Authors:N. Morozova, P. Semyannikov, S. Sysoev, V. Grankin, and I. Igumenov
The temperature dependency of the saturated vapor pressure of Ir(acac)3 has been measured by the method of calibrated volume (MCV), the Knudsen method, the flow transpiration method, and the membrane
method. The thermodynamic parameters of phase transition of a crystal to gas were calculated using each of these methods,
and the following values of ΔHT0 (kJ mol−1) and ΔST0 (J mol−1K−1), respectively, were obtained: MCV: 101.59, 156.70; Knudsen: 130.54, 224.40; Flow transpiration: 129.34, 212.23; Membrane:
Coprocessing of obtaining data (MCV, flow transportation method and Knudsen method) at temperature ranges 110−200C as also
conducted:ΔHT0 =127.92.1 (kJ mol−1 ); ΔST0 =215.25.0 (J mol−1 K−1 ).
Authors:U. Griesser, M. Szelagiewicz, U. Hofmeier, C. Pitt, and S. Cianferani
In order to determine the applicability of vapor pressure studies on polymorphic modifications, pairs of enantiotropically related modifications of caffeine, theophylline and carbamazepine were investigated. The studies were performed over a wide temperature range (71 to 191°C) and accordingly over a wide vapor pressure range (0.02 to 400 Pa) using an automatic instrument constructed on the basis of the gas saturation principle. This instrument enables an analytical determination of the main component and the impurities present by the chromatographic separation of the substances transported in the gas flow. Therefore, the real partial pressure of the main component can be measured. Due to the high precision of the applied method it was possible to determine partial pressure curves and the thermodynamic transition temperature — the point at which the vapor pressure of two crystal polymorphs is equal. The thermodynamic transition temperatures of caffeine and theophylline were determined to be 136 and 232°C, respectively. These values are in agreement with experimental or calculated values derived from DSC investigations but are more reliable. Vapor pressure measurements of carbamazepine are only meaningful in the low temperature range due to its decomposition at high temperatures. The thermodynamics, advantages and limits of vapor pressure determinations of polymorphic modifications are discussed.
Authors:V. Lazarev, J. Greenberg, Z. Ozerova, and G. Sharpataya
DSC and vapour pressure measurements are presented on some Be, Al and Cr complexes with 2,4-pentanedione tetramethyl-3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione and hexafluoro-2,4-pentanedione. Thermodynamic functions are given for the sublimation, vaporization and melting processes of the substances.
Authors:J. Rouland, S. Makki, J. Fournival, and R. Céolin
The sulfaguanidine—water (SG-H2O) system is a binary system with non-negligible vapour pressure which presents a monohydrate. The phase diagram of this system
is drawn from DTA experimental results, using the temperature-specific volume-molar fraction (T-v-x) model which was described in part I of this work.
The melting of the monohydrate (SG, H2O) is found to be congruent. Isochoric sections are drawn; they make it possible to determine the limits of the two eutectic
invariant planes. The composition and specific volume of the vapour phase at the eutectic equilibrium of theSG-SG, H2O subsystem are given. The triple line solid-liquid-vapour of the one-component phase diagram of the monohydrate is drawn.
The experimental results are consistent with the congruent melting of the monohydrate. These results also show that the solid,
liquid and vapour phase at the triple line have not the same composition.
A simplified approach was developed to estimate the vapor pressure of pure compounds from experimental data obtained by isothermal
thermogravimetric (TG) analysis. A numerical procedure was developed to estimate the Antoine parameters of the substance by
the analysis of isothermal TG data. The results of the experimental validations carried out evidenced that at least a preliminary
estimation of vapour pressures of pure substances by the analysis of TG data is possible. The limited time and the reduced
amounts of sample required for the experimental runs make the technique attractive with respect to the conventional and more
accurate techniques for vapor pressure assessment.
Authors:M. Muthukumar, Shekhar Kumar, P. Sinha, U. Mudali, and R. Natarajan
Tri-iso-amyl phosphate is an alternate solvent, proposed in literature as an alternate to the PUREX/UREX solvent tri-n-butyl
phosphate for better physical properties. Its PVT properties and accurate expression for estimation of its vapour pressure
are not available in the literature. Recently PVT properties of TiAP were estimated by authors and its vapour pressure was
measured in a ASTM certified vapor pressure measurement system at temperatures ranging from 273.15 to 373.15 K. In this paper,
results of these studies are presented.
Authors:M. Aizenberg, E. Fedoseev, S. Travnikov, A. Davydov, and B. Myasoedov
The temperature dependence of the vapour pressure of californium-249 hexafluoroacetylacetonate adducts with tributylphosphate /TBP/, tributylphosphineoxide /TBPO/ and dipropylsulphoxide /DPSO/ is determined. The enthalpy and entropy sublimation of the compounds are calculated.
Authors:Manuel Monte, Luís Santos, José Fonseca, and Carlos Sousa
The vapour pressures of six para-substituted benzoic acids were measured using the Knudsen effusion method within the pressure range (0.1–1 Pa) in the following
temperature intervals: 4-hydroxybenzoic acid (365.09–387.28) K; 4-cyanobenzoic acid (355.14–373.28) K; 4-(methylamino)benzoic
acid (359.12–381.29) K; 4-(dimethylamino)benzoic acid (369.29–391.01) K; 4-(acetylamino)benzoic acid (423.10–443.12) K; 4-acetoxybenzoic
acid (351.28–373.27) K. From the temperature dependence of the vapour pressure, the standard molar enthalpy, entropy and Gibbs
energy of sublimation, at the temperature 298.15 K, were derived for each of the studied compounds using estimated values
of the heat capacity differences between the gaseous and the crystalline phases. Equations for estimating the vapour pressure
of para substituted benzoic acids at the temperature of 298.15 K are proposed.
The kinetics of the thermal dehydration of yttrium formate dihydrate was studied by means of isothermal gravimetry under various water vapour pressures from 5×10−4 to 8 torr. On the whole, the dehydration was described as the three dimensional phase boundary reaction, R3. An unusual dependence of the rate of dehydration on the atmospheric water vapour pressure was observed: with increasing water vapour pressure, the rate increased at first, passed through a maximum, and then decreased gradually to a constant value. These phenomena were similar to the Smith-Topley effect. The mechanism of the phenomena can be described on the basis of the crystallinity of the dehydrated product phase.