Thermodynamics of Transfer of Some Alkyl Acetates from Water to Water–Ethanol Mixtures

 The solubility of methyl acetate (MeOAc), ethyl acetate (EtOAc), 1-propyl acetate(1-PrOAc), 1-butyl acetate (1-BuOAc), 2-methyl-1-propyl acetate (iso-BuOAc), 2-butyl acetate (sec-BuOAc), 2-methyl-2-propyl acetate (tert-BuOAc), 1-pentyl acetate (1-PeOAc), and 1-hexyl acetate(1-HeOAc) in 2.5, 5.0, 7.5, and 10.0 weight per cent of ethanol in water were determined at 298.2 K. The solubility of the same compounds, except for tert-BuOAc, 1-PeOAc, and 1-HeOAc, was determined as a function of temperature at 10.0 weight per cent of ethanol in water. From the solubility measurements the standard Gibbs energy (), enthalpy (), and entropy () of transfer were determined. The calculated thermodynamic functions show that the predominant factors in the transfer of alkyl acetate molecules are the transfer of the cavity and the hydrophobic interaction of the non-polar alkyl chain. Scaled particle theory calculations were used to determine the thermodynamics of cavity transfer, which were combined with the experimental total transfer quantities to obtain the corresponding interaction transfer quantities. It was found that the Gibbs energy of interaction for the transfer is negative, whereas the enthalpy and entropy of interaction for the transfer are positive; almost complete compensation of enthalpy and entropy components occurs.     

Cholesterol complexes with some proton acceptors in benzene and toluene solutions

Abstract  Cholesterol complexes with tri-n-butyl phosphate, tri-n-octylamine, N,N-dimethylacetamide, and cyclohexanone in benzene and toluene solutions were studied using conventional IR spectroscopy. The spectra were recorded in the region of fundamental OH stretching (3,700–3,100 cm⁻¹) at 298 K. The experimental spectra were resolved into bands corresponding to the cholesterol monomer and particular oligomeric and complex species. The formation constants of complexes were determined from the-least squares plots of the linearized expressions of Bjerrum’s formation function. The stoichiometry of complexes was also identified in this way. The identification of the particular resolved bands was performed from their location, and from the dependence of their intensity on the cholesterol monomer and free base concentration. Graphical Abstract        

Osmotic Coefficients of Aqueous Solutions of Some Poly(oxyethylene) Glycols at the Freezing Point of Solution

Summary. The freezing temperatures of dilute aqueous solutions of some poly(oxyethylene) glycols (PEG, HO–(CH₂CH₂O) _n –H, n varying from 4 to 117) were measured over a solute to solvent mass ratio from 0.0100 to 0.3900. The second and third osmotic virial coefficient (A ₂₂ and A ₂₂₂) of poly(oxyethylene) glycols in aqueous solution were determined. The molecular weight dependence of the second virial coefficient can be described by a simple relation A ₂₂=2×10^–5 M _n ^1.86, and the third virial coefficient is A ₂₂₂=0.038A ₂₂ ². The activity coefficients of the solute were calculated using the Gibbs-Duhem equation as applied by Bjerrum. From the osmotic and activity coefficients the excess Gibbs energies of solution, as well as the respective partial molar functions of solute and solvent and the virial pair interaction coefficients for the excess Gibbs energies were estimated. The second and the third osmotic virial coefficients are correlated with the Mc-Millan-Mayer virial coefficients.     

Dipole moment and self-association of cyclohexylsulfamic acid in 1,4-dioxane solution at 298.15?K

Abstract  

The density, refractive index, and electrical permittivity of cyclohexylsulfamic acid in 1,4-dioxane solutions were measured at 298.15 K. The limiting apparent specific volume, refraction, and polarization were calculated from the experimental data. The electrical dipole moment of cyclohexylsulfamic acid was estimated using the Debye, Onsager, and Kirkwood equations. The dipole association of cyclohexylsulfamic acid was treated with the assumption that the dipole moment of dimeric species is zero. The dimerization constant and dipole moment of monomeric species were evaluated.     

Salting-Out of Some Alkyl Acetates in Aqueous Sodium Chloride Solutions

Summary.  Solubilities of methyl acetate (MeOAc), ethyl acetate (EtOAc), 1-propyl acetate (1-PrOAc), 1-butyl acetate (1-BuOAc), 2-methyl-1-propyl acetate (iso-BuOAc), 2-butyl acetate (sec-BuOAc), 2-methyl-2-propyl acetate (ter-BuOAc), 1-pentyl acetate (1-PeOAc) and 1-hexyl acetate (1-HeOAc) in water and in aqueous sodium chloride solutions at concentrations ranging up to 1.0 molċdm⁻³ were determined at 25.0°C by analyzing the saturated aqueous or salt solutions. Solubility ratios of alkyl acetates in pure water and in aqueous sodium chloride solution were calculated and found to be linearly dependent on the concentration of sodium chloride. The solubility ratios were also calculated by the approach of the scaled particle theory and according to the theories of McDevit and Long, Cross, Conway et al., and Aveyard. All these theories, except that of Conway, correctly predict the order of magnitude of the experimental results, but do not discriminate between isomeric butyl acetates. The theoretical values obtained from the scaled particle and Aveyard theories coincide well with the experimental values, especially for the higher alkyl acetates. The purely electrostatic theory of Conway et al. not even predicts the salting-out effect for the alkyl acetates investigated. Received July 12, 1999. Accepted September 23, 1999     

Electrical Conductivity Studies of Quinic Acid and its Sodium Salt in Aqueous Solutions

The electrical conductivities of aqueous solutions of quinic acid and its sodium salt were measured from 293.15 to 328.15 K in steps of 5 K. The molar conductivities of the sodium salt were treated by the Lee–Wheaton equation, in the form of Pethybridge and Taba, and the Kohlrausch equations. The limiting molar conductivities of the quinate anion were estimated, as well as the corresponding ionic association constants and standard thermodynamic functions of the ionic association reaction. The hydrodynamic radius of the quinate anion was calculated from the Walden rule and compared with the van der Waals radius. The dissociation constant of quinic acid was evaluated from the known value of the limiting molar conductivity of quinic acid using the conductivity equation of Pethybridge and Taba. The standard thermodynamic functions of the dissociation process, i.e., the Gibbs energy, enthalpy, entropy and heat capacity, were obtained using the non-empirical procedure given by Clarke and Glew. The standard thermodynamic functions of dissociation of quinic acid are discussed in terms of solute–solvent interactions and stabilization of the quinate anion due to hydrogen bonding of the α-hydroxyl group to the carboxyl group.