One-phase

In vapor-liquid equilibria, if one phase composition is given, there are basically four types of problems, characterized by those variables which are specified and those which are to be calculated. Let T stand for temperature, P for total pressure, for the mole fraction of component i in the liquid phase, and y for the mole fraction of component i in the vapor phase. For a mixture containing m components, the four types can be organized in this way ... 

Assuming an initial reservoir pressure above the bubble point (undersaturated reservoir oil), only one phase exists in the reservoir. The volume of oil (rm or rb) at reservoir conditions of temperature and pressure is calculated from the mapping techniques discussed in Section 5.4. 

A general prerequisite for the existence of a stable interface between two phases is that the free energy of formation of the interface be positive were it negative or zero, fluctuations would lead to complete dispersion of one phase in another. As implied, thermodynamics constitutes an important discipline within the general subject. It is one in which surface area joins the usual extensive quantities of mass and volume and in which surface tension and surface composition join the usual intensive quantities of pressure, temperature, and bulk composition. The thermodynamic functions of free energy, enthalpy and entropy can be defined for an interface as well as for a bulk portion of matter. Chapters II and ni are based on a rich history of thermodynamic studies of the liquid interface. The phase behavior of liquid films enters in Chapter IV, and the electrical potential and charge are added as thermodynamic variables in Chapter V. 

The idea that unsymmetrical molecules will orient at an interface is now so well accepted that it hardly needs to be argued, but it is of interest to outline some of the history of the concept. Hardy [74] and Harkins [75] devoted a good deal of attention to the idea of force fields around molecules, more or less intense depending on the polarity and specific details of the structure. Orientation was treated in terms of a principle of least abrupt change in force fields, that is, that molecules should be oriented at an interface so as to provide the most gradual transition from one phase to the other. If we read interaction energy instead of force field, the principle could be reworded on the very reasonable basis that molecules will be oriented so that their mutual interaction energy will be a maximum. 

If two pure, immiscible liquids, such as benzene and water, are vigorously shaken together, they will form a dispersion, but it is doubtful that one phase or the other will be uniquely continuous or dispersed. On stopping the agitation, phase separation occurs so quickly that it is questionable whether the term emulsion really should be applied to the system. A surfactant component is generally needed to obtain a stable or reasonably stable emulsion. Thus, if a little soap is added to the benzene-water system, the result on shaking is a true emulsion that separates out only very slowly. Theories of... 

Figure A2.5.1. Schematic phase diagram (pressure p versus temperature 7) for a typical one-component substance. The full lines mark the transitions from one phase to another (g, gas liquid s, solid). The liquid-gas line (the vapour pressure curve) ends at a critical point (c). The dotted line is a constant pressure line. The dashed lines represent metastable extensions of the stable phases.

Figure A2.5.4. Themiodynamic fimctions (i, n, and C as a fimction of temperature T at eonstant pressure and eomposition x = 1/2) for the two-eomponent system shown in figure A2.5.3. Note the diflferenee between these and those shown for the one-eomponent system shown in figure A2.5.2. The fiinetions shown are dimensionless as in figure A2.5.2. The dashed lines represent metastable extensions (superheating or supereooling) of the one-phase systems.

It is important to note that, in this example, as in real seeond-order transitions, the eiirves for the two-phase region eaimot be extended beyond the transition to do so would imply that one had more than 100% of one phase and less than 0% of the other phase. Indeed it seems to be a quite general feature of all known seeond-order transitions (although it does not seem to be a themiodynamie requirement) that some aspeet of the system ehanges gradually until it beeomes eomplete at the transition point. 

Some binary systems show a minimum at a lower eritieal-sohition temperature a few systems show elosed-loop two-phase regions with a maximum and a minimum.) As the temperature is inereased at any eomposition other than the eritieal eomposition v = the eompositions of the two eoexisting phases adjust themselves to keep the total mole fraetion unehanged until the eoexistenee eurve is reaehed, above whieh only one phase... 

Figure A2.5.7. Constant temperature isothenns of reduced Helmlioltz free energy A versus reduced volume V. The two-phase region is defined by the line simultaneously tangent to two points on the curve. The dashed parts of the smooth curve are metastable one-phase extensions while the dotted curves are unstable regions. (The isothenns are calculated for an unphysical r = 0.1, the only effect of which is to separate the isothenns...

Finally, we consider the isothennal compressibility = hi V/dp)y = d hi p/5p) j, along tlie coexistence curve. A consideration of Figure A2.5.6 shows that the compressibility is finite and positive at every point in the one-phase region except at tlie critical point. Differentiation of equation (A2.5.2) yields the compressibility along the critical isochore ... 

Figure A2.5.17. The coefficient Aias a fimction of temperature T. The line IRT (shown as dashed line) defines the critical point and separates the two-phase region from the one-phase region, (a) A constant K as assumed in the simplest example (b) a slowly decreasing K, found frequently in experimental systems, and (c) a sharply curved K T) that produces two critical-solution temperatures with a two-phase region in between.

Consider simulating a system m the canonical ensemble, close to a first-order phase transition. In one phase, is essentially a Gaussian centred around a value j, while in the other phase tlie peak is around Ejj. 

Catalysis in a single fluid phase (liquid, gas or supercritical fluid) is called homogeneous catalysis because the phase in which it occurs is relatively unifonn or homogeneous. The catalyst may be molecular or ionic. Catalysis at an interface (usually a solid surface) is called heterogeneous catalysis, an implication of this tenn is that more than one phase is present in the reactor, and the reactants are usually concentrated in a fluid phase in contact with the catalyst, e.g., a gas in contact with a solid. Most catalysts used in the largest teclmological processes are solids. The tenn catalytic site (or active site) describes the groups on the surface to which reactants bond for catalysis to occur the identities of the catalytic sites are often unknown because most solid surfaces are nonunifonn in stmcture and composition and difficult to characterize well, and the active sites often constitute a small minority of the surface sites. 

The two coordinates that define the plane in which the loop located were discussed in Section n. In loops that encircle a conical intersection, there is always at least one phase-inverting reaction—we can choose its coordinate as the phase-inverting one. Let us assume that this is the reaction connecting A and... 

Figure 29, The effect of the phase-preserving component of the degenerate 2 distorting mode, It may be regarded as a major component of the reaction coordinate that leads to the A] structure (going left, one phase of the mode). Going right, the other phase of the same vibration, the B2 state is formed. (A type-V structure is also obtained along the same coordinate).

Solubilisation is usually treated in terms of the pseudophase model, in which the bulk aqueous phase is regarded as one phase and tire micellar pseudophase as another. This allows the affinity of the solubilisate for the micelle to be quantified by a partition coefficient P. Different definitions of P can be found in the literature, differing in their description of the micellar phase. Frequently P is... 

The solvent used m catalytic hydrogenation is chosen for its ability to dissolve the alkene and is typically ethanol hexane or acetic acid The metal catalysts are insoluble m these solvents (or indeed m any solvent) Two phases the solution and the metal are present and the reaction takes place at the interface between them Reactions involving a substance m one phase with a different substance m a second phase are called het erogeneous reactions... 

The process by which a solute is transferred from one phase to a new phase. 

In a simple liquid-liquid extraction the solute is partitioned between two immiscible phases. In most cases one of the phases is aqueous, and the other phase is an organic solvent such as diethyl ether or chloroform. Because the phases are immiscible, they form two layers, with the denser phase on the bottom. The solute is initially present in one phase, but after extraction it is present in both phases. The efficiency of a liquid-liquid extraction is determined by the equilibrium constant for the solute s partitioning between the two phases. Extraction efficiency is also influenced by any secondary reactions involving the solute. Examples of secondary reactions include acid-base and complexation equilibria. 

A ratio expressing the total concentration of solute in one phase relative to a second phase all forms of the solute are considered in defining the distribution ratio (D). 

Conservation of mass requires that the moles of solute initially present in one phase equal the combined moles of solute in the aqueous and organic phases after the extraction thus... 

Analytical separations may be classified in three ways by the physical state of the mobile phase and stationary phase by the method of contact between the mobile phase and stationary phase or by the chemical or physical mechanism responsible for separating the sample s constituents. The mobile phase is usually a liquid or a gas, and the stationary phase, when present, is a solid or a liquid film coated on a solid surface. Chromatographic techniques are often named by listing the type of mobile phase, followed by the type of stationary phase. Thus, in gas-liquid chromatography the mobile phase is a gas and the stationary phase is a liquid. If only one phase is indicated, as in gas chromatography, it is assumed to be the mobile phase. 

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