Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry.

RATIONALE: CeO2 -WO3 and CeO2 -MoO3 catalysts have shown excellent performance in the selective reduction of NOx by ammonia (NH3 -selective catalytic reduction) over a wide temperature range. Strong interaction between CeO2 and WO3 or MoO3 might be the dominant reason for the high activity of these mixed oxides. Studies of ceria-containing gaseous salts involve considerable experimental difficulties, since the transition of such salts to vapor requires high temperatures. To predict the possibility of the existence of gaseous associates formed by cerium and molybdenum (tungsten) oxides it is important to know their thermodynamic characteristics. Until the present investigation, gaseous cerium oxyacid salts were unknown. METHODS: Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species and the equilibrium constants of gas-phase reactions, as well as the formation and atomization enthalpies of gaseous cerium molybdates and tungstates. CeO2 was evaporated from molybdenum and tungsten effusion cells containing gold metal as a pressure standard. A theoretical study of gaseous cerium gaseous molybdates and tungstates was performed by several quantum chemical methods. RESULTS: In the temperature range 2050-2400 K, CeO, CeO2 , XO2 , XO3 , CeWO3 , CeXO4 , CeXO5 (X = Mo, W) and CeMo2 O7 were found to be the main vapor species over the CeO2 - Mo (W) systems. On the basis of the equilibrium constants of the gaseous reactions, the standard formation enthalpies of gaseous CeWO3 , CeXO4 , CeXO5 (X = Mo, W) and CeMo2 O7 at 298 K were determined. Energetically favorable structures of gaseous cerium salts were found and vibrational frequencies were evaluated in the harmonic approximation. CONCLUSIONS: The thermal stability of gaseous cerium oxyacid salts was confirmed by high-temperature mass spectrometry. Reaction enthalpies of the gaseous cerium molybdates and tungstates from gaseous cerium, molybdenum and tungsten oxides were evaluated theoretically and the obtained values are in reasonable agreement with the experimental one.

Thermodynamic properties of the La2 O3 -ZrO2 system by Knudsen effusion mass spectrometry at high temperature.

RATIONALE: Zirconia doped with a lanthanum oxide system is of high interest due to its exceptional thermal stability for the development of high-performance ceramics. It possesses the beneficial properties of pure zirconia, such as heat resistance, mechanical strength and inertness, but also eliminates its main disadvantage, i.e. brittleness. At high temperatures, components of such systems may vaporize selectively, leading to significant change in composition, and hence, the thermal resistance, phase stability and performance of the ceramic materials. Therefore, information on the vaporization processes and thermodynamic properties of the La2 O3 -ZrO2 system is of great importance. METHODS: Knudsen effusion mass spectrometry was used to study the vaporization processes and thermodynamic properties of solid solutions in the La2 O3 -ZrO2 system at 2110 K. Pure La2 O3 was used as a reference substance. Comprehensive characterization of the precursors and ceramics was performed via SEM, STA, XRD and PSD analysis. RESULTS: Zirconia-doped lanthania precursor powders and ceramics with La2 O3 of 33.3, 50, 70 and 90 mol.% content were manufactured by solid-state synthesis and the original cryochemical technique. La, LaO, ZrO and ZrO2 were found to be the main vapor species over the samples studied. The activities and thermodynamic properties of La2 O3 were calculated. Via XRD analysis it was shown that the phase composition of xLa2 O3 -(100-x)ZrO2 powders (x = 0.33, 0.5, 0.7 and 0.9 mol. fraction) significantly depends on the synthesis technique chosen. CONCLUSIONS: According to the XRD results combined with Rietveld refinement of the patterns, 33.3 La2 O3 -66.7 ZrO2 ceramics after solid-state synthesis are composed of well-formed cubic pyrochlore-type La2 Zr2 O7 with 5 wt.% admixture of monoclinic and cubic ZrO2 whereas 33.3 La2 O3 -66.7 ZrO2 precursor powders after cryochemical synthesis correspond to low-crystalline La(OH)3 . The components of the La2 O3 -ZrO2 system evaporate separately: there is no temperature range where lanthanum and zirconium gaseous species are present together. It was found that the activities of lanthania have low negative deviation from the ideal case.

Formation and thermodynamics of gaseous germanium and tin vanadates: a mass spectrometric and quantum chemical study.

The stabilities of gaseous germanium and tin vanadates were confirmed by high temperature mass spectrometry, and its structures were determined by quantum chemical calculations. A number of gas-phase reactions involving these gaseous salts were studied. On the basis of the equilibrium constants, the standard formation enthalpies of gaseous GeV2O6 (-1520 ± 42 kJ mol(-1)) and SnV2O6 (-1520 ± 43 kJ mol(-1)) were determined at a temperature of 298 K.

High-temperature mass spectrometric study and modeling of thermodynamic properties of binary glass-forming systems containing Bi2O3.

RATIONALE: Binary glass-forming systems containing bismuth(III) oxide, especially the Bi2O3-SiO2 system, are of great importance in modern materials science: preparation of thin films, fiber optics, potential solar converters, and radiation shields in nuclear physics. Information on vaporization processes and thermodynamic properties obtained in the present study and the results of modeling of this system will be useful for optimization of the synthesis and applications of Bi2O3-containing materials at high temperatures. METHODS: High-temperature Knudsen effusion mass spectrometry was used to study the vaporization processes and to determine the partial pressures of components of the Bi2O3-SiO2 system. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two iridium-plated molybdenum effusion cells containing the sample under study and pure bismuth(III) oxide (reference substance). Modeling of the thermodynamic properties and structure of glasses and melts in the Bi2O3-SiO2 and Bi2O3-B2O3 systems was performed using a modified approach based on the generalized lattice theory of associated solutions (GLTAS). RESULTS: At a temperature of 1000 K, Bi and O2 were found to be the main vapor species over the samples studied. The Bi2O3 activity as a function of composition of the Bi2O3-SiO2 system was obtained from the measured partial pressures of the vapor species. The thermodynamic properties of mixing from oxides in this system were calculated. The advantages of GLTAS for modeling of glasses and melts in the binary systems containing Bi2O3 were demonstrated. CONCLUSIONS: The thermodynamic functions of mixing in glasses and melts of the Bi2O3-SiO2 system determined at 1000 K in the present study, as well as in the Bi2O3-B2O3 system, demonstrated negative deviations from ideality. Modeling of the obtained experimental data using GLTAS allowed a correlation to be found between the thermodynamic properties and the relative number of bonds of various types formed in the glasses and melts of these systems.

High-temperature mass spectrometric study of the vaporization processes and thermodynamic properties of melts in the PbO-B2O3-SiO2 system.

RATIONALE: The unique properties of the PbO-B2O3-SiO2 system, especially its extensive range of glass-forming compositions, make it valuable for various practical applications. The thermodynamic properties and vaporization of PbO-B2O3-SiO2 melts are not well established so far and the data obtained on these will be useful for optimization of technology and thermodynamic modeling of glasses. METHODS: High-temperature Knudsen effusion mass spectrometry was used to study vaporization processes and to determine the partial pressures of components of the PbO-B2O3-SiO2 melts. Measurements were performed with a MS-1301 mass spectrometer. Vaporization was carried out using two quartz effusion cells containing the sample under study and pure PbO (reference substance). Ions were produced by electron ionization at an energy of 25 eV. To facilitate interpretation of the mass spectra, the appearance energies of ions were also measured. RESULTS: Pb, PbO and O2 were found to be the main vapor species over the samples studied at 1100 K. The PbO activities as a function of the composition of the system were derived from the measured PbO partial pressures. The B2O3 and SiO2 activities, the Gibbs energy of formation, the excess Gibbs energy of formation and mass losses in the samples studied were calculated. CONCLUSIONS: Partial pressures of the vapor species over PbO-B2O3-SiO2 melts were measured at 1100 K in the wide range of compositions using the Knudsen mass spectrometric method. The data enabled the PbO, B2O3, and SiO2 activities in these melts to be derived and provided evidence of their negative deviations from ideal behavior.

Thermodynamic study of gaseous vanadium phosphates by high-temperature mass spectrometry.

Knowledge of the structures of gaseous oxyacid salts of the M(m) XO(n) type is of interest for understanding the nature of chemical bonds. Gaseous VPO(2) and VPO(3) have been identified by Knudsen effusion mass spectrometry during the vaporization of mixtures of V(2)O(3) and alkali earth phosphates from molybdenum and tungsten effusion cells. The structures and molecular parameters of the gaseous vanadium phosphates under study were determined using quantum chemical calculations. On the basis of equilibrium constants measured for gas-phase reactions, the standard formation enthalpies were determined to be -273 ± 17 and -615 ± 16 kJ·mol(-1) for VPO(2) and VPO(3), respectively.

High-temperature mass spectrometric study of the vaporization processes of V2O3 and vanadium-containing slags.

A Knudsen effusion mass spectrometric method was used to study the vaporization processes and thermodynamic properties of pure V(2)O(3) and 14 samples of vanadium-containing slags in the CaO-MgO-Al(2)O(3)-SiO(2) system in the temperature range 1875-2625 K. The system was calibrated using gold in the liquid state as the standard. Vaporization was carried out from double tungsten effusion cells. First it was shown that, in vapor over V(2)O(3) and the vanadium-containing slags in the temperature range 1875-2100 K, the following vapor species were present: VO(2), VO, O, WO(3) and WO(2), with the latter two species being formed as a result of interaction with the tungsten crucibles. The temperature dependencies of the partial pressures of these vapor species were obtained over V(2)O(3) and the slags. The ion current comparison method was used for the determination of the V(2)O(3) activities in slags as a function of temperature with solid V(2)O(3) as a reference state. The V(2)O(3) activity coefficients in the slags under investigation indicated positive deviations from ideality at 1900 K and a tendency to ideal behavior at 2100 K. It was shown that the V(2)O(3) activity as a function of the slag basicity decreased at 1900 K and 2000 K and was practically constant in the slag melts at 2100 K. The results are expected to be valuable in the optimization of slag composition in high-alloy steelmaking processes as well as for their environmental implications.

Thermodynamic properties of the gaseous gallium molybdates and tungstates.

A number of gaseous oxyacid salts have been identified by Knudsen effusion mass spectrometry by vaporizing Ga(2)O(3) from molybdenum and tungsten cells. The stability of gaseous molecules Ga(2)MoO(4), Ga(2)WO(4), Ga(2)Mo(2)O(7), and Ga(2)W(2)O(7) was deduced from the measurements. The structures and molecular parameters of all salts investigated were obtained using quantum chemical calculations. On the basis of equilibrium constants measured for gas-phase reactions, the standard formation enthalpies were determined to be -827 +/- 26, -843 +/- 26, -1578 +/- 32, and -1525 +/- 34 kJ.mol(-1) for Ga(2)MoO(4), Ga(2)WO(4), Ga(2)Mo(2)O(7), and Ga(2)W(2)O(7), respectively.

High-temperature mass spectrometric study of the vaporization processes in the system CaO-MgO-Al2O3-Cr2O3-FeO-SiO2.

Knudsen effusion mass spectrometry was used to study vaporization processes and thermodynamic properties of twenty samples of chromium-containing slags in the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 system in the temperature range 1850-2750 K. Tungsten cells were used and Cr2O3 solid was used as a reference material. The system was calibrated using liquid gold. As FeO was the first emanating vapor species, monitoring of the chromium-containing species could be carried out only after the complete vaporization of FeO. This, however, was found to have very little impact on the concentration of the slags investigated. During the measurements, the ion current intensities of CrO+ and CrO2+ species in the mass spectra of the vapor over the CaO-MgO-Al2O3-Cr2O3-FeO-SiO2 samples were monitored and compared with those corresponding to solid Cr2O3. Data on the partial pressures of vapor species as well as the activities of Cr2O3 as a function of temperature were obtained. The results are expected to be valuable in the optimization of slag composition in high alloy steelmaking processes.

Thermodynamic study of some chromium-containing gaseous molecules by high-temperature mass spectrometry.

A number of gaseous oxyacid salts have been identified by Knudsen effusion mass spectrometry, while vaporizing Cr(2)O(3) and mixtures of Cr(2)O(3)+Nb(2)O(5), Cr(2)O(3)+Ta(2)O(5), Cr(2)O(3)+BaO, and Cr(2)O(3)+Mg(2)P(2)O(7) from molybdenum and tungsten cells. The stabilities of the gaseous molecules CrMoO(3), CrMoO(4), CrMoO(5), CrWO(3), CrWO(4), CrWO(5), CrNbO(3), CrTaO(3), CrPO(2), CrPO(3), BaCrO(2) and BaCrO(3) were deduced from the measurements. The thermodynamic properties of this gaseous chromium-containing species are summarized. Prediction is tentatively made of the stability of as-yet unstudied gaseous molecules.