Dew curve

In order to better demonstrate whether a system follows Raoult s law, a diagram of the phase equilibrium called T-x-y should be plotted. This plot (Figure 2) shows the equilibrium temperatures at which either a liquid solution will start bubbling (bubble curve) or a vapor mixture starts condensing (dew curve). The two systems with their experimental data and the calculation curve of the ideal solution is shown in Figure 2. In Figure 2, the system of hexane-benzene at the pressure of 101.33 kPa [10] and the system of ethylacetate-benzene [11] show negative deviations from RaoulTs law. 

If one is interested in finding the bubble and dew curves for an ideal solution at low to moderate pressures, then ... 

The essential features of vapor-liquid equilibrium (VLE) behavior are demonstrated by the simplest case isothermal VLE of a binary system at a temperature below the critical temperatures ofboth pure components. Forthis case ( subcritkaT VLE), each pure component has a well-defined vapor-liquid saturation pressure ff, and VLE Is possible for the foil range of liquid and vapor compositions xt and y,. Figure 1.5-1 ffiustrates several types of behavior shown by such systems. In each case, (he upper solid curve ( bubble curve ) represents states of saturated liquid (he lower solid curve ( dew curve ) represents states of saturated vtqtor. 

The phenomenon only occurs with mixtures of a certain composition. Above and below these limits the dew curves are quite normal. This is shown by the curves DC and OC5 in Fig. 92. C is the plait-point and the line joining the plait-points C2, C2, C4,.. 

Figure 2.3-2 (a) Vapor-liquid equilibrium of the system C02-toluene at 311 K. Experimental bubble points (O) and dew points ( ) are shown as a function of the pertinent composition. The bubble and dew curves are calculated with the Peng-Robinson equation of state, (b) Percent volumetric expansion of the liquid phase in the system C02-toluene at 298 K as a function of pressure. The curve was calculated with the Peng-Robinson equation of state. 

In Figure 9.5 we see that, except near the critical point, the slope of the bubble curve has the same sign as the slope of the dew curve. We now prove that this is usually the case. First, use Table 6.3 to write the Gibbs-Duhem equation for the fugacities in each phase ... 

For pure fluids, it is most common to represent the saturated vapor and saturated liquid transport properties as simple polynomial functions in temperature, although polynomials in density or pressure could also be used. Exponential expansions may be preferable in the case of viscosity (Bmsh 1962 Schwen Puhl 1988). For mixtures, the analogous correlation of transport properties along dew curves or bubble curves can be similarly regressed. In the case of thermal conductivity, it is necessary to add a divergent term to account for the steep curvature due to critical enhancement as the critical point is approached. Thus, a reasonable form for a transport property. 

Figure 6.30 shows the grand composite curve plotted from the problem table cascade in Fig. 6.186. The starting point for the flue gas is an actual temperature of 1800 C, which corresponds to a shifl ed temperature of (1800 — 25) = mS C on the grand composite curve. The flue gas profile is not restricted above the pinch and can be cooled to pinch temperature corresponding to a shifted temperature of 145 C before venting to the atmosphere. The actual stack temperature is thus 145 + 25= 170°C. This is just above the acid dew point of 160 C. Now calculate the fuel consumption ...

When the two components are mixed together (say in a mixture of 10% ethane, 90% n-heptane) the bubble point curve and the dew point curve no longer coincide, and a two-phase envelope appears. Within this two-phase region, a mixture of liquid and gas exist, with both components being present in each phase in proportions dictated by the exact temperature and pressure, i.e. the composition of the liquid and gas phases within the two-phase envelope are not constant. The mixture has its own critical point C g. 

With a further increase in the temperature the gas composition moves to the right until it reaches v = 1/2 at the phase boundary, at which point all the liquid is gone. (This is called the dew point because, when the gas is cooled, this is the first point at which drops of liquid appear.) An unportant feature of this behaviour is that the transition from liquid to gas occurs gradually over a nonzero range of temperature, unlike the situation shown for a one-component system in figure A2.5.1. Thus the two-phase region is bounded by a dew-point curve and a bubble-point curve. 

It has good capacity and drying capabiHty as illustrated by the vapor pressure curves in Figure 5. At 25°C, the dew point attainable in gases dried with 95% sulfuric acid is less than —75°C. 

Adsorption Plots. Isotherm plots are the most common method of presenting adsorption data. An isotherm is a curve of constant temperature the adsorbed water content of the adsorbent is plotted against the water partial pressure in equiHbrium with the adsorbent. An isostere plot shows curves of constant adsorbed water content the vapor pressure in equiHbrium with the adsorbent is plotted against temperature. Figure 13 shows isosteres for the three primary adsorbents described previously. In this case, the dew points for the three adsorbents are plotted at 0.5, 5, and 10 kg... 

The calculation for a point on the flash curve that is intermediate between the bubble point and the dew point is referred to as an isothermal-flash calculation because To is specified. Except for an ideal binary mixture, procedures for calculating an isothermal flash are iterative. A popular method is the following due to Rachford and Rice [I. Pet. Technol, 4(10), sec. 1, p. 19, and sec. 2, p. 3 (October 1952)]. The component mole balance (FZi = Vy, + LXi), phase-distribution relation (K = yJXi), and total mole balance (F = V + L) can be combined to give... 

A third fundamental type of laboratory distillation, which is the most tedious to perform of the three types of laboratory distillations, is equilibrium-flash distillation (EFV), for which no standard test exists. The sample is heated in such a manner that the total vapor produced remains in contact with the total remaining liquid until the desired temperature is reached at a set pressure. The volume percent vaporized at these conditions is recorded. To determine the complete flash curve, a series of runs at a fixed pressure is conducted over a range of temperature sufficient to cover the range of vaporization from 0 to 100 percent. As seen in Fig. 13-84, the component separation achieved by an EFV distillation is much less than by the ASTM or TBP distillation tests. The initial and final EFN- points are the bubble point and the dew point respectively of the sample. If desired, EFN- curves can be established at a series of pressures. 

The temperature coefficient curve is given in Figure 9.5(b). This is plotted on the assumption that the insulation resistance doubles for each I8°C reduction in temperature (above the dew point). 

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, yz is not linearly related to p, and a graph of p against yz is not a straight line. The graph of the vapor line, which is also known as the dew pressure curve, is shown in Figure 8.13 for (y C-C6HnCH3 + V2C-C6H12) as the lower curve at T= 308.15 K. 

If a mixture of benzene and toluene is heated in a vessel, closed in such a way that the pressure remains atmospheric and no material can escape and the mole fraction of the more volatile component in the liquid, that is benzene, is plotted as abscissa, and the temperature at which the mixture boils as ordinate, then the boiling curve is obtained as shown by ABCJ in Figure 11.5. The corresponding dew point curve ADEJ shows the temperature at which a vapour of composition y starts to condense. 

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