Vapour diagram

When oil and gas are produced simultaneously into a separator a certain amount (mass fraction) of each component (e.g. butane) will be in the vapour phase and the rest in the liquid phase. This can be described using phase diagrams (such as those described in section 4.2) which describe the behaviour of multi-component mixtures at various temperatures and pressures. However to determine how much of each component goes into the gas or liquid phase the equilibrium constants (or equilibrium vapour liquid ratios) K must be known. 

Figure A2.5.1. Schematic phase diagram (pressure p versus temperature 7) for a typical one-component substance. The full lines mark the transitions from one phase to another (g, gas liquid s, solid). The liquid-gas line (the vapour pressure curve) ends at a critical point (c). The dotted line is a constant pressure line. The dashed lines represent metastable extensions of the stable phases.

Figure A2.5.11. Typical pressure-temperature phase diagrams for a two-component fluid system. The fiill curves are vapour pressure lines for the pure fluids, ending at critical points. The dotted curves are critical lines, while the dashed curves are tliree-phase lines. The dashed horizontal lines are not part of the phase diagram, but indicate constant-pressure paths for the T, x) diagrams in figure A2.5.12. All but the type VI diagrams are predicted by the van der Waals equation for binary mixtures. Adapted from figures in [3].

The boiling point increases regularly. The boiling point - composition diagram for such a system is shown in Fig. 1, 4, 2 (the complementary vapour pressure - composition diagram is depicted in Fig. I, 4, 3 for purposes of comparison only). Let us consider the behaviour of such a liquid pair upon distillation. If a solution of composition is heated, the vapour pressure will rise until at the point ij it is equal to the pressure of the atmosphere, and boiling commences at temperature The com-... 

To appreciate the action of a drying agent of class (a), let us imagine some anhydrous copper sulphate in an evacuated vessel provided with a pressure gauge, and water is allowed to enter slowly the temperature is assumed constant at 25°. The results may be best expressed by means of a vapour pressure - composition diagram (Fig. 7, 20, 1). The initial system is represented by the point A the pressure will rise along AB until the monohydrate CuS04,H20 commences to form at B. 

A one-component system (C = 1) has two independent state variabies (T and p). At the tripie point three phases (soiid, iiquid, vapour) coexist at equiiibrium, so P = 3. From the phase ruie f = 0, so that at the tripie point, T and p are fixed - neither is free but both are uniqueiy determined. If T is free but p depends on T (a sloping line on the phase diagram) then f = 1 and P = 2 that is, two phases, solid and liquid, say, co-exist at equilibrium. If both p and T are free (an area on the phase diagram) F = 2 and P = 1 only one phase exists at equilibrium (see Fig. A1.18). 

It is unnecessary to go to the lengths of calculating the oxygen or sulphur potentials of gas phases in order to use these diagrams in certain simple cases. Consider the oxidation of a metal by a hydrogen/water-vapour atmosphere. The reaction involved here is... 

Over the years, Pourbaix and his co-workers in the CEBELCOR Institute, founded under his direction, extended these diagrams by including lines for metastable compounds. Figure 7.66 illustrates such a presentation for the Fe-O system over the temperature range 830-2200 K. Pourbaix used these diagrams as a basis for a discussion of the stability of metallic iron (solid, liquid and vapour phases), the oxides of iron as a function of oxygen pressure and temperature from which he explained the protection of iron at high temperature by immunity and passivation. He also pointed out the... 

Free-energy-concentration diagrams have been used in the study of the thermodynamic influence on the non-stoichiometry of the solid titanium carbide deposited from H2-CH4-TiCl4 gas mixtures at 1 900 K. The authors show how, from the partial pressure measurements of Ti vapour over a range of... 

Figure 7.87 shows a AG -concentration diagram for Fe(j,-Zn( ). It was constructed from the experimental data shown in Table 7.37. The method of construction is described elsewhere. Figure 7.87 can now be used, by applying the constraints imposed by the tangency rule, to explain why in Fig. 7.88a and b, where the chemical potentials (shown in the diagram) of zinc vapour varied between 0 and - 1 - 81 kJ molthe total interaction surface layer consisted of T, T, 6, and flayers in Fig. 7.88c at a chemical potential only slightly lower ( — 2-11 kJmol ) only T and T, layers were present whilst at -2-55 kJ mol only a F outermost layer was formed. 

The micrographs in Fig. 7.88 show clearly how from a knowledge of the AG -concentration diagrams it is possible to select the exact reaction conditions for the production of tailor-made outermost surface phase layers of the most desired composition and thus of the optimum physical and chemical properties for a given system. In addition it shows that according to thermodynamics, there can be predictable differences in the composition of the same outermost phase layer prepared at the same conditions of temperature but under slightly different vapour pressures. 

A more informative diagram is the pressure-enthalpy chart which shows the liquid and vapour states of the fluid (Figure 2.6). In this diagram, a fluid being heated passes from the suhcooled state (a), reaches hoiling point (h) and is finally completely evaporated (c) and then superheated (d). The distance along the sector h-c shows the proportion which has heen evaporated at any enthalpy value. 

A diagram of a suitable apparatus is shown in Fig. 21.7. The mercury vapour is flushed out of the reaction vessel by bubbling argon through the solution, into the absorption tube. 

Metastable states are represented on the indicator diagram by the prolongations of the isotherms of homogeneous states beyond the intersections with the line of heterogeneous states. Thus, the productions of the liquid and vapour portions of the isotherm, Fig. 38, meet the heterogeneous parts of the isotherms d2y 03 at Q, P, respectively. At each of these points there are two conditions of existence possible for the system, thus ... 

If the temperatures corresponding with coexisting compositions of the two phases at constant pressure are represented on a diagram, one obtains two curves which may be called the T-liquid and T-vapour curves respectively. 

Fig. 12. Schematic representation of variations in dehydration rates (ft) with prevailing water vapour pressure (Ph2o) These examples include Smith—Topley behaviour and indicate correlations with phase stability diagrams. (After Bertrand et al. [596], reproduced with permission, from Journal of Inorganic and Nuclear Clemistry.)...

Figure 13.5. Humidity-enthalpy diagram for air-water vapour system at atmospheric pressure...

Figure 6.1 Diagram to show the essential components of a vapour phase osmometer...

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