Vapor Liquid Equilibrium The Critical Point

A condition of phase equilibrium is the equality of the chemical potentials in the two phases. Therefore, at all points along the two-phase line, //(g) = p( ). But, as we have noted above, the approach to the critical point brings the liquid and gas closer and closer together in density until they become indistinguishable, At the critical point, all of the thermodynamic properties of the liquid become equal to those of the gas. That is, Hm(g) = Um(g) - /m(l), 

A similar form can be used to represent the difference of densities as well 

In both equations, k and k are proportionality constants and 0 is a constant known as the critical exponent. Experimental measurements have shown that 0 has the same value for both equations and for all gases. Analytic8 equations of state, such as the Van der Waals equation, predict that 0 should have a value of i. Careful experimental measurement, however, gives a value of 0 = 0.32 0.01.h Thus, near the critical point, p or Vm varies more nearly as the cube root of temperature than as the square root predicted from classical equations of state. 

The form of equations (8.11) and (8.12) turns out to be general for properties near a critical point. In the vicinity of this point, the value of many thermodynamic properties at T becomes proportional to some power of (Tc - T). The exponents which appear in equations such as (8.11) and (8.12) are referred to as critical exponents. The exponent 6 = 0.32 0.01 describes the temperature behavior of molar volume and density as well as other properties, while other properties such as heat capacity and isothermal compressibility are described by other critical exponents. A significant scientific achievement of the 20th century was the observation of the nonanalytic behavior of thermodynamic properties near the critical point and the recognition that the various critical exponents are related to one another  

The implications of the approach to indistinguishability of the two phases at the critical point are far-reaching. As we will show next, quantities such as the compressibility and coefficient of expansion become infinite. 

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