Phase equilibria binary vapor-liquid

Figure 4.24 shows the reactive arheotrope trajectories according to Eq. (83) for various amounts of the liquid phase mass transfer resistance - that is, for various values of Kiiq and a low sweep gas flow rate G (at large NTt/ -values). As a result, the reactive arheotropic composition X, 02 is shifted to larger values as the liquid phase mass transfer resistance becomes more important - that is, as the value of Kuq decreases. Note that the interface liquid concentrations are in equilibrium with the vapor phase bulk concentrations. Therefore, gas phase mass transfer resistances cannot have any influence on the position of the reactive arheotrope compositions. On the other hand, liquid phase mass transfer resistances do have an effect, though the value of all binary hiq have been set equal. Again, this effect results from the competition between the diffusion fluxes and the Stefan flux in the liquid phase. 

FIG. 13-18 Typical binary equilibrium curves. Curve A, system with normal volatility. Curve B, system with homogeneous azeotrope (one liquid phase). Curve C, system with heterogeneous azeotrope (two liquid phases in equilibrium with one vapor phase). 

UST/VIG4] Ustyugov, G. P., Vigdorovich, E. N., Bezobrazov, E. G., Liquid-vapor phase equilibrium in binary systems of tellurium with impurities, Inorg. Mater., 5, (1969), 300-301. Cited on page 183. 

Lam, D.H., Jangkamolkulchai, A. and Luks, K.D. (1990) Liquid-liquid-vapor phase equilibrium behavior of certain binary ethane + n-alkanol mixtures. Fluid Phase Equilibria, 59, 263-277. 

Lam, D.H., JangkamoUculchai, A. and Luks, K.D. (1990) Liquid-liquid-vapor phase equilibrium behavior of certain binary carbon dioxide + n-alkanol mixtures. Fluid Phase Equilibria, 60,131-141. Gurdial, G.S., Foster, N.R., Jimmy Yun, S.L. and Tilly, KJ3. (1993) Phase behavior of supercritical fluid-entrainer systems, in Siqtercritical Fluid Engineering Science, Fundamentals and Applications, E. Kiran and JJ. Brennecke (Eds.), ACS Symposium Series No. 514, pp. 34-45. 

Another common way of representing a binary liquid-vapor equilibrium is through a temperature-composition phase diagram, in which the pressure is held fixed and phase coexistence is examined as a function of temperature and composition. Figure 9.13 shows the temperature-composition phase diagram for the benzene-toluene system at a pressure of 1 atm. In Figure 9.13, the lower curve (the boiling-point curve)... 

We need to examine the effects of changes in temperature on the composition of a binary solution in equilibrium with the vapor phase. The situation is somewhat complicated because the composition of the two phases, as well as the total pressure, is altered with temperature changes. For, an increase in T favors the evaporation of the more volatile component, thereby enriching the gas phase and depleting the liquid phase of this component. Thus, both x,- and x/ are changed, even though the overall composition of the closed system remains the same. To simplify matters we impose the additional restriction that the total pressure remain fixed. This may be done in principle by use of a moveable piston. We now invoke the equilibrium constraint for each species /i,(g) = Mi(0. Then, according to Eqs. (2.4.15) and (2.5.1),... 

Tsirlin, Yu. A. Vasileva, V. A. Liquid-vapor phase equilibrium of the binary furfuryl aleohol - tetrahy-drofurfuryl aleohol mixture at redueed pressures [Russ]. Zh. Prikl. Khim. (Leningrad) 1973, 46, 232-234. 

Two additional illustrations are given in Figures 6 and 7 which show fugacity coefficients for two binary systems along the vapor-liquid saturation curve at a total pressure of 1 atm. These results are based on the chemical theory of vapor-phase imperfection and on experimental vapor-liquid equilibrium data for the binary systems. In the system formic acid (1) - acetic acid (2), <() (for y = 1) is lower than formic acid at 100.5°C has a stronger tendency to dimerize than does acetic acid at 118.2°C. Since strong dimerization occurs between all three possible pairs, (fij and not... 

In Equation (24), a is the estimated standard deviation for each of the measured variables, i.e. pressure, temperature, and liquid-phase and vapor-phase compositions. The values assigned to a determine the relative weighting between the tieline data and the vapor-liquid equilibrium data this weighting determines how well the ternary system is represented. This weighting depends first, on the estimated accuracy of the ternary data, relative to that of the binary vapor-liquid data and second, on how remote the temperature of the binary data is from that of the ternary data and finally, on how important in a design the liquid-liquid equilibria are relative to the vapor-liquid equilibria. Typical values which we use in data reduction are Op = 1 mm Hg, = 0.05°C, = 0.001, and = 0.003... 

VPLQFT is a computer program for correlating binary vapor-liquid equilibrium (VLE) data at low to moderate pressures. For such binary mixtures, the truncated virial equation of state is used to correct for vapor-phase nonidealities, except for mixtures containing organic acids where the "chemical" theory is used. The Hayden-0 Connell (1975) correlation gives either the second virial coefficients or the dimerization equilibrium constants, as required. 

To express the composition of the vapor in equilibrium with the liquid phase of a binary liquid mixture, we first note that the definition of partial pressure (PA = xAP for component A) and Dalton s law (P = PA + PB) allow us to express the composition of the vapor of a mixture of liquids A and B in terms of the partial pressures of the components ... 

In contrast to the Gibbs ensemble discussed later in this chapter, a number of simulations are required per coexistence point, but the number can be quite small, especially for vapor-liquid equilibrium calculations away from the critical point. For example, for a one-component system near the triple point, the density of the dense liquid can be obtained from a single NPT simulation at zero pressure. The chemical potential of the liquid, in turn, determines the density of the (near-ideal) vapor phase so that only one simulation is required. The method has been extended to mixtures [12, 13]. Significantly lower statistical uncertainties were obtained in [13] compared to earlier Gibbs ensemble calculations of the same Lennard-Jones binary mixtures, but the NPT + test particle method calculations were based on longer simulations. 

Mackay, D., Shiu, W.Y., Wolkoff, A.W. (1975) Gas chromatographic determination of low concentrations of hydrocarbons in water by vapor phase extraction. ASTM STP 573, pp. 251-258, Am. Soc. Testing and Materials, Philadelphia, Pennsylvania. Macknick, A.B., Prausnitz, J.M. (1979) Vapor pressures of high-molecular-weight hydrocarbons.. /. Chem. Eng. Data 24, 175-178. Mac/ynski. A., Wioeniewska-Goclowska, B., Goral, M. (2004) Recommended liquid-liquid equilibrium data. Part 1. Binary alkane-water systems. J. Phys. Chem. Ref. Data 33, 549-577. 

Separation systems include in their mathematical models various vapor-liquid equilibrium (VLE) correlations that are specific to the binary or multicomponent system of interest. Such correlations are usually obtained by fitting VLE data by least squares. The nature of the data can depend on the level of sophistication of the experimental work. In some cases it is only feasible to measure the total pressure of a system as a function of the liquid phase mole fraction (no vapor phase mole fraction data are available). 

A procedure is presented for correlating the effect of non-volatile salts on the vapor-liquid equilibrium properties of binary solvents. The procedure is based on estimating the influence of salt concentration on the infinite dilution activity coefficients of both components in a pseudo-binary solution. The procedure is tested on experimental data for five different salts in methanol-water solutions. With this technique and Wilson parameters determined from the infinite dilution activity coefficients, precise estimates of bubble point temperatures and vapor phase compositions may be obtained over a range of salt and solvent compositions. 

Basically, DESIGNER can use different physical property packages that are easy to interchange with commercial flowsheet simulators. For the case considered, the vapor-liquid equilibrium description is based on the UNIQUAC model. The liquid-phase binary diffusivities are determined using the method of Tyn and Calus (see Ref. 72) for the diluted mixtures, corrected by the Vignes equation (57), to account for finite concentrations. The vapor-phase diffusion coefficients are assumed constant. The reaction kinetics parameters taken from Ref. 202 are implemented directly in the DESIGNER code. 

The vapor pressures of pure liquids A and B at 300 K are 200 and 500 mm Hg, respectively. Calculate the mole fractions in the vapor and the liquid phases of a solution of A and B when the equilibrium total vapor pressure of the binary liquid solution is 350 mm Hg at the same temperature. Assume that the liquid and vapor phases are ideal. 

Ternary System. The values of all binary parameters used in predicting the ternary data are shown in Table IV. The predicted values of the vapor-liquid equilibrium data—i.e.9 the boiling point, and the composition of the vapor phase, y, for given values of the liquid composition, x, are presented in Tables V, VI, and VII. Also shown are the measured boiling points for the given values of the liquid composition. The RMSD value between the predicted and measured boiling points for the systems water-ethanol-l-propanol, water-ethanol-2-methyl-l-propanol, and water-ethanol-2-methyl-l-butanol are 0.23°C, 0.69°C, and 2.14°C. It seems therefore that since the NRTL equation successfully predicts temperature, the predicted values of y can be accepted confidently. 

A binary mixture of mole fraction zi is flashed to conditions T and P. For one of the following detemiine the equilibrium mole fractions x and yi of the liquid and vapor phases fomied, the molar fraction V of the vapor formed, and the fractional recovery TZ of species 1 in the vapor phase (defined as the ratio for species 1 of moles in the vapor to moles in the feed). Assume that Raoult s law applies. 

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