February 25, 2003

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Thermodynamics Variables are either extensive or intensive. To illustrate the difference between these kings of variables, think of mass and density. The mass of an object depends on the amount of material in the object, the density does not. Mass is an extensive variable, density is an intensive variable. In thermodynamics, T, p, and are intensive, the other variables that we have met, U, S , V , N, H, F, and G are extensive. We can develop some useful formal relationships between thermodynamic variables by relating these elementary properties of thermodynamic variables to the theory of homogeneous functions.

A polynomial

is of degree n if a_{n}0. A polynomial in more than one variable is said to be
homogeneous if all its terms are of the same degree, thus, the polynomial in two
variables

is homogeneous of degree two.

We can extend this idea to functions, if for arbitrary

it can be shown that

a function for which this holds is said to be homogeneous of degree n in the variable x. For reasons that will soon become obvious is called the scaling function. Intensive functions are homogeneous of degree zero, extensive functions are homogeneous of degree one.

Consider

this function is homogeneous of degree one in the variables U, V , and n, where n is the number of moles. Using the ideas developed above about homogeneous functions, it is obvious that we can write:

where is, as usual, arbitrary. We can gain some insight into the properties of such functions by choosing a particular value for . In this case we will choose = so that our equation becomes

Now, we can define = u, = v and S(u,v, 1) = s(u,v), the internal energy, volume and entropy per mole respectively. Thus the equation becomes

and the reason for the term scaling function becomes obvious.

Consider

differentiating with respect to (and changing sides of the equation) this becomes

which simplifies to

Recalling that is arbitrary, we now choose = 1, resulting in

and recognizing that the partial derivatives in this equations are now just the definitions of the extensive variables T, p, and n, we can rewrite this as

This equation, arrived at by purely formal manipulations, is the Euler equation, an equation that relates seven thermodynamic variables.

Starting from

and using

we have

So for a one component system G = n, for a j-component system, the Euler equation is

and so for a j-component system

The energy form of the Euler equation

expressed in differentials is

but, we know that

and so we find

This is the Gibbs-Duhem equation. It shows that three intensive variables are not independent - if we know two of them, the value of the third can be determined from the Gibbs-Duhem equation.