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.
The thermodynamic functions for the extraction of Sc3+ by liquid cation exchangers HD and HDEHP are determined radiometrically by the temperature coefficient method. The role of
diluent dielectric constant on the extraction of Sc3+ by HD is also studied. The thermodynamic parameters determined indicated that the free energy variation for the extraction
of Sc3+ by HD is mainly determined by the entropic terms arising from the hydration—dehydration process of the exchanged ions. In
the case of HDEHP as extractant, the free energy variations are determined mainly by the entalpic terms of the system.
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.
The extraction behavior of octahedral and tetrahedral cobalt(II) complexes from aqueous nitrate medium was studied in the
system 8-hydroxyquinoline (HOX) and dibenzo-18-crown-6 (Db 18C6) or dibenzylamine (DBA) in chloroform at different temperatures
to evaluate the thermodynamic functions as well as the equilibrium constants of each reaction. The stoichiometry of the extracted
organic phase species were established to be Co(OX)2·Db18C6 for the octahedral cobalt and Co(OX)2·DBA for the tetrahedral cobalt.
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.
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
The liquid-liquid extraction behavior of 2-ethylhexyltolylsulfoxide (EHTSO) towards uranium(VI) contained in nitric acid aqueous solution has been investigated. It was found that the extraction increases with increasing nitric acid concentration up to 5.0 mol/l and then decreases. Extraction also increases with increasing extractant concentration. The extracted species appears to be UO2(NO3)2.2EHTSO. The influences of temperature, NH4NO3 and Na2C2O4 concentrations on the extraction equilibrium were also investigated and the thermodynamic functions of the extraction reaction were obtained.
The liquid-liquid extraction behavior of octyldodecylsulfoxide (ODoSO) towards uranium(VI), contained in nitric acid aqueous solution, has been investigated. It was found that the extraction increased with increasing nitric acid concentration up to 2.0 mol/l and then decreased. Extraction also increases with increasing extractant concentration. The extracted species appears to be UO2(NO3)2.2ODoSO. The influences of temperature, sodium nitrate and oxalate concentrations on the extraction were also investigated and the thermodynamic functions of the extraction reaction were obtained.
A new extractant, N-octanoyl-2-methylpiperidine (OMPPD) has been synthesized. The extraction of U(VI) with N-octanoyl-2-methylpiperidine (OMPPD) in nitric acid has been studied. The dependence of the partition reaction of U(VI) on the concentrations of nitric acid, extractant, salting-out agent LiNO3, and temperature has been studied. In the light of the results, the extraction mechanism is discussed. The synergistic extracted complexes may be presented as UO2(NO3)2(OMPPD)2 . The related thermodynamic functions were calculated.
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.