Relations between partial derivatives used in the Maxwell relations

calculusderivatives

In the context of Maxwell's relations, there are two frequently used expressions relating the partial derivatives of different thermodynamic quantities:

$$\left(\frac{\partial x}{\partial y}\right)_{z} \left(\frac{\partial y}{\partial z}\right)_{x} \left(\frac{\partial z}{\partial x}\right)_{y}= -1 \tag{1}$$

$$\left(\frac{\partial y}{\partial x}\right)_{z}=1 \bigg{/} \left(\frac{\partial x}{\partial y}\right)_{z} \tag{2}$$

What is the mathematical background of these two expressions? Is there a simple demonstration for them?

Best Answer

These are known as the reciprocal and reciprocity theorems. I feel these are perhaps not stated as clearly as they should be in introductory courses. I always had trouble with them until I read Andrew Steane's fantastic book on Thermodynamics (pretty much the only book on the subject that I like), which I will be following in this answer.

The idea is to start with the well known theorem of partial derivatives. If $f$ is a function of two variables $x$ and $y$, then we can relate a change in $f$ to changes in $x$ and $y$ using the partial derivatives: $$\text{d}f = \left(\frac{\partial f}{\partial x}\right)_{y} \text{d}x + \left(\frac{\partial f}{\partial y}\right)_{x} \text{d}y.\label{1}\tag{1}$$

In the above formula, the notation $(\cdot)_x$ means that the partial derivative is taken while keeping the subscript (here, $x$) constant. Note that in general (I encourage you to try to come up with an example for this)$$\left(\frac{\partial f}{\partial x}\right)_{y} \neq \left(\frac{\partial f}{\partial x}\right)_{z}.$$

We can now use the above relation carefully, while realising that we can't quite be as cavalier with partial derivatives as we could with total derivatives. For example, we can't talk about quantities like $\text{d}f/\text{d}x$, since $f$ is a function of two variables, $x$ and $y$. You might naively call the quantity in question the "rate of change of $f$ with $x$", but since it depends on $y$ as well, we need to specify along which path we choose to describe this variation completely.

The Reciprocal Theorem:

let's start by dividing Equation (\ref{1}) by $\text{d}x$, while keeping $y$ constant. The second term in the equation would trivially be zero, since $\text{d}y=0$, and we'd get the trivial result: $$\left(\frac{\partial f}{\partial x}\right)_{y} = \left(\frac{\partial f}{\partial x}\right)_{y}.$$

A more interesting result appears if we carefully divide Equation (\ref{1}) by $\text{d}f$, but we still keep $y$ constant. In this case, it reduces to: $$1 = \left(\frac{\partial f}{\partial x}\right)_{y} \left(\frac{\partial x}{\partial f}\right)_{y},$$ from which you get the relation

$$\boxed{\left(\frac{\partial f}{\partial x}\right)_{y} = \left(\frac{\partial x}{\partial f}\right)_{y}^{-1}}.$$

The Reciprocity Theorem:

Let's go back to Equation (\ref{1}) again, and this time we divide throughout by $\text{d}x$ again, except we don't keep $y$ constant, but rather we do it while keeping $f$ constant. It should be easy to show that $$0 = \left(\frac{\partial f}{\partial x}\right)_{y} + \left(\frac{\partial f}{\partial y}\right)_{x} \left(\frac{\partial y}{\partial x}\right)_{f}.$$

Using the reciprocal theorem above, we can easily see that this means that $$\boxed{\left(\frac{\partial f}{\partial y}\right)_{x} \left(\frac{\partial y}{\partial x}\right)_{f} \left(\frac{\partial x}{\partial f}\right)_{y} = -1.}$$

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