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Thermodynamical data on Sb-Te system at 909,30 K, 911,85 K and 917,95 K. The integral molar enthalpies of formation of liquid Sb-Te alloys were measured at three temperatures by drop calorimetry.
A review is given of various metallurgical problems treated in the author's laboratory, for which quantitative calorimetry gave very valuable information. Measurements of thermodynamic data for phase diagram calculations, vacancies in ordered alloys, annealing of steels, and the recovery and crystallization of amorphous alloys are successively examined.
Abstract
The effect of temperature on the extraction of Co2+, Zn2+, Cd1+ and Hg2+ by salicylaldoxime diluted with carbon tetrachloride was investigated radiometrically. It is found that the extraction constants at 25°C increase linearly with l/r, where r is the effective coordination radius of the metal cation. The thermodynamic data calculated from the effect of temperature on the extraction showed that, 1) the extraction process is endothermic, 2) the dehydration of the metal cation in the extraction process is the predominating factor in determining the enthalpy variation and 3) the entropy variation is a contribution of the degree of order caused by the hydration of the proton and the highly ordered chelate structure of the extracted species.
Abstract
The removal behavior of hydrous titanium oxide and sodium titanate for Cs(I) from aqueous solutions by radiotracers was studied. Batch experiments revealed that an increase in Cs concentration (10–8 to 10–2 mol·dm–3), temperature (298 to 328 K) and pH (2.50 to 10.20) apparently enhanced the uptake of Cs(I) on hydrous titanium oxide whereas a high degree of uptake of Cs(I) on sodium titanate was almost unaffected by a change in adsorption temperature (298 to 328 K) and pH (2.50 to 10.20). Both systems follow Freundlich adsorption isotherm. Uptake of Cs(I) on hydrous titanium oxide obeys first order rate law. According to thermodynamic data the uptake is endothermic and apparently 
irreversible
in nature.
Abstract
Adiabatic calorimetry is a technique that has been introduced as an important approach to hazard evaluation of exothermically reactive systems. In this paper the free radical polymerization of methyl methacrylate (MMA) has been studied. One of the most important aspects of MMA polymerization is its exothermicity and autoaccelerating behaviour, these characteristics can generate the occurrence of a runaway reaction.In a runaway situation the reacting system is close to adiabatic behaviour because it is unable to eliminate the heat that is being generated. An even worse situation can be reproduced in the laboratory with the Phi-Tec pseudo-adiabatic calorimeter. Process design parameters that are usually calculated from thermodynamic data or using semiempirical rules, such as adiabatic temperature rise or maximum attainable pressure, can be directly determined.The existence of the ceiling temperature has been experimentally demonstrated.
Abstract
Phase diagram of the binary system CsNO3–LiNO3 has been drawn by using simultaneously direct and differential thermal analysis between 323 and 723 K. This system is characterized by a congruent intermediate equimolar compound with melting point at 463 K, two eutectic reactions at 447 and 433 K; the eutectic points are respectively at 0,47 and 0,63 mol fraction of LiNO3; a plateau due to the phase transition of CsNO3 at 428 K and an other one at 333 K due to the formation of CsLi(NO3)2. The miscibility in solid state seems to be nil or negligible. These results associated with some other thermodynamic data have been used to calculate the activities of the constituents along the liquidus curve and the activities of the liquid constituents at 723 K. The binary liquid (Cs–Li)NO3 exhibits a negative deviation from the ideal behaviour.
Abstract
A method has been purposed to calculate some of the thermodynamic quantities for the thermal deformation of a smectite without using any basic thermodynamic data. The Hançılı (Keskin, Ankara, Turkey) bentonite containing a smectite of 88% by volume was taken as material. Thermogravimetric (TG) and differential thermal analysis (DTA) curves of the sample were obtained. Bentonite samples were heated at various temperatures between 25–900°C for the sufficient time (2 h) until to establish the thermal deformation equilibrium. Cation-exchange capacity (CEC) of heated samples was determined by using the methylene blue standard method. The CEC was used as a variable of the equilibrium. An arbitrary equilibrium constant (K a) was defined similar to chemical equilibrium constant and calculated for each temperature by using the corresponding CEC-value. The arbitrary changes in Gibbs energy (ΔG a 0) were calculated from K a-values. The real change in enthalpy (ΔH 0) and entropy (ΔS 0) was calculated from the slopes of the lnK vs. 1/T and ΔG vs. T plots, respectively. The real changes in Gibbs energy (ΔG 0) and real equilibrium constant (K) were calculated by using the ΔH 0 and ΔS 0 values. The results at the two different temperature intervals are summarized as below: ΔG 1 0=ΔH 1 0−ΔS 1 0 T=−RTlnK 1=47000−53t, (200–450°C), and ΔG 2 0=ΔH 2 0-ΔS 2 0T=−RTlnK 2=132000−164T, (500–800°C).
Abstract
Abstract
Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoyl pyrazolone-5 (HPMBP) and aliphatic sulfoxides of varying basicities, viz di-isoamyl (DIASO), di-n-hexyl (DHSO), di-n-septyl (DSSO), di-n-octyl (DOSO), di-n-nonyl (DNSO), di-n-decyl (DDSO) or di-n-undecyl (DuDSO) sulfoxide has been studied at 30±0.1°C. Extraction with some of these sulfoxides has been studied at various fixed temperatures also. The organic phase equilibrium constant (log Ks) has been found to increase with the basicity of the sulfoxide up to DOSO beyond which there is a gradual decreasing trend which has been attributed to the effect of possible steric hindrance (spatial) involved in the bonding of the higher sulfoxides (greater than 8 carbon atoms) with UO2 (PMBP)2 chelate. This has been supported by thermodynamic data involved in these systems. The entropy values for sulfoxides with eight or more carbon atoms are much more negative as compared to the lower sulfoxides and are also in contrast to HTTA and BTFA systems with these sulfoxides studied earlier.
Abstract
The role of dead biomasses viz., mango (Mangifera indica) and neem (Azadirachta indica) bark samples are assessed in the removal behavior of, one of important fission fragments, Cs(I) from aqueous solutions employing a radiotracer technique. The batch type studies were carried out to obtain various physico-chemical data. It is to be noted that the increase in sorptive concentration (from 1.0·10−8 to 1.0·10−2 mol·dm−3), temperature (from 298 to 328 K) and pH (2.6 to 10.3) apparently favor the uptake of Cs(I) by these two bark samples. The concentration dependence data obeyed Freundlich adsorption isotherm and the uptake follows first order rate law. Thermodynamic data evaluation and desorption experiments reveal the adsorption to be irreversible and endothermic in nature proceeding through ion-exchange and surface complexation for both dead biomasses. Both bark samples showed a fairly good radiation stability in respect of adsorption uptake of Cs(I) when irradiated with a 300 mCi (Ra-Be) neutron source having an integral neutron flux of ∼3.85·106 n·cm−2·s−1 and associated with a nominal γ-dose of ∼1.72 Gy·h−1.
