Statistical Mechanics, Spring 2013

I.

I CORRECTIONS TO THE IDEAL GAS EQUATION OF STATE

CORRECTIONS TO THE IDEAL GAS

EQUATION OF STATE

We start our discussion by examining the corrections to the ideal gas equation of state. The total pressure, including the ideal gas part is given by the pressure equation, 22 P = kB T 3

drr3 U (r)g (r).

0

(1)

in our theory for the pair distribution function in an interacting uid, we worked out a density expansion for g (r) and concluded that the rst term in the expansion is g (r) exp(U (r)). In this approximation, the pressure equation becomes P kB T 22 3

drr3 U (r) exp [U (r)] .

0

(2)

Thus, the pressure can also be expanded in terms of the density, P = + B2 (T )2 + O(2 ), kB T (3)

where the temperature-dependent coecient B2 (T ) is called the second virial coecient. In a low density uid, it is the rst correction to the ideal gas law equation of state. B2 (T ) can actually vanish at nite temperatures. The temperature at which B2 (T ) vanishes is called the Boyle temperature. It represents the temperature at which an interacting gas behaves like an ideal one. While we will discuss the second virial coecient in the context of interacting uids, it does have other applications. For example, homopolymers in solution have a temperature, called the -temperature, at which they behave like ideal noninteracting polymers. This is also the temperature at which the second virial coecient vanishes. As we will see, there is a problem with the application of the pressure equation directly, Eq. 1. Wed like to be able to model pair potential functions that are piecewise continuous. The reason is that the short-distance and long-distance behavior can be really dierent. Attractions are usually weak, noncovalent interactions, while the short-ranged interactions are steeply repulsive. It is inconvenient to use a single mathematical function that exhibits this behavior. Thus, potentials often take the form U (r) = Ushort (r) + Ulong (r). Such potentials may not have well-behaved derivatives with respect to position. 1 (4)

Statistical Mechanics, Spring 2013

I CORRECTIONS TO THE IDEAL GAS EQUATION OF STATE

Lets nd a way to get rid of the derivative term, U (r). The second virial coecient for an isotropic and homogeneous uid is 2 drr3 U (r) exp [U (r)] . B2 (T ) = 3 0 2 d = drr3 exp [U (r)] . 3 0 dr (5) (6)

If I try to integrate by parts, Im going to be in trouble. The reason is that exp(U (r)) goes to 1 as r . But, note that, because the derivative of a constant is zero, 2 3
0

d 2 drr exp [U (r)] = dr 3

3

drr3
0

d (exp [U (r)] 1) . dr

(7)

Now I can safely integrate by parts.

B2 (T ) = 2
0

drr2 (exp [U (r)/kB T ] 1) .

(8)

Youll recognize the quantity in parenthesis as being the complementary function to g (r), h(r) = g (r) 1.

A.

The hard sphere uid

A conceptually simple model potential of a uid is a system of hard spheres. The potential energy is U (r) = r 0 r > . (9)

is the diameter of the hard spheres. This is a model without any long-ranged part, Ulong = 0. In the low density approximation to g (r), we have that g (r) = 0 if r and g (r) = 1 otherwise. This means that the integrand is only nonzero for r , and when r its value is -1. The second virial coecient is

B2 (T ) = 2
0

r2 dr =

2 3 . 3

(10)

The second virial coecient is always positive and independent of temperature and equal to half the volume of one of the particles. Why is it independent of temperature?