Fisika Termal – PAP3109

Thermodynamic Potentials

Jurusan Fisika, Fakultas MIPA1– Universitas Andalas

Fisika Termal – PAP3109 Click to edit Master text styles
 Thermodynamic Potentials
So far, we have been using the total internal energy U and, sometimes, the enthalpy
H to characterize various macroscopic systems. These functions are called the
thermodynamic potentials: all the thermodynamic properties of a system can be
found by taking partial derivatives of the TP.
For each TP, a set of so-called “natural variables” exists:
d U  T d S  P dV   d N d H  T d S  V dP   d N
Today we’ll introduce the other two thermodynamic potentials: the Helmholtz free
energy F and Gibbs free energy G. Depending on the type of a process, one of these
four thermodynamic potentials provides the most convenient description (and is
tabulated). All four functions have units of energy.

Potential Variables
When considering different types of processes,
we will be interested in two main issues:
U (S,V,N) S, V, N
 What determines the stability of a system
H (S,P,N) S, P, N
and how the system evolves towards an
F (T,V,N) V, T, N equilibrium;
G (T,P,N) P, T, N  How much work can be extracted from a
system.
Fisika Termal – PAP3109
Fisika Termal – PAP3109 22 Click to edit Master text styles
 Isolated Systems, independent variables S and V
Advantages of U : it is conserved for an isolated system (it also has a simple physical
meaning – the sum of all the kin. and pot. energies of all the particles).
In particular, for an isolated system Q=0, and dU = W.
Earlier, by considering the total differential of S as a function of variables U, V, and N,
we arrived at the thermodynamic identity for quasistatic processes :
dU  S ,V , N   TdS  PdV   dN
The combination of parameters on the right side is equal to the exact differential of
U . This implies that the natural variables of U are S, V, N,
Considering S, V, and N as  U   U   U 
dU ( S ,V , N )    dS    dV    dN
independent variables:   S V , N   V S ,N   N  S ,V

Since these two equations for dU must yield  U   U   U 

the same result for any dS and dV, the    T     P    
  S V , N   V S ,N   N  S ,V
corresponding coefficients must be the same:
Again, this shows that among several macroscopic variables that characterize the
system (P, V, T, , N, etc.), only three are independent, the other variables can be
found by taking partial derivatives of the TP with respect to its natural variables.
Fisika
FisikaTermal – PAP3109
Termal – PAP3109 33 Click to edit Master text styles
 Equilibrium in Isolated Systems
For a thermally isolated system Q = 0. If the
UA, VA, SA UB, VB, SB volume is fixed, then no work gets done (W = 0)
and the internal energy is conserved: U  const

While this constraint is always in place, the system might be out of equilibrium (e.g., we
move a piston that separates two sub-systems, see Figure). If the system is initially out of
equilibrium, then some spontaneous processes will drive the system towards equilibrium. In
a state of stable equilibrium no further spontaneous processes (other than ever-present
random fluctuations) can take place. The equilibrium state corresponds to the maximum
multiplicity and maximum entropy. All microstates in equilibrium are equally accessible
(the system is in one of these microstates with equal probability).
S eq  max
This implies that in any of these spontaneous processes, the entropy tends to
increase, and the change of entropy satisfies the condition
dS  0 S
Suppose that the system is characterized by a parameter x
which is free to vary (e.g., the system might consist of ice and
water, and x is the relative concentration of ice). By
spontaneous processes, the system will approach the stable
equilibrium (x = xeq) where S attains its absolute maximum. xeq x
Fisika Termal – PAP3109
Fisika Termal – PAP3109 44 Click to edit Master text styles
 Enthalpy (independent variables S and P)
The volume V is not the most convenient independent variable.
In the lab, it is usually much easier to control P than it is to
control V.
To change the natural variables, we can use the following trick:

Legendre Trans.: U  S ,V   U  S , P   PV

dH  d U  PV   dU  PdV  VdP
dH  TdS  VdP dH S , P, N   T dS  VdP  dN
dU  T dS  PdV
H (the enthalpy) is also a thermodynamic potential, with its natural variables S, P, and N.
- the internal energy of a system plus the work needed to make room for it at P=const.

The total differential of H in terms  H   H   H 

dH S , P, N     dS    dP    dN
of its independent variables :  S  P , N  P  S , N  N  S , P

 H   H   H 
Comparison yields the relations:   T   V   
 S  P , N  P  S , N  N  S , P

In general, if we consider processes with “other” work: dH  TdS  VdP   Wother

Fisika Termal – PAP3109
Fisika Termal – PAP3109 55 Click to edit Master text styles
 Processes at P = const , Wother = 0
At this point, we have to consider a system which is not isolated: it is in a thermal
contact with a thermal reservoir.

dH  TdS  VdP   Wother   Q  VdP   Wother

Let’s consider the P = const processes with purely “expansion” work (Wother = 0),
dH P,W other 0
 Q

For such processes, the change of enthalpy is equal to the thermal energy (“heat”)
received by a system.

 Q   H  For the processes with P = const and  Wother = 0, the

CP     
 T P  T P enthalpy plays the same part as the internal energy
for the processes with V = const and Wother = 0.

Example: the evaporation of liquid from an open vessel is such a process, because
no effective work is done. The heat of vaporization is the enthalpy difference
between the vapor phase and the liquid phase.
Fisika Termal – PAP3109
Fisika Termal – PAP3109 66 Click to edit Master text styles
 Systems in Contact with a Thermal Reservoir

There are two complications:

(a) the energy in the system is no longer fixed (it may flow
between the system and reservoir);
(b) in order to investigate the stability of an equilibrium, we
need to consider the entropy of the combined system (=
the system of interest + the reservoir) – according to the
2nd Law, this total entropy should be maximized.

What should be the system’s behavior in order Reservoir R

UR - Us
to maximize the total entropy?
System S
Stotal  Ssystem  Sreservoir Us

Fisika Termal – PAP3109

Fisika Termal – PAP3109 77 Click to edit Master text styles
Helmholtz Free Energy (independ. variables T and V)
Let’s do the trick (Legendre transformation) again, now to exclude S :
U S ,V   U T ,V   T S F U T S
d U  TS   TdS  PdV  SdT  TdS   SdT  PdV

dF T ,V , N    SdT  PdV  dN

 F   F   F 
dF T ,V , N   
The natural variables for
 dT    dV    dN
F are T, V, N:  T V , N  V T , N  N T ,V

 F   F   F 
   S    P   
 T V , N  V T , N  N T ,V
 F   F   U   S 
    P can be rewritten as: P        T  
 V T , N  V T , N  V T , N  V T , N
The first term – the “energy” pressure – is dominant in most solids, the second term – the
“entropy” pressure – is dominant in gases. (For an ideal gas, U does not depend on V, and
only the second term survives).
Fisika Termal – PAP3109
Fisika Termal – PAP3109 88 Click to edit Master text styles
 The Minimum Free Energy Principle (V,T = const)

U  U R  U s , U R Us  N , V of both are fixed Reservoir R

UR - Us

S R  s U R ,U s   S R U  U s   S s U s   max
System S
Us

system’s parameters only

 S  U 
S R  s U ,U s   S R U    R  U s   S s U s   S R U    s  S s   S R U   s
F
 U  T  T

SR+s reservoir loss in SR due to gain in Ss due to

+system transferring Us to transferring Us to the
the system system

Us
dU s 1
Fs
dS R  s U ,U s   dS s     dU s  TdS s 
T T
system
dFs
stable Us dS R  s  Fs  min
equilibrium T
Fisika Termal – PAP3109
Fisika Termal – PAP3109 99 Click to edit Master text styles
 Processes at T = const
In general, if we consider processes with “other” work: dF   SdT  PdV   Wother
For the processes at T = const
(in thermal equilibrium with a large reservoir):
dF T   PdV   Wother T
The total work performed on a system at T = const in a reversible process is equal to the
change in the Helmholtz free energy of the system. In other words, for the T = const
processes the Helmholtz free energy gives all the reversible work.
Problem: Consider a cylinder separated into two parts by an adiabatic piston.
Compartments a and b each contains one mole of a monatomic ideal gas, and their initial
volumes are Vai=10l and Vbi=1l, respectively. The cylinder, whose walls allow heat transfer
only, is immersed in a large bath at 00C. The piston is now moving reversibly so that the final
volumes are Vaf=6l and Vbi=5l. How much work is delivered by (or to) the system?

The process is isothermal : dF T   PdV T

Vaf Vbf

UA, VA, SA UB, VB, SB

The work delivered
to the system:
 W   Wa   Wb   dFa   dFb
Vai Vbi
3 3 T V 
F  U  TS  RT   RT ln  RT ln  Tf ( N , m ) 
For one mole of
2 2 T0 V0 
Vaf Vbf
monatomic ideal gas:  W   RT ln  RT ln  2.5  103 J
Vai Vbi
Fisika Termal – PAP3109
Fisika Termal – PAP3109 10
10 Click to edit Master text styles
Gibbs Free Energy (independent variables T and P)
Let’s do the trick of Legendre transformation again, now to exclude both S and V :

U S ,V   U T , P   T S  PV
G  U  T S  PV the thermodynamic potential G is called the Gibbs free energy.

Let’s rewrite dU in terms of independent variables T and P :

dU  TdS  PdV  d (TS )  SdT  d PV   VdP d U  TS  PV    SdT  VdP

dGT , P, N    SdT  VdP  dN

 G   G   G 
Considering T, P, and N as dGT , P, N     dT    dP    dN
independent variables:  T  P,N  P T , N  N T , P

Comparison yields the  G   G   G 

   S   V   
relations:  T  P,N  P T , N  N T , P

Fisika Termal – PAP3109

Fisika Termal – PAP3109 11
11 Click to edit Master text styles
 Gibbs Free Energy and Chemical Potential
G  G T , P, N  & extensive: bG T , P, N   G T , P, bN   G  N
b is a arbitary constant.

This gives us a new interpretation of the chemical potential: at least for the
systems with only one type of particles, the chemical potential is just the
Gibbs free energy per particle.

 G  G
The chemical potential    
 N T ,P N
If we add one particle to a system, holding T and P fixed, the Gibbs free energy
of the system will increase by . By adding more particles, we do not change the
value of  since we do not change the density:   (N).

Note that U, H, and F, whose differentials also have the term dN, depend on N
non-linearly, because in the processes with the independent variables (S,V,N),
(S,P,N), and (V,T,N),  = (N) might vary with N.
Fisika Termal – PAP3109
Fisika Termal – PAP3109 12
12 Click to edit Master text styles
 Example:
Pr.5.9. Sketch a qualitatively accurate graph of G vs. T for a pure substance as it
changes from solid to liquid to gas at fixed pressure.

 G  the slope of the graph G(T ) at fixed P should be –S.

   S Thus, the slope is always negative, and becomes
 T  P , N steeper as T and S increases. When a substance
G undergoes a phase transformation, its entropy
increases abruptly, so the slope of G(T ) is
discontinuous at the transition.
solid
liquid gas
 G 
   S G   ST
T  T  P
S
these equations allow computing Gibbs
free energies at “non-standard” T (if G is
solid tabulated at a “standard” T)
gas
liquid

T
Fisika Termal – PAP3109
Fisika Termal – PAP3109 13
13 Click to edit Master text styles
 The Minimum Free Energy Principle (P,T = const)
S R  s U R ,U s   S R U  U s   S s U s   max

dSR  s U ,U s   dSs   dVs   dU s  TdSs  PdVs   

dU s P 1 dGs
T V T T
Under these conditions (fixed P, V, and N), the maximum
SR+s reservoir
entropy principle of an isolated system is transformed into
+system a minimum Gibbs free energy principle for a system in the
thermal contact + mechanical equilibrium with the
Us reservoir.
Gs

dGT , P, N  0
system

stable Us G  min
equilibrium

Thus, if a system, whose parameters T,P, and N are fixed, is in thermal contact with a
heat reservoir, the stable equilibrium is characterized by the condition:
G/T is the net entropy cost that the reservoir pays for allowing the system to have volume
V and energy U, which is why minimizing it maximizes the total entropy of the whole
combined system.
Fisika Termal – PAP3109
Fisika Termal – PAP3109 14
14 Click to edit Master text styles
 Processes at P = const and T = const
Let’s consider the processes at P = const and T = const in general, including the
processes with “other” work:
 W   PdV   Wother
Then
dG  d U  T S  PV T , P  Q  PdV   Wother T , P  TdS  PdV
  Q T , P   Wother T , P  TdS   Wother T , P

The “other” work performed on a system at T = const and P =

const in a reversible process is equal to the change in the Gibbs
free energy of the system.
In other words, the Gibbs free energy gives all the reversible
work except the PV work. If the mechanical work is the only
kind of work performed by a system, the Gibbs free energy is
conserved: dG = 0.
Gibbs Free Energy  the Spontaneity of Chemical Reactions
Fisika Termal – PAP3109
Fisika Termal – PAP3109 15
15 Click to edit Master text styles
 Maxwell relation

T.P. are state functions, i.e. cross derivatives are equal.

e.g. dU  TdS  PdV   dN
 T    U    U   P 
         
 V  S , N V  S  S  V   S V , N

 T      P    
similarly,     ,     
 N 
 S ,V  V , N 
S N  S ,V  V S ,N

More in Problem 5.12

Fisika Termal – PAP3109

Fisika Termal – PAP3109 16
16 Click to edit Master text styles
 Summary

Potential Variables
dU S ,V , N   T dS  PdV  dN
U (S,V,N) S, V, N
dH S , P, N   T dS  VdP  dN
H (S,P,N) S, P, N
dF T ,V , N    S dT  PdV  dN
F (T,V,N) V, T, N
G (T,P,N) P, T, N dGT , P, N    S dT  VdP  dN

 T   P 
Maxwell relation:      ,
 V  S , N  S V , N

Fisika Termal – PAP3109

Fisika Termal – PAP3109 17
17 Click to edit Master text styles