Authors:A. F. Bykov, N. B. Morozova, I. K. Igumenov, and S. V. Sysoev
By means of a tensimetric flow method and a static method with a silica-membrane zero gauge, the dependence of vapour pressure on temperature was obtained for tris(2,4-pentanedionato)ruthenium(III), Ru(aa)3, and tris(1,1,1-trifluoropentane-2,4-dionato)ruthenium(III), Ru(tfa)3. The thermodynamic characteristics of vaporization and sublimation of these complexes were determined. The processes of thermal decomposition of the vapour of the compounds in vacuum, hydrogen and oxygen were investigated by using mass spectrometry in the temperature range 170–550‡C for Ru(aa)3 and 150–620‡C for Ru(tfa)3. The threshold temperatures of the stability of the vapour of the complexes and the rate constants of the thermolysis processes were determined. The main gaseous products of the thermal decomposition and the dependences of their composition on the presence of hydrogen and oxygen were established.
Authors:E. Filatov, S. Sysoev, Ludmila Zelenina, Tamara Chusova, V. Logvinenko, P. Semyannikov, and I. Igumenov
of a series of lithium β-diketonates: Li(dpm) (dpm=dipivaloylmethanate
(2,2,6,6-tetramethylheptane-3,5- dionate)), Li(pta) (pta=pivaloyltrifluoracetonate
(2,2-dimethyl-6,6,6-trifluoro-3,5-hexanedionate)), Li(tfa) (tfa=trifluoracetylacetonate
(1,1,1-trifluoro-2,4-pentandionate)), Li(hfa) (hfa=hexafluoracetylacetonate
(1,1,1,5,5,5-hexafluoro-2,4-pentandionate)) has been investigated. Gas phase
composition of these complexes has been established. Temperature dependences
of vapor pressure of lithium compounds were obtained by static and dynamic
methods, and thermodynamic parameters were calculated. Dependence of compound
volatility on ligand structure is shown. For Li(dpm) detailed investigation
has been done by differential scanning calorimetry (DSC).
Authors:Kseniya V. Zherikova, Ludmila N. Zelenina, Natalia B. Morozova, and Tamara P. Chusova
these compounds, determination of the fundamental quantitative thermodynamic data is the relevant problems for further efficient development of technological deposition processes. To this moment, vaporpressure data obtained for vaporization of the row
Radiolabeled morphine and cocaine vapors have been used to determine the approximate binding site densities of immobilized, airdried antibodies toward these substances. Vapor pressures of the radiolabeled substances have also been determined.
Authors:A. Hazra, K. Alexander, D. Dollimore, and A. Riga
The present study was aimed at determining the kinetics of evaporation and establishing vapor pressure curves for both single and multi-component systems by thermogravimetry (TG) and differential scanning calorimetry (DSC). Essential oils (e.g. lavender oil, orange oil, clove oil and eucalyptus oil, etc.) are typically multi-component systems consisting of various volatile pure components (e.g. linalyl acetate, limonene, cinnamaldehyde, etc.) which resemble single component systems. In this study linalyl acetate was taken as the calibration compound for TG. The vapor pressure curves for the pure substances were plotted using TG and vapor pressure plots for clove oil and eucalyptus oil were constructed using DSC. The thermodynamic and kinetic parameters of the pure compounds were compared to that of the multi-component systems to quantitatively and qualitatively measure the influence of different compounds on each other. The k-value from the vapor pressure data for linalyl acetate was calculated as 112006 Pa kg0.5mol0.5s-1 m-2 K-0.5. The vapor pressure values were used to determine the Antoine constants using the SPSS 10.0 software.
The heat, equilibrium, and kinetics of adsorption of 1-ethoxy-2-propanol vapours on granulated activated carbon were determined simultaneously by a reaction calorimeter SETARAM C80 D at T=298.15 K at various relative vapour pressures (0.1< p/ps<0.8). The adsorption isotherm was correlated by the Freundlich equation. It was observed that the enthalpies of adsorption decrease slightly with increasing of the relative vapour pressure of the adsorptive. The rate of adsorption were calculated from analysis of the heat flux signals and it was found that the mass-transfer coefficient for 1-ethoxy-2-propanol vapours in granulated activated carbon increased with increasing relative vapour pressure of the adsorptive.
Authors:G. Perlovich, Tatyana Volkova, and Annette Bauer-Brandl
The thermodynamic relationship between crystal modifications of paracetamol was studied by alternative methods. Temperature
dependence of saturated vapor pressure for polymorphic modifications of the drug paracetamol (acetaminophen) was mea sured
and thermodynamic functions of the sublimation process calculated. Solution calorimetry was carried out for the two modifications
in the same solvent. Thermodynamic parameters for sublimation for form I (monoclinic) were found: ΔGsub298=60.0 kJ mol−1; ΔHsub298=117.9�0.7 kJ mol−1; ΔSsub298=190�2 J mol−1 K−1. For the orthorhombic modification (form II), the saturated vapor pressure could only be studied at 391 K. Phase transition
enthalpy at 298 K, ΔHtr298(I→II)=2.0�0.4 kJ mol−1, was derived as the difference between the solution enthalpies of the noted polymorphs in the same solution (methanol). Based
on ΔHtr298 (I→II), differences between temperature dependencies of heat capacities of both modifications and the vapor pressure value
of form II at 391 K, the temperature dependence of saturated vapor pressure and thermodynamic sublimation parameters for modification
II were also estimated (ΔGsub298=56.1 kJ mol−1; ΔHsub298=115.9�0.9 kJ mol−1; ΔSsub298=200�3 J mol−1 K−1). The results indicate that the modifications are monotropically related, which is in contrast to findings recently reported
found by classical thermochemical methods.
Derivatograph Q-1500D was completed with a partial vapour pressure control unit in order to study the sorption phenomena. The proposed arrangement allows to perform time consuming experiments at ambient atmospheric pressure in the temperature range 10–200°C.
Authors:F. Chehimi-Moumen, P. Llewellyn, F. Rouquerol, G. Vacquier, D. Ben Hassen-Chehimi, M. Ferid, and M. Trabelsi-Ayadi
The aim of this work is the optimization of the preparation of anhydrous gadolinium hydrogen phosphate with good fluorescence
properties. The products obtained by dehydration of gadolinium hydrogen phosphate trihydrate depend on the conditions chosen
for the thermal treatment. For this reason, the dehydration was followed by Constant Rate Thermal Analysis whilst strictly
controlling the water vapour pressure above the sample. Intermediate samples, obtained during dehydration were characterised
by IR spectroscopy and X-ray diffraction. It has thus been shown that the thermal pathway taken for the dehydration depends
on the water vapour pressure above the sample in the region from 10-2to 5 mbar. Under the lowest water vapour pressure (510-3mbar), the elimination of the crystallization water is carried out in a continuous way and produces a quasi-amorphous intermediate.
Under higher water vapour pressure (5 mbar), well crystallized intermediate products are obtained. The results obtained suggest
that the trihydrate contains zeolitic water which confirms a prior structural study.
A calorimetric method for the study of solid-vapor interactions is described. In one calorimetric chamber a vapor evaporates;
in a second calorimetric chamber the vapor is absorbed by a sample. The two chambers are connected by a tube and form part
of a double twin microcalorimeter. As vapor is sorbed by the sample the vapor pressure in the sorption chamber will increase
from a low value to near saturation. The flow rate of the vapor is governed by diffusion through the tube between the vessels.
From the thermal power measured in the vaporization calorimeter it is possible to evaluate the sorption isotherm, and using
information from both calorimeters the heat of sorption may be calculated as a function of equilibrium vapor pressure. By
conducting experiments with different sized samples it is also possible to study the kinetics of the sorption process. The
paper describes some recent improvements of the technique and gives examples of its use.