Ternary mixtures phase equilibrium

The two liquids thus formed are immiscible, but in thermodynamic equilibrium. Therefore, we may speak of a dynamic system of two immiscible phases. Figure 3.10 shows an example of a practical system applied to create a dynamic LLC phase system. A practical phase system can be created by pumping a mobile phase through a column, the composition of which corrresponds to a ternary mixture that is in dynamic equilibrium with another mixture (the two mixtures can be connected by a nodal line). If the mobile phase is the more polar one of the two ternary mixtures in equilibrium, then a non-polar (hydrophobic) solid support must be used and a reversed phase system can be generated. If the mobile phase is the less polar of the two mixtures in equilibrium, a polar support is required. 

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. ... 

Equilibrium Phase Behaviour. Phase studies were performed using approximately 10 g samples of oil-surfactant mixture diluted sequentially by the weighed addition of water. The initial binary mixture contained 5-70 w/w surfactant at 5 intervals. Phase boundaries were determined to + 0.5 water. The ternary mixtures in Pyrex glass tubes fitted with PTFE lined caps were equilibrated to the required temperature (20-65 0.1°C) for 2 hours and then thoroughly mixed for 5 minutes using a Fisons orbitsil whirlimixer. The tubes were then returned to the waterbath and left undisturbed for 48 hours before identification of the phase type using a crossed polarised viewer and an optical microscope. 

The potential of supercritical extraction, a separation process in which a gas above its critical temperature is used as a solvent, has been widely recognized in the recent years. The first proposed applications have involved mainly compounds of low volatility, and processes that utilize supercritical fluids for the separation of solids from natural matrices (such as caffeine from coffee beans) are already in industrial operation. The use of supercritical fluids for separation of liquid mixtures, although of wider applicability, has been less well studied as the minimum number of components for any such separation is three (the solvent, and a binary mixture of components to be separated). The experimental study of phase equilibrium in ternary mixtures at high pressures is complicated and theoretical methods to correlate the observed phase behavior are lacking. 

A recirculation apparatus for the determination of high pressure phase equilibrium data for mixtures of water, polar organic liquids and supercritical fluids was constructed and operated for binary and ternary systems with supercritical carbon dioxide. 

To illustrate the system behavior, the ternary mixture 1 = iso-propanol, 2 = water, and 3 = air is considered here. In order to obtain an algebraic solution, both the dif-fusivities of iso-propanol in air and iso-propanol in water vapor were assumed to be approximately the same, which is not far from reality. The liquid phase mass transfer resistance was negligibly small, as will be shown below. The phase equilibrium constants K/,c and Kjrs were calculated with activity coefficients from van Laar s equation. Water vapor diffuses 2.7-fold faster in the inert gas air than iso-propanol. The ratio of the respective mass transfer coefficients kj3 equals the ratio of the respective diffusivities to the power of 2/3rd according to standard convective mass transfer equations Sh =J Re, Sc). 

Similar patterns of behavior can be observed in reactive distillation columns or other integrated reaction separation processes with fast reversible reactions [11, 23] as illustrated in Fig. 5.3 for a pure rectifying column with a ternary mixture and a reaction of type 2B A + C taking place in the liquid phase. However, due to the reaction equilibrium the profiles consist of a single concentration front, which is clearly different from the nonreactive problem illustrated in Fig. 5.2. 

Mujtaba (1989) and Mujtaba and Macchietto (1992) considered a ternary separation using Butane-Pentane-Hexane mixture. Only the optimal operation for the first main-cut and the first off-cut was considered. Table 8.7 lists a variety of separation specification (on CUT 1) and column configurations in each case. A fresh feed of 6 kmol at a composition of <0.15, 0.35, 0.50> (mole fraction) is used in all cases. Also in each case a constant condenser vapour load of 3 kmol/hr is used. For convenience Type IV-CMH model was used with ideal phase equilibrium. 

A residue curve map (RCM) consists of a plot of the phase equilibrium of a mixture submitted to distillation in a batch vessel at constant pressure. RCM is advantageous for analyzing ternary mixtures. More exactly, a residue curve shows explicitly the evolution of the residual liquid of a mixture submitted to batch distillation. 

The experimental and predicted results for the ternary system carbon dioxide-methanol-water are listed in Table 7. Chang and Rousseau [47] have measured the solubilities of carbon dioxide in methanol-water mixtures at differents pressures and at temperatures below the critical temperature of carbon dioxide while Yoon [51] have measured the liquid and vapor phase equilibrium composition but overestimates shightly these of carbon dioxide in the liquid phase. 

An interesting investigation of the ternary mixture H2S + C02+CH4 was performed by Ng et al. (1985). Although much of this study was at temperatures below those of interest in acid gas injection, it provides data useful for testing phase-behavior prediction models. The multiphase equilibrium that Ng et al. observed for this mixture, including multiple critical points for a mixture of fixed composition, should be of interest to all engineers working with such mixtures. It demonstrates that the equilibria can be complex, even for relatively simple systems. 

An additional program took the energy parameters of the binary systems making up ternary mixtures and calculated the boiling point of the ternary and the equilibrium composition of the vapor phase. Comparison of the measured boiling point with the predicted boiling point for the same composition and pressure was used as a criterion of successful performance of the NRTL equation. 

The equilibrium composition of phases can be represented vividly with the help of the diagram for ternary mixture. As seen in fig,4 points 1, 2, 3 of intersection of connecting line with binodales describing the composition of the rubber phase of POO-... 

Initial values of the binary interaction parameters were obtained from vapor-liquid equilibrium data for ternary mixtures (9). These interaction parameters were then adjusted to minimize the difference between calculated and measured phase compositions for the three-phase equilibria measured at 50 C. 

Quinones et al. [17] measured by frontal analysis multisolute adsorption equilibrium data for the system benzyl alcohol, 2-phenylethanol and 2-methyl benzyl alcohol in a reversed-phase system. Data were acquired for the pure compoimds, for nine binary mixtures (1 3,1 1, and 3 1) and four ternary mixtures (1 1 3,1 3 1, 3 1 1, and 1 1 1). These data exhibited very good thermod5mamic consistency. The thermodynamic functions of adsorption were derived from the single-solute ad-... 

Rovetto, L.J. Bottini, S.B. Peters, C.J. Phase equilibrium data on binary and ternary mixtures of methyl palmitate, hydrogen and propane. J. Supercrit. Fluids 2004, 31, 111-121. 

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