Fluid phase mixtures

The diagram (Fig. 5.21) shows that as the pressure is reduced below the dew point, the volume of liquid in the two phase mixture initially increases. This contradicts the common observation of the fraction of liquids in a volatile mixture reducing as the pressure is dropped (vaporisation), and explains why the fluids are sometimes referred to as retrograde gas condensates. 

There has been extensive activity in the study of lipid monolayers as discussed above in Section IV-4E. Coexisting fluid phases have been observed via fluorescence microscopy of mixtures of phospholipid and cholesterol where a critical point occurs near 30 mol% cholesterol [257]. 

The CS pressures are close to the machine calculations in the fluid phase, and are bracketed by the pressures from the virial and compressibility equations using the PY approximation. Computer simulations show a fluid-solid phase transition tiiat is not reproduced by any of these equations of state. The theory has been extended to mixtures of hard spheres with additive diameters by Lebowitz [35], Lebowitz and Rowlinson [35], and Baxter [36]. 

As shown in section C2.6.6.2, hard-sphere suspensions already show a rich phase behaviour. This is even more the case when binary mixtures of hard spheres are considered. First, we will mention tire case of moderate size ratios, around 0.6. At low concentrations tliese fonn a mixed fluid phase. On increasing tire overall concentration of mixtures, however, binary crystals of type AB2 and AB were observed (where A represents tire larger spheres), in addition to pure A or B crystals [105, 106]. An example of an AB2 stmcture is shown in figure C2.6.11. Computer simulations confinned tire tliennodynamic stability of tire stmctures tliat were observed [107, 1081. 

A second case to be considered is that of mixtures witli a small size ratio, <0.2. For a long time it was believed tliat such mixtures would not show any instability in tire fluid phase, but such an instability was predicted by Biben and Flansen [109]. This can be understood to be as a result of depletion interactions, exerted on the large spheres by tire small spheres (see section C2.6.4.3). Experimentally, such mixtures were indeed found to display an instability [110]. The gas-liquid transition does, however, seem to be metastable witli respect to tire fluid-crystal transition [111, 112]. This was confinned by computer simulations [113]. 

The phase rule specifies the number of intensive properties of a system that must be set to estabUsh all other intensive properties at fixed values (3), without providing information about how to calculate values for these properties. The field of appHed engineering thermodynamics has grown out of the need to assign numerical values to thermodynamic properties within the constraints of the phase rule and fundamental laws. In the engineering disciplines there is a particular demand for physical properties, both for pure fluids and mixtures, and for phase equiUbrium data (4,5). 

Equations of State. Equations of state having adjustable parameters are often used to model the pressure—volume—temperature (PVT) behavior of pure fluids and mixtures (1,2). Equations that are cubic in specific volume, such as a van der Waals equation having two adjustable parameters, are the mathematically simplest forms capable of representing the two real volume roots associated with phase equiUbrium, or the three roots (vapor, Hquid, sohd) characteristic of the triple point. 

J. Zhao and S. V. Olesik, Phase diagram studies of methanol-CHFj and methanol-FI20-CF1F3 mixtures. Fluid Phase Equilib. 154 261-284 (1999). 

The conditions which lead a homogeneous fluid mixture to split into two separate fluid phases can be described by classical thermodynamic stability analysis as discussed in numerous textbooks.9 Such analysis has often been... 

For more comprehensive calculations of the fugacity coefficients in mixtures, see J. M. Prausnitz, R. N. Lichtenthaler, and E. G. de Azevedo. Modular Thermodynamics of Fluid Phase Equilibria, Prentice Hall. Englewood Cliffs. N.J., 19S6. Chapter 5. 

I. F. Holscher, G. M. Schneider and J. B. Ott, "Liquid-Liquid Phase Equilibria of Binary Mixtures of Methanol with Hexane, Nonane, and Decane at Pressures up to 150 MPa", Fluid Phase Equilib., 27, 153-169 (1986). 

For streamline flow of non-Newtonian liquids, the situation is completely different and the behaviour of two-phase mixtures in which the liquid is a shear-thinning fluid is now... 

The forced fluid flow in heated micro-channels with a distinct evaporation front is considered. The effect of a number of dimensionless parameters such as the Peclet, Jacob numbers, and dimensionless heat flux, on the velocity, temperature and pressure within the liquid and vapor domains has been studied, and the parameters corresponding to the steady flow regime, as well as the domains of flow instability are delineated. An experiment was conducted and demonstrated that the flow in microchannels appear to have to distinct phase domains one for the liquid and the other for the vapor, with a short section of two-phase mixture between them. 

Liquid-Fluid Equilibria Nearly all binary liquid-fluid phase diagrams can be conveniently placed in one of six classes (Prausnitz, Licntenthaler, and de Azevedo, Molecular Thermodynamics of Fluid Phase Blquilibria, 3d ed., Prentice-Hall, Upper Saddle River, N.J., 1998). Two-phase regions are represented by an area and three-phase regions by a line. In class I, the two components are completely miscible, and a single critical mixture curve connects their criticsu points. Other classes may include intersections between three phase lines and critical curves. For a ternary wstem, the slopes of the tie lines (distribution coefficients) and the size of the two-phase region can vary significantly with pressure as well as temperature due to the compressibility of the solvent. 

Thermodynamic models are widely used for the calculation of equilibrium and thermophysical properties of fluid mixtures. Two types of such models will be examined cubic equations of state and activity coefficient models. In this chapter cubic equations of state models are used. Volumetric equations of state (EoS) are employed for the calculation of fluid phase equilibrium and thermophysical properties required in the design of processes involving non-ideal fluid mixtures in the oil and gas and chemical industries. It is well known that the introduction of empirical parameters in equation of state mixing rules enhances the ability of a given EoS as a tool for process design although the number of interaction parameters should be as small as possible. In general, the phase equilibrium calculations with an EoS are very sensitive to the values of the binary interaction parameters. 

Trebble, M.A. Bishnoi, P.R. Extension of the Trebble-Bishnoi Equation of State to Fluid Mixtures. Fluid Phase Equilibria, 40, 1-21 (1988). 

The above method was developed using an assumption that the two-phase mixture could be treated as a homogeneous fluid, which was acceptable only at high mass flux, above 7.2 X 10s lb/hr ft2 (3.5 X 106 kg/m2 s). 

This regime is characterized by the presence of two continuous fluid phases and an interface which can easily be described. The term separated flows is frequently employed to describe these situations in both horizontal and vertical systems. Some flow patterns in Regime I are advantageous for transferring heat between the tube wall and the fluid mixture or for carrying out two-phase reactions. The special case of laminar-laminar flow is included in this regime, and two studies seem to be of interest, Byers and King (B7) and Bentwich and Sideman (B3). 

Zirrahi Z., Azin R., et al. Mutual solubility of CH4, C02, H2S, and their mixtures in brine under subsurface disposal conditions. 2012 Fluid Phase Equilibria 299 171—... 

Hougen- Watson Models for Cases where Adsorption and Desorption Processes are the Rate Limiting Steps. When surface reaction processes are very rapid, the overall conversion rate may be limited by the rate at which adsorption of reactants or desorption of products takes place. Usually only one of the many species in a reaction mixture will not be in adsorptive equilibrium. This generalization will be taken as a basis for developing the expressions for overall conversion rates that apply when adsorption or desorption processes are rate limiting. In this treatment we will assume that chemical reaction equilibrium exists between various adsorbed species on the catalyst surface, even though reaction equilibrium will not prevail in the fluid phase. 

Vrabec, J. Loth, A. Fischer, J., Vapour liquid equilibria of Lennard-Jones model mixtures from the NPT plus test particle method, Fluid Phase Equil. 1995,112, 173-197... 

Evaluation of each term in Eq. (15-51) is straightforward, except for the friction factor. One approach is to treat the two-phase mixture as a pseudo-single phase fluid, with appropriate properties. The friction factor is then found from the usual Newtonian methods (Moody diagram, Churchill equation, etc.) using an appropriate Reynolds number ... 

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