Partial Molar Volumes Research Articles

Volumetric and viscometric study on the interaction of amino acid (valine) with an aqueous solution of cationic surfactant, Cetyltrimethylammonium Bromide (CTAB), at 298.15, 303.15, 308.15, and 313.15 K

Interactions between the surfactant (CTAB) and amino acid (valine) were investigated using density and viscosity data. These data were utilized to calculate apparent molar volume, fv, and partial molar volume also known as limiting molar volume f0v and these parameters were further used to find out solute-solvent interactions between amino acid and surfactant at 298.15, 303.15, 308.15 and 313.15 K temperatures.

Understanding of lactobionic acid in aqueous-glycol mixtures at different temperatures: Ultrasonic investigation and spectroscopic study

The proposed investigation focused on the study of liquid mixtures that contain polyethylene glycols (PEGs) such as polyethylene glycol-200 and polyethylene glycol-400, and lactobionic acid aqueous solutions. The study aimed to examine the density and ultrasonic speed of these mixtures at different temperatures (288.15 K, 298.15 K, 308.15 K, and 318.15 K) and concentrations (0.01, 0.02 and 0.03) mol.kg-1 of lactobionic acid in aqueous medium. The experimental data obtained were used to estimate various density and sound-speed characteristics, and to calculate the apparent molar, partial molar, and transfer properties of volume and isentropic compressions, including (Vϕ, Vϕ0, ΔVϕ0 and Kϕ,s,Kϕ,s0, ΔKϕ,s0). The interaction coefficients (VAB, VABB, KAB and KABB) were determined using the values of ΔVϕ0and ΔKϕ,s0. Additionally, the study computed the limiting apparent molar expansibilities, its derivative, and empirical parameters. The findings of the study were evaluated in terms of interactions among the solutes and solvents in the liquid mixtures. Moreover, the spectroscopic study of the binary mixture of lactobionic acid and water at different their concentrations was done to find the different stretching and bonds available in the mixture.

A study of enhancing the solubility of streptomycin sulphate in sorbitol using volumetric, acoustic and viscometric properties

The various molecular interactions present between streptomycin sulphate and sorbitol were evaluated using density (ρ), speed of sound (u) and viscosity (η) studies. All these studies have been obtained at different temperatures (300.15, 305.15, 310.15 ad 315.15) K and at 0.1 MPa pressure. The values obtained from these studies have been utilized to calculate the various thermodynamic parameters such as apparent molar volume (ΦV), apparent molar isentropic compression (ΦK), partial molar volume (ΦVo), partial molar isentropic compression (ΦKo), partial molar expansibility (ΦEo) of solute for SMS in various solutions of sorbitol. The data obtained from viscosity studies have been utilized to determine Falkenhagen coefficient (A), Jones- Dole coefficient (B), dB/dT and viscosity B-coefficient of transfer (Btr). A complete discernment into the physicochemical interactions present in the studied system have been redeemed through the scrutiny of above calculated parameters.

Exploring the effects of saccharides on the solvation behaviour of L-Citrulline in aqueous medium: Volumetric, transition state theory, transfer parameters and spectroscopic approach

This study examines the volumetric, viscometric and UV–vis characteristics of L-Citrulline in water and aqueous saccharides at atmospheric pressure across the whole concentration range and the absorber operating temperature range of 293.15 K -313.15 K. Density, partial molar volume, apparent molar isobaric expansion, Hepler's constant and hydration number were among the examined volumetric parameters, and viscosity coefficients, viscosity deviation and free energy for viscous flow activation were among the examined viscometric parameters. Stronger interactions between L-Citrulline and L-Arabinose were indicated by the increase in the transfer characteristics in the following order: L-Arabinose > D-xylose. A comparison of the taste behaviours of L-Citrulline in water and in an aqueous solution of saccharides has also been attempted. L-Citrulline interacts with all solvents in a significant way, as evidenced by the UV–visible spectra suggested by the shift in UV–visible absorption maxima that correspond with a rise in L-Citrulline content in the solvent systems chosen.

CO2 absorption using two morpholine protic ionic liquids: measurement, model, and quantum chemical calculation

Two kinds of protic ionic liquids, N-methylmorpholinium formate ([NMMH][For]) and N-ethylmorpholinium formate ([NEMH][For]), were synthesized by the acid-base neutralization method. The solubility of carbon dioxide (CO2) in the two ionic liquids was measured at temperatures of 298.15 to 338.15 K and pressures of up to 900 kPa. The solubility increases linearly with pressure, indicating that CO2 is physically absorbed in ionic liquids. The solubility of CO2 in [NEMH][For] is higher than that of [NMMH][For]. Absorption behavior was investigated by thermodynamic properties, such as the Henry's law constant, partial molar Gibbs free energy, partial molar enthalpy, and partial molar entropy. The Pitzer's model and the Soave-Redlich-Kwong (SRK) cubic equation of state were used to fit the solubility data, respectively. The Pitzer's model is found to have better prediction accuracy. The interaction of two protic ionic liquids with CO2 was analyzed using quantum chemistry. The molecular mechanism of CO2 absorption by two protic ionic liquids was explained from the microscopic point of view. CO2 + [NEMH][For] has more hydrogen bonds and a higher interaction energy. The cation–anion interaction of [NEMH][For] diminishes in the presence of CO2, resulting in an increase in the cation–anion distance. These factors result in higher solubility of CO2 in [NEMH][For].

Study on the molecular interactions of some binary mixtures through thermodynamic properties and FT-IR spectra and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u) and viscosities (η) were measured for three binary mixtures of propargyl alcohol with tetra chloromethane, trichloromethane, and dichloromethane from 303.15 K to 313.15 K at atmospheric pressure across the composition range. Excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of activation of viscous flow were calculated. Partial molar properties and infinite dilution molar partial properties were also determined for each system. Results suggest heteroassociates forming cross complexes and chemical forces with specific interactions. PFP theory was used to identify the predominant molecular interactions. The Jouyban–Acree model findings were discussed, considering mean relative deviation (MRDs) and individual relative deviation (IRD) between calculated and experimental data. FTIR studies were included to corroborate the experimental findings.

Design of nonflammable mixed refrigerants based on the partial molar enthalpy difference in mixed-refrigerant Joule-Thomson refrigerators with/no pre-cooling stage

Mixed-refrigerant Joule-Thomson refrigeration (MJTR) is an important cooling method at temperatures from 80 to 230 K. It can be used in cryosurgery, high-temperature superconductivity and sensor cooling etc. However, most of the studies are on nitrogen-hydrocarbon refrigerants, which are not allowed in applications where there is a special need to avoid flammability risks. Therefore, non-flammable mixed refrigerants were investigated in this study.The composition of the mixed refrigerant is a key factor in the system performance (refrigeration temperature, refrigeration capacity, etc). However, the purely mathematical optimization methods lack system knowledge in the optimization of the process, and may have the disadvantages of being a time-consuming process. In this study, the isothermal throttling effect of mixed refrigerants is optimized, and the optimization process is based on the partial molar enthalpy difference of each component. The method is based on thermodynamic properties and is time-saving relative to purely mathematical optimization techniques.Non-flammable mixed refrigerants (NFMR) with refrigeration temperatures from 100 K to 140 K were designed in this study. The results show that the designed mixed refrigerant has a higher COP compared to the reference. Argon has an advantage at refrigeration temperatures from 120 K to 140 K, while nitrogen has an advantage from 100 K to 120 K. In addition, mixed refrigerants for systems with pre-cooling stage were optimized and the results showed that the highest exergy efficiency is achieved at a pre-cooling temperature of 250 K. The exergy efficiencies with pre-cooling stage are nearly twice as high as those without that. Therefore, a pre-cooling stage for nonflammable mixed refrigerants is necessary where there is no requirement for system size.

Modeling of experimental excess molar enthalpy with Wilson, UNIQUAC, and NRTL for mixtures of acetophenone with chloro derivatives of ethane and ethene at T = 298.15 K

The excess molar enthalpy HmE, was determined for systems consisting of acetophenone with chloro alkanes and alkenes derivatives. These derivatives include 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, trichloroethene and tetrachloroethene at a temperature of T = 298.15 K. The Redlich-Kister relation fitting was used to analyze the HmE values obtained from this experimental data. Additionally, the excess partial molar enthalpy HiE was derived from the experimental HmE values. The intermolecular interaction function such as ∂HiE∂xi and ∂HjE∂xjwere also calculated. For the system consisting of acetophenone + 1,1,1-trichloroethane or + tetrachloroethene, the HmE values were found to be positive. Conversely, the HmE values for acetophenone + 1,2-dichloroethane or + 1,1,2,2- tetrachloroethane or + trichloroethene were observed to be negative. The magnitude of the HmE values increased in chloroethanes as the number of chlorine atoms increased, and became more negative in chloroethenes. Based on the local composition theory, the Wilson model, the universal quasichemical (UNIQUAC) model, and the non-random two-liquid (NRTL) model were used to correlate these thermodynamic data. The results showed good agreement with the experimental enthalpy data.

Measurements of Thermodynamic Data of Water in Ca-Bentonite by Relative Humidity Method

Buffer material (compacted bentonite), one of the engineered barrier elements in the geological disposal of a high-level radioactive waste, develops swelling stress due to groundwater penetration from the surrounding rock mass. Montmorillonite is the major clay mineral component of bentonite. Even previous studies provide few mechanical and thermodynamic data on Ca-montmorillonite. In this study, thermodynamic data on Ca-montmorillonite were obtained as a function of water content by measuring relative humidity (RH) and temperature. The activities of water and the relative partial molar Gibbs free energies of water were determined from the experimental results, and the swelling stress of Ca-bentonite was calculated using the thermodynamic model and compared with measured data. The activities of water and the relative partial molar Gibbs free energies obtained in the experiments decreased with decreasing water content in water contents lower than about 25%. This trend was similar to that of Na-montmorillonite. The swelling stress calculated based on the thermodynamic model was approximately 200 MPa at a montmorillonite partial density of 2.0 Mg/m3 and approximately 10 MPa at a montmorillonite partial density of 1.4 Mg/m3. The swelling stresses in the high-density region (around 2.0 Mg/m3) were higher than that of Na-montmorillonite and were similar levels in the low-density region (around 1.5 Mg/m3). Comparison with measured data showed the practicality of the thermodynamic model.

Excess properties and intermolecular interactions of 2-methoxyethanol + ethylenediamine binary system: Density, viscosity, spectral analyses, computational chemistry, and CO2 absorption property

To examine the fundamental physicochemical properties as well as intermolecular interactions for the 2-methoxyethanol (EGME) (1) + ethylenediamine (EDA) (2) binary system, this work systemically measured the density (ρ) and viscosity (η) values of the binary system with various mole ratios at P = 100.5 kPa and T = (298.15–318.15) K with the growth gap of 5 K. The as-measured values of the pure substances were compared with literature data. Multiple semi-empirical formulas were used to fit ρ and η values, and the absolute average deviations (AAD%) were calculated. After that, the excess molar volume (VmE), partial molar volume (V¯), apparent molar volume (Vφ), viscosity deviation (Δη), excess activation of Gibbs free energy (ΔG∗E), and several thermodynamic properties of the binary system were systemically analyzed. According to analysis results, it has been proven that the interaction exists between EGME and EDA molecules. And then, excess properties were fitted to the Redlich-Kister equation using multi-parametric nonlinear regression analyses, and standard deviations (σ) were calculated. In addition, based on various characterization methods including Raman, ultraviolet (UV), and nuclear magnetic resonance hydrogen (1H NMR) spectral analyses and density functional theory (DFT) calculation results, it is demonstrated that there is intermolecular hydrogen bonds in EGME (1) + EDA (2) binary system as the form of –OH⋯NH2–, which was consistent with the existence forms of intermolecular hydrogen bonds in different alcohol-amine systems from references. Finally, CO2 absorption capacity by pure EDA, pure EGME, and the EGME (1) + EDA (2) binary system were severally determined.

Swelling Stress of Bentonite: Thermodynamics of Interlayer Water in K-Montmorillonite in Consideration of Alteration

The buffer material that makes up the geological disposal system of high-level waste swells by contact with groundwater and seals space with rock mass and fractures in rock mass. The buffer material has a function of mechanical buffer with rock pressure, and swelling stress is important in this case. The alteration of bentonite may occur due to the initial replacement of cations (Na+ ions) in the interlayer with K+ ions upon contact with groundwater, but there are no studies on the swelling stress of K-bentonite. In this study, the author prepared K-montmorillonite samples and obtained thermodynamic data on interlayer water as a function of water content using a relative humidity method. The swelling stress was analyzed based on a thermodynamic model developed in earlier studies and compared with measured data. The activity and the relative partial molar Gibbs free energy of porewater decreased with decreasing water content in the region, below approximately 15%. This behavior significantly differs from that of other ions, such as Na. The swelling stress calculated based on the thermodynamic model and date occurred in the region of high density of 1.9 Mg/m3 with montmorillonite partial density. It was indicated for the first time that K-bentonite scarcely swells under realistic design conditions.

Photodecarboxylation of ketoprofen studied by transient absorption spectroscopy and transient grating method: Estimation of the partial molar volume of carbon dioxide

The photoreaction of ketoprofen, a widely used nonsteroidal anti-inflammatory drug (NSAID), was intensively investigated in methanol by transient absorption spectroscopy and transient grating (TG) method. From quantitative analyses of the transient absorption and of the TG signal due to CO2, we successfully determined the partial molar volume of CO2 to be 46 ± 2 cm3 mol−1. With the partial molar volume of CO2 obtained in this work, the reaction quantum yield of photodecarboxylation of other NSAIDs can be estimated from only the TG signal. The approach with the TG method would be a new tool for evaluating photoreactivity of NSAIDs.

A volumetric, ultraacoustical study and computational study of molecular interactions in 4-aminoantipyrine-aqueous-β-cyclodextrin solutions

Present work reports experimental densities and corresponding apparent and standard partial molar volumes, ultrasonic velocities and isentropic, apparent and standard partial molar compressibilities of 4-Aminoantipyrine-aqueous-β-cyclodextrin (0.000 mol∙kg−1, 0.001 mol∙kg−1, 0.005 mol∙kg−1, 0.010 mol∙kg−1and 0.015 mol∙kg−1) solutions at different temperatures. Transfer properties like transfer volumes and compressions were calculated. The refractive indices of these systems were also measured. The computational properties such as solvation energy (ΔESol), relative stabilization energy (ΔERel), complexation energy (ΔEComp) and change in volume (ΔV) were computed using DFT. The results from volumetric and acoustical studies have been evaluated in terms of molecular interactions and their existence confirmed from experimental and computational studies. The values of transfer volumes and compressibilities indicate the hydrophilic-hydrophilic interactions between polar groups of 4-Aminoantipyrine and hydroxyl groups of β-cyclodextrin dominating over hydrophobic-hydrophobic interactions between the phenyl group of 4-Aminoantipyrine and hydrophobic interior of β-cyclodextrin.

Density, Speed of Sound and Derived Properties of Binary Mixtures Propiophenone + Butoxyethanol at T = (303.15, 308.15, 313.15 and 318.15) K

The current study reports the experimental density (ρ) and sound speed (u) values for binary mixes of liquids propiophenone + 2-butoxyethanol at atmospheric pressure (0.1 MPa) and T = (303.15, 308.15, 313.15 and 318.15) K for the full spectrum of composition. densities and sound speed measurements from experiments have been used to estimate excess isentropic compressibility (κsE), excess molar volume (VEm), excess molar isentropic compressibility (KEs,m), excess isobaric thermal expansivity (αEp) and excess sound speed (uE). The Redlich-Kister polynomials were used to correlate excess parameters. Excess partial molar volume quantities (VEm,1 and VEm,2) at infinite dilution and their limiting values (V0Em,1 and V0Em,2) have been analytically determined using Redlich-Kister polynomials from the experimental density data. The results have been analyzed in light of strength and interactions among molecular entities scope and extent prevalent in these mixtures.

Study on the molecular interactions of binary mixtures of allyl alcohol and amino-alcohol solvents through thermodynamic properties and FT-IR spectra and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of allyl alcohol with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol (aminomethyl propanol), and 1-amino propan-2-ol (isopropanol amine) were calculated at temperatures ranging from 303.15 to 313.15K and at atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and partialmolar properties at infinite dilution are also calculated. The Prigogine–Flory–Patterson (PFP) theory is applied to identify the predominant molecular interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation (MRDs) and individual relative deviation (IRD) between the calculated and experimental parameters as an accuracy criterion. FTIR studies have also been added to confirm the experimental findings of the investigated mixtures.

Influence of concentration-dependent material properties on the fracture and debonding of electrode particles with core–shell structure

Core–shell electrode particle designs offer a route to improved lithium-ion battery performance. However, they are susceptible to mechanical damage such as fracture and debonding, which can significantly reduce their lifetime. Using a coupled finite element model, we explore the impacts of diffusion-induced stresses on the failure mechanisms of an exemplar system with an NMC811 core and an NMC111 shell. In particular, we systematically compare the implications of assuming constant material properties against using Li concentration-dependent diffusion coefficient and partial molar volume. With constant material properties, our results show that smaller cores with thinner shells avoid debonding and fracture regimes. When factoring in a concentration-dependent partial molar volume, the maximum values of tensile hoop stress in the shell are found to be significantly lower than those predicted with constant properties, reducing the likelihood of fracture. Furthermore, with a concentration-dependent diffusion coefficient, significant barriers to full electrode utilisation are observed due to reduced lithium mobility at high states of lithiation. This provides a possible explanation for the reduced accessible capacity observed in experiments. Shell thickness is found to be the dominant factor in precluding structural integrity once the concentration dependency is accounted for. These findings shed new light on the performance and effective design of core–shell electrode particles.

FT-IR studies and excess thermodynamic properties of binary mixtures at various temperatures and correlation with the Jouyban–Acree model

ABSTRACT Densities (ρ), speeds of sound (u), and viscosities (η) for three binary mixtures of 4-Hydroxy-4-methyl-pentan-2-one with 3-amino-propan-1-ol, 2-amino-2-methyl-propan-1-ol, and 1-amino propan-2-ol were calculated at temperatures ranging from 303.15 to 313.15 K and atmospheric pressure over the entire composition range. Experimental measurements were used to calculate the excess molar volume, excess isentropic compressibility, deviation in viscosity, and excess Gibbs free energy of the activation of viscous flow. Partial molar properties and infinite dilution molar partial properties are also calculated for each binary system. Heteroassociates molecules forming complexes and chemical forces with specific interactions can be discussed from the results. The Prigogine–Flory–Patterson theory is used to identify the most important interaction. The results of the Jouyban–Acree model are discussed in terms of the mean relative deviation and individual relative between the calculated and experimental densities, speed of sound, and viscosities as an accuracy criterion. FTIR studies confirm the experimental findings of the investigated mixtures.

Thermo-acoustic properties of monosaccharides D(−)-ribose and D(+)-xylose in aqueous diammonium hydrogen phosphate solutions at different temperatures

The volumetric and acoustic properties are used for investigating the interactions of polyhydroxy solutes D(−)-ribose and D(+)-xylose in different concentrations of diammonium hydrogen phosphate (DAP) solutions. Densities and speeds of sound of D(−)-ribose and D(+)-xylose in aqueous diammonium hydrogen phosphate (DAP) solutions have been measured over a temperature range of (298.15–318.15) K and at experimental pressure p = 0.1 MPa. Different parameters viz apparent molar volumes, Vϕ, partial molar volumes, apparent molar isentropic compression, partial molar isentropic compression, partial molar volume of transfer and molar isentropic compression of transfer are obtained using experimental density and ultrasonic speed data. The calculated parameters are discussed in rapports of solute–solvent interactions in solutions indicated the presence of ion-ion, ion-polar, hydrophilic-hydrophilic and hydrophobic–hydrophobic interactions in these ternary solutions, which was also confirmed from obtained positive values of apparent molar volume and negative values of apparent molar isentropic compressibility. Pair (VAB, KAB) and triplet (VABB, KABB) interaction coefficients determined by means of McMillan-Mayer theory are used to acquire valuable information about the dominance of pairwise interactions in the studied mixtures.

Density, viscosity, excess properties, and intermolecular interaction of propylene glycol methyl ether + 1,2-propylenediamine binary system

In this work, the systematic measurements of physicochemical properties, viz., density (ρ) and viscosity (η) values of propylene glycol methyl ether (PGME) + 1,2-propylenediamine (1,2-PDA) binary system, including pure substances, over the entire mole fraction range at the temperatures of T/K = (298.15 to 318.15) under atmospheric pressure of P = 100.5 kPa. The fundamental data were used to calculate several excess properties, including excess molar volume (VmE), viscosity deviation (Δη), and excess activation Gibbs free energy (ΔG∗E). Meanwhile, the work further investigated the values of thermal expansion coefficient (αp), partial molar volume (V¯) and apparent molar volume (Vφ), thereby offering a comprehensive understanding on non-ideal behavior of the binary system. Furthermore, the variations in ρ values with various molar ratios and temperatures were evaluated through Jouyban-Acree model and nonlinear least squares method. Simultaneously, Grunberg-Nissan model, Eyring-Margules model, Heric model, and McAllister model, were used to fit the dependence of η values on the molar ratio. Arrhenius equation was employed to fit the temperature dependency of η values. In addition, Redlich-Kister (R-K) equation was utilized to fit the VmE, Δη, and ΔG∗E values of binary system. Based on spectral analyses of Raman, ultra-violet (UV), and 1H Nuclear Magnetic Resonance (NMR) and density functional theory (DFT) calculation, the intermolecular hydrogen bond (IHB) of PGME with 1,2-PDA was discussed in depth.

Effect of caffeine on the aggregation of amyloid-β-A 3D RISM study.

Alzheimer's disease is a detrimental neurological disorder caused by the formation of amyloid fibrils due to the aggregation of amyloid-β peptide. The primary therapeutic approaches for treating Alzheimer's disease are targeted to prevent this amyloid fibril formation using potential inhibitor molecules. The discovery of such inhibitor molecules poses a formidable challenge to the design of anti-amyloid drugs. This study investigates the effect of caffeine on dimer formation of the full-length amyloid-β using a combined approach of all-atom, explicit water molecular dynamics simulations and the three-dimensional reference interaction site model theory. The change in the hydration free energy of amyloid-β dimer, with and without the inhibitor molecules, is calculated with respect to the monomeric amyloid-β, where the hydration free energy is decomposed into energetic and entropic components, respectively. Dimerization is accompanied by a positive change in the partial molar volume. Dimer formation is spontaneous, which implies a decrease in the hydration free energy. However, a reverse trend is observed for the dimer with inhibitor molecules. It is observed that the negatively charged residues primarily contribute for the formation of the amyloid-β dimer. A residue-wise decomposition reveals that hydration/dehydration of the side-chain atoms of the charged amino acid residues primarily contribute to dimerization.