Question about the derivation of Exact Differentials in thermo

In summary, the reason why ##dS## is expanded in only two differentials is because the other variables, P and U, are not independent of V and T. This is due to the fact that for an ideal gas, varying V and T determines dP through the ideal gas law. Additionally, according to the phase rule, a pure single phase material is determined by only two independent parameters, meaning that the four quantities mentioned are not independent.
  • #1
Jacob Nie
9
4
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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  • #2
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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  • #3
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].
 
  • #4
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.
 
  • #5
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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1. What is the concept of exact differentials in thermodynamics?

The concept of exact differentials in thermodynamics refers to a mathematical expression that describes the change in a thermodynamic property of a system in terms of its state variables, such as temperature, pressure, and volume. It is a fundamental concept in thermodynamics that allows for the calculation of the work and heat exchanged in a thermodynamic process.

2. How are exact differentials derived in thermodynamics?

The derivation of exact differentials in thermodynamics involves using the first and second laws of thermodynamics, as well as the concept of reversible processes. This involves considering infinitesimal changes in the state variables of a system and using mathematical techniques such as partial differentiation and integration to arrive at the exact differential expression.

3. What is the significance of exact differentials in thermodynamics?

Exact differentials are significant in thermodynamics because they allow for the calculation of the work and heat exchanged in a thermodynamic process, which is essential for understanding the behavior of systems and predicting their outcomes. They also provide a mathematical foundation for the laws and principles of thermodynamics.

4. Can exact differentials be used to determine the spontaneity of a process?

No, exact differentials alone cannot determine the spontaneity of a process. The concept of spontaneity in thermodynamics is determined by the change in entropy of a system. While exact differentials can provide information about the work and heat exchanged in a process, they do not take into account the change in entropy.

5. How do exact differentials relate to inexact differentials in thermodynamics?

Exact differentials are different from inexact differentials in that they are path-independent, meaning that the value of the differential is the same regardless of the path taken to reach a particular state. Inexact differentials, on the other hand, are path-dependent and are associated with properties that are not conserved, such as heat and work.

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