Journal of Solution Chemistry最新文献

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

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 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)

1-Benzofuran is a heterocyclic compound with fused benzene and furan rings that is used in materials science, nonlinear optics, drug development and pharmacology. This study investigated how solvent polarity and temperature affect vibrational spectra, photophysical properties, and thermodynamic behavior. Using semiempirical, Hartree–Fock, and DFT (B3LYP) methods with basis sets such as 6–31 + G (d,p), 6–311 + G (d,p), and aug-cc-pVDZ, it was found that solvent polarity influenced bond angles, bond lengths, dipole moments, HOMO‒LUMO gaps, and thermodynamic properties. Solvation effects in water were observed in the FT-IR and FT-Raman spectra, with peak shifts due to hydrogen bonding. The electrostatic potential map revealed electrophilic and nucleophilic regions important for receptor binding. The nonlinear optical properties increased significantly with increasing solvent polarity, reaching α = 230.14 a.u. and β = 314.02 a.u. in polar solvents. As the temperature increased from 100 to 1000 K, the heat capacity, enthalpy, and entropy increased, leading to instability. The absorption spectra showed peaks at 240–300 nm in polar solvents, with a bathochromic shift of 5.11 nm. This study offers insights into the photophysical and optical properties of 1-benzofuran in different solvents and at different temperatures.

Graphical Abstract

This work examined the impact of sodium dodecyl sulfate (SDS) surfactant on the oxidation kinetics of D-glucose employing imidazolium fluorochromate (IFC) as the oxidant. The experiments were conducted under pseudo-first-order conditions at 30 °C, with D-glucose in a significantly higher concentration than IFC. The solvent medium used was 50% (v/v) aqueous acetic acid. The reaction demonstrated a first-order dependence on [IFC] and [HClO₄]. The order for [D-glucose] oxidation kinetics was slightly less than one. Perchloric acid acted as a catalyst in this process. The addition of acrylonitrile had no effect on rate constants (k_obs). k_obs decreased with an increase in the concentration of Mn(II) ions. An increase in the dielectric constant of the medium had an inverse effect on k_obs. The initial increase in [SDS] led to a corresponding rise in k_obs, though a saturation in k_obs was observed for elevated [SDS]. The Menger-Portnoy and Piszkiewicz models were used to quantitatively assess the experimental results. The binding constant (K_p), cooperativity index (n), and various thermodynamic parameters in the presence of SDS were calculated. Infrared and mass spectroscopy were used to ascertain D-gluconolactone as the primary product of the reaction. Based on these findings, a reaction scheme has been suggested.

This study investigates the solubility of triethylamine hydrochloride (TEA·HCl) in acetonitrile (ACN) and dimethyl carbonate (DMC) mixtures, crucial for optimizing TEA·HCl separation during vinylene carbonate (VC) synthesis. Solubility was measured experimentally at 0.1 MPa from 308.15 K to 343.15 K across ACN mass fractions (({w}_{1})) from 0.1 to 1.0. Results reveal a positive correlation between TEA·HCl solubility, temperature, and ({w}_{1}). The Jouyban–Acree, Van’t Hoff–Jouyban–Acree, and Apelblat–Jouyban–Acree models were employed to correlate the solubility data. While generally accurate (average ARD ≈ 8.3%), these models exhibited substantial errors at ({w}_{1}) = 0.1 (ARD > 40%). Thermodynamic analysis revealed an endothermic, enthalpy-driven dissolution process. Density Functional Theory (DFT) calculations identified a sharp change in solvation free energy at ({w}_{1}) = 0.1, correlating with the observed solubility deviations and model inaccuracies. This study provides essential solubility data and thermodynamic insights for enhancing TEA·HCl crystallization and separation during VC production, emphasizing the critical role of solvent composition.

The conductivities of aqueous KCl + sucrose solutions were measured at KCl concentrations up to 0.0067 mol dm⁻³ and sucrose concentrations up to saturation, at temperatures from 293.15 K to 313.15 K. The data were correlated and analyzed by using the low-concentration chemical model (lcCM) version of the Fuoss–Justice equation. The calculated Walden products and the (Lambda^{infty }) and (K_{text A}) are in accordance with the previous studies and the results agree well with the Lee–Wheaton model. Eyring enthalpies of activation for charge transport were evaluated. Calculated thermodynamic quantities for ion association ((Delta G^{^circ } ,Delta H^{^circ } ,Delta S^{^circ })) are consistent with the results from other methods (exergonic, endothermic, and enhanced degree of freedom). Splitting the standard Gibbs energy change, into coulombic and non-coulombic terms, shows that the electrostatic contribution is of major importance.

Modelization of adsorption and desorption of phenol from granular activated carbon (GAC) by organic solvent acetone and green solvent limonene and then by mixture of both solvents is investigated in this paper. The results showed that the pseudo-second-order kinetic model more appropriately described the phenol adsorption and desorption. The adsorption isotherms at 20, 30, and 40 °C indicated that the Langmuir model better expressed adsorption, while desorption isotherms revealed that desorption is well fitted by Freundlich model. Following adsorption isotherms, the surface occupied with phenol could be calculated indicating that not the whole surface was covered with phenol molecules due to the acidic surface. The negative ΔH° showed that adsorption (− 0.0144 kJ·mol⁻¹) and desorption (acetone: − 0.0179 kJ·mol⁻¹ limonene: − 0.0174 kJ·mol⁻¹) were exothermic processes. In addition, the negative ΔS° showed that adsorption (− 0.0178 kJ·mol⁻¹·K⁻¹) implies the non-affinity of the surface for phenol; however, the positive ΔS° in desorption (acetone: 0.0157 kJ·mol⁻¹·K⁻¹ limonene: 0.0182 kJ·mol⁻¹·K⁻¹) means an affinity between adsorbent surface and adsorbate. The negative values of free energy ΔG° obtained for adsorption and desorption indicate the feasibility and spontaneous nature of adsorption and desorption process.