Journal of Solution Chemistry最新文献

Thermophysical properties such as density (ρ), and viscosity (η) of pure components and binary mixtures of pyridine (PY) with 2-alcohols viz., 2-propanol (2-PPL), 2-butanol (2-BTL), and 2-pentanol (2-PTL) were measured over the entire range of composition of pyridine at varying temperatures T = (298.15, 303.15 and 308.15) K and at pressure 0.1 MPa. Using measured data, excess molar volume (({V}_text{m}^text{E})), and viscosity variation (∆η) were derived and correlated to the Redlich–Kister (R–K) polynomial equation. Further, the apparent molar volumes (({V}_{text m,varnothing ,1}) and ({V}_{text m,varnothing ,2})), partial molar volumes (({overline{V} }_{text m,1}) and ({overline{V} }_{text m,2})), and excess partial molar volumes (({overline{V} }_{text m,1}^{text E}) and ({overline{V} }_{text m,2}^{text E})) values were also derived. These characteristics are employed to explain the emergence of new intermolecular interactions (H-bonding, packing efficiency, and OH–π interaction) between dissimilar molecules. Over the whole range of pyridine composition, the ({V}_text{m}^text{E}) values showed a negative trend, while the ∆η values showed a positive trend. Furthermore, using thermodynamic results, discuss about how temperature affects molecular interactions between molecules.

In the present study, the density (ρ) and dynamic viscosity (η) of binary liquid mixtures such as glycerol (GLY) + isomers of butanol (1-butanol (1-BU), 2-butanol (2-BU), and tert-butanol (T-BU)) were experimentally measured as a function of glycerol mole fraction at T = (293.15 to 318.15) K and a pressure of 0.1 MPa. Using these experimental data, the deviation in viscosity (∆η), molar volume (({V}_{text m})), excess molar volume (({V}_text{m}^text{E})), apparent molar volumes (({V}_{text {m},varnothing ,1}) and ({V}_{text {m},varnothing ,2})), partial molar volumes (({overline{V} }_{text {m},1}) and ({overline{V} }_{text {m},2})), and excess partial molar volumes (({overline{V} }_{text {m},1}^{text E}) and ({overline{V} }_{text {m},2}^{text E})) values were calculated. The observed ({V}_text{m}^text{E}) and ∆η results were associated with the Redlich–Kister (R-K) model. Further, the ({V}_text{m}^text{E}) values were interpreted using the Prigogine–Flory–Patterson (PFP) model. The obtained ({V}_text{m}^text{E}) showed a negative deviation, and ∆η showed a positive deviation over the entire composition range of glycerol. The derived parameters in binary mixtures are affected by H-bonding. Moreover, the development of new H-bonding interactions between unlike molecules was further described using ¹H-NMR spectroscopy studies.

Endocrine-disrupting chemicals (EDCs) leach from consumer products, are persistent in the environment, and are implicated in adverse health outcomes. Commonly suspected to be xenoestrogens, binding and subsequent removal of EDCs such as bisphenol A (BPA), bisphenol S (BPS), parabens, nonylphenols, triclosan, and phthalates is important for both human and environmental health. Cyclodextrins (CDs) are known to bind estrogens and the EDCs bisphenol A and bisphenol S. We investigated the host–guest interactions of α-, β-, and γ- CDs with a range of suspected xenoestrogens via isothermal titration calorimetry (ITC) in aqueous solution and calculated binding stoichiometry, association constants, Gibbs free energy, enthalpy, and entropy for each EDC-CD pair. We found the strongest complexation between the suspected xenoestrogens and β-CD, with no significant interaction observed with any of the selected EDCs and α-CD and only two EDCs showing complexation with γ-CD. Those EDCs that exhibit higher binding may be more likely to adopt an estrogen-like conformation in aqueous solution, and we anticipate these data will provide information useful for future research in removing these harmful chemicals from the environment.

The solubility of dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate (TKX-50) in three binary mixed solvents (ethanol + H₂O, DMSO + H₂O, and DMF + H₂O) was determined using a laser dynamic monitoring technique at various temperatures ranging from 293.15 to 333.15 K and at atmospheric pressure (P = 0.1 MPa). The results show that the solubility of TKX-50 in mixed solvents increases with temperature, decreases with increasing water content in DMSO + H₂O and DMF + H₂O, and increases with increasing water content in ethanol + H₂O. The experimental solubility data were used for correlation analysis using the Modified Apelblat equation, van’t Hoff equation, CNIBS/R-K equation, and Jouyban–Acree–Apelblat equation. All of these models yielded satisfactory results in binary solvents. Subsequently, the effects of hydrogen bonding, solvent polarity, and intermolecular interaction forces on the dissolution behavior of TKX-50 were analysed using Hansen solubility parameter (HSPs), Hirshfeld surface analysis (HS), and molecular electrostatic potentials (MEPs). In addition, the thermodynamic properties enthalpy, entropy, and Gibbs energy were calculated and discussed based on experimental data.

The main objective of this study is to understand the effect of a bio medically important organic salt on molecular interactions of ionic liquids. Volumetric and ultra-acoustic studies of two immidazolium based ionic liquids, 1-butyl-3 methyl imidazolium chloride and 1-ethyl-3-methyl imidazolium ethyl sulphate are carried out in presence of potassium dihydrogen citrate. Experimentally obtained and derived parameters are analysed in the light of ionic, hydrophilic, and hydrophobic interactions taking place between different ionic, polar, and nonpolar segments of the ILs and the citrate salt. The effect of the said salt on the interactions of the ILs with water are explored in terms of apparent molar volume ({(V}_{phi })), partial molar volume (({V}_{phi }^{0})), and partial molar expansibility ({(E}_{phi }^{0})), compressibility and apparent compressibility behaviour of solution at different concentrations ({{(K}_{s} text{and} K}_{phi ,s})) and at infinite dilution (({{K}_{s }^{0} text{and} K}_{phi ,s}^{0})). Transfer values are calculated to understand the solute–co-solute interactions and overlapping of hydration co-spheres. Hydration numbers are calculated to reinforce the compressibility data. Structural changes of water induced by the solute–co-solute and solute–solvent interactions are determined by the magnitude and sign of well-known Hepler’s constant.

Graphical Abstract

This work presents new data on the solubility of cadmium iodide in a mixture of N,N-dimethylacetamide (DMA) and N,N-dimethylformamide (DMF), as well as on the composition of crystalline compounds in equilibrium with the saturated solution. The solubility of the salt varies nonlinearly across the entire range of mixed solvent compositions. The solubility isotherm comprises four regions, each corresponding to the crystallization of individual solvates. The crystalline solvates exhibit similar structures and consist of the complex anion [Cd₂I₆]²⁻ and a complex cation, whose composition depends on the ratio of the components in the binary solvent. The cation includes either one of the amides or both in a 1:2 ratio, [Cd(DMA)₄(DMF)₂]²⁺ and [Cd(DMA)₂(DMF)₄]²⁺. Standard heats of dissolution in water were determined for both solvents and all solvates. From these data, the standard enthalpies of formation of the solvates were calculated. The enthalpies of formation of the solvates correlate with the molar ratio of amides in the complex cation and exhibit a direct dependence on the donor number of the amide.

Thermophysical properties such as density, and speed of sound of binary liquid systems of benzyl acetate (BZA) with 1-alkanols (1-propanol (PPL), 1-butanol (BTL), 1-pentanol (PTL), 1-hexanol (HXL), and 1-heptanol (HPL) at T = (298.15 to 308.15) K under atmospheric pressure, were reported complete composition of benzyl acetate. Using experimental data, thermodynamic properties like molar volume (({V}_{text{m}})), excess molar volume (({V}_{text{m}}^text{E})), apparent molar volumes (({V}_{text{m},varnothing ,1}) and ({V}_{text{m},varnothing ,2})), acoustic impedance (Z), isentropic compressibility (({k}_{text{s}})), intermolecular free length (L_f), excess isentropic compressibility (({k}_{text{s}}^{text{E}})), and excess intermolecular free length (({L}_{text{f}}^{text{E}})) were considered. Using these data, we may forecast the formation of new molecular interactions between dissimilar components, as well as explain how temperature influences those interactions. Further, the ({V}_{text{m}}^{text{E}}), and ∆κ_s variables were fitted using the Redlich–Kister (R–K) equation. Furthermore, the geometrical structure of the monomer and all conceivable H-bonded (molecular interaction) dimers is fully optimized using density functional theory with the Lee–Yang–Parr correlation function (B3LYP) and the 6-311++G(d, p) basis set. An extensive examination of the computational results is carried out to confirm the complex formation through H-bonding.

This is an experimental study of the complex formation between aqueous Ge(IV) and organic ligands of the α- and β-hydroxycarboxylate, α- and β-aminocarboxylate and (poly-)amino(poly-)carboxylate types in aqueous solution at 25.0 °C. α-substituted ligands (such as α-amino acid anions and ligands of the EDTA-family) were found to give rise to kinetically inert systems, which must be studied by a discontinuous potentiometric titration technique (i.e., for each titration point, an individual solution is prepared and left to equilibrate for extended periods of time). β-substituted ligands formed much weaker complexes and their reactions were labile. Speciation diagrams are presented and discussed for all the studied systems.

This study measured the density (ρ) and viscosity (η) of the binary system at pressures of 1005 hPa (Tianjin, China) over the temperature range of 298.15 K to 318.15 K, with 5 K increments, and systematically analyzed its thermophysical properties and intermolecular interactions. The excess molar volume (({{V}}_{text{m}}^{text{E}})) was calculated based on the density data, and the most stable molar ratio of 1,2-PDA to HG was determined to be 2:3. The viscosity deviation (Δη) and thermodynamic properties were calculated based on the viscosity data, and the molecular dynamic characteristics were analyzed. Spectroscopic characterization (FTIR and ¹H NMR) and density functional theory (DFT) calculations confirmed the presence of hydrogen bonding between 1,2-PDA and HG in the form of [–OH···NH₂–]. This study fills a research gap in the thermodynamic and dynamic properties of the 1,2-PDA and HG binary system, providing new insights into intermolecular interactions in complex molecular systems and offering valuable guidance for applications in the chemical and materials fields.

This research investigates the development and sensing characteristics of innovative conjugated azo dye derivative obtained from dicyanoisophorones. This compound represents push–pull molecules with a donor-π-acceptor (D-π-A) structure. In our approach, we utilized Resorcinol as an electron-donating component, while strategically placing the cyano acceptor and diazo groups as donor units. The synthesized compound demonstrated significant solvatochromism, with their emission spectra ranging from green to red, indicating high responsiveness to environmental polarity. Furthermore, the addition of a dicyanovinyl group to a compound resulted in a highly sensitive colorimetric and fluorescent detector for cyanide ions, which induced a shift towards shorter wavelengths in the emission spectrum.

Graphical Abstract

Synthesis, characterization, and applications of dicyanoisophorone-based conjugated azo dyes (Probe 1)