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This is a remarkable equation because it does not explicitly contain any constant characteristic of the substance. If the Van der Waals hypothesis were correct, (2.33) would hold for all substances. The assertion that the equation of state when expressed in terms of P, T, and V is a universal equation valid for all substances is called the law of corresponding states. * Looking at the isotherms of the Van der Waals equation of state we notice that the "kink" in a typical isotherm is unphysical, for it implies a negative compressibility. Its occurrence may be attributed to the implicit assumption that the system is homogeneous, with no allowance made for the possible coexistence of two phases. The situation may be improved by making what is called a Maxwell construction in the following manner. We ask whether it is possible to have two different states of the Van der Waals system coexisting in equilibrium. It is immediately obvious that for this to be possible the two states must have the same P and T. Therefore only states like those at volumes Vi' V2 , V3 in Fig. 2.10 need be considered as candidates. The further principle we apply is the minimiza"For experimental evidence for the law of corresponding states, see 16, especially Fig. 16.2.

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tion of free energy. Let the temperature and the total volume of the system be fixed. Then we assume that the system is either in one homogeneous phase, or is composed of more than one phase. The situation that has the lower free energy is the equilibrium situation. The free energy may be calculated by integrating - P dV along an isotherm:

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A(T, V) =

(2.34)

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This may be done graphically, as shown in Fig. 2.11. It is seen that the states 1 and 2 can coexist because they have the same T and P. Further, the point b, which lies between 1 and 2 on the common tangent passing through 1 and 2, represents a state in which part of the system is in state 1 and part in state 2, because the free energy of this state is obviously a linear combination of those of 1 and 2. We note that point b lies lower than point a, which represents the free energy of a homogeneous system at the same T and V. Hence b, the phase separation case, is the equilibrium situation. Thus between the points 1 and 2 on

the isotherm the system breaks up into two phases, with the pressure remaining constant. In other words the system undergoes a first-order phase transition. In the P- V diagram the points 1 and 2 are so located that the areas A and Bare equal. To show this, let us write down all the conditions determining 1 and 2:

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(equal pressure) (common tangent)

VI) = -(A 2 VI)

whose geometrical meaning is precisely A = B. This geometrical construction is known as the Maxwell construction. The Maxwell construction shows that we obtain a much more sensible equation of state when we incorporate into our scheme of description the possibility that the system can separate into two phases. A more formal way to see this is given in Section 7.8, in the context of the choice of "ensembles" in statistical mechanics.

If we cover one end of an open glass tube with a "semipermeable membrane" that is permeable to water but not to sugar in solution, fill the tube with a sugar solution, and then dip this end of the tube into a beaker of water, we find that the sugar solution rises to a height h above the level of the water, as illustrated in Fig. 2.12. This indicates that the sugar solution has a pressure pgh higher than that of pure water at the same temperature. This pressure must be due to the presence of the sugar, and is called the ,osmotic pressure exerted by the sugar in solution. It is by virtue of this pressure that a living cell, which is mostly water, can absorb sugar when it is immersed in a sugar solution. The osmotic pressure P' exerted by n i moles of solute in a very dilute solution of temperature T and volume V is experimentally given by V We derive this result with the help of the second law of thermodynamics. Consider a solution containing no moles of solvent and n I moles of solute, with P' = -

(16.40)

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