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1.
Solubilities of carbon dioxide in aqueous ethanol solutions, determined at 15, 20, 25, 30 and 35°C at atmospheric pressure, show a minimum at each temperature. Thermodynamics functions for the solution process were calculated and compared with the predictions of the Pierotti gas solubility theory. The abnormal behavior of these solutions is demonstrated.  相似文献   

2.
The solubilities of amino acids have been measured in water and aqueous poly(ethylene glycol) (PEG) solutions as a function of temperature and PEG concentration. The free energies of transfer from water to aqueous PEG solutions forl-alanine,l-valine,l-isoleucine andl-leucine were positive, while those forl-phenylalanine andl-tryptophan were negative. The corresponding enthalpies of transfer were almost zero for all amino acids. The equilibrium constants of the binding of amino acids to PEG chain were estimated from the solubility data. Amino acids with larger hydrophobicity are bound more strongly to the PEG chain due to the hydrophobic interaction between the methylene groups of PEG and the side chain of amino acid. The equilibrium constants showed a correlation with the dynamic hydration number (n DHN) which expresses the hydration properties of amino acids in aqueous solution.  相似文献   

3.
The glass-forming composition regions of aqueous tetraalkylammonium nitrate solutions (alkyl = ethyl and n-propyl) were determined by a simple DTA method with a cooling rate of about 600 K-min–1. The glass transition temperatures Tg of these solutions vary in a different manner from those for simple inorganic salt solutions such as aqueous LiCl, MgCl2,and AlCl3 solutions. Liquid-liquid immiscibilities are observed in these solutions at low temperatures.  相似文献   

4.
The solubilities of cuprous bromide were measured at 24.8°C in aqueous KBr and in aqueous KBr-KNO3 mixtures. The results have been analyzed to give equilibrium constanns from formation of neutral and negatively charged complexes of CuBr, and sets of virial parameters suitable for calculation of activity coefficients for the complexes.  相似文献   

5.
An automated vapor pressure apparatus has been used to obtain highly precise values of the total pressure and composition of aqueous solutions of ethanol and of 2-propanol in the water-rich region at 25 and 35°C. From these results, values of the partial pressures and fugacities of the components and osmotic coefficients have been inferred. Interaction virial coefficients derived from the present results are compared with interaction parameters previously reported for alcohol molecules in dilute aqueous solution. A discussion is given of the relative importance of hydrophobic effects and hydrogen-bonding in producing the unusual thermodynamic properties of aqueous alcohol solutions.  相似文献   

6.
The solubility of carbon dioxide in aqueous solutions of sodium chloride was measured in the temperature range from 40 to 160°C, up to 6 mol-kg salt solutions and total pressures up to 10 MPa. Pitzer's(1) equations as well as the Chen and Evans(2) model were used to correlate the new data. Results are reported and compared to literature data and correlations.  相似文献   

7.
The thermal effects of dissolution of ammonium bromide in water and its mixtures with formamide (FA) at 277–328 K were studied by the calorimetry method in the region of small additions of the nonaqueous component. The standard values of enthalpy and heat capacity of solution, as well as the temperature changes in the solution entropy and reduced dimensionless Gibbs energy, were calculated. The parameters of electrolyte-amide pair interactions were calculated using the McMillan-Mayer formalism. The contributions of the cation and anion to the pair interaction parameters were determined by the group additivity method. The results are compared with the data obtained previously for solutions of tetrabutyl-and tetraethylammonium bromides in aqueous solutions of FA and hexamethylphoshotriamide (HMPT). At elevated temperatures the system becomes less structured in amide solutions of tetraalkylammonium bromides (except solutions of Et4NBr in aqueous HMPT) but more structured in solutions of ammonium bromide and in aqueous FA and HMPT.  相似文献   

8.
The activity coefficients at 25‡C of DL-serine and L-serine in aqueous solutions of NaCl and KC1 were measured. This study examines the effect of the nature of the cation of the electrolyte on the activity coefficients of the optical-isomers of serine in aqueous solutions for molality of serine up to 0.4 and molality of electrolyte up to 1. An electrochemical cell with two ion-selective electrodes, a cation, and an anion ion selective electrode,vs. a double-junction reference electrode was used to measure the activity coefficients of the electrolyte and the results were converted to the activity coefficients of serine in the aqueous electrolyte solution. The comparison of the results obtained for DL- and L-serine indicates that the two optical isomers have identical interactions with electrolytes in aqueous solutions and that for this amino acid the effect of the cation of the electrolyte is not significant. Comparison of these results with previous measurements for DL-alanine in aqueous solutions of the same electrolytes show the notable effect of the backbone of the amino acid.  相似文献   

9.
The solubilities of barium sulfate in aqueous solutions of sodium sulfate were studied at ionic strengths from 0.0005 to 0.02 mol-kg–1 and at 0, 20, 40, 60, and 80°C. The solubility data were used to calculate the solubility constants using an extrapolation method. The solubility constant obtained were in good agreement with literature data. The mean activity coefficients of barium sulfate in aqueous solutions of sodium sulfate were also studied.  相似文献   

10.
The osmotic coefficients of acetamide, propionamide and butyramide in water were measured at 293.15, 298.15 and 308.15 K using the isopiestic method. The activity coefficients were calculated for the aliphatic amides and the pairwise free energy coefficients for solute-solute interactions were determined according to the McMillan-Mayer theory. The osmotic and activity coefficients of amides are discussed in terms of solute-solute interactions.  相似文献   

11.
The ostwald absorption coefficient of argon was measured in aqueous solutions of two surfactants; sodium n-octanoate and in sodium dodecylsulfate, at several concentrations and at a few temperatures between 10–25°C. The free energies, entropies and enthalpies of solution were computed. A tentative interpretation of the results is given, based on a competition between the solubilization and the salting-out effects of the surfactants.  相似文献   

12.
The hydrolysis-precipitation equilibrium reaction of aqueous gallium(III) solution was investigated in 0–3 mol-kg-1 NaCl media at low pH at 100°C using a pressure-tight glass vessel. All precipitates were identified as GaOOH. The results were analyzed with a nonlinear least-squares computer program to obtain the solubility product Kso for gallium(III) oxyhydroxide using a single-parameter type of Debye-Hückel equation. The value of log Kso for GaOOH(s) + 3H+ ⇆ Ga3+ + 2H2O was -0.60 at 100°C. The solubility product calculated from thermodynamic data was compared with the experimental result.  相似文献   

13.
The solubility of carbon dioxide, methane, and propane in poly(dimethyl silmethylene) [(CH3)2SiCH2]x and poly(tetramethyl silhexylene siloxane) [(CH3)2Si (CH2)6Si (CH3)2O]x was measured in the temperature range from 10.0 to 55.0°C and at elevated pressures. The present results are compared with similar measurements made with other silicone polymers. At a given temperature and pressure, the solubility of the above three gases is highest in poly(dimethyl siloxane) (Me2SiO)x. The gas solubility is decreased by either backbone-chain or side-chain substitutions of functional groups in (Me2SiO)x which increase the stiffness of the polymer chains and decrease the specific or fractional free volume of the polymers. It is conjectured that a decrease in the free volume of silicone polymers has a greater effect in decreasing the gas solubility than differences in gas/polymer interactions [with the exception of specific interactions (e.g., between CO2 and polar groups in the polymer)]. © 1993 John Wiley & Sons, Inc.  相似文献   

14.
Using diallylmethyl alkyl ammonium salts (CCX) (X is alkyl's chain length, represents 12, 14, 16, and 18, respectively) as a comonomer of methacrylic (MAA), hydrophobically modified hydrogels of poly diallylmethyl alkyl ammonium salts‐methacrylic acid (PCCX‐MAA) were prepared by free radical copolymerization in aqueous solution. The synthetic conditions, such as dosage of cross‐linking agent, reaction concentration and length of alkyl chain were studied in detail. Results indicated that the swelling degree of hydrogels was decreased with dosage of cross‐linking agent, or monomer concentration increased at different pH. Incorporation of the different length of alkyl chain hydrophobic CCX units on PMAA chains by random distribution can change reswelling kinetics. The required time for reaching equilibrium swelling state was longest for PCC16‐MAA. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

15.
A. Valtz 《Thermochimica Acta》2006,443(2):245-250
Specially designed equipment based on a static-analytic method with Rolsi™ pneumatic samplers for on line gas chromatograph analysis has been used for this work. Operating pressures and temperatures are between 0.3 and 10 MPa and between 293 and 393 K. Vapor pressures over liquid-liquid mixtures and benzene solubility data are reported herein for benzene with amine aqueous solutions (methyldiethanolamine (MDEA) and diglycolamine (DGA)). Modelling of solubility data is achieved using a simple model based on activity coefficients.  相似文献   

16.
The solubilities of methane, ethane, propane, and n-butane were measured in aqueous solutions of sodium dodecylsulfate (NaDS) (0–0.1M) from 15 to 27°C. From these measurements the standard Gibbs energies, entropies, and enthalpies for the process of transferring the solute molecules from the gaseous phase into the solutions were calculated. An approximate relationship was found relating the volume fraction of the micelles to NaDS concentration.  相似文献   

17.
The specific heat capacities of hexamethylphosphoric triamide, diethylpropionamide, their aqueous solutions, and mixtures of hexamethylphosphoric triamide with formamide were measured in the temperature range from 288.15 to 318.15 K. The dependences of the partial molar heat capacity of aqueous solutions of amides on the composition of the mixture have maxima in the region of 0.02–0.04 molar fractions of amide. The maximum on a similar dependence for solutions of hexamethylphosphoric triamide corresponds to the concentration of 0.01 molar fractions. The conclusion on the formation of solvates (hydrates) in the systems studied was made. The heat capacity coefficients of pair and triple interactions were calculated in terms of the McMillan-Mayer theory. A change in the heat capacity characteristics with the temperature change was analyzed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2479–2483, December, 1998.  相似文献   

18.
Enthalpies of solution of amides of formic, acetic, and propionic acids with different degrees of N-substitution in aqueous solutions of ethylene glycol were measured at 298.15 K. The concentration of ethylene glycol did not exceed 4 mol kg–1. The reasons for increasing endothermic values of the enthalpies characterizing the amide transfer from water to a mixed aqueous-organic solvent on going from primary to tertiary amides and from formamides to the corresponding acetamides are discussed. The enthalpic coefficients of pair interactions between amides and ethylene glycol in water were calculated. The endothermicity of the interaction of the alkyl groups of the amide molecules with ethylene glycol results in positive values of the coefficients. The coefficient values increase with the enhancement of the hydrophobic properties of hydrophilic non-electrolytes (urea, formamide, ethylene glycol) due to an increase in the contribution of the hydrophobic component and a decrease in the contribution from the interaction of the polar groups of amides to the total interaction.  相似文献   

19.
Surfactant–polymer interactions in aqueous solutions have been studied using dynamic surface tension, polyelectrolyte titration, nephelometric turbidity, and dynamic light scattering. For the preparation of complexes, a technical cationic surfactant was used in combination with two poly(maleic acid-co-polymers) of similar structure but different hydrophobicity. The dynamic surface tensions of mixed solutions as functions of surfactant concentration at constant polyelectrolyte content, as well as changes in the surface activity due to the influence of polyanion at constant surfactant concentration are discussed in terms of a complex or aggregate formation in the bulk phase. The interaction of the surfactant with poly(maleic acid-alt-propene) (P-MS-P) and poly(maleic acid-alt--methylstyrene) (P-MS-MeSty), respectively, is strong in both cases and results in the formation of nanoparticles with properties depending on the composition of the corresponding mixture.  相似文献   

20.
Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (NH). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (NH = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the NH value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (NH = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004  相似文献   

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