What is the relationship between partial derivatives in thermodynamics?

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Discussion Overview

The discussion revolves around the relationship between partial derivatives in thermodynamics, particularly focusing on the application of Euler's chain rule and its implications for thermodynamic variables. Participants explore mathematical techniques relevant to thermodynamic concepts, including the use of partial derivatives under various conditions.

Discussion Character

  • Technical explanation
  • Mathematical reasoning
  • Exploratory

Main Points Raised

  • One participant presents a relationship involving partial derivatives and expresses uncertainty about applying Euler's chain rule with an additional variable (u).
  • Another participant suggests differentiating the expression for dz with respect to y at constant u as a potential approach to solve the problem.
  • A later reply indicates that the initial participant successfully resolved their query, implying some level of understanding was achieved.
  • Further discussion introduces the concept of comparing heat capacities at constant pressure and volume, expanding on the relationship between entropy and temperature, and presenting various equations involving partial derivatives.
  • One participant asserts that constant pressure specific heat is always higher than constant volume specific heat based on the positivity of certain terms in their derived equations.

Areas of Agreement / Disagreement

While some participants express agreement on the usefulness of certain mathematical techniques, the discussion includes multiple approaches and interpretations of the relationships between variables, indicating that no consensus is reached on all aspects of the topic.

Contextual Notes

The discussion includes various assumptions about the conditions under which the derivatives are taken, and the implications of these assumptions are not fully resolved. There are also references to specific thermodynamic properties that may depend on the context of the variables involved.

Jacobpm64
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Show that: \left(\frac{\partial z}{\partial y}\right)_{u} = \left(\frac{\partial z}{\partial x}\right)_{y} \left[ \left(\frac{\partial x}{\partial y}\right)_{u} - \left(\frac{\partial x}{\partial y}\right)_{z} \right]

I have Euler's chain rule and "the splitter." Also the property, called the "inverter" where you can reciprocate a partial derivative.

If I write Euler's chain rule, I only know how to write it when there are 3 variables, I usually write it in the form:
\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

Where I can write x,y,z in any order as long as each variable is used in every spot. However, I do not know how to work this chain rule if I have an extra variable (u in this case).

I also tried using the "splitter" to do something like writing:
\left(\frac{\partial z}{\partial y} \right)_{u} = \left(\frac{\partial z}{\partial x} \right)_{u} \left(\frac{\partial x}{\partial y}\right)_{u}

However, I do not know what to do with this because I have the term
\left(\frac{\partial z}{\partial x} \right)_{u} , which doesn't appear in the original problem.

Any help would be appreciated.

Thanks in advance.

(This is for a thermodynamics course, but we are still in the mathematics introduction.)
 
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You can write dz as

dz=\left(\frac{\partial z}{\partial x}\right)_y dx + \left(\frac{\partial z}{\partial y}\right)_x dy

Now differentiate both sides with respect to y at constant u, and continue trying out Euler's chain rule in various places, and you should have it.
 
Woot I got it.

Thanks a lot.
 
Last edited:
Cool. That trick is useful if you want to compare relationships at different constant conditions. For example, which is larger, heat capacity at constant pressure or constant volume? Expand entropy the same way:

<br /> dS=\left(\frac{\partial S}{\partial T}\right)_V dT + \left(\frac{\partial S}{\partial V}\right)_T dV<br />

<br /> \left(\frac{\partial S}{\partial T}\right)_p=\left(\frac{\partial S}{\partial T}\right)_V + \left(\frac{\partial S}{\partial V}\right)_T \left(\frac{\partial V}{\partial T}\right)_p<br />

<br /> T \left(\frac{\partial S}{\partial T}\right)_p-T\left(\frac{\partial S}{\partial T}\right)_V =C_p-C_V=T \left(\frac{\partial S}{\partial V}\right)_T \left(\frac{\partial V}{\partial T}\right)_p=T \left(\frac{\partial P}{\partial T}\right)_V \left(\frac{\partial V}{\partial T}\right)_p=-T\left(\frac{\partial T}{\partial V}\right)_p^{-1}\left(\frac{\partial V}{\partial p}\right)_T^{-1}\left(\frac{\partial V}{\partial T}\right)_p=\frac{\alpha^2 V T}{\beta}<br />

Since all these terms are positive (thermal expansion can be negative, but it's squared), constant pressure specific heat is always higher.
 

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