Curve coexistence

Below T, liquid and vapour coexist and their densities approach each other along the coexistence curve in the T-Vplane until they coincide at the critical temperature T. The coexisting densities in the critical region are related to T-T by the power law... 

The equation of state detemiined by Z N, V, T ) is not known in the sense that it cannot be written down as a simple expression. However, the critical parameters depend on e and a, and a test of the law of corresponding states is to use the reduced variables T, and as the scaled variables in the equation of state. Figure A2.3.5 bl illustrates this for the liquid-gas coexistence curves of several substances. As first shown by Guggenlieim [19], the curvature near the critical pomt is consistent with a critical exponent (3 closer to 1/3 rather than the 1/2 predicted by van der Waals equation. This provides additional evidence that the law of corresponding states obeyed is not the fomi associated with van der Waals equation. Figure A2.3.5 (b) shows tliat PIpkT is approximately the same fiinction of the reduced variables and... 

The T, p coexistence curve can be calculated numerically to any desired precision and is shown in figure A2.5.10. The spinodal curve (shown dotted) satisfies the equation... 

Figure A2.5.10. Phase diagram for the van der Waals fluid, shown as reduced temperature versus reduced density p. . The region under the smooth coexistence curve is a two-phase liquid-gas region as indicated by the horizontal tie-lines. The critical point at the top of the curve has the coordinates (1,1). The dashed line is the diameter, and the dotted curve is the spinodal curve.

If the small temis in p- and higher are ignored, equation (A2.5.4) is the Taw of the rectilinear diameter as evidenced by the straight line that extends to the critical point in figure A2.5.10 this prediction is in good qualitative agreement with most experiments. However, equation (A2.5.5). which predicts a parabolic shape for the top of the coexistence curve, is unsatisfactory as we shall see in subsequent sections. 

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 ... 

At the critical pohit (and anywhere in the two-phase region because of the horizontal tie-line) the compressibility is infinite. However the compressibility of each conjugate phase can be obtained as a series expansion by evaluating the derivative (as a fiuictioii of p. ) for a particular value of T, and then substituting the values of p. for the ends of the coexistence curve. The final result is... 

Although the previous paragraphs hint at the serious failure of the van der Waals equation to fit the shape of the coexistence curve or the heat capacity, failures to be discussed explicitly in later sections, it is important to recognize that many of tlie other predictions of analytic theories are reasonably accurate. For example, analytic equations of state, even ones as approximate as that of van der Waals, yield reasonable values (or at least ball park estmiates ) of the critical constants p, T, and V. Moreover, in two-component systems... 

The leading tenn in equation (A2.5.17) is the same kind of parabolic coexistence curve found in section A2.5.3.1 from the van der Waals equation. The similarity between equation (A2.5,5t and equation (A2.5.17) should be obvious the fomi is the same even though the coefficients are different. 

Figure A2.5.16. The coexistence curve, = KI(2R) versus mole fraction v for a simple mixture. Also shown as an abscissa is the order parameter s, which makes the diagram equally applicable to order-disorder phenomena in solids and to ferromagnetism. The dotted curve is the spinodal.

As in tire one-fluid case, the experimental sums are in good agreement with the law of the rectilinear diameter, but the experimental differences fail to give a parabolic shape to tlie coexistence curve. 

The integral under the heat capacity curve is an energy (or enthalpy as the case may be) and is more or less independent of the details of the model. The quasi-chemical treatment improved the heat capacity curve, making it sharper and narrower than the mean-field result, but it still remained finite at the critical point. Further improvements were made by Bethe with a second approximation, and by Kirkwood (1938). Figure A2.5.21 compares the various theoretical calculations [6]. These modifications lead to somewhat lower values of the critical temperature, which could be related to a flattening of the coexistence curve. Moreover, and perhaps more important, they show that a short-range order persists to higher temperatures, as it must because of the preference for unlike pairs the excess heat capacity shows a discontinuity, but it does not drop to zero as mean-field theories predict. Unfortunately these improvements are still analytic and in the vicinity of the critical point still yield a parabolic coexistence curve and a finite heat capacity just as the mean-field treatments do. 

As we have seen, all the analytic coexistence curves are quadratic in the limit, so for all these analytic theories, tire exponent (3=1/2. 

It is curious that he never conuuented on the failure to fit the analytic theory even though that treatment—with the quadratic fonn of the coexistence curve—was presented in great detail in it Statistical Thermodynamics (Fowler and Guggenlieim, 1939). The paper does not discuss any of the other critical exponents, except to fit the vanishing of the surface tension a at the critical point to an equation... 

In 1953 Scott [H] pointed out that, if the coexistence curve exponent was 1/3, the usual conclusion that the corresponding heat capacity remamed finite was invalid. As a result the heat capacity might diverge and he suggested an exponent a= 1/3. Although it is now known that the heat capacity does diverge, this suggestion attracted little attention at the time. 

The coexistence curve is nearly flat at its top, with an exponent p = 1/8, instead of the mean-field value of 1/2. The critical isothemi is also nearly flat at the exponent 8 (detemiined later) is 15 rather than the 3 of the analytic theories. The susceptibility diverges with an exponent y = 7/4, a much stronger divergence than that predicted by the mean-field value of 1. 

An unexpected conclusion from this fonuulation, shown in various degrees of generality in 1970-71, is that for systems that lack tlie synunetry of simple lattice models the slope of the diameter of the coexistence curve... 

Figure A2.5.25. Coexistence-curve diameters as functions of reduced temperature for Ne, N2, C2H4, and SFg. Dashed lines indicate linear fits to the data far from the critical point. Reproduced from [19] Pestak M W, Goldstein R E, Chan M H W, de Bniyn J R, Balzarini D A and Ashcroft N W 1987 Phys. Rev. B 36 599, figure 3. Copyright (1987) by the American Physical Society.

Similar equations apply to the extended scaling of the heat capacity and the coexistence curve for the determination of a and p. 

For simple fluids Nq is estimated to be about 0.01, and Kostrowicka Wyczalkowska et aJ [29] have vised this to apply crossover theory to the van der Waals equation with interesting resnlts. The critical temperature is reduced by 11% and the coexistence curve is of course flattened to a cvibic. The critical density is almost unchanged (by 2%), bnt the critical pressure p is reduced greatly by 38%. These changes redvice the critical... 

Povodyrev et aJ [30] have applied crossover theory to the Flory equation ( section A2.5.4.1) for polymer solutions for various values of N, the number of monomer units in the polymer chain, obtaining the coexistence curve and values of the coefficient p jj-from the slope of that curve. Figure A2.5.27 shows their comparison between classical and crossover values of p j-j for A = 1, which is of course just the simple mixture. As seen in this figure, the crossover to classical behaviour is not complete until far below the critical temperature. 

Figure A2.5.27. The effective coexistence curve exponent P jj = d In v/d In i for a simple mixture N= 1) as a fimction of the temperature parameter i = t / (1 - t) calculated from crossover theory and compared with the corresponding curve from mean-field theory (i.e. from figure A2.5.15). Reproduced from [30], Povodyrev A A, Anisimov M A and Sengers J V 1999 Crossover Flory model for phase separation in polymer solutions Physica A 264 358, figure 3, by pennission of Elsevier Science.

Sengers and coworkers (1999) have made calculations for the coexistence curve and the heat capacity of the real fluid SF and the real mixture 3-methylpentane + nitroethane and the agreement with experiment is excellent their comparison for the mixture [28] is shown in figure A2.5.28. 

Figure A2.5.28. The coexistence curve and the heat capacity of the binary mixture 3-methylpentane + nitroethane. The circles are the experimental points, and the lines are calculated from the two-tenn crossover model. Reproduced from [28], 2000 Supercritical Fluids—Fundamentals and Applications ed E Kiran, P G Debenedetti and C J Peters (Dordrecht Kluwer) Anisimov M A and Sengers J V Critical and crossover phenomena in fluids and fluid mixtures, p 16, figure 3, by kind pemiission from Kluwer Academic Publishers.

Figure A2.5.29. Peak positions of the liquid-vapour heat capacity as a fiinction of methane coverages on graphite. These points trace out the liquid-vapour coexistence curve. The frill curve is drawn for p = 0.127. Reproduced from [31] Kim H K and Chan M H W Phys. Rev. Lett. 53 171 (1984) figure 2. Copyright (1984) by the American Physical Society.

Jungst S, Knuth B and Hensel F 1985 Observation of singular diameters in the coexistence curves of metals Phys. Rev. Lett. 55 2160-3... 

Figure A3.3.2 A schematic phase diagram for a typical binary mixture showmg stable, unstable and metastable regions according to a van der Waals mean field description. The coexistence curve (outer curve) and the spinodal curve (iimer curve) meet at the (upper) critical pomt. A critical quench corresponds to a sudden decrease in temperature along a constant order parameter (concentration) path passing through the critical point. Other constant order parameter paths ending within tire coexistence curve are called off-critical quenches.

Figure A3.3.5 Tliemiodynamic force as a fiuictioii of the order parameter. Three equilibrium isodiemis (fiill curves) are shown according to a mean field description. For T < J., the isothemi has a van der Waals loop, from which the use of the Maxwell equal area constmction leads to the horizontal dashed line for the equilibrium isothemi. Associated coexistence curve (dotted curve) and spinodal curve (dashed line) are also shown. The spinodal curve is the locus of extrema of the various van der Waals loops for T < T. The states within the spinodal curve are themiodynaniically unstable, and those between the spinodal and coexistence...

For initial post-quench states in the metastable region between the classical spinodal and coexistence curves,... 

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