Partial derivatives of thermodynamic state functions

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SUMMARY

The discussion centers on the relationship between partial derivatives of thermodynamic state functions, specifically the internal energy \(E\) as a function of temperature \(T\), volume \(V\), and number of particles \(N\). The participant seeks clarification on whether \((\frac {\partial E} {\partial V})_{T,N} = -p\) holds true in equilibrium thermodynamics. It is established that the internal energy is a natural function of entropy, volume, and particle number, and that the correct expression for pressure in terms of energy requires holding the appropriate variables constant. The discussion concludes that the relationship can be derived as \((\frac{\partial E}{\partial V})_{T,N} = -p + T(\frac{\partial S}{\partial V})_{T,N}\).

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  • Understanding of multivariable calculus, particularly partial derivatives
  • Familiarity with thermodynamic state functions and equations of state
  • Knowledge of the First Law of Thermodynamics
  • Concept of Legendre transforms in thermodynamics
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  • Study the derivation of the First Law of Thermodynamics and its implications for state functions
  • Learn about the Helmholtz free energy and its relation to internal energy
  • Explore the concept of natural variables in thermodynamics
  • Investigate the application of Legendre transforms in thermodynamic systems
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Graduate students in physics, particularly those studying statistical mechanics and thermodynamics, as well as researchers and educators looking to deepen their understanding of thermodynamic state functions and their derivatives.

physlosopher
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I'm in a first-year grad course on statistical mechanics and something about multivariable functions that has confused me since undergrad keeps popping up, mostly in the context of thermodynamics. Any insight would be much appreciated!

This is a general question, but as an example imagine you're given an equation of state of a thermodynamic system, specifically its internal energy in terms of temperature, volume, and number of particles (say there's one species of particle).
$$E=E(T,V,N)$$
My ultimate questions are, is the partial derivative ##(\frac {\partial E} {\partial V})_{T,N}## something equilibrium thermodynamics can tell us about, and is it (generally) the case that ##(\frac {\partial E} {\partial V})_{T,N}=-p##?

My immediate inclination is that if I want to say anything about pressure for this system, I should write down the exact differential of the internal energy using the First Law: ##dE = TdS - pdV + \mu dN##. Please correct me if I'm wrong: this exact differential suggests that the internal energy is a natural function of the entropy, volume, and number, and so if I want to relate ##-p## to the energy by a partial derivative, i.e. ##\frac {\partial E} {\partial V}=-p##, I really need to be holding the other natural variables constant - that is, I'm really interested in the partial ##(\frac {\partial E} {\partial V})_{S,N}=-p##, where the subscripts denote the variables held constant.

But I have E as a function of T, so if I want the pressure given my equation of state, I'd want to first write temperature in terms of entropy in order to express E in its natural variables, or apply a Legendre transform from the internal energy to the Helmholtz free energy (call it A), in which case I'd have the relationship ##(\frac {\partial A} {\partial V})_{T,N}=-p##, correct?

Thanks in advance for any help!
 
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As you say
A=E-TS
dA=-SdT-pdV+\mu dN
(\frac{\partial A}{\partial V})_{T,N}=-p
From here you can derive
(\frac{\partial E}{\partial V})_{T,N}=-p+T(\frac{\partial S}{\partial V})_{T,N}
 
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