Why are some Maxwell relations written in reverse order?

In summary, in thermodynamics, we use exact differential relations to find Maxwell relations. These relations are necessary for a function of x and y, z=z(x,y) to hold. One of these relations can be seen in the Helmholtz free energy equation, where the partial derivatives of pressure and temperature are equal to the partial derivatives of entropy and volume. Some textbooks may write this relation in reverse order, which is also valid. This can be understood by looking at the potential H=E+PV instead of F=E-TS. It is important for students to be taught these rules, as they are not commonly known among engineers and physics majors.
  • #1
KFC
488
4
In thermodynamics, we always need to use exact differential relations to find the so called Maxwell relations. For a function of x and y, z=z(x,y)

if dz = M(x,y)dx + N(x, y)dy

the complete conditon for above equation to be hold is

[tex]\frac{\partial M}{\partial y} = \frac{\partial N}{\partial x}[/tex]

Now, let see one of the relation on Helmholtz free energy

[tex]dF = -SdT - PdV[/tex]

apply the condition mentioned above, we get

[tex]\left(\frac{\partial P}{\partial T}\right)_V = \left(\frac{\partial S}{\partial V}\right)_T[/tex]

Well, in many materials (including some textbooks), they like to write it

[tex]\left ( {\partial T\over \partial p} \right )_{V,N} = \left ( {\partial V\over \partial S} \right )_{T,N}[/tex]

I don't know why they like to inverse those relation! What interesting is only this relations I found to be in reverse order, the others Maxwells relations are just fine!
 
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  • #2
There's absolutely no difference; the reciprocals of Maxwell relations are also valid. We can also get to this one by looking at the potential [itex]H=E+PV[/itex] rather than [itex]F=E-TS[/itex]. It is odd that some textbooks would switch just one without comment. It would be a good teaching opportunity to explain that this is OK.
 
  • #3
this page: http://en.wikipedia.org/wiki/Exact_differential#Reciprocity_Relation
might be enlightening. I know it helped me. At the school I go to, most of the engineers or physics majors (same math requirement more or less) I have talked to don't really know about these rules. I'm pretty sure that means we were never taught them. It's kind of annoying.
 

Related to Why are some Maxwell relations written in reverse order?

1. What is a Maxwell relation?

A Maxwell relation is a mathematical equation that relates the partial derivatives of thermodynamic properties such as temperature, pressure, and volume.

2. How many Maxwell relations are there?

There are four Maxwell relations, each relating two of the four thermodynamic potentials: internal energy, enthalpy, Helmholtz free energy, and Gibbs free energy.

3. Why is there doubt on one of the Maxwell relations?

There is doubt on one of the Maxwell relations because it was originally derived assuming that the thermodynamic properties are continuous and differentiable. However, there are situations where this assumption does not hold, leading to doubts about the accuracy of the relation.

4. Which Maxwell relation is doubted?

The Maxwell relation that is doubted is the relation between the partial derivatives of the Helmholtz free energy and the Gibbs free energy.

5. How does the doubt on this Maxwell relation affect thermodynamics?

The doubt on this Maxwell relation does not significantly affect thermodynamics as it is still widely used and can provide accurate results in most cases. However, it is important for scientists to be aware of this doubt and use caution when applying this relation in certain situations.

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