Question about the derivation of Exact Differentials in thermo

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SUMMARY

The discussion centers on the derivation of exact differentials in thermodynamics, specifically the expression for the differential of entropy, dS. The user questions why dS is expressed solely in terms of dV and dT, omitting dP and dU, which are dependent on the first two variables. The clarification provided emphasizes that for a pure single phase material, only two parameters are independently variable, in accordance with the phase rule. This understanding is crucial for accurately describing thermodynamic systems.

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  • Understanding of thermodynamic principles, particularly the phase rule.
  • Familiarity with the concepts of exact differentials in calculus.
  • Knowledge of the ideal gas law and its implications on state variables.
  • Basic comprehension of entropy and its relationship with other thermodynamic quantities.
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  • Explore the derivation of exact differentials in thermodynamic contexts.
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This discussion is beneficial for students and professionals in thermodynamics, particularly those studying physical chemistry, chemical engineering, and anyone interested in the mathematical foundations of thermodynamic principles.

Jacob Nie
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Homework Statement
There is an equation in Riley's Mathematical Methods that I am confused about:

Applying (4.43) to ##dS##, with variables ##V## and ##T##, we find
$$dU = T \ dS - P \ dV = T\left[ \left(\dfrac{\partial S}{\partial V}\right)_T \ dV + \left(\dfrac{\partial S}{\partial T}\right)_V \ dT\right] - P \ dV.$$
Relevant Equations
Eq 4.43:
$$ dU = \left(\dfrac{\partial U}{\partial X}\right)_Y \ dX + \left(\dfrac{\partial U}{\partial Y}\right)_X \ dY$$
What I don't understand is why ##dS## is expanded in only the two differentials ##dV## and ##dT.## Why doesn't it look more like:
$$dS = \left(\dfrac{\partial S}{\partial V}\right)_{T,P,U} \ dV + \left(\dfrac{\partial S}{\partial T}\right)_{V,P,U} \ dT + \left(\dfrac{\partial S}{\partial P}\right)_{V,T,U} \ dP + \left(\dfrac{\partial S}{\partial U}\right)_{V,T,P} \ dU$$
?
 
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Those other variables, P and U, aren't independent of V and T. For an ideal gas, for example, if you vary V and T, you've determined dP through the ideal gas law.
 
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In this problem,
the fuller description of the energy is U(S,V) [thinking of the energy as function on the S-V plane]
and
the fuller description of the entropy is S(V,T) [thinking of the entropy as function on the V-T plane].
 
Thank you for the responses - that makes sense.

I forgot to read the sentence of the book that said:
These four quantities are not independent, since only two of them are independently variable.
 
According to the phase rule, the thermodynamic equilibrium state of a pure single phase material is determined by only two independent parameters.
 
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