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The phase diagrams of binary organic systems of benzidine with pyrogallol andp-nitrophenol give a double simple eutectic type phase diagram showing formation of a 1∶1 molecular complex with congruent melting point and two eutectics. The growth data on the pure components, the eutectics and the molecular complexes, determined by measuring the rate of movement of growth front in a capillary, justify the square relationship between growth velocity and undercooling. While enthalpy of mixing values suggest intermolecular hydrogen bonding, the excess thermodynamic functions reveal strong interactions among the components forming eutectics and addition compounds.

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Abstract  

A thermodynamic study of the influence of the thermal treatments (annealing), below the glass transition temperature, on the thermal behavior and enthalpy of maltitol glass was carried out by differential scanning calorimetry (DSC). An enthalpic effect (exothermal) produced by the isothermal treatment of the quenched glass was found and measured. The origin of the thermal effect was assigned to a physicochemical transformation of molecular associations in the solid (glass). To achieve a correct description of the thermodynamic functions of glasses, another parameter, in addition to T and P, is introduced, namely the degree of advance of the above mentioned transformation.

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Abstract

The temperature dependence of the molar heat capacities of the tellurites PbTeO3, Pb2Te3O8 and Ge(TeO3)2 are determined. By statistical manipulation of the values obtained, the parameters in the equations for the corresponding compounds showing this dependence are determined using the least-squares method. These equations and the standard molar entropies are used to determine the thermodynamic functions Δ0 T S m 0, ΔT T H m 0 and (Φm 00 T H m 0/T) for T′=298.15 K.

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Abstract  

The temperature dependence of the molar heat capacities of the tellurites Fe2(TeO3)3, Fe2TeO5 and Fe2Te4O11 were determined. By statistical manipulation of the values obtained, the parameters in the equations for the corresponding compounds showing this dependence were determined using the least-squares method. These equations together with the standard molar entropies were used to determine the thermodynamic functions Δ0 T S m 0, ΔT T,H m 0 and (Φm 0 + Δ0 T’ H m 0 / T) for T’=298.15 K.

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Journal of Thermal Analysis and Calorimetry
Authors:
X.-C. Lv
,
Z.-C. Tan
,
Z.-A. Li
,
Y.-S. Li
,
J. Xing
,
Q. Shi
, and
L.-X. Sun

Abstract  

The (R)-BINOL-menthyl dicarbonates, one of the most important compounds in catalytic asymmetric synthesis, was synthesized by a convenient method. The molar heat capacities C p,m of the compound were measured over the temperature range from 80 to 378 K with a small sample automated adiabatic calorimeter. Thermodynamic functions [H TH 298.15] and [S TS 298.15] were derived in the above temperature range with a temperature interval of 5 K. The thermal stability of the substance was investigated by differential scanning calorimeter (DSC) and a thermogravimetric (TG) technique.

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A new bifunctional extractant named phenyl-N,N-dibutylcarbamoylmethyl sulfoxide (PCMSO) is synthesized and characterized in order to investigate its selectivity and capability in the extraction from acidic nitrate media in nuclear reprocessing. The extraction of uranium (VI) with PCMSO in toluene has been studied at various concentrations of nitric acid, extractant and salting-out agent (LiNO3). The mechanism of extraction is discussed in the light of the results obtained. The extracted species has also been investigated using FT-IR spectrometry. The related thermodynamic functions were calculated. The IR spectral study was also made of the extracted species.

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Enthalpies of dissolution of benzo-15-crown-5 ether (B15C5) in mixtures of acetonitrile with water and in solutions of NaI and NaBPh4 (I=0.05 mol dm−3) in these mixtures were measured at 298.15 K. From the obtained results and appropriate literature data, the thermodynamic functions of B15C5/Na+ complex formation in acetonitrile-water mixtures were determined. The enthalpies of transfer of the complex B15C5/Na+ from pure acetonitrile to the examined mixtures were calculated and are discussed.

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Summary  

The sorption of 60Co2+, 115mCd2+ and 203Hg2+ from diluted solutions (as analogues for radioactive waste waters) on ETS-4 microporous titanosilicate was studied at 277, 293, 313 and 333 K by measuring the sorption kinetics using a batch-method. The sorption of these radiocations was compared by means of the distribution coefficient and of the sorption capacity. The maximum sorption capacities follow the order: 203Hg2+>115mCd2+³60Co2+. The thermodynamic functions of the sorption processes have been estimated. The increase of the absolute value of DG° with increasing temperatures shows that higher temperatures favor ionic exchange.

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Abstract  

The i-butyldodecylsulfoxide (BDSO) was synthesized. The extraction of uranium(VI) has been carried out with BDSO in toluene from various HNO3 concentrations. It was found that the distribution ratio increases with increasing nitric acid concentration up to 3.0 mol/l and then decreases. The distribution ratios also increase with increasing extractant concentration. The extracted species appears to be UO2(NO3)2·2BDSO and the equilibrium constant value is 15.2. The influence of temperature, sodium nitrate and oxalate concentrations on the extraction was also investigated, and the thermodynamic functions of the extraction reaction were obtained.

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Abstract  

The extraction coefficients for the actinyl ions extracted with tri-n-butyl phosphate (TBP) from 2.0M CH3 COOH, CH2 ClCOOH and CCl3 COOH in various temperatures have been measured. Distinct discontinuities of the lnD vs. 1/T plots were interpreted as a proof for the extraction mechanism changes. Results obtained were used to calculate the thermodynamic functions of the actinyl complexation in the aqueous phase and of the partition process. It is proposed that the inner-sphere complex formation increases in the order acetates < chloroacetates < trichloroacetates.

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