Vapor-liquid equilibrium composition diagram

Once the equilibrium total pressure has been computed for a given liquid composition using Eqs. 10.1-2 or 10.1-4, the equilibrium composition of the vapor can be calculated using Eqs. 10.1-1 or 10.1-3, as appropriate. Indeed, we can prepare a complete vapor-liquid equilibrium composition diagram, or x-y diagram, at constant temperature by choosing a collection of values for the composition of one of the phases, say the liquid-phase composition x, and then using the vapor pressure data to compute the... 

The vapor-liquid equilibrium compositions can also be shown on a distribution diagram (jc vs. ) as in Fig. 92b. Point P on the diagram represents the tie line DF, for example. Since the vapor is richer in the more volatile substance, the curve lies above the 45 diagonal line, which has been drawn in for comparison. 

Since the boiling point properties of the components in the mixture being separated are so critical to the distillation process, the vapor-liquid equilibrium (VLE) relationship is of importance. Specifically, it is the VLE data for a mixture which establishes the required height of a column for a desired degree of separation. Constant pressure VLE data is derived from boiling point diagrams, from which a VLE curve can be constructed like the one illustrated in Figure 9 for a binary mixture. The VLE plot shown expresses the bubble-point and the dew-point of a binary mixture at constant pressure. The curve is called the equilibrium line, and it describes the compositions of the liquid and vapor in equilibrium at a constant pressure condition. 

Thus, by knowing aAB from vapor-liquid equilibrium and by specifying xA, A can be calculated. Figure 4.3a also shows a typical vapor-liquid equilibrium pair, where the mole fraction of benzene in the liquid phase is 0.4 and that in the vapor phase is 0.62. A diagonal line across the x-y diagram represents equal vapor and liquid compositions. The phase equilibrium behavior shows a curve above the diagonal line. This indicates that benzene has a higher concentration in the vapor phase than toluene, that is,... 

The vapor-liquid x-y diagram in Figures 4.6c and d can be calculated by setting a liquid composition and calculating the corresponding vapor composition in a bubble point calculation. Alternatively, vapor composition can be set and the liquid composition determined by a dew point calculation. If the mixture forms two-liquid phases, the vapor-liquid equilibrium calculation predicts a maximum in the x-y diagram, as shown in Figures 4.6c and d. Note that such a maximum cannot appear with the Wilson equation. 

The three sets of vapor-liquid equilibrium data appearing on the x-y diagram show some disagreement, so that great accuracy cannot be expected from determination of tray requirements, particularly at the low water concentrations. The upper operating line in the first column is determined by the overall material balance so it passes through point (0.995, 0.995), but the initial point on the operating line is at x = 0.53, which is the composition of the reflux. The construction is shown for 50% vaporized feed. That result and those for other feed conditions are summarized ... 

Pressure has a marked effect on the azeotropic composition and vapor-liquid equilibrium diagrams of alcohol-ketone systems (J). This is due to the fact that the slopes of the vapor pressure curves of alcohols are appreciably greater than for ketones it results in an unusually larger change in the relative boiling points of the components of an alcohol-ketone system with change in pressure. 

Obtain (or plot from data) a phase diagram for the benzene/toluene system. Vapor-liquid equilibrium behavior of binary systems can be represented by a temperature-composition diagram at... 

Using the vapor-liquid equilibrium data, plot a y-x diagram. Draw a number of operating lines at a slope of 0.75. Note the composition at the 45° intersection, and step off seven plates on each to find the equilibrium value of the bottoms. Some of the results are tabulated in the following table ... 

Vapor-liquid equilibrium is a mapping from a liquid composition to a vapor composition. It can be done by including tie lines from one to the other for all compositions. On a line, such a mapping is very difficult to visualize, so we typically use a second dimension where we can plot vapor composition versus liquid composition as in a McCabe-Thiele plot or as in a temperature versus composition diagram. For three or four species, showing tie lines is fairly direct. The important point is that equilibrium is not a line (as we might think because of our familiarity with McCabe-Thiele plots) but a mapping. 

The separation process depends on the nature of the vapor-liquid equilibrium relationships of the system, which can be represented on a ternary diagram. Figure 10.3a shows a ternary diagram at some fixed system pressure. Components A and B are close boilers, and A forms an azeotrope with the entrainer E. The curves in the triangle represent liquid isotherms. A corresponding vapor isotherm (not shown) could be drawn to represent the vapor at equilibrium with each liquid curve with tie lines joining vapor and liquid compositions at equilibrium. The temperature of the isotherms reaches a minimum at point Z that corresponds to the composition of the azeotrope formed between A and E. 

Example 18.1. A mixture of 50 mole percent benzene and 50 mole percent toluene is subjected to flash distillation at a separator pressure of 1 atm. The vapor-liquid equilibrium curve and boiling-point diagram are shown in Figs. 18.2 and 18.3. Plot the following quantities, all as functions of f, the fractional vaporization (n) the temperature in the separator, b) the composition of the liquid leaving the separator, and (c) the composition of the vapor leaving the separator. 

For the analysis of distillation and other vapor-liquid separation processes one must estimate the compositions of the vapor and liquid in equilibrium. This topic is considered in detail in this chapter with particular reference to the preparation of mixture vapor-liquid equilibrium (VLE) phase diagrams, partial vaporization and condensation. calculations, and the use of vapor-liquid equilibrium ippasurements to,obtain infonnac-. 

Few liquid mixtures are ideal, so vapor-liquid equilibrium calculations can be more complicated than is the case for the hexane-triethylamine system, and the system phase diagrams can be more structured than Fig. 10.1-6. These complications arise from the (nonlinear) composition dependence of the species activity coefficients. For example, as a result of the composition dependence of y, the equilibrium pressure in a fixed-temperature experiment will no longer be a linear function of mole fraction. Thus nonideal solutions exhibit deviations from Raoult s law. We will discuss this in detail in the following sections of this chapter. However, first, to illustrate the concepts and some of the types of calculations that arise in vapor-liquid equilibrium in the simplest way, we will assume ideal vapor and liquid solutions (Raoult s law) here, and then in Sec. 10.2 consider the calculations for the more difficult case of nonideal solutions.. ... 

Note the difference between this method of calculation and the one used in the previous illustration. There we did vapor-liquid equilibrium calculations only for the conditions needed, and then solved the mass balance equations analytically. In this illustration we first had to do vapor-liquid equilibrium calculations for all compositions (to construct the. t- v diagram), and then for this binary mixture we were able to do all further calculations graphically. As shown in the following discussion, this makes it easier to consider other reflux ratios than the one u.sed in this illustration. 

The figure-that follows for the ethanol + water sy.s-tem is an unusual one in that it shows both vapor-liquid equilibrium and the enthalpy concentration diagrams on a single plot. This is done as follows. The lower collection of heavy lines give the enthalpy concentration data for the liquid at various temperatures and the upper collection of lines is the enthalpy-concentration data for the vapor, each at two pressures, 0.1013 and 1 013 bar. (There are also enthalpy-concentration lines for several other temperatures.) The middle collection of lines connect the equilibrium compositions of liquid and vapor. For example, at a pressure of 1.013 bar, a saturated-vapor containing 71 wt % ethanol with an enthalpy of 1535 kJ/kg is in equilibrium with a liquid containing 29 wt % ethanol with an enthalpy of 315 kJ/kg at a temperature of 85°C. Note also that the azeotropes that form in the ethanol -f water system are indicated at each pressure. 

In Figure 8.12 the outer envelope is the locus of saturated equimolar liquid states and saturated equimolar vapor states. However, note that Figure 8.12 is not a phase-equilibrium diagram in Figure 8.12 every point on the two-phase line represents an equimolar mixture, but phases in vapor-liquid equilibrium generally do not have the same composition. Consequently, Figure 8.12 contains no tie lines across the two-phase region. Outside the saturation envelope, the mixtures are stable one-phase fluids. Underneath that envelope, the mixtures may be metastable one-phase fluids or they may be unstable to one phase (that is, they may exist as two-phases). 

Figure 9.8 Pressure-temperature diagram for the alkane(l)-aromatic(2) mixture in Figures 9.4-9.7. Solid lines are pure vapor-pressure curves, ending at pure critical points (filled circles). Dashed line is the mixture critical line. Dash-dot lines are liquid constant-composition lines small dashed lines are vapor constant-composition lines. Filled square at A is a vapor-liquid equilibrium point it occurs at 14.5 bar, 386.7 K, Xj = 0.25, t/j = 0.75.

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