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1.
Darja?Rudan-Tasic Cveto?KlofutarEmail author 《Monatshefte für Chemie / Chemical Monthly》2004,135(7):773-784
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. 相似文献
2.
Cveto Klofutar Mateja Ajnihar Nata?a Poklar Ulrih Darja Rudan-Tasic 《Monatshefte für Chemie / Chemical Monthly》2010,80(2):23-30
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. 相似文献3.
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. 相似文献
4.
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
相似文献
5.
Cveto Klofutar Jaka Horvat Darja Rudan-Tasic 《Monatshefte für Chemie / Chemical Monthly》2006,137(9):1151-1162
Summary. The apparent molar volume of rubidium, caesium, and ammonium cyclohexylsulfamate was determined from the density data of their
aqueous solutions at 293.15, 298.15, 303.15, 313.15, 323.15, and 333.15 K. From the apparent molar volume, determined at various
temperatures, the apparent molar expansibility was calculated. The limiting apparent molar volume and apparent molar expansibility
were evaluated and apportioned into their ionic components. The limiting partial molar ionic volumes and expansibilities are
discussed in terms of the various effects of the ion in solution on the structure of water. It was shown that the limiting
partial molar ionic expansibilities of the alkali-metal cations increase with their ionic radii. The coefficients of thermal
expansion of the investigated solutions at 298.15 K were calculated and are presented graphically together with some alkali-metal
cyclohexylsulfamates and tetramethylammonium cyclohexylsulfamate. The densities of the investigated solutions can be adequately
represented by an equation derived by Redlich. 相似文献
6.
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. 相似文献
7.
8.
9.
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 相似文献
10.
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. 相似文献