Computing phase equilibria

Oellrich L, Plocker U, Prausnitz J.M and Knapp H (1981) Equation-of-state Methods for Computing Phase Equilibria and Enthalpies, Int Chem Eng, 21(1) 1. 

Thanos Panagiotopoulos developed an ingenious method to compute phase equilibria of fluids. The basic idea is to simultaneously simulate samples of two bulk phases in equiUbrium. 

For multicomponent mixtures, graphical representations of properties, as presented in Chapter 3, cannot be used to determine equilibrium-stage requirements. Analytical computational procedures must be applied with thermodynamic properties represented preferably by algebraic equations. Because mixture properties depend on temperature, pressure, and phase composition(s), these equations tend to be complex. Nevertheless the equations presented in this chapter are widely used for computing phase equilibrium ratios (K-values and distribution coefficients), enthalpies, and densities of mixtures over wide ranges of conditions. These equations require various pure species constants. These are tabulated for 176 compounds in Appendix I. By necessity, the thermodynamic treatment presented here is condensed. The reader can refer to Perry and Chilton as well as to other indicated sources for fundamental classical thermodynamic background not included here. 

In modern separation design, a significant part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Enthalpy estimates are important not only for determination of heat loads, but also for adiabatic flash and distillation computations. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the Gibbs-Helmholtz equation. ... 

Given the estimate of the reactor effluent in Example 4.2 for fraction of methane in the purge of 0.4, calculate the.actual separation in the phase split assuming a temperature in the phase separator of 40°C. Phase equilibrium for this mixture can be represented by the Soave-Redlich-Kwong equation of state. Many computer programs are available commercially to carry out such calculations. 

The N equations represented by Eq. (4-282) in conjunction with Eq. (4-284) may be used to solve for N unspecified phase-equilibrium variables. For a multicomponent system the calculation is formidable, but well suited to computer solution. The types of problems encountered for nonelectrolyte systems at low to moderate pressures (well below the critical pressure) are discussed by Smith, Van Ness, and Abbott (Introduction to Chemical Engineering Thermodynamics, 5th ed., McGraw-Hill, New York, 1996). 

Availability of large digital computers has made possible rigorous solutions of equilibrium-stage models for multicomponent, multistage distillation-type columns to an exactness limited only by the accuracy of the phase equilibrium and enthalpy data utilized. Time and cost requirements for obtaining such solutions are very low compared with the cost of manual solutions. Methods are available that can accurately solve almost any type of distillation-type problem quickly and efficiently. The material presented here covers, in some... 

The computation of equilibrium structures and phases of the system with several thousand atoms and all its electrons is still a problem which is far beyond tractability by present-day computers. Thus good approximative schemes or parameterizations of interaction potentials are important. 

With a suitable equation of state, all the fugacities in each phase can be found from Eq. (6), and the equation of state itself is substituted into the equilibrium relations Eq. (67) and (68). For an A-component system, it is then necessary to solve simultaneously N + 2 equations of equilibrium. While this is a formidable calculation even for small values of N, modern computers have made such calculations a realistic possibility. The major difficulty of this procedure lies not in computational problems, but in our inability to write for mixtures a single equation of state which remains accurate over a density range that includes the liquid phase. As a result, phase-equilibrium calculations based exclusively on equations of state do not appear promising for high-pressure phase equilibria, except perhaps for certain restricted mixtures consisting of chemically similar components. 

The computational problem of polymer phase equilibrium is to provide an adequate representation of the chemical potentials of each component in solution as a function of temperature, pressure, and composition. 

Another general type of behavior that occurs in polymer manufacture is shown in Figure 3. In many polymer processing operations, it is necessary to remove one or more solvents from the concentrated polymer at moderately low pressures. In such an instance, the phase equilibrium computation can be carried out if the chemical potential of the solvent in the polymer phase can be computed. Conditions of phase equilibrium require that the chemical potential of the solvent in the vapor phase be equal to that of the solvent in the liquid (polymer) phase. Note that the polymer is essentially involatile and is not present in the vapor phase. 

Since we did not measure the conversion during the experiment, we computed the equilibrium vapor pressure at the average solution temperature. We believe that, for safety design, the equilibrium vapor pressure is an adequate estimate of the styrene vapor pressure. For example, even at a 50% conversion, the difference is only 10 at the experimental temperatures. Figures 6, 7 and 8 compared the observed pressures with the computed total pressures. The latter were based on the equilibrium vapor pressure. As expected, there were increasing variations in Tests 1, 2 and 3 respectively because of their higher initial conversions. From these figures we can verify that our pressure and temperature measurements were in phase with respect to time. 

It should be kept in mind that an objective function which does not require any phase equilibrium calculations during each minimization step is the basis for a robust and efficient estimation method. The development of implicit objective functions is based on the phase equilibrium criteria (Englezos et al. 1990a). Finally, it should be noted that one important underlying assumption in applying ML estimation is that the model is capable of representing the data without any systematic deviation. Cubic equations of state compute equilibrium properties of fluid mixtures with a variable degree of success and hence the ML method should be used with caution. 

Data at two temperatures were obtained from Zeck and Knapp (1986) for the nitrogen-ethane system. The implicit LS estimates of the binary interaction parameters are ka=0, kb=0, kc=0 and kd=0.0460. The standard deviation of kd was found to be equai to 0.0040. The vapor liquid phase equilibrium was computed and the fit was found to be excellent (Englezos et al. 1993). Subsequently, implicit ML calculations were performed and a parameter value of kd=0.0493 with a standard deviation equal to 0.0070 was computed. Figure 14.2 shows the experimental phase diagram as well as the calculated one using the implicit ML parameter estimate. 

Using the estimated interaction parameters phase equilibrium computations were performed. It was found that the EoS is able to represent the VL2E behavior of the methane-n-hexane system in the temperature range of 198.05 to 444.25 K reasonably well. Typical results together with the experimental data at 273.16 and 444.25 K are shown in Figures 14.14 and 14.15 respectively. However, the EoS was found to be unable to correlate the entire phase behavior in the temperature range of 195.91 K (Upper Critical Solution Temperature) and 182.46K (Lower Critical Solution Temperature). 

Michelsen, M.L. Phase Equilibrium Calculations. What is Easy and What is Difficult Computers Chem. Eng, 17,431-439 (1993). 

The present paper deals with one aspect of this problem the calculation of phase separation critical points in reacting mixtures. The model employed is the Soave-Redlich-Kwong equation of state (1 ), which is typical of several equations of state (2, 5) which have relatively recently come into wide use as phase equilibrium models for light gas mixtures, sometimes including water and the acid gases as components (4, . 5, 6). If the critical point contained in the equation of state (perhaps even for the mixture at reaction equilibrium) can be found directly, the result will aid in other equilibrium computations. 

STANJAN The Element Potential Method for Chemical Equilibrium Analysis Implementation in the Interactive Program STANJAN, W.C. Reynolds, Thermosciences Division, Department of Mechanical Engineering, Stanford University, Stanford, CA, 1986. A computer program for IBM PC and compatibles for making chemical equilibrium calculations in an interactive environment. The equilibrium calculations use a version of the method of element potentials in which exact equations for the gas-phase mole fractions are derived in terms of Lagrange multipliers associated with the atomic constraints. The Lagrange multipliers (the element potentials ) and the total number of moles are adjusted to meet the constraints and to render the sum of mole fractions unity. If condensed phases are present, their populations also are adjusted to achieve phase equilibrium. However, the condensed-phase species need not be present in the gas-phase, and this enables the method to deal with problems in which the gas-phase mole fraction of a condensed-phase species is extremely low, as with the formation of carbon particulates. 

The phase equilibrium between a liquid and a gas can be computed by the Gibbs ensemble Monte Carlo method. We create two boxes, where the first box represents the dense phase and the second one represents the dilute phase. Each particle in the boxes experiences a Lennard-Jones potential from all the other particles. Three types of motion will be conducted at random the first one is particle translational movement in each box, the second one is moving a small volume from one box and adding to the other box, the third one is removing a particle from one box and inserting in the other box. After many such moves, the two boxes reach equilibrium with one another, with the same temperature and pressure, and we can compute their densities. 

The data from microwave spectroscopy have been interpreted with a dihedral angle H—O—O—H = 120.0° for the gas-phase equilibrium structure of H202. The nonplanarity of the peroxide gives rise to a stereogenic 0—0 axis . The computed total parity violating energy shift of —1.9 x 10 kJmoH between the two enantiomers, however, is too small in order to be measured with contemporary devices. ... 

In order for a process to be controllable by machine, it must represented by a mathematical model. Ideally, each element of a dynamic process, for example, a reflux drum or an individual tray of a fractionator, is represented by differential equations based on material and energy balances, transfer rates, stage efficiencies, phase equilibrium relations, etc., as well as the parameters of sensing devices, control valves, and control instruments. The process as a whole then is equivalent to a system of ordinary and partial differential equations involving certain independent and dependent variables. When the values of the independent variables are specified or measured, corresponding values of the others are found by computation, and the information is transmitted to the control instruments. For example, if the temperature, composition, and flow rate of the feed to a fractionator are perturbed, the computer will determine the other flows and the heat balance required to maintain constant overhead purity. Economic factors also can be incorporated in process models then the computer can be made to optimize the operation continually. 

In a recent paper Shapiro Shapley [4] have considered the problem of the uniqueness of equilibrium of systems of reactions in several phases in great detail. The computation of equilibrium compositions by direct minimization of the Gibbs free energy function has proved a valuable tool in the discussion of very complex systems and it is important to show that this minimum is unique and achieved under the same conditions that satisfy the mass action laws. This is what Shapiro Shapley have done Sellers has suggested some improvements [5]. 

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