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  • volume  (7)
  • heat capacities  (3)
  • 1
    ISSN: 1572-8927
    Schlagwort(e): Mixed micelles ; surfactants ; alcohols ; thermodynamic transfer functions ; volume ; heat capacity ; hydrophobic solutes ; chemical equilibrium model and distribution constant
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.
    Materialart: Digitale Medien
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  • 2
    ISSN: 1572-8927
    Schlagwort(e): Activities ; relative enthalpies ; volumes ; heat capacities ; expansibilities ; phase diagrams ; 2,6-dimethylpyridine-water mixtures ; 2-isobutoxyethanol-water mixtures ; critical demixing
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Phase diagrams, volumes and heat capacities of aqueous mixtures of 2,6-dimethylpyridine (2,6-L) and 2-isobutoxyethanol (iBE) and activities of 2,6-L in aqueous mixtures were measured in the monophasic region near the lower critical solution temperature (LCST). With 2,6-L some measurement were also made just above the LCST. From the temperature dependence of these data, partial molar relative enthalpies (2,6-L), expansibilities and the temperature derivative of heat capacities were calculated and show that iBE undergoes a microphase transition at low concentration which is not related to the phase separation. On the other hand, the properties of 2,6-L in the water-rich region at temperatures well below the LCST indicates that this solute has only a slight tendency to associate. The heat capacities of 2,6-L show an important increase near the LCST. Such changes are not observed for iBE and other alkoxyethanols and amines since these systems already exist in the form of microphases; the partial molar properties of iBE near the LCST are nearly equal to the molar values of the pure liquid, and the changes in thermodynamic properties corresponding to the macroscopic phase transition, are therefore too small to be measured by the present techniques.
    Materialart: Digitale Medien
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  • 3
    ISSN: 1572-8927
    Schlagwort(e): Volumes ; apparent molal ; heat capacities ; apparent molal ; ultrasonic vibration potential ; acetonitrile ; electrolytes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The ultrasonic vibration potentials and apparent molal volumes for many inorganic and organic electrolytes were measured in acetonitrile at 25°C and combined to obtain ionic contributions to the standard partial molal volumes V°(ion). Monatomic cations and anions of the same size essentially have the same V°(ion). Their size dependence can be interpreted through Hepler's equation. The apparent molal heat capacities were also measured in acetonitrile and used to derive standard values. Various methods of estimating C p 0 (ion) were investigated and an ionic scale is proposed. It is concluded that C p 0 (ion) of large organic ions are very close to the intrinsic heat capacities of the ions, and the solvation contribution to monatomic ions is positive for both cations and anions.
    Materialart: Digitale Medien
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  • 4
    ISSN: 1572-8927
    Schlagwort(e): Solubility ; enthalpy of solution ; heat capacity ; volume ; compressibility ; sound velocity ; benzene and 2-propanol ; microemulsions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The solubilities, enthalpies of solution, heat capacities, densities and ultrasonic velocities of benzene in 2-propanol-water mixtures were measured at 25°C. The apparent molal volumes, heat capacities and isentropic compressibilities and the free energies, enthalpies and entropies of transfer of benzene were calculated. The benzene concentration is sufficiently low that all thermodynamic quantities can be considered in the standard state. All these functions show large changes in the aqueous end. Large extrema are observed for 2-propanol mole fractions (XP) near 0.08, and at higher XP the functions rapidly tend to the values in pure 2-propanol. The free energy of transfer of benzene from water to alcohol-water mixtures decreases linearly with the alcohol concentration up to XP of 0.07 and then more abruptly. On the other hand, at low temperature, this free energy becomes positive at low XP. These data are consistent with the existence of microphases in 2-propanol-water mixtures for Xp〉0.1. At low XP benzene is in an aqueous medium but beyond this critical region dissolves preferentially in the organic microphases. Benzene also enhances the formation of 2-propanol microphases and this leads to the observed extrema near Xp=0.08.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1572-8927
    Schlagwort(e): Mixed micelles ; surfactant ; alcohol-water mixture ; solubilization ; thermodynamic function of transfer ; volume ; enthalpy ; hydrophobic solutes ; heat capacity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Mixed micelles can be formed in water between various pairs of hydrophobic solutes such as surfactants, alcohols and hydrocarbons. These systems can often be studied through the thermodynamic functions of transfer of one of the solutes, usually kept near infinite dilution, from water to an aqueous solution of the other solute. When mixed micelles are formed, these functions change significantly, and often go through extrema, in the region where the binary system micellizes or undergoes some microphase transition.Three main effects are responsible for the observed trends: pair-wise interactions between both solutes in the monomeric form, a distribution of the reference solute between the aqueous and micellar phases and a shift in the monomer-micelle equilibrium in the vicinity of the reference solute. Simple equations can be derived for these three effects which can account for the sign and magnitude of the observed trends using parameters which are derived for the most part from the two binary systems.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 21 (1992), S. 433-443 
    ISSN: 1572-8927
    Schlagwort(e): Volumes ; phase diagrams ; heat capacities ; liquid mixtures ; non-ideality
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Liquid systems which have strong non-idealities, as seen from their thermodynamic properties, often show evidence of these interactions in the solid-liquid phase diagrams. This suggests that some of the structures present in the solid state can persist in the solution state, on a time average, up to temperatures much higher than the melting point. Volumes and heat capacities of typical systems were either taken from the literature or measured to illustrate this correlation with the phase diagrams. With mixtures of aprotic solvents which show nearly-ideal simple eutectic phase diagrams, the properties of the solutions are also nearly ideal. Examples of systems investigated which show strong non-idealities are ionic surfactant solutions, alcohol-water mixtures, chloroform-triethylamine mixtures and lithium salts in aprotic solvents.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 23 (1994), S. 121-133 
    ISSN: 1572-8927
    Schlagwort(e): Phase diagrams ; volume ; heat capacity ; non-aqueous micelle ; non-aqueous microemulsion ; mixtures of 1,2-hexanediol ; ethyleneglycol and hexane ; mixtures of Genapol X-060 ; decane and poly(ethyleneglycol) 400
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Blends of immiscible polymers are often stabilized by block copolymers which can form non-aqueous micelles and microemulsions in the liquid polymers. The phase diagrans, apparent volumes and apparent heat capacities of model non-aqueous binary and ternary systems were studied in order to investigate the conditions under which such self-assembly systems could form. 1,2-Hexanediol, which can cosolubilize hexane and ethyleneglycol, forms inverse micelles in hexane and weak microaggregates in ethyleneglycol. Genapol X-060, a commercial alcoholic surfactant containing on the average an aliphatic chain of 13 carbons and 6 oxyethylenes (C13E6), forms microaggregates in poly(ethyleneglycol) 400. These self-assembly systems are strengthen in the presence of a third component which has an affinity for the inner phase.
    Materialart: Digitale Medien
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  • 8
    ISSN: 1572-8927
    Schlagwort(e): Heat capacity ; density ; expansibility ; volume ; aqueous solutions ; 2-propanol ; neopentanol ; t-amylalcohol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The heat capacities per unit volume and the densities of aqueous solutions of 2-propanol, neopentanol, tert-amylalcohol, 2-amino-2-methylpropanol, triethylamine and diethylmethylamine were measured, in many cases as a function of temperature, over the whole mole fraction or solubility range. Apparent and partial molal heat capacities, volumes and expansibilities were derived. The concentration dependence of these functions suggest the existence of transitions in some of these systems, in the water-rich region, qualitatively similar to micellization. The large relaxation contribution observed with some of the thermodynamic functions of hydrophobic alcohols and amines suggests a reinforcement of hydrophobic hydration due to strong hydrogen-bonding interactions of the polar groups with water.
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  • 9
    ISSN: 1572-8927
    Schlagwort(e): Association constant ; Bjerrum model ; electrolyte ; heat capacity ; compressibility ; volume ; standard partial molar quantities ; water ; acetonitrile ; propylene carbonate
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The Bjerrum association model, which has already been applied successfully to volumes and enthalpies of dilution of electrolyte solutions, has now been extended to apparent molar heat capacities and compressibilities of these systems. The proposed method of calculation, which takes into account the relaxation effect observed in second derivatives of the excess Gibbs free energy, can be used to extrapolate to infinite dilution the experimental data for systems showing a wide range of association constants in acetonitrile, propylene carbonate, and water. The concentration dependence of the thermodynamic properties can be reproduced quantitatively by the addition of one or two virial coefficients. Literature data for C P,2,ψ and K S,2,ψ of electrolytes in aprotic solvents were refitted with this equation. For dissociated or slightly associated systems (K A 〈 10), the standarY 2 o d infinite dilution quantities () are in excellent agreement with literature values. For systems with high K A, Y 2 o obtained by the model are systematically lower than those reported in the literature. This is not surprising, since the traditional method of extrapolation using the Debye–Hückel limiting law or the Pitzer equation does not take association into account. A computer software that performs the calculations for the application of the Bjerrum model to thermodynamic properties has been designed and is presented in the appendix.
    Materialart: Digitale Medien
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  • 10
    ISSN: 1572-8927
    Schlagwort(e): Ethylammonium nitrate ; acetonitrile ; water ; solid-liquid phase diagram ; volume ; heat capacity ; expansibility ; conductivity ; viscosity ; ion association
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Ethylammonium nitrate (ETAN), a low melting fused salt which is completely miscile in water and in many non-aqueous solvents, was used as a model system for the study of concentrated non-aqueous electrolyte solutions. Acetonitrile (AN) was chosen as a representative aprotic solvent. Some data were also obtained for water as solvent. The properties investigated over the whole mole fraction range, many as a function of temperature, were solid-liquid phase diagram, volume, heat capacity, conductivity and viscosity. Most properties in both solvents vary in a regular fashion over the whole mole fraction range and the properties at high concentration rapidly tend to those of the molten salt. The apparent volumes and heat capacities vary linearly with lnX2 over a large mole fraction range. There is evidence of significant association in AN (K A =1094 l-mol−) but not in water. The low concentration thermodynamic data were fitted with an association model using the above K A to obtain the partial molar quantities of ETAN at infinite dilution and in the associated state. These latter values are of the same magnitude as the molar quantities of the molten electrolyte.
    Materialart: Digitale Medien
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