5LAY3R95
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Homework Statement
How to demonstrate that U is minimized at constant V and S, while H at constant P and S?
Homework Equations
ΔS universe = ΔS system + ΔS environment ≥ 0
ΔU system = δq reversible + δw reversible = δq irreversible + δw irreversible
ΔS environment = −∫(δq reversible / T)
dU = TdS − PdV = δq + δw
The Attempt at a Solution
ΔS universe = ΔS system + ΔS environment > 0
ΔS universe = ΔS system − ∫ ( δq rev /T ) > 0
ΔS universe = ΔS system − ∫( δq irrev/T + δw irrev − δw rev ) > 0
TΔS system − T∫( δq irrev/T + δw irrev − δw rev ) > 0
T∫( δq irrev/T + δw irrev − δw rev ) − TΔS system < 0
If the process is isoentropic, it follows that it's an adiabatic process with δq irrev = 0
T∫( δw irrev − δw rev ) < 0
* If, furthermore, the volume of the system is constant, it follows that irreversible and reversible works are 0, leading to a senseless expression.* If not the volume but the pressure is constant, we get
T∫( δw irrev − δw rev ) < 0
T∫( δq rev − δq irrev ) < 0 and we recover ∫δq irrev = ΔH
Now, since reversible −∫PdV is minimum in reversible process, δ rev is maximum.
It follows that the T∫(positive quantity) < 0
Which is another senseless expression.
I guess the flaw comes from the assumption that an isoentropic process is always adiabatic... but how?