dd331 said:
Why the Legendre transform (LT) in thermodynamics ??.
Callen, one of the first to convert to the LT-approach of thermodynamics, writes in 1987 (Thermodynamics etc, p138): "
the introduction of the transformed representations is purely a matter of convenience". Zia etal (in the above link provided), state more or less the same (p10):
Physically, we have motivated the LT and as facilitating a way of thinking about a complex problem in terms of a more naturally controllable independent variable.
Zia etal add a condition to the existence /usefulness of the LT a function F(x) with respect to x: F(x) must be strictly convex in x. Strictly convex means F"(x)>0. To test for convexity we need the specification of F(x), eg F(x) = ½mx2. If we do not know this specification we cannot differentiate and and cannot test for strict convexity.
If we limit the discussion at this point to thermodynamics (because the devastation there is more profound then in mechanics), we have now at least two criteria to test the LT-hypothesis: Convenience and convexity.
1. First of all: there is nothing convenient about the Legendre transform. It is more simple to define H as H=U+pV as the sum of two forms of energy (where H and U can be expressed in variables of choice), then to define H(p,S) = (dU/dV)SV -U(V,S), ie as an LT of U(S,V), where one has to prove that (dU/dV)S = -/+p for all physical systems, and needs U written as a function of S and V. Zia etal do not report that the LT of U(x,y) does not yield H,F or G, unless U(x,y)=U(S,V), so we need the function U(S,V), which is very inconvenient. Note that there is also a sign-problem to make H a true LT and make the 2 approaches match.
2. In general (for an arbitrary, but well defined system), both U(V,S) and H(p,S) are unknown (unspecified) functions: This means that it is not known whether these functions are strictly convex, and also that the actual LT cannot be performed.
3. If we want to know the enthalpy H of 100 g water (example of a well defined system), we look it up in a table (where it arrived through calorimetric measurements, not through a LT) and find it to be -15.9 kJ, at T=298K and p=1 atm. We can calculate H as function of T by using the heat-capacity at constant pressure. Hence H(100g water, 1 atm) = -15.9 + 0.418(T-298). This is a convenient function, already expressed in an intensive variable. Applying a LT on this function will get you absolutely nowhere.
4. Zia writes:
For historic reasons, LT variables (in thermodynamics) are not always chosen as conjugate pairs. This defeats the whole idea of the LT. In addition one has to fiddle with signs, which destroys the property of duality, inherent in a true LT.
It can be concluded that there is no reason to assume that H is a LT of U, and that it surely would be very inconvenient if it would (Zia etal note problems in teaching). For F and G (as LT) we apply one of the principles of Roman Law:
Quod gratis assertibus gratis negatur. =What is presented without proof can be denied without proof. Note that U,H, F and G have physical meaning: they are not mathematical auxiliary functions, as suggested by LT.
The why-question for application of the LT in mechanics (Lagrangean<=>Hamiltonian) remains unresolved here, but must be addressed as well.