What are Helmholtz free energy and Gibbs free energy?
Both Helmholtz and Gibbs free energies are important thermodynamic functions known as Thermodynamic potentials.
The Helmholtz free energy is defined as,
The above definition may be obtained from the internal energy function by means of one Legendre transform.
The Helmholtz free energy has
Differentiating the expression for
Using the combined mathematical form of first and second laws of thermodynamics,
That is why the Helmholtz free energy is known as thermodynamic potential at constant volume.
It stays constant during any isothermal-isochoric change.
For such a system, the Helmholtz free energy tends to minimize as the system tends to equilibrium.
Now coming to Gibbs free energy, the expression is,
The above relation may be derived from the internal energy function by means of Legendre's transformations to change variables.
It may also be cast in the form,
Again using the combined mathematical form of the first and second law of thermodynamics (for reversible transformations),
The Gibbs function is also called thermodynamic potential at constant pressure.
For an Isothermal-isobaric transformation,
Such a system tending to equilibrium requires
It may also be of some interest to mention that the specific heats at constant volume and pressure are related respectively to
The Gibbs' free energy is the energy available to do non-PV work in a thermodynamically-closed system at constant pressure and temperature.
The Helmholtz free energy is the maximum amount of "useful" (non-PV) work that can be extracted from a thermodynamically-closed system at constant volume and temperature.
The following are derivations that prove these definitions at the undergraduate level. It will involve some minor multi-variable calculus.
#delta#will indicate path functions (inexact differentials), meaning those that are dependent on the path taken, and are not state functions.)
The Gibbs' free energy is a thermodynamic function of the natural variables, temperature
#dG = dH - TdS - overbrace(cancel(SdT))^(DeltaT = 0 " assumed")# #" "" "bb((1))#
#DeltaG = DeltaH - TDeltaS#from general chemistry.)
#dH = dU + PdV + overbrace(cancel(VdP))^(DeltaP = 0 " assumed")# #" "" "bb((2))#
(which may be familiar from general chemistry as
#DeltaH = DeltaU + PDeltaV#at constant pressure.)
#dG = dU + PdV - TdS#
If we examine only the non-PV work, i.e. the mechanical work that does not relate to expansions/compressions, we ignore PV work (
#=> dG = dU - TdS# #" "" "bb((3))#,
From the first law of thermodynamics, the change in internal energy
#dU = deltaq_(rev) + cancel(deltaw_(rev,PV))^"assumed 0" + deltaw_(rev,non-PV)# #" "" "bb((4))#,
#deltaw_(rev,PV) = -PdV#.
As a result, from utilizing
#dG = deltaq_(rev) + deltaw_(rev,non-PV) - TdS#
Lastly, entropy can be defined as the influence of the reversible heat flow at a given temperature:
#dS = (deltaq_(rev))/T#,
So for reversible heat flow:
#dG = cancel(TdS) + deltaw_(rev,non-PV) - cancel(TdS)#
#color(blue)(dG = deltaw_(rev,non-PV))# #" "#( #"const. T and P"#)
So, in a reversible process in a thermodynamically-closed system, the Gibbs' free energy is the maximum amount of non-PV work with respect to the surroundings that can be accomplished at constant temperature and pressure.
HELMHOLTZ FREE ENERGY
#dA = dU - TdS# #" "" "bb((5))#
(Note that even though
#dA = cancel(TdS) + overbrace(cancel(deltaw_(rev,PV)))^"0 at const. V" + deltaw_(rev,non-PV) - cancel(TdS)#
As a result,
#color(blue)(dA = deltaw_(rev,non-PV))# #" "#( #"const. T and V"#)
and the Helmholtz free energy for a reversible process in a thermodynamically-closed system is analogously the maximum available non-PV (useful) work with respect to the surroundings at constant temperature and volume.