Thermodynamic functions of Ni(II) complexes with 5-(2-hydroxyphenyl)-pyrazole derivatives. A potentiometric study

Proton-ligand dissociation constants of five biologically important pyrazole derivatives, viz. [5-(2-hydroxyphenyl)-3-(pyridin-3-yl)-4-benzoyl]-pyrazol (HPPBP), [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-(3-pyridinoyl)]-pyrazol (HPNPPP), [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-benzoyl]-pyrazol (HPNPBP), [5-(2-hydroxyphenyl)-3-phenyl-4-(3-pyridinoyl)]-pyrazol (HPPPP), and [5-(2-hydroxyphenyl)-3-(3-nitrophenyl)-4-(2-furoyl) pyrazol (HPNPFP) and metal ligand stability constants of their Ni(II) complexes in 70% (v/v) dioxane-water and 0.1 M KNO₃ were determined at 298.15, 303.15, and 308.15 K by potentiometric method. Thermodynamic functions, such as, free energy change (ΔG ^○), enthalpy change (ΔH ^○) and entropy (ΔS ^○) change for dissociation and complex formation have been estimated form temperature dependence of proton-ligand and metal-ligand stability constants and interpreted in terms of feasibility of these processes.     

Intermolecular interactions in dioxane-water solutions of substituted coumarins according to ultrasonic data

Density, ultrasonic velocity of pure dioxane (Dx) and ligands, 4,6-dimethyl-7-hydroxycoumarin (L₁), 6-ethyl-7-hydroxy-4-methylcoumarin (L₂), and 3-chloro-7-hydroxy-4-methylcoumarin (L₃) in different percent of Dx-water mixture have been investigated at 303.15 K. Acoustical parameters such as adiabatic compressibility (β), intermolecular free length (L _f ), acoustical impedance (Z), relative association (R _A ), apparent molar compressibility (Φ_β), and apparent molar volume (Φ _V ) have also been evaluated from the experimental data of density and ultrasonic velocity. An excellent correlation between a given parameters is observed at all percent of dioxane-water and the result suggests nature of intermolecular interactions between the components.     

Acoustical studies of some derivatives of 4-amino antipyrene in 1,4-dioxane and dimethylformamide at 318.15 K

For three derivatives of 4-amino antipyrene, density, viscosity and ultrasonic velocity are measured at 318.15 K in 1,4-dioxane (DO) and dimethylformamide (DMF). From these experimental data, various acoustical properties such as specific impedance (Z), isentropic compressibility (κ_s), Rao’s molar sound function (R_m), the van der Waals constant (b), molar compressibility (W), intermolecular free length (L_f), relaxation strength (r), relative association (R_A), free volume (V_f), etc. and apparent molar volume and apparent molar compressibility were calculated. The results are interpreted in terms of molecular interactions occurring in the solutions. It is observed that in 1,4-dioxane solutions, solute–solute interactions exist whereas solvent–solute interactions predominant in DMF system.     

Ultrasonic study on some monosaccharides in aqueous media at 298.15 K

The ultrasonic velocity (U), density (ρ) and viscosity (η) at 298.15 K have been measured in the binary systems of monosaccharides (glucose, fructose and galactose) in aqueous medium. The acoustical parameters such as adiabatic compressibility (β), free length (L_f), free volume (V_f), internal pressure (π_i), acoustical impedance (Z), relative association (R_A), molar sound velocity (R) and molar sound compressibility (W) are calculated. The results are interpreted in terms of molecular interaction between the components of the mixtures.     

Studies of some acoustical properties in binary solutions

Various acoustical properties such as isentropic compressibility, specific impedance, molar sound velocity, molar compressibility, van der Waals constant, intermolecular free length, excess molar volume (V^E), excess viscosity, excess adiabatic compressibility, Gibb’s free energy of activation for viscous flow etc. have been calculated in three binary systems: anisole+methanol, anisole+chloroform and anisole+dimethyl foramide from sound velocity (2 MHz), density and viscosity measurements at 30°C. The results are interpreted in terms of molecular interactions occurring in the solutions.     

Acoustical and Viscometric Studies of CdCl2 and KCl in Aqueous-Acetone Co-Solvent Between 25 and 45°C

Abstract

Ultrasonic velocity of CdCl₂ and KCl in co-solvent of Acetone and Water is measured at different concentrations from 298.15 K to 318.15 K using single crystal interferometer; operating at frequency of 2 MHz. Various acoustical parameters such as adiabatic compressibility (β_s), specific impedance (Z), apparent molar compressibility (Ø_K), relative association (R _A), Rao's molar sound function (R), molar compressibility (W), free volume (V _f) have been calculated. Results throw light on the solute-solvent and solute-solute interactions. Effect of temperature variation on these interactions has also been discussed.     

Acoustical parameters of toluene + chloroform + cyclohexane mixtures at 303.15, 308.15, and 313.15 K

Ultrasonic velocity, density and viscosity of the ternary mixture of toluene + chloroform + cyclohexane, were measured at 303.15, 308.15, and 313.15 K. The thermodynamically parameters such as adiabatic compressibility (??), intermolecular free length (L _f), free volume (V _f), internal pressure (?? _i ), acoustic impedance (Z), molar sound velocity (R), and molar compressibility (W) have been obtained from the experimental data for all the mixtures, with a view to investigate the exact nature of molecular interaction. Adiabatic compressibility and intermolecular free length decrease with increase in concentration and temperature. The other parameters show almost increasing concentration of solutes. These parameters have been further used to interpret the molecular interaction part of the solute and solvent in the mixtures.     

Temperature-dependent volumetric and viscometric properties of amino acids in aqueous solutions of an antibiotic drug

Volumetric and viscometric properties of glycine and methionine (amino acids) in a 0.2 vol. % amikacin sulphate (antibiotic drug) aqueous solution with the molality range of 0.025 mol kg^?1–0.25 mol kg^?1 were measured over the temperature range of 20°C–40°C at the interval of 5°C. Different parameters like apparent molar volume (? _V), apparent molar adiabatic compression (? _κ ), isentropic compression (κ _S) along with other acoustical parameters were calculated. Parameters like viscous relaxation time (τ), free volume (V _F), internal pressure (Π _I), and molar cohesive energy (MCE) were calculated from dynamic viscosity measurements. The ? _V values are positive in both cases, but with higher magnitude observed in methionine. These positive values of ? _V are indicative of strong solute-solvent interactions at all temperatures. In case of methionine there is a sharp initial increase in the ? _V values which become almost constant with further additions of the amino acid. Structural differences in the two amino acids studied are clearly reflected in the different nature of the plots of different parameters. In case of an amino acid-drug system, dynamic viscosity increase has been attributed to the increase in the hydrophilic-ionic and hydrophilic-hydrophilic interactions with the increase in the amino acid concentration which in turn may cause more frictional resistance to the flow of the solution. All other parameters are discussed in terms of solute-solvent and solvent-solvent interactions.     

Thermo-physical properties of the binary mixture of benzaldehyde with bromobenzene at 303.15, 308.15, and 313.15?K

The values of density, viscosity, and ultrasonic velocity for the binary liquid mixture of benzaldehyde with bromobenzene have been measured over the entire range of composition at 303.15, 308.15, and 313.15?K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (????), deviation in velocity (?U), deviation in isentropic compressibility (??? _s), excess internal pressure (???), excess intermolecular free length (?L _f), and excess acoustic impedance (?Z). McAllister??s three-body-interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich?CKister polynomial equation to obtain their coefficients and standard deviations. The thermo-physical properties (density, viscosity, and ultrasonic velocity) under the study were fitted to the Jouyban?CAcree model.     

Volumetric,Acoustic and Transport Properties of Metformin Hydrochloride Drug in Aqueous <Emphasis Type="SmallCaps">d</Emphasis>-Glucose Solutions at <Emphasis Type="Italic">T</Emphasis> = (298.15–318.15) K

Apparent molar volumes, apparent molar adiabatic compressibilities and viscosity B-coefficients for metformin hydrochloride in aqueous d-glucose solutions were determined from solution densities, sound velocities and viscosities measured at T = (298.15–318.15) K and at pressure p = 101 kPa as a function of the metformin hydrochloride concentrations. The standard partial molar volumes (\( \phi_{V}^{0} \)) and slopes (\( S_{V}^{*} \)) obtained from the Masson equation were interpreted in terms of solute–solvent and solute–solute interactions, respectively. Solution viscosities were analyzed using the Jones–Dole equation and the viscosity A and B coefficients discussed in terms of solute–solute and solute–solvent interactions, respectively. Adiabatic compressibility (\( \beta_{s} \)) and apparent molar adiabatic compressibility (\( \phi_{\kappa }^{{}} \)), limiting apparent molar adiabatic compressibility (\( \phi_{\kappa }^{0} \)) and experimental slopes (\( S_{\kappa }^{*} \)) were determined from sound velocity data. The standard volume of transfer (\( \Delta_{t} \phi_{V}^{0} \)), viscosity B-coefficients of transfer (\( \Delta_{t} B \)) and limiting apparent molar adiabatic compressibility of transfer (\( \Delta_{t} \phi_{\kappa }^{0} \)) of metformin hydrochloride from water to aqueous glucose solutions were derived to understand various interactions in the ternary solutions. The activation parameters of viscous flow for the studied solutions were calculated using transition state theory. Hepler’s coefficient \( (d\phi /dT)_{p} \) indicated the structure making ability of metformin hydrochloride in the ternary solutions.     

Ultrasonic investigation on aqueous polysaccharide (starch) at 298.15 K

The ultrasonic velocity, density and viscosity at 298.15 K have been measured in the binary system of starch in aqueous medium. The acoustical parameters such as adiabatic compressibility (β), free length (L_f), free volume (V_f), internal pressure (π_i), acoustical impedance (Z), relative association (R_A), Rao’s constant (R), Wada’s constant (W), classical absorption coefficients (α/f²), relaxation time (τ) and relaxation strength (r) are calculated. The results are interpreted in terms of molecular interaction between the components of the mixtures.     

Physico-chemical studies on some saccharides in aqueous cellulose solutions at different temperatures – Acoustical and FTIR analysis

The ultrasonic velocity (u), density (ρ) and viscosity (η) of Fructose, Lactose and Sucrose in 0.4 M of Hydroxy Propyl Methyl Cellulose (HPMC) solutions have been investigated at 303, 313 and 323 K, respectively. The acoustical parameters such as adiabatic compressibility (β), intermolecular free length (L_f), internal pressure (π_i), Rao’s constant (R_a), relaxation time (τ), acoustical impedance (Z_a), absorption coefficient (α/f²), free volume (V_f), cohesive energy (CE) and solvation number (S_n) have been computed. The non linear variations of acoustical parameters with concentration and temperature indicated the existence of strong molecular interaction in the systems studied. The FTIR spectroscopic analysis revealed the possibility of intermolecular hydrogen bonding in various saccharides.     

Effect of Temperature and Solvent on the Ultrasonic Velocity and Allied Acoustical Parameters of the Epoxy Oleate of 9,9′-Bis(4-hydroxyphenyl) Anthrone-10 Solutions

Density (ρ), viscosity (η) and ultrasonic velocity (U) (2 MHz) of the pure solvents (chloroform, THF and 1,4-dioxane) and solutions of the epoxy oleate of 9,9′-bis(4-hydroxyphenyl) anthrone-10 (EBANO) have been investigated at 303, 308 and 313 K. Acoustical parameters such as specific acoustical impedance (Z), adiabatic compressibility (κ _a ), intermolecular free path length (L _f ), classical absorption coefficient (α/f ²)_cl and viscous relaxation time (τ) have been determined from the ρ, η and U data and are correlated with concentration. A fairly good to excellent correlation between a given parameter and concentration is observed at all temperatures and solvent systems studied. Linear or nonlinear increases or decreases of acoustical parameters with concentration and temperature indicated the existence of strong molecular interactions.     

Thermodynamic and aggregation behavior of mixed micellar systems of sodium decanoate and ethoxylated alcohols in water at 25°C

Densities and ultrasonic velocities of binary aqueous systems of sodium decanoate (C₁₀Na), of a medium chain length alkoxyethanol with varying number of ethylene oxide groups (C₄EO_0-3), and of ternary systems of these compounds have been measured as a function of surfactant and alcohol concentrations at 25°C. The derived apparent molar volume and molar adiabatic compressibility properties of C₁₀Na in water were fitted with a mass-action model to obtain the thermodynamic micellization parameters of C₁₀Na. The infinite dilution transfer molar volume and transfer molar adiabatic compressibility properties of C₄EO_0-3 from water to aqueous C₁₀Na solutions were obtained from the corresponding apparent molar properties using a chemical equilibrium model. The results of simulating the experimental transfer function data of these alcohols at a given low concentration of 0.05m_A show that the solubilization of C₄EO_0-3 compounds in C₁₀Na micelles is enhanced by increasing the number of ethylene oxide groups (EO) in the alcohol. The mean aggregation number of C₁₀Na, which is 34 in the absence of alcohol, remains unchanged in the presence of 0.05m_A while the average number of alcohol molecules per micelle increases steadily as a function of the number of EO groups in the alcohol.     

Solute–solvent interactions in 2,4-dihydroxyacetophenone isonicotinoylhydrazone solutions in N,N-dimethylformamide and dimethyl sulfoxide at 298–313 K on ultrasonic and viscometric data

The speed of sound (u), density (ρ), and viscosity (η) of 2,4-dihydroxyacetophenone isonicotinoylhydrazone (DHAIH) have been measured in N,N-dimethyl formamide and dimethyl sulfoxide at equidistance temperatures 298.15, 303.15, 308.15, and 313.15 K. These data were used to calculate some important ultrasonic and thermodynamic parameters such as apparent molar volume (V _{? s} ^st ), apparent molar compressibility (K _?), partial molar volume (V _? ⁰ ) and partial molar compressibility (K _? ⁰ ), were estimated by using the values of (V _? ⁰ ) and (K _?), at infinite dilution. Partial molar expansion at infinite dilution, (? _E ⁰ ) has also been calculated from temperature dependence of partial molar volume V _? ⁰ . The viscosity data have been analyzed using the Jones–Dole equation, and the viscosity, B coefficients are calculated. The activation free energy has been calculated from B coefficients and partial molar volume data. The results have been discussed in the term of solute–solvent interaction occurring in solutions and it was found that DHAIH acts as a structure maker in present systems.     

Volume and compressibility effects in the formation of metal-EDTA complexes

We used precise measurements of ultrasonic velocity and density to study the complexation of ethylendiaminetetraacetic acid (EDTA) with Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ at 25‡C and pH 12. From these measurements we obtained the changes in the molar concentration increment of the ultrasonic velocity δA, the apparent molar adiabatic compressibility δK_sΦ, and the apparent molar volume δV_Φ of complex formation. The hydration contributions δ(AV_h) to the volume effect of binding range from 39.6 to 46.6 cm³-mol^-1 while the hydration contribution to the adiabatic compressibility change in the binding, δ(δK_h), ranges from 103.9X 10^-4 to 131.1 X 10^-4 cm³-mol^-1-bar^-1. These data are interpreted in terms of dehydration of interacting molecules,i.e., transfer of water molecules from the hydration shells of cations and EDTA into the bulk water. The ratio δ(δV_h)/ δ(δV_h) is in the range 0.35 to 0.38 bar, indicating a dominant contribution from the dehydration of charged atomic groups in the volume and the compressibility effects of complex formation.     

Ultrasonic studies of polysaccharide (pectin) in aqueous media at 298.15 K

The ultrasonic velocity, density and viscosity of pectin in aqueous medium were measured at 298.15 K. The acoustical parameters such as adiabatic compressibility (β), free length (L _f), free volume (V _f), internal pressure (π_i), acoustical impedance (Z), and relative association (R _A), Rao’s constant (R) and Wada’s constant (W) are calculated. The results are interpreted in terms of molecular interaction between the components of the mixtures. Further, some more acoustical parameters such as relaxation time (τ), absorption coefficient (α/f ²) and relaxation strength (r) are calculated with various percentage of pectin has been studied which reveals interaction between the solvent and the polymer (pectin) at various concentration of the polymer. The observed values suggested the solute-solvent interaction is favored.     

Apparent molar volume and apparent molar adiabatic compressibility of 2-hydroxy-5-methyl acetophenone in <Emphasis Type="Italic">N,N</Emphasis>-dimethylformamide at different temperatures

The speed of sound and density of 2-hydroxy-5-methyl acetophenone in dimethylformamide have been measured over the range of temperatures 25–40 °C. From the experimentally determined data, values of apparent molar volume (V _ϕ), adiabatic compressibility (β_s), apparent molar adiabatic compressibility (K _s,ϕ) and their limiting values have been computed. Values at infinite dilution provide information regarding solute–solvent interaction. The density and velocity increases with increase in concentration and decreases with increase in temperature. These results have been analyzed in terms of molecular interactions between acetophenone and dimethylformamide.     

Remarkable Chichibabin-type cyclotrimerisation of 3-nitrotyrosine, tyrosine and phenylalanine to 3,5-diphenylpyridine derivatives induced by hypochlorous acid

Reaction of 3-nitrotyrosine with HOCl in aqueous phosphate buffer (pH 7.4) leads to a mixture of extractable products, including 3,5-di(4-hydroxy-3-nitrophenyl)pyridine (15% isolated yield) and 3,5-di(4-hydroxy-3-nitrophenyl)-2-(4-hydroxy-3-nitrophenylmethyl)pyridine (3%) arising by a Chichibabin-like pyridine synthesis via N-chloroimine intermediates. Under the same conditions, phenylalanine gives 3,5-diphenylpyridine in 9% isolated yield, while tyrosine leads to 3,5-di(4-hydroxyphenyl)pyridine (3%) and 3-(3-chloro-4-hydroxyphenyl)-5-(4-hydroxyphenyl)pyridine (3%).     

Molecular interactions in β-alanine-water-methanol solutions at 308.15 K on volumetric, viscometeric, and acoustic data

The density, viscosity and ultrasonic velocity for β-alanine solutions in aqueous and aqueous methanol medium at different concentrations has been determined at 308.15 K. The experimentally obtained data were used to evaluate the apparent molal volume and apparent molal adiabatic compressibility. The related thermodynamic parameters like partial molal volume as well as partial molal adiabatic compressibility at infinite dilution along with their corresponding constants S _v and S _k , respectively, give an insight to the nature of molecular interactions. The viscosity coefficient has also been calculated using Jones-Dole equation.