Phase pressure-composition

The breaking up of azeotropic mixtures. The behaviour of constant boiling point mixtures simulates that of a pure compound, because the composition of the liquid phase is identical with that of the vapour phase. The composition, however, depends upon the pressure at which the distillation is conducted and also rarely corresponds to stoichiometric proportions. The methods adopted in practice will of necessity depend upon the nature of the components of the binary azeotropic mixture, and include —... 

Separation operations achieve their objective by the creation of two or more coexisting zones which differ in temperature, pressure, composition, and/or phase state. Each molecular species in the mixture to be separated reacts in a unique way to differing environments offered by these zones. Consequently, as the system moves toward equilibrium, each species establishes a different concentration in each zone, and this results in a separation between the species. 

Figure 1. Ideal pressure-composition isotherms showing the hydrogen solid-solution phase, a, and the hydride phase, j3. The plateau marks the region of coexistence of the a and fl phases. As the temperature is increased the plateau narrows and eventually disappears at some consolule temperature...

There are few systematic guidelines which can be used to predict the properties of AB2 metal hydride electrodes. Alloy formulation is primarily an empirical process where the composition is designed to provide a bulk hydride-forming phase (or phases) which form, in situ, a corrosion— resistance surface of semipassivating oxide (hydroxide) layers. Lattice expansion is usually reduced relative to the ABS hydrides because of a lower VH. Pressure-composition isotherms of complex AB2 electrode materials indicate nonideal behaviour. 

Table II shows the "heats of formation" of the conjugate phases, that is, the excess enthalpies for mixing the appropriate amounts of water and amphiphile (at the same initial temperature and pressure as the final system) to make a unit amount of the conjugate phase. Values labeled "calorimeter" and "phase volume," respectively, are based on the same set of calorimetric titrations. In the former case the phase composition was taken from the calorimetric measurements, and in the latter case the composition was taken from our phase-volume compositions. Literature values for the heats of formation are based on data from references 13-16.

In part II of the present report the nature and molecular characteristics of asphaltene and wax deposits from petroleum crudes are discussed. The field experiences with asphaltene and wax deposition and their related problems are discussed in part III. In order to predict the phenomena of asphaltene deposition one has to consider the use of the molecular thermodynamics of fluid phase equilibria and the theory of colloidal suspensions. In part IV of this report predictive approaches of the behavior of reservoir fluids and asphaltene depositions are reviewed from a fundamental point of view. This includes correlation and prediction of the effects of temperature, pressure, composition and flow characteristics of the miscible gas and crude on (i) Onset of asphaltene deposition (ii) Mechanism of asphaltene flocculation. The in situ precipitation and flocculation of asphaltene is expected to be quite different from the controlled laboratory experiments. This is primarily due to the multiphase flow through the reservoir porous media, streaming potential effects in pipes and conduits, and the interactions of the precipitates and the other in situ material presnet. In part V of the present report the conclusions are stated and the requirements for the development of successful predictive models for the asphaltene deposition and flocculation are discussed. 

For a binary mixture under constant pressure conditions the vapour-liquid equilibrium curve for either component is unique so that, if the concentration of either component is known in the liquid phase, the compositions of the liquid and of the vapour are fixed. It is on the basis of this single equilibrium curve that the McCabe-Thiele method was developed for the rapid determination of the number of theoretical plates required for a given separation. With a ternary system the conditions of equilibrium are more complex, for at constant pressure the mole fraction of two of the components in the liquid phase must be given before the composition of the vapour in equilibrium can be determined, even for an ideal system. Thus, the mole fraction yA in the vapour depends not only on X/ in the liquid, but also on the relative proportions of the other two components. 

The pressure-temperature-composition diagram presented by Morey is shown in Fig. 8. The vapor pressure of pure water (on the P-T projection) terminates at the critical point (647 K, 220 bar). The continuous curve represents saturated solutions of NaCl in water, i.e., there is a three-phase equilibrium of gas-solution-solid NaCl. The gas-phase pressure maximizes over 400 bar at around 950 K. Olander and Liander s data for a 25 wt. % NaCl solution are shown, and T-X and P X projections given. At the pressure maximum, the solution phase contains almost 80% NaCl. 

Partial substitution of fluorine for oxygen in VO2 and V 2O5 has been achieved by treating these oxides with aqueous hydrofluoric acid under pressure. The new phases of composition V02. xFjc (for 0 < x < 0.2) and V205 Fj( (for 0 < X < 0.025) were obtained and characterized by X-ray diffraction studies. The oxide-fluoride bronze K0.25VO0.75F2.25 has been prepared from the high-temperature reaction of KVO3 and VF3 and the unit cell parameters have been determined. 

Figure 5.23 Pressure composition isotherms for critical temperature 7. The construction of the hydrogen absorption in atypical metal (left). The van t Hoff plot is shown on the right. The slope of solid solution (a-phase), the hydride phase the line is equal to the enthalpy of formation (p-phase) and the region ofthe coexistence ofthe divided by the gas constant and the intercept with two phases. The coexistence region is the axis is equal to the entropy of formation...

The thermodynamic aspects of hydride formation from gaseous hydrogen are described by means of pressure-composition isotherms in equilibrium (AG = 0). While the solid solution and hydride phase coexist, the isotherms show a flat plateau, the length of which determines the amount of H2 stored. In the pure P-phase, the H2 pressure rises steeply vfith increase in concentration. The two-phase region ends in a critical point T, above which the transition from the a- to the P-phase is continuous. The equilibrium pressure peq as a function of temperature is related to the changes AH° and AS° of enthalpy and entropy ... 

One of the most useful features of metal-hydrogen systems are their pressure-composition-temperature data, P-C-T. Such relationships for palladium-hydrogen are shown in Figure 1. For compositions and temperatures within the envelope, two solid phases coexist, as required by the phase rule. The lower hydrogen-content a-phase represents solution of hydrogen into the metal, and the higher hydrogen-content jS-phase is the hydride. Both a and (3 are... 

It has been shown that the two-phase pressure variation for palladium-hydrogen yields values of ASa— and AHa—/ , and that these values are closely temperature independent. The temperature independence results because the value of the integral in Equation 21 can be approximated closely by the corresponding relative partial value at the critical composition. Variations of ASg o and AHh—o with temperature (see Figure 6) are apparently too small to be detected in the plot of In /22(two-phase) against T ly but can be detected by the more sensitive plot of RT In P /2 against T or possibly could be detected by calorimetric determinations of AHa—over a wide temperature range. 

Typical pressure-composition isotherms for the LaNi5-H2 system are shown in Figure 2 (14). From plots of In Pplateau vs- 1 / T, several workers determined the experimental heats and entropies of Reaction 1. The enthalpies are the heats of formation for the /J-phase hydride from the a-phase hydrogen-saturated alloy (see Table I). 

Pressure-composition-temperature (P-C-T) relationships were reported for hydrogen and deuterium in a-titanium. Both systems obey Sieverts Law in the dilute region (10) i.e., the square root of equilibrium pressure is linearly proportional to the solute content. McQuillan (3) extended the hydrogen P-C-T data into the 7-phase. For a maximum equilibrium hydrogen pressure of 500... 

Figure 2—21 gives a typical pressure-composition diagram for a two-component mixture at a single temperature. Combinations of composition and pressure which plot above the envelope indicate conditions at which the mixture is completely liquid. Combinations of composition and pressure which plot below the envelope indicate conditions at which the mixture is gas. Any combinations of pressure and composition which plot within the envelope indicate that the mixture exists in two phases, gas and liquid. Bubble point and dew point have the same definitions as previously discussed. 

Gas chromatography involves chemical equilibria between phases to bring about a particular separation. Thus, a brief discussion of phase equilibria is pertinent at this point. Phase equilibria separations can be understood with the use of the second law of thermodynamics. The phase rule states that if we have a system of C components which are distributed between. P phases, the composition of each of these phases will be completely defined by C-l concentration terms. Thus, to have the compositions of P phases defined it is necessary to have P(C-l) concentration terms. The temperature and pressure also are variables and are the same for all the phases. Assuming no other forces influence the equilibria it follows that. 

Azeotropic and Partially Miscible Systems. Azeotropic mixtures are those whose vapor and liquid equilibrium compositions are identical. Their x-y lines cross or touch the diagonal. Partially miscible substances form a vapor phase of constant composition over the entire range of two-phase liquid compositions usually the horizontal portion of the x-y plot intersects the diagonal, but those of a few mixtures do not, notably those of mixtures of methylethylketone and phenol with water. Separation of azeotropic mixtures sometimes can be effected in several towers at different pressures, as illustrated by Example 13.6 for ethanol-water mixtures. Partially miscible constant boiling mixtures usually can be separated with two towers and a condensate phase separator, as done in Example 13.7 for n-butanol and water. 

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