Boundary vapour

The strict definition of a phase is any homogeneous and physically distinct region that is separated from another such region by a distinct boundary . For example a glass of water with some ice in it contains one component (the water) exhibiting three phases liquid, solid, and gaseous (the water vapour). The most relevant phases in the oil industry are liquids (water and oil), gases (or vapours), and to a lesser extent, solids. 

As the temperature of the liquid phase is increased, the system ultimately reaches a phase boundary, the bubble point at which the gas phase (vapour) begins to appear, with the composition shown at the left end of the horizontal two-phase tie-line . As the temperature rises more gas appears and the relative amounts of the two phases are detemiined by applying a lever-ami principle to the tie-line the ratio of the fractionof molecules in the gas phase to that hn the liquid phase is given by the inverse of the ratio of the distances from the phase boundary to the position of the overall mole fraction Xq of the system. 

Surface waves at an interface between two innniscible fluids involve effects due to gravity (g) and surface tension (a) forces. (In this section, o denotes surface tension and a denotes the stress tensor. The two should not be coiifiised with one another.) In a hydrodynamic approach, the interface is treated as a sharp boundary and the two bulk phases as incompressible. The Navier-Stokes equations for the two bulk phases (balance of macroscopic forces is the mgredient) along with the boundary condition at the interface (surface tension o enters here) are solved for possible hamionic oscillations of the interface of the fomi, exp [-(iu + s)t + i V-.r], where m is the frequency, is the damping coefficient, s tlie 2-d wavevector of the periodic oscillation and. ra 2-d vector parallel to the surface. For a liquid-vapour interface which we consider, away from the critical point, the vapour density is negligible compared to the liquid density and one obtains the hydrodynamic dispersion relation for surface waves + s>tf. The temi gq in the dispersion relation arises from... 

Because densification occurs via tire shrinkage of tliennodynamically unstable pores, densification and microstmcture development can be assessed on tire basis of tire dihedral angle, 0, fonned as a result of tire surface energy balance between tire two solid-vapour and one solid-solid interface at tire pore-grain boundary intersection [, 78, 79 and 80],... 

Examples of this procedure for dilute solutions of copper, silicon and aluminium shows the widely different behaviour of these elements. The vapour pressures of the pure metals are 1.14 x 10, 8.63 x 10 and 1.51 x 10 amios at 1873 K, and the activity coefficients in solution in liquid iron are 8.0, 7 X 10 and 3 X 10 respectively. There are therefore two elements of relatively high and similar vapour pressures, Cu and Al, and two elements of approximately equal activity coefficients but widely differing vapour pressures. Si and Al. The right-hand side of the depletion equation has the values 1.89, 1.88 X 10- , and 1.44 X 10 respectively, and we may conclude that there will be depletion of copper only, widr insignificant evaporation of silicon and aluminium. The data for the boundaty layer were taken as 5 x lO cm s for the diffusion coefficient, and 10 cm for the boundary layer thickness in liquid iron. 

Types of columns and packings. A slow distillation rate is necessary to ensure that equilibrium conditions operate and also that the vapour does not become superheated so that the temperature rises above the boiling point. Efficiency is improved if the column is heat insulated (either by vacuum jacketing or by lagging) and, if necessary, heated to Just below the boiling point of the most volatile component. Efficiency of separation also improves with increase in the heat of vaporisation of the liquids concerned (because fractionation depends on heat equilibration at multiple liquid-gas boundaries). Water and alcohols are more easily purified by distillation for this reason. 

Similar results, to the Fe-Zn system were obtained in the Ti,j,-Al(,) and Ti(j)-Al, ) system where, in the solid-liquid couples some of the expected surface layer phases were not formed, whereas in the solid-vapour system it was possible to obtain all the phases and predict from the AG -concen-tration curves the compositions at the different layer phase boundaries. 

If any component is absent from a particular phase (for example, the vapour phase, or a solid phase), there is one variable the less, but also one boundary condition the less, for migration of that component cannot occur with respect to the phase considered. Equation a) is therefore still true. 

Fig. 13. Plot of variations of activation energy ( /kJ mole"1) with water vapour pressure (PHjO/Torr) for dehydration of calcium sulphate. Data from Ball et al. [281,590, 591] who discuss the significance of these kinetic parameters. Dehydrations of CaS04 2 H2O, nucleation ( ), boundary (o) and diffusion (e) control Q-CaSC>4 5 H2O, diffusion control, below (X) and above (+) 415 K j3-CaS04 5 H20, diffusion control ( ).

The theoretical treatment which has been developed in Sections 10.2-10.4 relates to mass transfer within a single phase in which no discontinuities exist. In many important applications of mass transfer, however, material is transferred across a phase boundary. Thus, in distillation a vapour and liquid are brought into contact in the fractionating column and the more volatile material is transferred from the liquid to the vapour while the less volatile constituent is transferred in the opposite direction this is an example of equimolecular counterdiffusion. In gas absorption, the soluble gas diffuses to the surface, dissolves in the liquid, and then passes into the bulk of the liquid, and the carrier gas is not transferred. In both of these examples, one phase is a liquid and the other a gas. In liquid -liquid extraction however, a solute is transferred from one liquid solvent to another across a phase boundary, and in the dissolution of a crystal the solute is transferred from a solid to a liquid. 

Van der Waals, whose theory has been further developed by Hulshoff and by Bakker, went one step further than Gibbs by assuming that there exists a perfectly continuous transition from one medium to the other at the boundary. This assumption limits him to the consideration of one particular case that of a liquid in contact with its own saturated vapour, and mathematical treatment becomes possible by the further assumption that the Van der Waals equation (see Chapter II.) holds good throughout the system. The conditions of equilibrium thus become dynamical, as opposed to the statical equilibrium of Laplace s theory. Van der Waals arrives at the following principal results (i) that a surface tension exists at the boundary liquid-saturated vapour and that it is of the same order of magnitude as that found by Laplace s theory (2) that the surface tension... 

Tropospheric chemistry is strongly dependent on the concentration of the hydroxyl radical (OH), which reacts very quickly with most trace gases in the atmosphere. Owing to its short boundary layer lifetime ( 1 s), atmospheric concentrations of OH are highly variable and respond rapidly to changes in concentrations of sources and sinks. Photolysis of ozone, followed by reaction of the resulting excited state oxygen atom with water vapour, is the primary source of the OH radical in the clean troposphere ... 

Let us first consider how the density of the condensed phase changes with temperature. As our material in the vapour phase is cooled at constant pressure the density increases until the boiling point is reached. Further cooling then allows us to differentiate between the vapour and liquid states by the formation of a boundary. Further cooling increases the liquid density but at a much slower rate than that of the gaseous phase. The density of many liquids can be described by a simple linear equation over a wide temperature range 5... 

An alternative explanation concerns the existence of two equilibria. As the vapour/liquid equilibrium is disturbed by the passage of air, the concentration of dissolved compounds in the liquid phase falls, disturbing the solid /liquid equilibrium. The kinetics of transfer across this latter phase boundary are much slower than for the liquid/vapour transfer, so that the extraction of odour becomes limited by the rate of diffusion into the liquid phase. 

In the gas/vapour phase the dimensionless distance tj ranges from 0 to 1, where tj — 1 corresponds to the position of the interface. In the liquid phase this parameter ranges from 0 to 1 for the mass transfer film and from 0 to Le for the heat transfer film. Hence, rj = 0 corresponds to the position of the interface and rj = I and t] = Le correspond, respectively, to the boundaries of the mass and heat transfer film. The mass and energy fluxes can now be calculated by solving the differential equations (4) and (8)-(12) subject to the boundary conditions (15). Due to the non-linearities a numerical solution procedure has been used which will be discussed subsequently. 

Due to chemical conversion in the liquid-phase mass transfer film the mass flux of A at the vapour-liquid interface and the mass flux of A at the boundary between this film and the liquid bulk will differ. Figures 9(a) and (b) show the values of these fluxes as a function of the reaction rate constant ko for equilibrium constants K = 1 and X = 100. The... 

Fig. 9. The molar flux of component A at the vapour-liquid interface (°) and at the boundary between mass transfer film and liquid bulk (S) as function of reaction rate constant in case (a) the mass transfer coefficients are equal and (b) the mass transfer coefficients are different.

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