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Van der Waals attempted to find a simple qualitative way to improve the equation of state of a dilute gas by incorporating the effects of molecular interaction. The result is the Vander Waals equation of state. In most substances the potential energy between two molecules as a function of the intermolecular separation has the qualitative shape shown in Fig. 2.8. The attractive part of the potential energy originates from the mutual electric polarization of the two molecules and the repulsive part from the Coulomb repulsion of the overlapping electronic clouds of the molecules. Van der Waals idealized the situation by approximating the repulsive part by an infinite hard-sphere repulsion, so that the potential energy looks like that illustrated in Fig. 2.9. Thus each molecule is imagined to be a hard elastic sphere of diameter d surrounded by an attractive force field. The effects of the repulsive and attractive parts are then discussed separately.

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The main effect of the hard core would be to forbid the presence of any other molecule in a certain volume centered about a molecule. If Y is the total volume occupied by a substance, the effective volume available to one of its molecules would be smaller than Y by the totality of such excluded volumes, which is a constant depending on the molecular diameter and the number of molecules present:

(2.26)

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where b is a constant characteristic of the substance under discussion. The qualitative effect of the attractive part of the potential energy is a tendency for the system to form a bound state. If the attraction is sufficiently strong, the system will exist in an N-body bound state, which requires no external wall to contain it. Thus we may assume that the attraction produces a decrease in the pressure that the system exerts on an external wall. The amount of decrease is proportional to the number of pairs of molecules, within interaction range, in a layer near the wall. This in tum is roughly proportional to N 2/y 2 Since N and the range of interaction are constants, the true pressure P of the system may be decomposed into two parts:

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By now it should be clear how to draw and use the Fibonacci retracement. We now turn our attention to an equally useful tool, the Fibonacci fan. The application and interpretation of fans is very similar to retracements. As with a retracement, you need to identify a low and a high extreme to place your reference line, at which point the fans will be automatically placed for you. And, as with retracement, the fan lines indicate important support, resistance, and consolidation points for price action. Except for the fact that fan lines are at an angle, the interpretation of

= Pkinetic -

(2.27)

where a is another constant characteristic of the system and P kinetic is defined by the equation itself.

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(2.28)

This is the Van der Waals equation of state. Some isotherms corresponding to this equation of state are shown in Fig. 2.10. There exists a temperature Tc ' called the critical temperature, at which the "kink" in the isotherm disappears. The point of inflection c is called the critical point. Its pressure Pc, volume Vc' and temperature Tc can be expressed in terms of a and b as follows. For a given T and P, (2.28) generally has three roots in V (e.g., the values VI' V2 , V3 shown in Fig. 2.10). As T increases these roots move together, and at T = Tc they merge into Vc Thus in the neighborhood of the critical point the equation of state must read or

(2.29)

This is to be compared with (2.28) when we put T = 1;; and P = Pc:

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(2.30)

(15.15)

Let us define three 2 n X 2 n matrices Vi, V2 , and V3 whose matrix elements are respectively given by

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