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1.
The heat capacity and density of solutions of calcium and cadmium nitrates in N-methylpyrrolidone (MP) at 298.15 K are studied by calorimetry and densimetry. The obtained data are discussed in relation to certain features of solvation and complex formation in solutions of these salts. The standard partial molar heat capacities and volumes ( $\overline {C_{p^2 }^0 }$ and $\overline {V_2^0 }$ ) of the electrolytes in MP are calculated. The standard heat capacities $\overline {C_{p^i }^0 }$ and volumes $\overline {V_i^0 }$ of Ca2+ and Cd2+ ions in MP at 298.15 K were determined, along with the contribution from specific interactions to the values of $\overline {C_{p^i }^0 }$ and $\overline {V_i^0 }$ of Cd2+ ions in MP solution.  相似文献   

2.
The heat capacity and density of solutions of lithium and sodium nitrates in N-methylpyrrolidone (MP) at 298.15 K are studied by calorimetry and densimetry. The standard partial molar heat capacities and volumes (C? p,2° and V? 2°) of LiNO3 and NaNO3 in MP are calculated. The standard heat capacities C? p,i ° and volumes V? i ° of Li+ and Na+ ions in MP at 298.15 K are determined on the basis of a proposed scale of ionic contributions of C? p,2° and V? 2° values. The obtained data are discussed in relation to certain features of solvation in solutions of the investigated salts.  相似文献   

3.
The heat capacity and density of solutions of cadmium and mercury diiodides in methylpyrrolidone (MP) at 298.15 K were studied by calorimetry and densimetry. The data obtained are discussed in relation to the special features of solvation and complex formation in solutions of the salts. The standard partial molar heat capacities and volumes (
and
) of the electrolytes in MP were calculated. The standard heat capacities
and volumes
of the Cd2+ and Hg2+ ions in solutions in MP at 298.15 K were determined.
  相似文献   

4.
Heat capacities of solutions of alkali metal iodides (MeI) in N-methylpyrrolidone (MP)-water mixed solvent were measured over the range of compositions. The influence of the composition of the mixed solvent on the heat capacity of MeI-MP-H2O ternary systems is discussed. Standard partial molar heat capacities $ \bar C_{p_2 }^o $ \bar C_{p_2 }^o (MeI) in the MP-water mixed solvent at 298.15 K are calculated.  相似文献   

5.
The heat capacity and density of potassium iodide solutions in a mixed N-methylpyrrolidone (MP)-water solvent with a low content of the organic component are measured via calorimetry and densimetry at 298.15 K. Standard partial molal heat capacities \(\bar C_{p,2}^ \circ \) and volumes \(\bar V_2^ \circ \) of potassium iodide in MP-water mixtures are calculated. Standard heat capacities \(\bar C_{p,i}^ \circ \) and volumes \(\bar V_i^ \circ \) of potassium and iodide ions are determined. The character of the changes in heat capacity and volume are discussed on the basis of calculating additivity coefficients δ c and δ v upon the mixing of isomolal binary solutions KI-MP and KI-water, depending on the composition of the MP-H2O mixture and the concentration of the electrolyte.  相似文献   

6.
The standard partial molar volumes of electrolytes and ions in N-methylpyrrolidone (MP) at 298.15 K are presented. Separate components of ionic volumes in solutions in MP at infinite dilution, \(\overline {V_i^0 } \), are considered. The influence of various volume effects on ion-solvent interactions is analyzed.  相似文献   

7.
The heat capacity and density of solutions of lithium chloride, bromide, and iodide in N-methylpyrrolidone (I) were determined by calorimetry and densimetry techniques. The standard partial molar heat capacities and volumes ( $\overline {C^\circ _{p2} } $ and $\overline {V^\circ _2 } $ ) of lithium halides in I were calculated. The $\overline {C^\circ _{pi} } $ and $\overline {V^\circ _i } $ values for halogen and lithium ions in I were determined. The coordination numbers of the Li+, Cl?, Br?, and I? ions in solutions in I at 298.15 K were calculated.  相似文献   

8.
The standard partial molar heat capacities of singly charged ions in methylpyrrolidone (MP) at 298.15 K are reported. Heat capacity changes caused by the solvation of ions in MP and water are used to analyze the influence of various effects on ion-solvent interactions.  相似文献   

9.
The heat capacity and density of solutions of sodium and potassium perchlorates in N-methylpyrrolidone (MP) at 298.15 K were studied by calorimetry and densimetry. The standard partial molar heat capacities $ \bar C_{p2}^ \circ $ \bar C_{p2}^ \circ and volumes $ \bar V_2^ \circ $ \bar V_2^ \circ of NaClO4 and KClO4 in MP were calculated. The standard heat capacities $ \bar C_{pi}^ \circ $ \bar C_{pi}^ \circ and volumes $ \bar V_i^ \circ $ \bar V_i^ \circ of the perchlorate ion in an MP solution at 298.15 K were determined. The results are discussed with allowance for the specifics of solvation in the solutions of the salts under study. The coordination number of the ClO4 ion in an MP solution at 298.15 K was calculated.  相似文献   

10.
Summary Conductance measurements for NaI, KI, RbI, and CsI in water/N,N-dimethylformamide mixtures over the whole composition range at 298.15K are reported. The data were analyzed employing theFuoss-Justice equation in terms of limiting molar conductances (o),Walden products (o), and association constants (K A). The results indicate that the salts are weakly associated in the above solvent mixture. Variation in theWalden products with solvent composition are briefly discussed. The results were also compared with values reported previously for some alkali metal chlorides and bromides.
Untersuchungen zur elektrischen Leitfähigkeit einiger Alkalimetalliodide in wäßrigen N,N-Dimethylformamidlösungen bei 298.15K
Zusammenfassung Die elektrische Leitfähigkeite von NaI, KI, RbI und CsI wurde in N,N-Dimethylformamid-Wasser-Mischungen verschiedener Zusammensetzung bei 298.15K gemessen. Die erhaltenen Daten wurden analysiert und bezüglich der Grenzäquivalenzleitfähigkeiten (o), derWalden-Produkte (o) und der Assoziationskonstanten (K A) ausgewertet. Die Ergebnisse zeigen, daß diese Salze in den verwendeten Lösungsmittelgemischen nur schwach assoziiert sind. Die Änderungen derWalden-Produkte in Abhängigkeit der Lösungsmittelzusammensetzung werden kurz diskutiert. Abschließend werden die Resultate mit Ergebnissen früherer Messungen, in denen das Verhalten von Alkalimetallchloriden und Alkalimetallbromiden untersucht wurde, verglichen.
  相似文献   

11.
《Fluid Phase Equilibria》1999,164(2):225-255
An apparatus for a rapid and simultaneous determination of the thermophysical properties excess enthalpy, isobaric heat capacity, kinematic viscosity, density and thermal conductivity has been developed. The experimental setup is subject of this paper. At 298.15 and 323.15 K, the systems ethylene glycol dimethyl ether–n-dodecane, diethylene glycol dimethyl ether–n-dodecane, triethylene glycol dimethyl ether–n-dodecane, tetraethylene glycol dimethyl ether–n-dodecane and diethylene glycol dibutyl ether–n-dodecane have been investigated. The experimental results are correlated and the macroscopic properties are interpreted.  相似文献   

12.
The heat capacity and density of KNCS-N-methylpyrrolidone (MP), Cd(NCS)2-MP, and KNCS-Cd(NCS)2-MP solutions at 298.15 K are studied by means of calorimetry and densitometry. Standard partial molar heat capacities and volumes ( $\bar C^\circ _{p,2} $ and $\bar V^\circ _2 $ ) of the studied electrolytes in MP are calculated. Standard values of heat capacity $\bar C^\circ _{p,i} $ and volume $\bar V^\circ _i $ of NCS? ions in MP at 298.15 K are determined. Values of the heat capacity and volume changes upon the formation of the three-component system KNCS-Cd(NCS)2-MP from binary solutions are obtained and discussed.  相似文献   

13.
Based on the assumption that there exists a distribution of hydrates over the hydration number, expressions for the hydration number, activity coefficients of the components, and excess Gibbs energy were obtained. It was demonstrated that the van Laar formula for the activity coefficients corresponds to the Poisson distribution of hydrates. It was established that, at a constant ratio of the variance to the mathematical expectation of the distribution of hydrate, the model’s equations adequately describe the available experimental data on the vapor pressure and water activity for the glycerol-water system over the entire concentration range.  相似文献   

14.
The heat of dissolution of potassium chlorate in water at 298.15 K has been measured on an LKB 8700-1 calorimeter in the concentration range 0.063–0.659 m. The concentration dependence of the measured data was fitted by an empirical equation ΔHm (kJ mole?1) = 41.3538 + 1.8626m12 ? 6.4300m which was derived from our and Andauer—Lange data. The heat of crystallization calculated from this dependence was ΔHcryst. = 34.7 ± 0.5 kJ mole?1, which agrees with data calculated for potassium chlorate from solubility and activity data.  相似文献   

15.
Excess isobaric heat capacities of mixture (2-methoxyethanol+water) were measured at T=298.15 K and excess enthalpies at T=293.15 and 298.15 K. Excess enthalpies were extremely exothermic, up to -1290 J mol-1 atT=293.15 K and -1240 J mol-1 at T=298.15 K. Excess isobaric heat capacities were positive and very large, approximately 9 J K-1 mol-1 at the maximum. In contrast to the data reported by Page and coworkers, the excess heat capacity data were positive in the entire composition range and there was no change in their signs. Consistently, no crossing was found between the curves of excess enthalpies at T=298.15 and 293.15 K. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

16.
The paper presents the results of experimental studies of thermoelectrochemical systems comprising silver chloride and quinhydrone electrodes in aqueous-methanolic solutions of hydrogen, lithium, potassium, and cesium chlorides. These results and literature data are used to calculate the standard entropies of transfer of electrolytes, Soret thermal diffusion coefficients, and entropies of moving ions at 298.15 K. The influence of the nature of electrolytes and mixed solvent composition on the characteristics of thermal diffusion transfer in the systems studied is discussed.  相似文献   

17.
18.
Enthalpies of dilution of tetrabutylammonium butyrate are reported as a function of temperature between 10° and 50°C. Heat capacities of aqueous solutions of tetrabutylammonium butyrate were measured in order to obtain values of cp at 15°, 25°, and 35°C. These data were combined with the enthalpy of dilution data to obtain cp as a function of molality and temperature. The apparent molal heat content L decreased with increasing temperature in concentrated solutions but increased with increasing temperatures in dilute solutions (below0.7 m). Over the temperature range studied cp shows a maximum as a function of molality at approximately 0.5m. The decrease in cp with increasing concentration of hydrophobic solute is consistent with the view that the hydrophobic hydration cages, formed under the influence of the tetrabutylammonium and butyrate ions, are saturated at about 0.5m, and that at higher molalities increased overlap of the hydration cages occurs.  相似文献   

19.
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