caffeine and the relation: ϕ V ∘ = a 0 + a 1 T + a 2 T 2 , have been used to describe the temperature dependence of the standard partial molar volumes ϕ V ∘ . These results have been used to deduce the standard volumes of transfer Δ ϕ V ∘ and viscosity B-coefficients of transfer Δ B for caffeine from water to aqueous Th(NO 3) 4 solutions for rationalizing various interactions in the ternary solutions. The structure-making or breaking ability of caffeine has been discussed in terms of the sign of ( δ 2 ϕ V ∘ / δ T 2 ) P . The Friedman–Krishnan co-sphere model was used to explain the transfer volume of caffeine with increasing Th(NO 3) 4 molarity. The activation parameters of viscous flow for the ternary solutions were also discussed in terms of transition state theory.

Volumetric and viscometric studies of urea in binary aqueous solutions of glucose at different temperatures

Densities and viscosities of urea in (1.0, 2.5, and 5.0) mass% of aqueous glucose solutions have been measured at T = (298.15, 303.15, 308.15, and 313.15) K, respectively. Apparent molar volumes, limiting partial molar volume, and relative viscosity have been obtained from the density and viscosity data. Limiting partial molar expansibilities have also been calculated from the temperature dependence of limiting partial molar volumes. The viscosity data has been analyzed using the Jones–Dole equation. The results are used to establish the nature of solute–solute and solute–solvent interactions. The activation parameters of viscous flow have also been calculated on the basis of transition state treatment of the relative viscosity. Result shows that the solute acts as water structure breaker and posses’ weak solute–solvent interaction.

Studies on Molecular Interactions of Some Thiocyanate Salts in Coaqueous Solutions of 1,3-Dioxolane + Water by Volumetric, Viscometric, and Speed of Sound Measurements

The densities and viscosities of some thiocyanate compounds, viz., ammonium thiocyanate, sodium thiocyanate, and potassium thiocyanate, in 10 %, 20 %, and 30 % by mass of 1,3-dioxolane + water mixtures have been determined at T = (298.15, 308.15, and 318.15) K and p = 0.1 MPa. The speeds of sound of the thiocyanate compounds in 10 %, 20 %, and 30 % by mass of 1,3-dioxolane + water mixtures have also been determined at 298.15 K. Apparent molar volumes (Vϕ), viscosity B-coefficients, and adiabatic compressibility (β) of these electrolytes were obtained from their densities, viscosities, and speed of sound data. The limiting apparent molar volumes (Vϕo) and experimental slopes (Sv*) derived from the Masson equation and the obtained parameters have been interpreted in terms of ion−solvent and ion−ion interactions, respectively. The viscosity data were evaluated by using the Jones−Dole equation. The structure making/breaking capacities of the electrolytes have been inferred from the sign of (δ2ϕVo/δT2)p and dB/dT. The activation parameters of viscous flow for the ternary solutions studied were also calculated and explained by the application of transition state theory.

Partial Molar Volumes and Viscosity B-Coefficients of Nicotinamide in Aqueous Resorcinol Solutions at T = (298.15, 308.15, and 318.15) K

Partial molar volumes \({( {\phi _{\rm v}^{\rm o}} )}\) and viscosity B-coefficients for nicotinamide in (0.00, 0.05, 0.10, 0.15, and 0.20) mol·dm−3 aqueous resorcinol solutions have been determined from solution density and viscosity measurements at (298.15, 308.15, and 318.15) K as a function of the concentration of nicotinamide (NA). Here the relation \({\phi _{v}^{\rm o} =a_0 +a_{1} T+a_{2} T^{2}}\), has been used to describe the temperature dependence of the partial molar volume \({\phi _v^{\rm o} }\). These results and the results obtained in pure water were used to calculate the standard volumes of transfer \({\Delta \phi _{v}^{\rm o} }\) and viscosity B-coefficients of transfer of nicotinamide from water to aqueous resorcinol solutions to study various interactions in the ternary solutions. The partial molar volume \({( {\phi _{v}^{\rm o}})}\) and experimental slopes obtained from the Masson equation have been interpreted in terms of solute–solvent and solute–solute interactions, respectively. The viscosity data have been analyzed using the Jones–Dole equation, and the derived parameters B and A have also been interpreted in terms of solute–solvent and solute–solute interactions, respectively, in the ternary solutions.The structure making or breaking ability of nicotinamide has been discussed in terms of the sign of \({( {\delta ^{2}\phi _v^o /\delta T^{2}})_P}\). The activation parameters of viscous flow for the ternary solutions studied were also calculated and explained by the application of transition state theory.

A viscometric study of the liquid crystalline phase of alkyloxybenzoic acids

The viscosities of three benzoic acid derivatives (p-n-heptyloxy-, p-n-decyloxy-, and p-n-dodecyloxy-) were measured on a unique viscometer of the class of CS-rheometer-viscometers with controlled shear stress over the whole temperature range of the liquid crystalline state. Shear rates were calculated and flow and viscosity curves constructed from the experimental shear stress values taking into account the Rabinovich-Moony correction. The smectic and nematic phases were characterized by non-Newton and Newton viscosities, respectively, in all the samples studied. The activation parameters of viscous flow were calculated for Newton viscosity. The results are discussed in terms of intermolecular interactions and structural peculiarities of liquid crystalline phases.

Ion-solvent and ion-ion interactions of phosphomolybdic acid in aqueous solution of catechol at 298.15, 308.15, and 318.15 K

Apparent molar volume (VO) and viscosity B-coefficients were measured for phosphomolybdicacid in aqueous solution of catechol from solution density (ρ) and viscosity (η) at 298.15, 308.15, and 318.15 K at various solute concentrations. The experimental density data were evaluated by Masson equation and the derived data were interpreted in terms of ion-solvent and ion-ion interactions. The viscosity data have been analyzed using Jones-Dole equation and the derived parameters, B and A, have been interpreted in terms of ion-solvent and ion-ion interactions respectively. The structure-making or breaking capacity of the solute under investigation has been discussed in terms of sign of (δ2VOo/δT2)P. The activation parameters of viscous flow were determined and discussed by application of transition state theory.

Apparent molar volume, viscosity, and adiabatic compressibility of some mineral sulfates in aqueous binary mixtures of formamide at 298.15, 308.15, and 318.15 K

The densities and viscosities of several sulfates, viz., ammonium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, zinc sulfate and cadmium sulfate in aqueous binary mixtures of formamide (FA) have been determined at 298.15, 308.15, and 318.15 K and at atmospheric pressure. The ultrasonic speeds of the electrolytic solutions have also been measured at 298.15 K. Apparent molar volumes (ϕ V ), viscosity B-coefficients and adiabatic compressibilities (K S) of these electrolytic solutions were calculated from the experimental densitiy, viscosity and acoustic data. The density and viscosity data were evaluated by using Masson’s and Jones-Dole equation respectively; the derived parameters have been analyzed in terms of ion-ion and ion-solvent interactions. The structure making/breaking capacities of the electrolytes have been inferred from the sign of (∂2ϕ 0 /∂T 2) P . The results showed that all the electrolytes act as structure-makers in these media. Also the compressibility data indicated electrostriction of the solvent molecules around the cations. The activation parameters of viscous flow were also determined and discussed by the application of transition state theory.

Viscosity, density, electric conductance and activation parameters of viscous flow for sodium salicylate in aqueous poly (vinyl alcohol) solution

Viscosity, density and electric conductance of the solution of sodium salicylate + poly (vinyl alcohol) + water at the temperatures 293.15, 298.15, 303.15, 308.15 and 313.15 K are measured experimentally. The partial molar volume, the molar conductance at infinite dilution, and the activation parameters of viscous flow were obtained. An approximately linear relation between the activation free energy of viscous flow and the molar conductance at infinite dilution is observed. Our result shows that, although PVA increases the viscosity of the medium, the diffusivity of ions does not decrease, the solvation volume of salt at infinite dilution changes little. Therefore, the increase in diffusivity is connected with the decrease in the free space of ion moving when PVA is added into water.

Ion–solvent and ion–ion interactions of sodium molybdate and sodium tungstate in mixtures of ethane-1,2-diol and water at 298.15, 308.15 and 318.15 K

Apparent molar volume ( V Ø) and viscosity B-coefficients were estimated for sodium molybdate and sodium tungstate in aqueous binary mixture of ethane-1,2-diol from measured solution density ( ρ) and viscosity ( η) at 298.15, 308.15 and 318.15 K at various electrolyte concentrations. The experimental density data were evaluated by Masson equation and the derived data were interpreted in terms of ion–solvent and ion–ion interactions. The viscosity data has been analyzed using Jones–Dole equation and the derived parameters, B and A, have also been interpreted in terms of ion–solvent and ion–ion interactions respectively. The structure-making or breaking capacity of the electrolyte under investigation has been discussed in terms of sign of ( δ 2V Ø 0 / δT 2) P . The activation parameters of viscous flow were also determined and were discussed by the application of transition state theory.

Density and Viscosity of Anhydrous Mixtures of Dimethylsulfoxide with Acetonitrile in the Range (298.15 to 318.15) K

The density and viscosity of dimethylsulfoxide (DMSO) + acetonitrile (AN) mixtures were determined over the whole composition range at T = (298.15, 303.15, 308.15, 313.15, and 318.15) K. Since experimental density values showed to be very sensitive to water content, the water-free values of these magnitudes were determined by extrapolation from data obtained on ternary mixtures with small, well-determined, amounts of water and constant xDMSO/xAN. Excess volumes of the anhydrous mixtures show positive values with a quite symmetrical behavior. Viscosity data were satisfactorily fitted with a sixth degree polynomial. Excess viscosities as well as activation parameters for viscous flow in the mixtures were calculated.

Ion-solvent and ion-ion interactions of sodium molybdate and sodium tungstate in mixtures of acetonitrile and water at 298.15, 308.15, and 318.15 K

The apparent molar volumes (Vϕ) and viscosity B-coefficients of sodium molybdate and sodium tungstate in aqueous binary mixtures of acetonitrile were determined from solution density and viscosity measurements at 298.15, 308.15 and 318.15 K and various electrolyte concentrations. The experimental density and viscosity data were evaluated by the Masson and Jones-Dole equations, respectively, and the parameters derived were interpreted in terms of ion-solvent and ion-ion interactions. The activation parameters of viscous flow were also determined and discussed using transition state theory.

Apparent molar volumes and viscosity B-coefficients of nicotinamide in aqueous tetrabutylammonium bromide solutions at T = (298.15, 308.15, and 318.15) K

Apparent molar volumes ϕ V and viscosity B-coefficients for nicotinamide in (0.00, 0.05, 0.10, and 0.15) mol · dm −3 aqueous tetrabutylammonium bromide (TBAB) solutions have been determined from solution density and viscosity measurements at temperatures over the range (298.15 to 318.15) K as function of concentration of nicotinamide (NA). In the investigated temperature range, the relation: ϕ V ∘ = a 0 + a 1 T + a 2 T 2 , have been used to describe the temperature dependence of the standard partial molar volumes ϕ V ∘ . These results have, in conjunction with the results obtained in pure water, been used to deduce the standard volumes of transfer Δ ϕ V ∘ and viscosity B-coefficients of transfer for nicotinamide from water to aqueous TBAB solutions for rationalizing various interactions in the ternary solutions. The structure making or breaking ability of nicotinamide has been discussed in terms of the sign of ( δ 2 ϕ V ∘ / δ T 2 ) P . An increase in the transfer volume of nicotinamide with increasing TBAB concentration has been explained by Friedman–Krishnan co-sphere model. The activation parameters of viscous flow for the ternary solutions investigated were also determined and discussed by the application of transition state theory.