Temperature liquid-vapor equilibrium

TABLE 5-1.4.1 Approximate Vapor-Liquid Equilibrium Temperatures for LFL, LMIE, and UFL Vapor Concentrations at Atmospheric Pressure... 

The vapor-liquid equilibrium temperature for specified pressure and liquid composition is found as the solution to Eqs. 10.1-2 or, if the system is ideal, as the solution to Eq..10.1-4. However, since the temperature appears only implicitly in these equations through the species vapor pressures, and since there is a nonlinear relationship between the vapor pressure and temperature (cf. the Clausius-Clapeyron equation, Eq. 

Both of these configurations have better economics than a reactive distillation column when there is a mismatch between favorable reaction temperatures and favorable vapor-liquid equilibrium temperatures. 

Bibliography of vapor-liquid equilibrium data, primarily for systems at low temperatures. 

Using UNIQUAC, Table 2 summarizes vapor-liquid equilibrium predictions for several representative ternary mixtures and one quaternary mixture. Agreement is good between calculated and experimental pressures (or temperatures) and vapor-phase compositions. ... 

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... 

Unfortunately, many commonly used methods for parameter estimation give only estimates for the parameters and no measures of their uncertainty. This is usually accomplished by calculation of the dependent variable at each experimental point, summation of the squared differences between the calculated and measured values, and adjustment of parameters to minimize this sum. Such methods routinely ignore errors in the measured independent variables. For example, in vapor-liquid equilibrium data reduction, errors in the liquid-phase mole fraction and temperature measurements are often assumed to be absent. The total pressure is calculated as a function of the estimated parameters, the measured temperature, and the measured liquid-phase mole fraction. 

The computer subroutines for calculation of vapor-liquid equilibrium separations, including determination of bubble-point and dew-point temperatures and pressures, are described and listed in this Appendix. These are source routines written in American National Standard FORTRAN (FORTRAN IV), ANSI X3.9-1978, and, as such, should be compatible with most computer systems with FORTRAN IV compilers. Approximate storage requirements for these subroutines are given in Appendix J their execution times are strongly dependent on the separations being calculated but can be estimated (CDC 6400) from the times given for the thermodynamic subroutines they call (essentially all computation effort is in these thermodynamic subroutines). 

Propylene oxide is a colorless, low hoiling (34.2°C) liquid. Table 1 lists general physical properties Table 2 provides equations for temperature variation on some thermodynamic functions. Vapor—liquid equilibrium data for binary mixtures of propylene oxide and other chemicals of commercial importance ate available. References for binary mixtures include 1,2-propanediol (14), water (7,8,15), 1,2-dichloropropane [78-87-5] (16), 2-propanol [67-63-0] (17), 2-methyl-2-pentene [625-27-4] (18), methyl formate [107-31-3] (19), acetaldehyde [75-07-0] (17), methanol [67-56-1] (20), ptopanal [123-38-6] (16), 1-phenylethanol [60-12-8] (21), and / /f-butanol [75-65-0] (22,23). 

A tabulation of the partial pressures of sulfuric acid, water, and sulfur trioxide for sulfuric acid solutions can be found in Reference 80 from data reported in Reference 81. Figure 13 is a plot of total vapor pressure for 0—100% H2SO4 vs temperature. References 81 and 82 present thermodynamic modeling studies for vapor-phase chemical equilibrium and liquid-phase enthalpy concentration behavior for the sulfuric acid—water system. Vapor pressure, enthalpy, and dew poiat data are iacluded. An excellent study of vapor—liquid equilibrium data are available (79). 

For mixtures containing more than two species, an additional degree of freedom is available for each additional component. Thus, for a four-component system, the equihbrium vapor and liquid compositions are only fixed if the pressure, temperature, and mole fractious of two components are set. Representation of multicomponent vapor-hquid equihbrium data in tabular or graphical form of the type shown earlier for biuaiy systems is either difficult or impossible. Instead, such data, as well as biuaiy-system data, are commonly represented in terms of ivapor-liquid equilibrium ratios), which are defined by... 

By using vapor-liquid equilibrium data the above integral can be evaluated numerically. A graphical method is also possible, where a plot of l/(y - xj versus Xr is prepared and the area under the curve over the limits between the initial and fmal mole fraction is determined. However, for special cases the integration can be done analytically. If pressure is constant, the temperature change in the still is small, and the vapor-liquid equilibrium values (K-values, defined as K=y/x for each component) are independent from composition, integration of the Rayleigh equation yields ... 

It is essential to calculate, predict or experimentally determine vapor-liquid equilibrium data in order to adequately perform distillation calculations. These data need to relate composition, temperature, and system pressure. 

K-factors for vapor-liquid equilibrium ratios are usually associated with various hydrocarbons and some common impurities as nitrogen, carbon dioxide, and hydrogen sulfide [48]. The K-factor is the equilibrium ratio of the mole fraction of a component in the vapor phase divided by the mole fraction of the same component in the liquid phase. K is generally considered a function of the mixture composition in which a specific component occurs, plus the temperature and pressure of the system at equilibrium. 

The minimum number of trays necessary to debutanize the effluent from an alkylation reactor will be calculated. The feed, products, and vapor-liquid equilibrium costants of the key components at conditions of temperature and pressure corresponding to the top tray and reboiler are shown in Table 8-1. 

Haman, S. E. M. et al, Generalized Temperature-Dependent Parameters of the Redlich-Kwong of State for Vapor-Liquid Equilibrium Calculations, Ind. Eng. Chem. Process Des. Dev. 16, 1, (1977) p. 51. 

Several authors, notably Leland and co-workers (L2), have discussed vapor-liquid equilibrium calculations based on corresponding-states correlations. As mentioned in Section II, such calculations rest not only on the general assumptions of corresponding-states theory, but also on the additional assumption that the characterizing parameters for a mixture do not depend on temperature or density but are functions of composition only. Further, it is necessary clearly to specify these functions (commonly known as mixing rules), and experience has shown that if good results are to be obtained, these... 

Liquid and vapor are in equilibrium when the pressure of the vapor phase is the vapor pressure. When the (vapor + liquid) equilibrium mixture is exposed to the atmosphere, the mixture will boil at a temperature where the vapor pressure equals the external (atmospheric) pressure. This temperature is known as the boiling temperature. At the normal boiling temperature, the substance has a vapor pressure of exactly one atmosphere (0.101325 MPa) and hence, boils at this external pressure. 

The (vapor + liquid) equilibrium line for a substance ends abruptly at a point called the critical point. The critical point is a unique feature of (vapor + liquid) equilibrium where a number of interesting phenomena occur, and it deserves a detailed description. The temperature, pressure, and volume at this point are referred to as the critical temperature, Tc. critical pressure, pc, and critical volume, Vc, respectively. For COi, the critical point is point a in Figure 8.1. As we will see shortly, properties of the critical state make it difficult to study experimentally. 

The critical point is unique for (vapor + liquid) equilibrium. That is, no equivalent point has been found for (vapor + solid) or (liquid + solid) equilibria. There is no reason to suspect that any amount of pressure would eventually cause a solid and liquid (or a solid and gas) to have the same //m, Sm, and t/m. with an infinite o and at that point. mC02 was chosen for Figure 8.1 because of the very high vapor pressure at the (vapor + liquid + solid) triple point. In fact, it probably has the highest triple point pressure of any known substance. As a result, one can show on an undistorted graph both the triple point and the critical point. For most substances, the triple point is at so low a pressure that it becomes buried in the temperature axis on a graph with a pressure axis scaled to include the critical point. 

Traditionally, the binary interaction parameters such as the ka, kb, k, ki in the Trebble-Bishnoi EoS have been estimated from the regression of binary vapor-liquid equilibrium (VLE) data. It is assumed that a set of N experiments have been performed and that at each of these experiments, four state variables were measured. These variables are the temperature (T), pressure (P), liquid (x) and vapor (y) phase mole fractions of one of the components. The measurements of these variables are related to the "true" but unknown values of the state variables by the equations given next... 

Experimental values for the activity coefficients for components 1 and 2 are obtained from the vapor-liquid equilibrium data. During an experiment, the following information is obtained Pressure (P), temperature (T), liquid phase mole fraction (x, and x2=l-X ) and vapor phase mole fraction (yi and y2=l—yi). 

GRAYSON, H. G. and STREED, C. W. (1963) Proc. 6th World Petroleum Congress, Frankfurt, Germany, paper 20, Sec. 7, 233. Vapor-liquid equilibrium for high temperature, high pressure hydrogen-hydrocarbon systems. 

In the case of vapor-liquid equilibrium, the vapor and liquid fugacities are equal for all components at the same temperature and pressure, but how can this solution be found In any phase equilibrium calculation, some of the conditions will be fixed. For example, the temperature, pressure and overall composition might be fixed. The task is to find values for the unknown conditions that satisfy the equilibrium relationships. However, this cannot be achieved directly. First, values of the unknown variables must be guessed and checked to see if the equilibrium relationships are satisfied. If not, then the estimates must be modified in the light of the discrepancy in the equilibrium, and iteration continued until the estimates of the unknown variables satisfy the requirements of equilibrium. 

If the K-value requires the composition of both phases to be known, then this introduces additional complications into the calculations. For example, suppose a bubble-point calculation is to be performed on a liquid of known composition using an equation of state for the vapor-liquid equilibrium. To start the calculation, a temperature is assumed. Then, calculation of K-values requires knowledge of the vapor composition to calculate the vapor-phase fugacity coefficient, and that of the liquid composition to calculate the liquid-phase fugacity coefficient. While the liquid composition is known, the vapor composition is unknown and an initial estimate is required for the calculation to proceed. Once the K-value has been estimated from an initial estimate of the vapor composition, the composition of the vapor can be reestimated, and so on. 

Consider first, a binary mixture of two Components A and B the vapor-liquid equilibrium exhibits only a moderate deviation from ideality, as represented in Figure 4.4a. In this case, as pure A boils at a lower temperature than pure B in the temperature-composition... 

Example 4.5 2-Propanol (isopropanol) and water form an azeotropic mixture at a particular liquid composition that results in the vapor and liquid compositions being equal. Vapor-liquid equilibrium for 2-propanol-water mixtures can be predicted by the Wilson equation. Vapor pressure coefficients in bar with temperature in Kelvin for the Antoine equation are given in Table 4.113. Data for the Wilson equation are given in Table 4.126. Assume the gas constant R = 8.3145 kJ-kmol 1-K 1. Determine the azeotropic composition at 1 atm. 

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