0

For the equation $$PV=nRT$$ where $nR$ is constant

$$\frac{\partial P}{\partial V}\cdot\frac{\partial V}{\partial T}\cdot\frac{\partial T}{\partial P} = -1$$

If we were to simplify this, it implies $\frac{\partial P}{\partial P} = -1$

What does this mean? Change of $P$ with respect to $P$ is negative? What does that mean?

mathnoob123
  • 1,373
  • Related: https://math.stackexchange.com/questions/942457/understanding-frac-partial-x-partial-y-frac-partial-y-partial-z-frac, https://math.stackexchange.com/questions/68039/simplifying-frac-partial-v-partial-t-cdot-frac-partial-t-partial-p, https://math.stackexchange.com/questions/345403/prove-that-frac-partial-x-partial-y-frac-partial-y-partial-z-frac-p – Hans Lundmark Dec 23 '17 at 15:50

2 Answers2

3

It doesn't simplify like that, because the different $\partial P$'s are not the same changes in $P$ and the same for the others. For example the first $\partial P$ is at constant $T$ while the second is at constant $V$. These generally don't change the same amount.

The more intuitive version of the triple product rule is

$$\frac{\partial z}{\partial y}=-\frac{\frac{\partial x}{\partial y}}{\frac{\partial x}{\partial z}}$$

or more explicitly

$$\left ( \frac{\partial z}{\partial y} \right )_x=-\frac{\left ( \frac{\partial x}{\partial y} \right )_z}{\left ( \frac{\partial x}{\partial z} \right )_y}.$$

The minus sign can be intuitively understood by considering the equation $dx=\frac{\partial x}{\partial y} dy + \frac{\partial x}{\partial z} dz = 0$, which can be rearranged to give the result provided that we interpret $dz/dy$ as $\frac{\partial z}{\partial y}$ (which is justified since we've assumed $dx=0$ in the first place).

For some physical intuition, think about the case $x=P,y=V,z=T$, in which case you find that the ratio on the right side is negative while the derivative on the left side must be positive.

Ian
  • 101,645
1

Note that:

$$\frac{\partial P}{\partial V}=-\frac{nRT}{V^2}$$

$$\frac{\partial V}{\partial T}=\frac{nR}{P}$$

$$\frac{\partial T}{\partial P}=\frac{V}{nR}$$

thus:

$$\frac{\partial P}{\partial V}\cdot\frac{\partial V}{\partial T}\cdot\frac{\partial T}{\partial P} = -\frac{nRT}{V^2}\frac{nR}{P}\frac{V}{nR}=-\frac{nRT}{PV}=-1$$

Simplify $$\frac{\partial P}{\partial P} = -1$$

is meaningless.

user
  • 154,566