Apparent Molar Volumes Research Articles

Hydration behavior of D-calcium pantothenate (vitamin B5) in the presence of sugar-based deep eutectic solvents at different temperatures: experimental and theoretical study

Considerable efforts have been devoted in recent years to enhancing the efficacy medicinal substance, leading to the discovery of innovative drug formulations and delivery techniques. The successful design of these processes necessitates a profound understanding at the molecular level of how these substances interact with biological membranes. Thorough thermodynamic investigations provide invaluable insights into these interactions and aid in selecting suitable compounds for pharmaceutical production. This study aims to determine the density and speed of sound for D-calcium pantothenate in mixtures of water and deep eutectic solvents (DESs), specifically choline chloride/sucrose, choline chloride/ glucose, and choline chloride/ fructose (with 2:1 molar ratio) over a temperature range of 288.15 K to 318.15 K under atmospheric pressure. In order to predict the behavior of molecules, COSMO model (the Conductor-Like Screening Model) offer complementary strengths in quantum chemistry. This approach allows for calculating solvation free energies, making it ideal for predicting properties like solubility, where understanding solvent-solute interactions is crucial. By correlating the measured parameters using standard relationships, important partial molar parameters such as apparent molar volumes and apparent molar isentropic compressibility are calculated. Additionally, apparent molar isobaric expansion, and Hepler’s constant are derived from the density and speed of sound data. The experimental apparent molar volumes, and apparent molar isentropic compressibility data is fitted to the Redlich-Meyer equation to obtain significant quantities such as standard partial molar volume, and partial molar isentropic compression. The comprehensive thermodynamic analysis of this studied system holds immense significance for advancements in the pharmaceutical industry.

Molecular interaction studies of Gamma-aminobutyric acid (GABA) in an aqueous medium at various temperatures: A comprehensive analysis using volumetric, thermoacoustic and DFT methods

The interaction of Gamma-aminobutyric acid (GABA) in an aqueous medium at various concentrations (0.101–1.086) mol·kg−1 as a function of temperature is being studied using volumetric, viscosity and acoustic analysis. The calculation of apparent molar volume (VΦ), partial molar volume (V∅o), apparent molar isentropic compression (Kϕ) and partial molar isentropic compression (Kϕ0) of GABA in an aqueous medium has been done by measuring the densities and speed of the sound in the temperature range of 298.15–323.15 K. The thermo-acoustic parameters like adiabatic compressibility (βs), acoustic impedance (Z), intermolecular free length (Lf), relative association (RA), relaxation time (τ), internal pressure (πi), enthalpy (ΔH), Gibbs free energy (ΔG), and change in entropy (ΔS) are also computed. The strength of the hydrogen bond interaction of GABA in an aqueous medium and its dipole moment are calculated using single-point energy calculations. These calculations employ IEFPCM and PCM solvation models using DFT/B3LYP and MP2 methods with the 6-311G++ (d, p) basis set. The outcomes are interpreted in terms of hydrogen bond interactions that exist in the mixture.

Apparent molar volume at infinite dilution, expansivities and electrochemical behaviours of binary system (tetramethylpiperidine 1-oxyl-based ionic liquids + water)

ABSTRACT At T = (278.15–318.15) K and atmospheric pressure, Hepler’s constant values, (∂2 V B/∂ T 2) P , and apparent molar expansivities (E φ) were calculated using the temperature dependence of apparent molar volumes (V B). Because of the increase in hydrophobic hydration of tetramethylpiperidine 1-oxyl-based ionic liquids (TILs), the Hepler’s constant values were found to change from positive to negative, indicating that the TILs under consideration changed primarily from structure-promoting to structure-breaking. The critical micelle concentration of conductivity (CMC) was calculated based on experimental conductivity, which reflects the dissociation and the interaction and aggregation behaviour of TILs.

Analysis of molecular interactions of an aqueous benzoates with glycolic and lactic acid: spectroscopic, acoustic, and volumetric approach

Volumetric as well as Acoustic properties for the ternary liquid combination (water + sodium methyl p-hydroxybenzoate + glycolic acid/lactic acid) are evaluated at several temperatures using a Densimeter (DSA 5000 M) over the range of concentrations (0.000, 0.015, 0.025, 0.035) mol.kg−1. Several thermo-acoustical properties were computed utilizing the experimental data. These values were then used to derive several parameters, including the apparent molar volume( V∅ ); partial molar volume (V∅0); apparent molar isentropic compression (K∅,S); transfer properties(Δ V∅0, Δ K∅,s0 ); partial molar isentropic compression (K∅,s0); apparent molar expansibility ( E∅0 ) as well as its first derivative ( ∂Eϕ0/∂T ) P; and coefficient of thermal expansivity( αp ). The obtained results are explained by analyzing the several interactions that take place inside the liquid system by implementing the theory of co-sphere overlap. Utilizing these thermodynamical parameters, the interaction coefficients are computed to evaluate the ternary mixture corresponding to the interactions between solutes and solvents. FTIR spectrum analysis revealed the presence of H-bonds along with the other molecular interactions in the analyzed systems, as shown by the shifting of the O-H stretching band.

Excess Thermodynamic Properties and FTIR Studies of Binary Mixtures of Toluene with 2-Propanol or 2-Methyl-1-Propanol

Physical properties of the binary solutions, toluene with 2-propanol and 2-methyl-1-propanol, were measured at T = 293.15, 298.15, 303.15, 308.15, and 313.15 K and P = 100 kPa. The experimental density values were tested with the Emmerling et al. and Gonzalez-Olmos–Iglesias equations. The results indicate that the equation by Emmerling et al. is the best to correlate the density for toluene + 2-methyl-1-propanol system, while for toluene + 2-propanol, both proposed equations are proper to correlate the density with composition and temperature. The viscosity results were verified with different models containing two adjustable parameters. The values of viscosity deviation (∆η), excess molar volume (VE), excess Gibbs energy (ΔG*E), partial molar volumes (V1¯ and V2¯), and apparent molar volume (Vφ,1 and Vφ,2) were calculated. The values of the excess molar volume were positive for both systems, while negative values were obtained for the viscosity deviation and the excess Gibbs energy. The excess properties of the mixtures were adjusted to the Redlich–Kister equation. The values of thermodynamic functions of activation of viscous flow were computed and analyzed. Additionally, the Prigogine–Flory–Patterson (PFP) theory was applied to calculate VE and then compared with experimental values. The values of the percentage absolute average deviation obtained suggest the validity of this theory. The Fourier transform infrared spectroscopy (FTIR) spectra of the binary solutions studied in this work allowed for the understanding of the interactions between the molecules of these systems.

Characterization of complexation of uracil with peptides through its volumetric properties in buffer saline solution at different temperatures

Densities of mixtures of uracil (Ura) with glycyl-glycine (GlyGly) and glycyl-phenylalanine (GlyPhe) in a buffered saline (pH 7.4) were measured at T=(288.15, 293.15, 298.15, 303.15, 308.15 and 313.15) K using the density meter DMA 5000 M (Anton Paar). The apparent molar volumes, limiting apparent molar volumes at infinite dilution and their derivatives with respect to temperature have been evaluated. Interactions of uracil (Ura) with glycylpeptides (GlyGly, GlyPhe, GlyTyr, GlyGlu) were studied with using review volumetric properties obtained early for Ura in GlyTyr and GlyGlu buffered solutions. The effect of concentration, ionic state and hydrophobicity of reagents on the Ura volume properties were discussed. The results indicate the complex formation between Ura and glycylpeptides with 1:1 stoichiometry. It was shown that the complexation of uracil with the glycylpeptides is accompanied by the positive changes of molar volume of Ura. The positive values of Hepler parameter indicate an increase in the ordering of the solvent in the environment of uracil with the addition of peptides. Uracil acts as a structure maker and its structure-making ability increases in series: Ura < GlyPhe < GlyGly < GlyGlu < GlyTyr.

Insights from volumetric, acoustic, conductance and spectroscopic studies to study the molecular interactions of drug Levocetirizine in aqueous and aqueous glucose solutions at varying temperatures

Levocetirizine, an antihistamine, has been analyzed in relation to temperature by volumetric, acoustic, and spectroscopic methods to investigate its interaction with glucose, the predominant carbohydrate. Density and ultrasonic velocity for LC (0–0.10 mol dm−3) at different temperature (298.15, 308.15 and 318.15 K) in water and in aqueous solution of glucose (0.05, 0.10 and 0.15 mol kg−1) have been recorded using Anton Paar DSA 5000 M. The apparent molar volume (Vϕ), limiting apparent molar volume (Vϕ0), apparent molar compressibility (Kϕ,S), limiting apparent molar compressibility (Kϕ,S0) were computed utilizing the experimental data. In addition, the transfer parameters of LC from water to aqueous glucose solutions were identified and elucidated using the co-sphere model. The transfer volumes have been utilized to estimate the interaction coefficients. Limiting apparent molar expansibility (ϕE0) and Hepler’s constant was obtained to throw light upon the structure-making or structure-breaking effect of solute. Multiple acoustical parameters like isentropic compressibility (KS), relaxation strength (r), intermolecular free length (Lf), specific acoustic impedance (Z), Wada’s constant (W), relative association (RA), Rao’s constant (Rm), molar volume (Vm), Van der Waals constant (b), and free volume (Vf) were determined to validate the thermodynamic results.

Physicochemical investigations on molecular interactions of adenine with aqueous D-glucose/D-maltose solvent media at varying temperatures and compositions

Adenine derivatives are used in pharmaceuticals, and carbohydrates like D-maltose and D-glucose which are often used as excipients or stabilizers in drug formulations. Studying their interactions can help in optimizing drug formulations for stability and effectiveness. Further, understanding their interactions, provide insights into flavor development, food stability, and potential applications in food technology. In this regard, we have analysed the physicochemical properties of adenine in aqueous saccharide solvent media which can contribute to various fields, including biochemistry, pharmaceuticals, catalysis, and material science, with use for both basic research and practical applications. So, in this research work, physicochemical properties of adenine have been investigated in aqueous and mixed aqueous (0.05, 0.10 and 0.15) mol kg−1 D-glucose/D-maltose solvent media at discrete temperatures (293.15–313.15) K and experimental pressure (0.1 MPa). The experimentally determined physical properties such as density, velocity of sound, and viscosity have been utilized for the estimation of several parameters such as apparent molar volume (Vϕ), limiting apparent molar volume (V0ϕ), hydration number (nH), limiting apparent molar expansivity (E0ϕ), Hepler’s constant (∂E0ϕ/∂T)P, apparent molar isentropic compression (Kϕ,s), limiting apparent molar isentropic compression (K0ϕ,s), viscosity B-coefficients, transfer parameters and thermodynamic parameters of viscous flow (Δμ01, Δμ02, TΔS02 and ΔH02). Further, the Co-sphere overlap model has been employed for the analysis of varied probable interactions operating in the prepared systems. The obtained results signify that in all solution systems, the solute–solvent interactions are advancing with rising temperature and concentrations of saccharides. Also, the structure breaking tendency of adenine has been investigated via inference of Hepler’s constant data and positive values of dB/dT data for all the investigated systems. Moreover, the deduced apparent specific volume data evidently specify that adenine has sweet taste in water and different concentrations of chosen saccharides.

Temperature-dependent physicochemical studies of sodium salicylate in aqueous solutions of ionic liquids {[BMIm]Br and [EMIm]Cl}

The current study explores the impact of two different imidazolium based ionic liquids, having diverse side chains and anions: 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) and 1‑butyl‑3-methylimidazolium bromide ([BMIm]Br) on the thermodynamic and transport properties of sodium salicylate. This inquiry examines the sodium salicylate's density, sound velocity, and viscosity within aqueous solutions of these ionic liquids across a temperature range of 283.15 K to 313.15 K at atmospheric pressure. Various parameters, including apparent molar volume (Vϕ), limiting apparent molar volume (Voϕ), transfer volume (ΔtrV∘ϕ), limiting apparent molar expansibility (E∘∅), Hepler's constant, apparent molar isentropic compression (Kϕ,s), limiting apparent molar isentropic compression (K∘ϕ,s), transfer parameter of isentropic compression (ΔtrK∘ϕ,S), and viscosity B-coefficient, were computed from experimental values. Additionally, we have analyzed the trends in computed parameters, considering the interactions between `solute and solvent along with solute-solute interactions in the systems under investigation. Our results suggest a predominance of hydrophilic-hydrophilic and ion-hydrophilic interactions within studied systems. The observed magnitudes of these parameters affirm a stronger interaction between sodium salicylate and [BMIm]Br in comparison to those with [EMIm]Cl.

Choline chloride and amino acid solutions taste and hydration behavior with experimental thermodynamic properties and COSMO-PC-SAFT calculation

Aqueous amino acid solutions have been introduced as dietary supplements for both animals and humans. This study investigates the physicochemical properties of the solutions containing amino acids (l-glycine, d,l-alanine, l-proline), choline chloride, and water at temperature range of 288.15 to 318.15 K. The results show that increasing concentrations of amino acids and choline chloride lead to higher solution densities. Analysis of apparent molar volume (Vφ) and apparent molar isentropic compressibility (κφ) reveals that Vφ values increase with choline chloride concentration and temperature, indicating enhanced solute–solvent interactions, while κφ values decrease, suggesting increased solution compression. Thermodynamic analysis using the Redlich-Mayer model and COSMO-based modeling provides insights into molecular interactions. However, COSMO-based parameters show high average relative deviation percentage (ARD %) values, indicating poor predictive performance for the density of these systems. In contrast, the ePC-SAFT equation of state effectively predicts the densities, particularly for l-proline-based solutions, which show very low ARD % values, indicating high accuracy. The ePC-SAFT model also performs reasonably well for l-glycine solutions but shows poorer results for d,l-alanine-based solutions. The study also examines the sweetness and saltiness criteria (ASV and ASIC) of these solutions. The ASV values, which serve as a sweetness criterion, are higher than the ideal range of 0.5 < ASV < 0.7, suggesting an overly sweet taste. The ASIC values follow a similar trend, indicating increased saltiness. To achieve an appropriate grade of sweetness and saltiness, dilution to lower concentrations of the solution is recommended. Furthermore, the use of choline chloride is found to increase salt intake and enhance the taste of salt, which can be beneficial in amino acid supplements used in animal food.

Exploring the molecular interactions of dorzolamide hydrochloride in aqueous solutions: a comprehensive study using thermophysical techniques and molecular simulations across various temperatures

This research begins with the initial assessment of key physical properties—density ( ρ), speed of sound ( u), and refractive index ( nD ) in binary aqueous solutions of dorzolamide hydrochloride. These properties were measured in solutions with varying molalities, ranging from 0.0 to 0.0276, under standard atmospheric conditions and at temperatures between 300.15 and 320.15 K. From these measurements, we were able to calculate a range of important parameters, including the apparent molar volume ( Vϕ), its limiting values ([Formula: see text]), limiting apparent molar expansivity ([Formula: see text]), Helper’s constant ([Formula: see text]), apparent molar isentropic compression ( κϕ), and its limiting values ([Formula: see text]), specific refraction ( RD), molar refraction ( RM), and hydration number ( nh). These calculated values provided insights into the strong interactions between the solute and solvent in the liquid system. They also shed light on the presence of various molecular interactions, such as inter- and intramolecular hydrogen bonds, dipole–dipole, and dipole-induced-dipole interactions, as well as the ability of the solute to influence the structure of the surrounding water molecules. Additionally, we derived the densities of dorzolamide hydrochloride solutions from molecular dynamics (MD) simulations, which showed a strong correlation with our experimental findings, underscoring the reliability of MD simulations in such studies. In the end, our combined study on dorzolamide hydrochloride in water demonstrates that it shapes structures because it has lower volumetric properties and stronger hydrogen bonds in MD simulations. More alchemical free energy calculations show that there are big changes in solvation energies. This is important for understanding how dorzolamide hydrochloride works in water.

Solvation behavior of chitosan monomers in aqueous [Hmim]CL solutions. Experimental and DFT studies

This paper reports densities and viscosities for the mixtures of D-glucosamine hydrochloride (GlcN·HCl) and N-acetyl-D-glucosamine (GlcNAc) with aqueous solutions of 1-hexyl-3-methylimidazolium chloride, [Hmim]Cl, between 293.15 and 318.15 K in 5 K increments and atmospheric pressure. Leveraging this data, we calculated volumetric properties such as apparent molar volume, Vϕ, limiting partial molar volume, Vϕ0, and standard molar volume of transfer, ΔVϕ0. We handled viscosity data to compute the viscosity B-coefficient and several activation parameters of viscous flow. Some of these are relevant in discussing interactions between monosaccharides (solute) and [Hmim]Cl (co-solvent) in aqueous media. The solute–solvent interactions were discussed based on ionic/ hydrophilic/ hydrophobic interactions using the co-sphere overlap model. ΔVϕ0 > 0 indicates that ionic/hydrophilic interactions predominate in the studied systems and are stronger in GlcN·HCl solutions than in GlcNAc at low [Hmim]Cl molalities. At higher [Hmim]Cl concentrations, decreasing values of ΔVϕ0 suggest the dominance of hydrophobic interactions over hydrophilic/ionic ones. We discuss (using Hepler’s constant and viscosity B-coefficient) the ability of monosaccharides to act as structure maker/breaker in aqueous [Hmim]Cl solutions. This indicates that GlcNAc is a better structure promoter than GlcN⋅HCl in aqueous [Hmim]Cl solutions. Finally, density functional theory (DFT) was used to model the molecular structure and compute the solute–solvent interaction energies using the GAMESS 2016 software.

Densities and Apparent Molar Volume of Benzimidazole in Pure and Binary Solvent Mixtures of Ethanol + Water

Densities and Apparent Molar Volume of Benzimidazole in Pure and Binary Solvent Mixtures of Ethanol + Water

An experimental-computational study on thermodynamic properties and intermolecular interactions of binary mixtures composed of quaternary ammonium salts-based deep eutectic solvents and [ETN] or [ACN]

To deep understand the thermodynamic properties and intermolecular interactions of quaternary ammonium salts-based deep eutectic solvents (DESs), two novel DESs systems ([TPAB]:[MA] and [TBAB]:[MA]) were synthesized using tetrapropylammonium bromide ([TPAB]) or tetrabutylammonium bromide ([TBAB]) as hydrogen bond acceptor (HBA) and malonic acid ([MA]) as hydrogen bond donor (HBD). Then, the ethanol (ETN) and acetonitrile (ACN) were used to prepare four DESs + solvent mixtures. Based on experimental data of density and surface tension of these four binary mixtures, the thermodynamic parameters such as apparent molar volume (Vϕ), excess molar volume (VE), limiting apparent molar expansibility (E0ϕ), molar surface entropy (s), molar surface Gibbs energy (gs), and molar surface enthalpy (h) were calculated. At the same temperature, the calculated VE values of binary mixtures were arranged in the following sequence: [TBAB]:[MA] + [ETN] > [TPAB]:[MA] + [ETN] > [TPAB]:[MA] + [ACN] > [TBAB]:[MA] + [ACN]. Based on the radial distribution functions (RDFs) theory, this observed phenomenon was attributed to the enhanced interaction between HBA and [ETN] in the DESs + [ETN] as compared to the interaction between HBA and [ACN] in the DESs + [ACN]. The predicted surface tension values (γ(pre)) of the four binary mixtures were calculated and highly correlated with the experimental surface tension values (γ(exp)). Moreover, the Br1 atom in [TPAB], the Br2 atom in [TBAB], and the H9 atom in [MA] were selected as reference sites. The interaction strength sequence between HBD and HBA was investigated using RDFs as follows: [TBAB]:[MA] + [ACN] > [TPAB]:[MA] + [ACN] > [TBAB]:[MA] + [ETN] > [TPAB]:[MA] + [ETN]. This study can provide an important theoretical support for further utilization of quaternary ammonium salts-based DESs.

The impact of thermophysical properties on eflornithine drug solute in acetone and ethyl acetate solvent interactions at varying concentrations and temperatures

The study was conducted on the impact of thermophysical properties on eflornithine drug solute–solvent interactions in aqueous ethyl acetate and acetone at different concentrations and temperatures. The aim of this study is to enhance the understanding of eflornithine’s behavior in different solvents, which is crucial for its effective use in pharmaceutical applications. The density, molar volume, viscometric, and conductometric characteristics of the eflornithine drug solutions (0.025, 0.05, 0.075, 0.1, and 0.125 mol/kg) in acetone and 25% (v/v) aqueous ethyl acetate were measured within a temperature range of 298.15 K–318.15 K. Based on the determined density parameters, the following parameters were assessed: viscosity (η), equivalent molar conductance, limiting apparent molar volume (V0φ), apparent molar volume of transfer (V0φtr), and apparent molar volume (Vφ). The Masson empirical relationship and the viscosity-to-Jones-Dole (JD) equation were used to evaluate the partial molar volume (Vφ), experimental slope (SV), viscosity, and density data. Temperature and concentration were used to determine each parameter. For each set of dilutions, conductometric studies were conducted in both study solvents. The gathered data was analyzed in order to evaluate the ion–solvent interactions. The Walden product Λomηo’s positive temperature coefficient values indicate that the drug eflornithine functions as a structural modifier in acetone and aqueous acetyl acetate systems. The structure-making and breaking characteristics of the polar solvents acetone and ethyl acetate were identified.

Molecular interactional study of SDS and CTAB in aqueous medium of anti-HIV drugs (Emtricitabine and Lamivudine) at different temperatures: A physicochemical investigation

The present study deals with the interactions of Emtricitabine and Lamivudine (anti-HIV drugs) with anionic surfactant sodium dodecylsulphate (SDS) and cationic surfactant cetyltrimethylammonium bromide (CTAB) at (298.15–313.15) K temperature range by volumetry, compressibility and viscometric approach. The experimental values of sound velocity and density are used to compute various parameters such as apparent molar volume (φv), isentropic compressibility (κs), and apparent molar adiabatic compression (φκ) by employing cosphere overlap model. Relative viscosity parameter (ηr) evaluated from viscosity data also helps to understand various interactions prevalent in surfactant-drug-water ternary system. This attempt of extracting information about various physicochemical interactions of anti-HIV drugs with surfactants can prove beneficial to develop novel anti-HIV agents with better viral resistance activity.

Volumetric properties of CO2-loaded and unloaded 3-amino-1- propanol/1-amino-2-propanol/3-dimethylamino-1-propanol + N, N-dimethylacetamide binary mixture at (288.15 to 323.15) K and 101 kPa

ABSTRACT In this work, the densities of CO2-loaded and unloaded alkanolamine (1) + N, N-dimethylacetamide (DMAC) (2) mixtures were determined at temperature of (288.15 to 323.15) K and 101 kPa. The alkanolamines were primary amines, 3-amino-1-propanol (3A1P) and 1-amino-2-propanol (1A2P), and tertiary amine, 3-dimethylamino-1-propanol (3DMA1P). There CO2-unloaded 3A1P/1A2P/3DMA1P + DMAC binary systems with the whole concentration and two CO2-loaded 3A1P/1A2P + DMAC systems with alkanolamine mass fraction of (0.2, 0.3 and 0.4) were investigated. Based on the density values of CO2-unloaded binary systems, the thermal expansion coefficient ( α p ), excess molar volume ( V m E ), and apparent molar volume ( V φ , i ) were calculated and discussed in terms of intermolecular interactions and spatial structure. The V m E values were positive under the studied conditions and increased with the temperature, and the maximum followed the decreasing order of 1A2P + DMAC > 3DMA1P + DMAC > 3A1P + DMAC. Additionally, the V m E data were well fitted with the Redlich-Kister equation with a small standard deviation (σ ≤ 0.024). For the CO2-loaded systems, the density values were correlated with temperature and concentration using different empirical equations, and the average relative deviations (ARD%) were less than 0.299%.

Standard partial molar volumes of single aqueous ions composing ionic liquids. Measurement and evaluation of temperature dependent values. Parsing and LSER correlation with molecular descriptors based on DFT/COSMO approach

The densities of highly dilute aqueous solutions (m < 0.2 mol·kg−1) of 50 common ionic liquids (ILs) or related salts were accurately measured at seven equidistant temperatures in the range of (288.15 to 318.15) K and ambient pressure. The examined set of ILs/salts composed of 31 ions was judiciously selected to cover wide ranges of ion sizes and chemical structures and allow reliable evaluation of ionic contributions. The data were duly analyzed to infer related thermodynamic properties and information on the behavior of these systems on a molecular level. Appropriate means of mathematical statistics were used to estimate data uncertainties, assign weights to data correlations, and judge the significance of the results obtained. The standard partial molar volumes V¯∞ of the ILs/salts at infinite dilution were evaluated through fitting the concentration dependence of respective apparent molar volumes to Redlich-Meyer equation and their temperature dependence was correlated to quadratic polynomial. The data presented were compared whenever possible with those available in the literature; good agreement was often found, although some data from the literature were also considerably dispersed or in error. Standard partial molar volumes of ILs/salts obeying ionic additivity were split by least-squares optimization into temperature-dependent single-ion values based on the Conway-Millero extrathermodynamic assumption. The ionic additivity of BV parameter was also identified. Its magnitude for anions is typically greater than that for cations, supporting the fact that an anion dominates the volumetric behavior of aqueous ILs. As the BV,anion and the second temperature derivative ∂2V¯anion∞/∂T2 were found to correlate, the two solute’s water structure making/breaking ability indicators appear to speak consistently. Enhanced values of standard partial molar expansion were observed for both strongly kosmotropic and chaotropic anions and a plausible explanation of this phenomenon was suggested. To correlate and analyze the effect of ionic structure on V¯ion,298∞, Linear Solvation Energy Relationship (LSER) methodology with the recently proposed four quantum chemistry computed descriptors based on DFT/COSMO approach was employed providing excellent fit (SD = 2.48 cm3·mol−1, R2 = 0.9996).

Thermodynamics of molecular multicomponent solutions: Evaluation of the partial molar volume at infinite dilution

The present work deals with the evaluation of the partial molar volumes at infinite dilution (v¯i∞) of n-components systems based on the dependence of the experimental density (ρ) on composition without involving binary systems. To do this, the multicomponent solution is interpreted by defining the component (1) as the solvent and the mixture of the remaining (n-1) components as the pseudocomponent (2n), characterized by the inner mole fraction xio. After the analysis of the concept of infinite dilution, equations are derived that allow evaluating the partial molar volumes at infinite dilution of the pseudocomponent (v¯2n∞), based on both the dependence of ln ρ(x2n) and the apparent molar volume ϕv2n(x2n). Then, on the basis of experimental evidences about the linear variation of v¯2n∞ on xio, the relationship between v¯i∞ and v¯2n∞ was established.The applicability of the derived expressions was verified in 36 different cases corresponding to 11 ternary systems in the temperature range of 293.15 ≤ T/K ≤ 323.15.Furthermore, the invariance of the partial molar volume at infinite dilution of the (n-1) components with the proportion in which they are mixed is verified.

Effect of Additive (1-Butyl-1-methyl Pyrrolidinium Tetrafluoroborate) on Volumetric, Acoustic and Conductance Properties of Binary Aqueous Solutions of Benzylamine at T = (288.15, 298.15, 308.15, 318.15) K

Effect of additive, 1-butyl-1-methyl pyrrolidinium tetrafluoroborate [BmPyrr+][BF4–] on the volumetric, acoustic and conductance properties of binary aqueous solution of benzylamine has been analyzed at equidistant temperature range using different techniques. Using density and speed of sound data, volumetric and acoustic parameters like apparent and partial molar volumes (Vφ and Vφ0), apparent and partial molar isentropic compressions (Kφ,S and K0φ,S), partial molar volume of transfer and partial molar isentropic compression of transfer (ΔVφ0 and ΔK0φ,S) have been calculated. Conductance parameters like molar conductance (Λm), limiting molar conductance (Λ°m) and activation energy are also calculated using conductance data. All these parameters were used to analyze various types of interactions present in the system. Furthermore, density functional theory (DFT) calculations were conducted for comprehensive understanding of structural variations of ion pairs affecting their physical properties. The hydrogen bond formation in the mixture components was examined by using IR spectrum. Both DFT and Hartee-Fock (HF) methods were used to analyze the results. In addition, the DFT/B3LYP-D3 calculations were also carried out to gather data on the molecular geometry, interactions and other molecular characteristics of the ionic liquid under study.