Oxygen pressure - thermodynamic equilibrium

Vapor pressures and vapor compositions in equilibrium with a hypostoichiometric plutonium dioxide condensed phase have been calculated for the temperature range 1500 I H 4000 K. Thermodynamic functions for the condensed phase and for each of the gaseous species were combined with an oxygen-potential model, which we extended from the solid into the liquid region to obtain the partial pressures of O2, 0, Pu, PuO and Pu02 as functions of temperature and of condensed phase composition. The calculated oxygen pressures increase rapidly as stoichiometry is approached. At least part of this increase is a consequence of the exclusion of Pu +... 

If one assumes that the reaction system is at thermodynamic equilibrium, the oxygen electrode method also allows one to infer the partial pressure of oxygen in equilibrium with the test solution. 

The hydrocarbon feedstock is reacted with a mixture of oxygen or air and steam in a sub-stoichiometric flame. In the fixed catalyst bed the synthesis gas is further equilibrated. The composition of the product gas will be determined by the thermodynamic equilibrium at the exit pressure and temperature, which is determined through the adiabatic heat balance based on the composition and flows of the feed, steam and oxygen added to the reactor. The synthesis gas produced is completely soot-free [28]. 

The formation of an oxide layer is thermodynamically favourable and kinetically rapid at room temperature, but as the temperature rises, the free energy of oxide formation (originally negative) increases to the point where the metal, oxide and oxygen are in equilibrium. At temperatures above this equilibrium value, and if the oxygen partial pressure is low enough, the oxide can decompose. 

Bevan and Anderson (32) deduced that adsorbed oxygen controlled the resistance of sintered zinc oxide at temperatures between 500°C and 1000°C. This conclusion was based on the observations that (1) the oxygen pressure had a reversible controlling effect on the resistance down to 500°C, too low a temperature for thermodynamic equilibrium to be... 

The relation between the non-stoichiometry and the equilibrium oxygen pressure mentioned in Section 1.1 can be deduced from the phase rule. For the purpose of the derivation of the phase rule, we shall review fundamental thermodynamics. Gibbs free energy G is defined by the relation... 

Fei O, called wiistite, has been studied from the viewpoints of thermodynamics and physicochemical properties. As mentioned in Section 1.1, stoichiometric FeO cannot be prepared under the usual conditions. Many investigators have studied the thermodynamic properties of wustite by use of various kinds of techniques. Here we introduce a study carried out by Fender and Rileywho used a solid electrolyte cell (see Section 1.4.8) to determine the equilibrium oxygen pressure Por The following cell was utilized,... 

A feed of 100 Ncm3 min-1 methane and 50 Ncm3 min-1 oxygen was introduced into the reactor at a pressure loss of < 2.5 mbar. The residence time of the reaction was 50 ms. 60% conversion was achieved along with a high carbon monoxide selectivity of 70% at 700 °C reaction temperature. Owing to the short residence times applied, no coke formation was observed and carbon monoxide selectivity was higher than expected from the thermodynamic equilibrium [46],... 

Careful analyses of the thermodynamic data of the praseodymium and terbium oxides led to the construction of their RCL-O2 phase diagrams (Hyde et al., 1966 Hyde and Eyring, 1965). The cerium oxides were studied by means of X-ray powder diffraction (Bevan, 1955) and the CeOx-02 phase diagram was constructed from equilibrium reaction studies at oxygen pressures down to 10-24 atm and temperatures up to 1200 °C (Bevan and Kordis, 1964 Ricken et al., 1984). It is worth to notice that the phase diagrams of Ce0x-02, PrCb-Cb, and Tb0x-02 systems... 

In semiconducting oxides such as iron-doped SrTi03 (e.g., SrTio.8Feo.2O3) the conductivity depends thermodynamically on the oxygen partial pressure. In the thermodynamic equilibrium a metal oxide exchanges lattice oxygen Oq with the ambient gas phase. 

The thermodynamic equilibrium is most favourable at high pressure and low temperature. The methanol synthesis process was developed at the same time as NH3 synthesis. In the development of a commercial process for NH3 synthesis it was observed that, depending on the catalyst and reaction conditions, oxygenated products were formed as well. Compared with ammonia synthesis, catalyst development for methanol synthesis was more difficult because selectivity is crucial besides activity. In the CO hydrogenation other products can be formed, such as higher alcohols and hydrocarbons that are thermodynamically favoured. Figure 2.19 illustrates this. 

Zirconia sensors have been used primarily in the exhaust system of automobiles to control the air-to-fuel ratio for meeting the federal requirements on such noxious gases as carbon monoxide, methane and nitrogen oxides. The applicability of zirconia sensors for this particular application is based on the assumption that, under thermodynamic equilibrium, the partial pressure of oxygen in the exhaust gas depends primarily on the air-to-fuel ratio. To compensate for the fact that in reality equilibrium is not reached, catalytic platinum electrics are incorporated in the zirconia sensor design [Stevens, 1986]. In the zirconia sensor, the outside of the zirconia tube is exposed to the exhaust gas while the inside is exposed to the ambient air as a reference atmosphere. 

Systems in which diffusion or chemical reaction is taking place at an appreciable rate are not in thermodynamic equilibrium, and consequently their state cannot be completely specified in a simple manner. Certain systems which are not in true equilibrium may nevertheless be treated by thermodynamic methods, provided the approach to equilibrium is so slow as to be undetectable over a considerable period of time. An instance of this type is represented by a mixture of hydrogen and oxygen gases under normal conditions of temperature and pressure. As mentioned earlier, reaction should take place with the formation of liquid water,... 

The Chreedimensional diagram obtained could serve both theoretical and technological computations concerning oxygen enrichment of air on K-clinoptilolite. It is a basis for determining of adsorption isobars, fictitious and real isotherms, as well as thermodynamic data for adsorption from binary C /Nj mixtures. Freundlich and Henry constants (for the real adsorption isotherms) correlated with the equilibrium concentration are useful for computation of the amounts adsorbed at arbitrary partial pressures and equilibrium concentrations. 

---