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101.
The connection between the dielectric and calorimetric relaxation behaviours of synthetic polyisoprene Cariflex IR 305 is studied. A similar comparison of dielectric and dilatometric results was described in [1]. The heat capacity was measured during heating of samples prepared with different thermal history. Experimental results were compared with the heat capacity curves calculated for a model based on the multiparameter theory of Kovacs et al. [4]. The model considers the relaxation system as being composed of a set of subsystems characterized by different relaxation times. The distribution of relaxation times and their temperature dependence were taken from the diclectric measurement. The relaxation time of a subsystem from posed to depend, not only on the actual, temperature of the sample, but also on the deviation of this subsystem from equilibrium, or alternatively, on the deviation of the system as a whole. The comparison between the measured and modeled curves shows that both influences must be taken into account in order to explain the experimental results.Dedicated to Prof. Dr. W. Pechhold on the occasion of his 60th birthday. 相似文献
102.
The excess Gibb's free energy of mixing, GE, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The HE and GE values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and GE>HE. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A2B molecular species describes well (within±10 J-mol–1 in the worst case) the general dependence of HE on XA (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA2B reactions along with the enthalpies of formation of AB and A2B molecular species have been calculated. 相似文献
103.
Densities have been measured as a function of composition for ternary-pseudobinary mixtures of [(benzene + toluene or methylcyclohexane)
+ (cyclohexane + toluene or methylcyclohexane)] by means of a vibrating-tube densimeter at atmospheric pressure and the temperature
298.15 K. The excess molar volumes, VmE, were calculated from the densities and correlated using the Redlich–Kister equation to estimate the coefficients and standard
errors. The experimental and calculated quantities are used to discuss the mixing behavior of the components. The results
show the third component, toluene and methylcyclohexane, influences the interaction between benzene and cyclohexane. 相似文献
104.
R. L. Arenosa R. G. Rubio C. Menduiña M. Díaz Peña 《Journal of solution chemistry》1985,14(5):345-354
The molar excess enthalpies for the ethylbenzene + n-decane and ethylbenzene + n-tetradecane systems have been measured at 25°C over the complete concentration range. These results and others from the literature for alkanes + ethylbenzene, and alkanes + toluene have been discussed in terms of the Prigogine-Flory-Patterson theory. 相似文献
105.
V. D. Kiselev G. G. Iskhakova E. A. Kashaeva L. N. Potapova A. I. Konovalov 《Russian Chemical Bulletin》2004,53(11):2490-2495
The densities of anthracene, tetracyanoethylene, maleic anhydride, N-phenylmaleineimide, trans, trans-1,4-diphenylbuta-1,3-diene, and their Diels-Alder adducts were measured in the solid state and in solution at 25 °C. The reaction volumes in the solid state were calculated from the difference in molar volumes. They turned out to be low, close to each other (–4 to –11 cm3 mol–1), and slightly different from the reaction volumes (–8±1 cm3 mol–1) calculated from the van der Waals radii. The reaction volumes in solutions (–15 to –32 cm3 mol–1) were found from the difference in partial molar volumes of the reactants in dioxane, acetonitrile, and 1,2-dichloroethane, The experimental Diels-Alder reaction volumes in solution are determined not only by the formation of new bonds in an adduct: a considerably higher contribution (to 75%) is made by a change in the volume of intermolecular empty spaces in solution on going from reactants to adducts.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2386–2390, November, 2004. 相似文献
106.
107.
Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V
2
o = 55.05 ± 0.02 cm3-mol–1, (V
2
o/T)p = 0.01486 ± 0.00318 cm3-K–1-mol–1, and (2
V
2
o/T
2)p = 0.02972 ± 0.00318 cm3-K–2-mol–1. Partial molar volumes of transfer from water to 1 mol-dm–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol. 相似文献
108.
A new theoretical approach of the isothermal crystallization of a thin polymer film is proposed. This model, derived from Evans' theory, is in very good agreement with a previous one, but is much more interesting because it makes it possible to calculate the transformed volume fraction anywhere in the film. The main effects of decreasing thickness are a slower average crystallization of the film and a decrease in the Avrami exponent caused by a slower crystallization of the polymer close to the surfaces.A slight modification of the model allows us to calculate the isothermal crystallization kinetics at any point of the film when it contains two identical transcrystalline regions on its surfaces.All the models are well verified by computer simulations. 相似文献
109.
The volume and compressibility changes on mixing aqueous solutions of the amino acid and poly(ethylene glycol) were measured with a vibration densimeter and a sing-around velocimeter at 298.15 K. For the system of alanine-PEG-H2O, the additivity rule for the mean apparent molal volume and compressibility at infinite dilution held, and the excess volume and compressibility changes on mixing were obtained. For the system of glycine-PEG-H2O, the additivity rule for the mean apparent molal compressibility at infinite dilution did not hold. While the mean apparent molal volume and compressibility changes were negative and positive for the systems of another amino acid-PEG-H2O, respectively, where amino acids were valine, isoleucine, leucine, phenylalanine, and tryptophan. These results suggest that glycine and alanine are excluded from the hydration layer around PEG chain and the amino acids with a larger side chain than alanine are bound to the PEG chain due to the hydrophobic interaction. The hydration number per monomer around PEG chain was estimated to be 3.9. 相似文献
110.
The apparent molar volumes V of KCl, BaCl2, K2SO4, LaCl3, Co(en)3Cl3 [Tris(ethylenediamine)cobalt(III) chloride], K3Co(CN)6, K3Fe(CN)6, K4Fe(CN)6, and Ba3[Co(CN)6]2 have been determined at 25°C in both light and heavy water. The V values in D2O are systematically lower and increase more rapidly with salt concentration than the V in H2O. The volume of transfer from H2O to D2O as well as the partial molar volume at infinite dilution in both solvents have also been calculated. These results together with literature values for other electrolytes were used to estimate both of these quantities for D2O solutions of individual ions. The predictions of ion hydration models and ion-ion interactions are compared with experimental observations. 相似文献