Coexistence boundary, liquid-vapor

The lines separating the regions in a phase diagram are called phase boundaries. At any point on a boundary between two regions, the two neighboring phases coexist in dynamic equilibrium. If one of the phases is a vapor, the pressure corresponding to this equilibrium is just the vapor pressure of the substance. Therefore, the liquid-vapor phase boundary shows how the vapor pressure of the liquid varies with temperature. For example, the point at 80.°C and 0.47 atm in the phase diagram for water lies on the phase boundary between liquid and vapor (Fig. 8.10), and so we know that the vapor pressure of water at 80.°C is 0.47 atm. Similarly, the solid-vapor phase boundary shows how the vapor pressure of the solid varies with temperature (see Fig. 8.6). 

Figure 7.1 Schematic phase diagram of water (not to scale), showing phase boundaries (heavy solid lines), triple point (triangle), critical point (circle-x), and a representative point (circle, dotted lines) at 25°C on the liquid-vapor coexistence curve.

The critical state is evidently an invariant point (terminus of a line) in this case, because it lies at a dimensional boundary between states of / =2 (p = 1) and /= 1 (p = 2). The critical point is therefore a uniquely specified state for a pure substance, and it plays an important role (Section 2.5) as a type of origin or reference state for description of all thermodynamic properties. Note that a limiting critical terminus appears to be a universal feature of liquid-vapor coexistence lines, whereas (as shown in Fig. 7.1) solid-liquid and solid-vapor lines extend indefinitely or form closed networks with other coexistence lines. 

A triple point is a point where three phase boundaries meet. For water, it occurs at 4.6 Torr and 0.01°C (see Fig. 8.5). At the triple point, all three phases (ice, liquid, and vapor) coexist in dynamic equilibrium. Under these conditions, water molecules leave ice to become liquid and return to form ice at the same rate liquid vaporizes and vapor condenses at the same rate and ice sublimes and vapor condenses directly to ice again at the same rate. The location of the triple point of a substance is a fixed property of that substance and cannot be changed by changing the conditions. The triple point of water is used to define the size of the kelvin by definition, there are exactly 273.16 kelvins between absolute zero and the triple point of water. The normal freezing point of water is found to lie 0.01 K below the triple point, so 0°C corresponds to 273.15 K. 

Figure 4.2 Variation of the vapor pressure, Pv, of a substance with the temperature, 7, showing the phase transition between solid, liquid and vapor phases. Two phases can coexist in equilibrium only at pressures and temperatures defined by the phase boundary lines in the phase diagram, such as liquid-vapor, solid-liquid and solid-vapor lines. The liquid-vapor phase boundary terminates at the critical point, 7C. All three phases can coexist in equilibrium only at the triple point, 73, which is the intersection of the three two-phase boundaries.

An isochoric equation has been developed for computing thermodynamic functions of pure fluids. It has its origin on a given liquid-vapor coexistence boundary, and it is structured to be consistent with the known behavior of specific heats, especially about the critical point. The number of adjustable, least-squares coefficients has been minimized to avoid irregularities in the calculated P(p,T) surface by using selected, temperature-dependent functions which are qualitatively consistent with isochores and specific heats over the entire surface. Several nonlinear parameters appear in these functions. Approximately fourteen additional constants appear in auxiliary equations, namely the vapor-pressure and orthobaric-densities equations, which provide the boundary for the P(p,T) equation-of-state surface. 

With the above objectives in mind, we constrain the equation to the liquid-vapor coexistence boundary. For any density, the coexistence temperature, Ta(p), is obtained by iteration from equations for the ortho-baric densities. Thus the vapor pressure, P[Pg.351]

Phe smooth curve passing through the critical point and bounding the two-phase liquid-vapor region in a pressure-volume diagram is familiar to every student of thermodynamics. The mathematical description p(P) of this coexistence curve or saturation boundary is the subject of this chapter. 

The phase equilibrium for pure components is illustrated in Figure 4.1. At low temperatures, the component forms a solid phase. At high temperatures and low pressures, the component forms a vapor phase. At high pressures and high temperatures, the component forms a liquid phase. The phase equilibrium boundaries between each of the phases are illustrated in Figure 4.1. The point where the three phase equilibrium boundaries meet is the triple point, where solid, liquid and vapor coexist. The phase equilibrium boundary between liquid and vapor terminates at the critical point. Above the critical temperature, no liquid forms, no matter how high the pressure. The phase equilibrium boundary between liquid and vapor connects the triple point and the... 

Alloys are classified broadly in two categories, single-phase alloys and multiple-phase alloys. A phase is characterized by having a homogeneous composition on a macroscopic scale, a uniform structure, and a distinct interface with any other phase present. The coexistence of ice, liquid water, and water vapor meets the criteria of composition and structure, but distinct boundaries exist between the states, so there are three phases present. When liquid metals are combined, there is usually some limit to the solubility of one metal in another. An exception to this is the liquid mixture of copper and nickel, which forms a solution of any composition between pure copper and pure nickel. The molten metals are completely miscible. When the mixture is cooled, a solid results that has a random distribution of both types of atoms in an fee structure. This single solid phase thus constitutes a solid solution of the two metals, so it meets the criteria for a single-phase alloy. 

Within the PV region delimited by the two saturation boundary curves, liquid and vapor phases coexist stably at equilibrium. To the right of the vapor saturation curve, only vapor is present to the left of the liquid saturation curve, vapor is absent. Let us imagine inducing isothermal compression in a system composed of pure H2O at T = 350 °C, starting from an initial pressure of 140 bar. The H2O will initially be in the gaseous state up to P < 166 bar. At P = 166 bar, we reach the vapor saturation curve and the liquid phase begins to form. Any further... 

Look back at the large phase diagram (Figure 7-1) and notice the intersection of the three lines at 0.01° and 6 X 10 atm. Only at this triple point can the solid, liquid, and vapor states of FljO all coexist. Now find the point at 374° C and 218 atm where the liquid/gas boundary terminates. This critical point is the highest temperature and highest pressure at which there is a difference between liquid and gas states. At either a temperature or a pressure over the critical point, only a single fluid state exists, and there is a smooth transition from a dense, liquid-like fluid to a tenuous, gas-like fluid. 

Figure 2.9 Phase diagram for C02, showing solid-gas (S + G, sublimation ), solid-liquid (S + L, fusion ), and liquid-gas (L + G, vaporization ) coexistence lines as PT boundaries of stable solid, liquid, or gaseous phases. The triple point (triangle), critical point (x), and selected 280K isotherm of Fig. 2.8 (circle) are marked for identification. Note that the fusion curve tilts slightly forward (with slope 75 atm K-1) and that the sublimation and vaporization curves meet with slightly discontinuous slopes (angle < 180°) at the triple point. The dotted and dashed half-circle shows two possible paths between a liquid (cross-hair square) and a gas (cross-hair circle) state, one discontinuous (dashed) crossing the coexistence line, the other continuous (dotted) encircling the critical point (see text).

As shown in Fig. 7.9, for a given vapor pressure P (dotted line), the compositions vBq, xBap of the coexisting phases are found from the intersections (small circles) with the liquid and vapor boundaries of the hatched two-phase region. These intersections are connected by a horizontal tie-line (heavy solid line) that spans the two-phase hole in the diagram. All points along this tie-line represent the same thermodynamic state (i.e., same temperature, pressure, chemical potentials, and compositions of each phase), but each differs only in the relative amounts of each phase (cf. Sidebar 7.2), whether nearly all vapor (at the extreme left of the tie-line), nearly all liquid (at the extreme right), or roughly equimolar amounts of liquid and vapor (near the middle). 

In the phase diagram, panel (a). solid C02 (Dry Ice) is in equilibrium with gaseous C02 at a temperature of —78.7°C and a pressure of 1.00 bar." The solid sublimes without turning into liquid. At any temperature above the triple point at —56.6°C, there is a pressure at which liquid and vapor coexist as separate phases. For example, at 0°C, liquid is in equilibrium with gas at 34.9 bar. Moving up the liquid-gas boundary, we see that two phases always exist until the critical point is reached at 31.3 C... 

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