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Thermodynamic Deriva ves

TdS Equa ons

In order to derive many of the thermodynamic rela ons we need to use the First and Second Laws simultaneously. Applying
them to a reversible process we obtain:

(1)

This rela on contains only state func ons and variables. Out of five func ons and variables we can chose any two as
independent variables. Let’s assume that S=S(T, V), U=U(T, V), and P=P(T, V). Then

(2)

And

(3)

Subs tu ng these rela ons into Eq.(1) we obtain:

Because this rela on must be true for any differen als dT, dV, we obtain:

(4)

Now, because S(T, V) and U(T, V) are state func ons, their second mixed par al deriva ves do not depend on the order of
differen a on. Hence

We arrive at a very important rela on:

(5)

For an ideal gas, for which P=nRT/V, we can immediately show that

This is the same conclusion that was reached from the experiments of Gay-Lussac and Joule. The present theore cal
approach is more sa sfying than that which depended upon not very precise experiments.

If we recall that CV=(¶ U/¶ T)V and use it together with Eq.(5) for Eqs.(1, 2), then we arrive at the first TdS rela on:

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(6)

To get the last equality, we had to use the chain rule, Eq.(A3a) and the defini ons of the expansivity b and compressibility k
.

The second TdS rela on can be derived similarly if we assume that S=S(T, P), U=U(T, P), and V=V(T, P). In this case we have
found that is be er to work with the enthalpy func on H=H(T, P) instead of internal energy U. Going through the same
steps that led us to Eq.(5), we will arrive at:

(7)

and

(8)

We can show (Try!) that for an ideal gas

Comment: Eq.(6) is easier to use in theory while Eq.(8) is more experiment friendly because it uses only intensive
parameters as the variables.

Try to derive the third TdS rela on by yourself:

(9)

Difference in the Specific Heat Capaci es

To find the difference in the specific heat capaci es let us subtract Eq.(6) from Eq.(8). Then

Dividing by (CP- CV) we obtain:

(10)

On the other hand, assuming temperature to be a func on of (V, P), we obtain:

(11)

Comparing Eqs.(10, 11) we obtain:

Both of the foregoing equa ons yield the result that

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(12)

Using Euler cyclical rela on, Eq.(A6):

we obtain

(13)

This is one of the most important equa ons of thermodynamics. It shows that

1. Since (¶ P/¶ V)T is always nega ve for all known substances and (¶ V/¶ T)P2 must be posi ve, CP can never be less
than CV.
2. As T® 0, CP® CV; or at the absolute zero the two heat capaci es are equal.
3. When (¶ V/¶ T)P =0 CP=CV. For example, this takes place for water at 4° C which its density is at a maximum.
4. Using the defini ons of the expansivity b and compressibility k we obtain:

(14)

Significance of this version of the (CP- CV) equa on is in that all the quan es there, except for CV, are measurable while CV
can be calculated theore cally. Then, Eq.(14) can be used to compare the theory with the experiment.

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