Thermodynamics of solvation of some small peptides in water at T = 298.15 K

The enthalpies of solution in water, Δ_solH_m, of some small peptides, namely the amides of five N-acetyl substituted amino acids of glycine, l-alanine, l-proline, l-valine, l-leucine and two cyclic anhydrides of glycine and l-sarcosine (diketopiperazines), were measured by isothermal calorimetry at T = (296.84, 306.89, and 316.95) K. The enthalpies of solution at infinite dilution at T = 298.15 K were derived and added to the enthalpies of sublimation, ${\mathrm{\Delta }}_{\mathrm{sub}}{H}_{\mathrm{m}}^{\circ }$, at the same temperature, to obtain the corresponding solvation enthalpies at infinite dilution, ${\mathrm{\Delta }}_{\mathrm{solv}}{H}_{\mathrm{m}}^{\infty }$. Moreover, the partial molar heat capacities at infinite dilution at T = 298.15 K, $C_{p\text{,}2}^{\infty }$, were calculated by adding molar heat capacities of solid small peptides, C_p,m(cr), to the ${\mathrm{\Delta }}_{\mathrm{sol}}{C}_{p\text{,}\mathrm{m}}^{\infty }$ values obtained from our experimental data. CH₂ group contributions, in terms of solvation enthalpy and partial molar heat capacity, were −3.2 kJ · mol⁻¹ and 89.3 J · K⁻¹ · mol⁻¹, respectively, in good agreement with the literature data. Simple additive methods were used to estimate the average molar enthalpy of solvation and partial molar heat capacity at infinite dilution for the 1/2CONH⋯CONH functional group in the small peptides. Values obtained were −46.7 kJ · mol⁻¹ for solvation enthalpy and −42.4 J · K⁻¹ · mol⁻¹ for partial molar heat capacity, significantly lower than values obtained for the CONH functional group in monofunctional model compounds.     

Thermodynamic and spectroscopic studies on binary mixtures of imidazolium ionic liquids in ethylene glycol

The thermodynamic behaviour of imidazolium based ionic liquids (ILs), 1-butyl-3-methylimidazolium chloride [C₄mim][Cl]; 1-octyl-3-methylimidazolium chloride [C₈mim][Cl], and 1-butyl-3-methylimidazolium methylsulfate [C₄mim][C₁OSO₃] in ethylene glycol [HOCH₂CH₂OH] (EG) have been investigated over the whole composition range at T = (298.15 to 318.15) K to probe the interactions in bulk. For the purpose, volumetric properties such as excess molar volume, $V_m^E$, apparent molar volume, V_?,i, and its limiting values at infinite dilution, $V_{?\text{,}i}^{\infty }$, have been calculated from the experimental density measurements. The molecular scale interactions between ionic liquids and EG have been investigated through Fourier transform infrared (FTIR) and ¹H NMR spectroscopy. The shift in the vibrational frequency for C–H stretch of aromatic ring protons of ILs and O–H stretch of EG molecules has been analysed. The NMR chemical shifts for various protons of RTILS or EG molecules and their deviations show multiple hydrogen bonding interactions of varying strengths between RTILs and EG in their binary mixtures.     

Activity coefficients at infinite dilution of hydrocarbons,alkylbenzenes, and alcohols in the paramagnetic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III) using gas–liquid chromatography

Activity coefficients at infinite dilution ${\gamma }_i^{\infty }$ of alkanes, alkenes, and alkylbenzenes as well as of the linear C₁–C₆ alcohols in the paramagnetic ionic liquid 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III) have been determined by gas chromatography using the ionic liquids as stationary phase. The measurements were carried out at different temperatures between (305 and 403) K. From the temperature dependence of the limiting activity coefficients partial molar excess enthalpies at infinite dilution $H_i^{E\text{,}\infty }$ of the solutes in the ionic liquids have been derived. Activity coefficients at infinite dilution ${\gamma }_i^{\infty }$ of ionic liquid with the ionic liquids containing 1-butyl-3-methyl-imidazolium cation and different non-magnetic anions have been compared at 298 K with results for 1-butyl-3-methyl-imidazolium tetrachloridoferrate(III). No significant effects caused by the paramagnetic anion anion have been observed.     

Interactions of some amino acids with aqueous manganese chloride tetrahydrate at T = (288.15 to 318.15) K: A volumetric and viscometric approach

Densities (ρ), sound velocities (u), and viscosities (η) of glycine, dl-α-alanine, dl-α-amino-n-butyric acid, l-valine, and l-leucine, in aqueous solutions (0.1, 0.5, 1.0, and 1.5) mol · kg⁻¹ of manganese chloride tetrahydrate, MnCl₂·4H₂O at different concentrations have been determined using a vibrating-tube digital densimeter, ultrasonic multifrequency interferometer and Ubbelohde type capillary viscometer attached with automatic viscosity measuring unit, respectively, within the temperature range (288.15 to 318.15) K. Partial molar volumes $V_2^{\text{o}}$, partial molar adiabatic compressibilities, $K_{\text{S,}2}^{\text{o}}$ and viscosity B-coefficients have been determined from the above measurements. Further these data were used to calculate the corresponding transfer parameters (${\mathrm{\Delta }}_{\text{t}}{V}_2^{\text{o}}$, ${\mathrm{\Delta }}_{\text{t}}{K}_{\text{S,}2}^{\text{o}}$ and Δ_tB), hydration numbers, n_H, side chain group contributions, partial molar expansibilities, $V_{\text{E}}^{\text{o}}$, dB/dT and related parameters. The data are discussed in terms of hydration of hydrophobic and hydrophilic parts of amino acids in these solutions.     

Physico-chemical properties of some electrolytes in water and aqueous sodiumdodecyl sulfate solutions at different temperatures

The viscosities of some mineral salt viz.; potassium chloride, potassium nitrate, magnesium chloride, magnesium nitrate, at different concentrations have been determined in water and in binary aqueous solution of sodiumdodecyl sulfate (SDS) (0.007 mol · kg⁻¹ and 0.01 mol · kg⁻¹) at different temperatures. The data have been analyzed using Jones–Dole equation and the derivative parameters B and A have been interpreted in terms of ion–solvent and ion–ion interactions respectively. The change of Gibbs free energy of activation $(\mathrm{\Delta }{G}_{\eta }^{\ne })$, enthalpy of activation $(\mathrm{\Delta }{H}_{\eta }^{\ne })$, and entropy of activation $(\mathrm{\Delta }{S}_{\eta }^{\ne })$ for viscous flow of the solutions were calculated using Eyring equation, which depicts the mechanism of viscous flow. The structure making/breaking nature of the studied electrolytes has been discussed in the light of first derivative of B-coefficient (dB/dT) over temperatures. Potassium chloride and potassium nitrate acts as structure breaker in water where as all the salts are structure makers in aqueous SDS solutions, i.e. the postmicellar and pre-micellar regions.     

Thermodynamic and physicochemical properties of binary mixtures of nitromethane with {2-methoxyethanol + 2-butoxyethanol} systems at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K

The density, relative permittivity, viscosity and speed of sound at T = (293.15, 298.15, 303.15, 308.15, and 313.15) K in the binary mixtures of nitromethane with 2-methoxyethanol and 2-butoxyethanol have been measured as a function of composition. From the experimental results, the excess molar volumes V^E, excess Gibbs free energy of activation for viscous flow $(\mathrm{\Delta }{G}^{1E})$, excess isentropic compressibility $({\kappa }_s^E)$ and the deviations in the relative permittivity, viscosity, and speed of sound from a mole fraction average have been calculated. The viscosity data, at T = 298.15 K, were correlated with equations of Hind et al., Grunberg and Nissan, Frenkel, and McAllister. The results are discussed in terms of intermolecular interactions and structure of studied binary mixtures.     

Thermodynamic study of (alkyl esters + α,ω-alkyl dihalides) III. HmEandVmE for 20 binary mixtures {xCu − 1H2u − 1CO2C4H9 + (1 − x)α,ω-ClCH2(CH2)v − 2CH2Cl}, where u = 1 to 4, α = 1 and v = ω = 2 to 6

In this article, the experimental data of excess molar enthalpies $H_{\mathrm{m}}^{\mathrm{E}}$ and excess molar volumes $V_{\mathrm{m}}^{\mathrm{E}}$ are presented for a set of 20 binary mixtures comprised of the first four butyl alkanoates (methanoate to butanoate) and five α,ω-dichloroalkanes (1,2-dichloroethane to 1,6-dichlorohexane), obtained at atmospheric pressure and at a temperature of 298.15 K. The results indicate the existence of specific interactions between both kinds of compounds resulting in exothermic processes for most mixtures, except for those containing butyl methanoate which give rise to net endo/exothermic effects. The $V_{\mathrm{m}}^{\mathrm{E}}$ are positive for mixtures of (butyl esters + 1,2-dichloroethane or 1,3-dichloropropane) and negative for the remaining ones. The change in $H_{\mathrm{m}}^{\mathrm{E}}$ with the dichloroethane chain length for a same ester is regular although the $V_{\mathrm{m}}^{\mathrm{E}}$ presents an irregular variation. It can, therefore, be deuced from this that the mixing process involves both effects, exothermic/endothermic and expansion/contraction, simultaneously. The behaviour of the mixtures is interpreted on the basis of the results observed and attributed to different effects taking place among the molecules studied.To improve application of the UNIFAC model using the version of Dang and Tassios, average values were recalculated again for parameters of the ester/chloride interaction, distinguishing, during its application, the functional group of the acid part of the ester. In spite of this, the model does not adequately reproduce the systems’ behaviour.     

Volumetric and acoustic study of aqueous binary mixtures of quinine hydrochloride,guanidine hydrochloride and quinic acid at different temperatures

In the present communication, we report the fundamental thermodynamic properties like volumetric and compressibility of very important bioactive compounds, viz. quinine hydrochloride, guanidine hydrochloride and quinic acid (0.01 to 0.1) mol · kg⁻¹ in water at temperatures T = (278.15, 288.15 and 298.15) K. The experimental values of density (ρ) of aqueous solutions and speed of sound (u) in aqueous solutions of the above compounds within the concentration range (0.01 to 0.1) mol · kg⁻¹ have been obtained. The apparent molar volumes (V_ϕ), and apparent molar isentropic compressibilities (κ_ϕ) of quinine hydrochloride, guanidine hydrochloride and quinic acid in water have been computed at three different temperatures. Speed of sound values have also been used to calculate the hydration number (n_H) of the solute. The temperature dependence of the apparent molar volume has been used to calculate the thermal expansion coefficient (α¹), apparent molar expansivity $(E_{\varphi }^0)$ and Hepler’s constant $\left({\partial }^2{V}_{\varphi }^0/\partial T^2\right)$. The derived parameters have been used to interpret the results in terms of (solute + solute)/(ion + ion), (solute + solvent) interactions, structure making and structure breaking tendencies of solutes in water.