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Thermodynamics and statistical mechanics

**Extensive thermodynamic potentials (single component)
**

name entropy energy enthalpy Helmholtz free energy Gibbs free energy independent variables , , , , , , differential form 1 integrated form

, , , ,

**Intensive thermodynamic potentials (single component)
**

name entropy per-particle energy per-particle enthalpy per-particle Helmholtz free energy per-particle Gibbs free energy per-particle independent variables , , , , , differential form 1 integrated relations

ChE 210A

Thermodynamics and statistical mechanics

Measurable quantities

name pressure volume constant-volume heat capacity constant-pressure heat capacity definition name temperature heat of phase change isothermal compressibility thermal expansivity definition 1 Δ ln ln

1

**Thermodynamic calculus manipulations
**

name inversion applies to... anything functional form 1 1 example 1

triple product rule

anything

Maxwell’s relations

**potential second derivatives anything ⁄ ,
**

to indicate the thermodynamic internal energy.

addition of variable

potential transformation nonnatural derivative

potentials

⁄

anything

is used instead of

Note: Sometimes the notation

ChE 210A

Thermodynamics and statistical mechanics

**Derivations and memory techniques
**

Triple product rule

Take, as an example, the function that the full differential is given by , , although we could consider any state function. We know

Now consider the case in which is held constant, such that differentials and at constant conditions. 0

0. Then we can combine the

Rearranging and using the inversion rule gives the triple product rule: 1 How can you remember this? It’s simple. Starting with one partial derivative, just rotate the variables by putting the constant one in the numerator, the numerator in the denominator, and the denominator in the constant. Do two rotations and remember the product is -1.

Maxwell’s relations

For constant conditions, as we have discussed here, there is a particularly convenient way to remember all the Maxwell relationships without having to go through all the derivations each time (although you should always be able to do so!). It’s called the “magic square”. Here is what it looks like:

G P H T S A V U

To get Maxwell relations from the magic square, you need to do draw arrows that swoop past the thermodynamic potentials along the side edges (not corners). Here is an example:

G P H T S A V U

The arrows indicate that . They both start at the numerator and end at the constant

value. The potential they swoop by is , which is also the potential from which this Maxwell relation is

ChE 210A

Thermodynamics and statistical mechanics

derived. The negative sign comes from the fact that is in the top-left quadrant (think of it as negative x and positive y). Maxwell relations about also have a negative sign, but those for and do not. To remember the order of the magic square, start at the top left hand corner and use the mnemonic “Great people have studied under very able teachers.” (No egoism intended.)

Potential transformation

As an example, let’s prove

⁄

. To do this, start with the fact that

Now, express as the derivative of :

Divide both sides by

:

1

Now, the RHS can be expressed as a derivative using the chain rule, giving finally: ⁄

Nonnatural derivative

What if we know , , but want to find ? Here, is not one of the natural variables that can :

be held constant. We start by writing the full differential

Then, we divide through by the desired derivative, taken at constant :

Substituting in some definitions gives,

ChE 210A

Thermodynamics and statistical mechanics

This procedure works with any complete state function, even with nonnatural variables. For example, starting with E , , we could show:

Carrying this a little further, to get to measurable variables:

Here, another nonnatural derivative was expanded in the first line, a Maxwell relation was used in the second, and the triple product rule was used in the third.

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