ME 7002 (522 M1460) Advanced Thermodynamics

Fall, 2018
Topic 3. Formal Relationships and Sample Systems
Instructor: Kuo-Long Pan

Contents
I. The Euler equation
II. The Gibbs-Duhem relation
III. Summary of formal structure
IV. The simple ideal gas and multicomponent simple ideal gases
V. The ideal van der Waals fluid
VI. Electromagnetic radiation
VII. The rubber band
VIII. Molar heat capacity and other derivatives

Reading
H. B. Callen, Thermodynamics and An Introduction to Thermostatistics, 2nd Ed., Chap. 3.

I. The Euler Equation

The Euler form with homogeneous first-order property
․ Because of homogeneous first-order property for the fundamental relation,
U S , X 1 ,, X t   U S , X 1 , , X t 
U , X k ,  S  U , X k ,  X j 
     U S , X 1 , , X t 
 S    X j  
U , X k , t
U , X k ,
 S  X j  U S , X 1 ,, X t 
 S  j 1  X j 
t
․ For  = 1 (true for any ), U  TS   Pj X j .
j 1

․ For a simple system, therefore, U  TS  PV  1 N1     r N r .

The entropy representation

t
S   Fj X j
j 0
․ Similarly, for the entropy representation,
1 P r
 
S   U   V    k  N k
T  T  k 1  T 

II. The Gibbs-Duhem Relation

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Dependency in the intensive parameters
․ The intensive parameters are not all independent, which are linked by a relation, as a
consequence of the homogeneous first-order property.
․ For a single-component system, the fundamental relation can be written as u = u(s, v); each
of the three intensive parameters is also a function of s and v.
․ Elimination of s and v from among the three equations of state yields a relation among T,
P, and . Therefore  can be written as a function of T and P.

A general case
․ U = U(S, X1, X2,…, Xt), yields (t + 1) equations of state, Pk = Pk(S, X1, X2,…, Xt).
․ Choosing  as 1/Xt, Pk = Pk(S/Xt, X1/Xt,…, Xt-1/Xt, 1). Therefore, each of these (t + 1)
intensive parameters is a function of just t variables.
․ Elimination of these t variables among the (t + 1) equations yields the desired relation
among the intensive parameters.

Gibbs-Duhem relation
․ Differential form
t t
dU  TdS  SdT   Pj dX j   X j dPj
j 1 j 1
t
 dU  TdS   Pj dX j
j 1
t
 SdT   X j dPj  0
j 1

 d   sdT  vdP for a single - component system

․ The variation of any one can be computed in terms of the variations of the other two.
․ The Gibbs-Duhem relation presents the relationship among the intensive parameters in
differential form. Integration of this equation yields an explicit form, leading to an
alternative procedure to determine the relation.

Thermodynamic degrees of freedom

․ The number of intensive parameters capable of independent variation is called the number
of thermodynamic degrees of freedom of a given system.
․ A simple system of r components has r + 1 thermodynamic degrees of freedom.
t
The entropy representation X j 0
j dF j  0

1 P r  
Ud    Vd     N k d  k   0
T   T  k 1 T 

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III. Summary of Formal Structure
U  U S , V , N 
Single-component simple system
T  T S , V , N   T s , v 
P  PS , V , N   Ps, v 
   S ,V , N    s, v 
․ To obtain the fundamental equation:
 Three equations of state can be substituted into the Euler relation. Thus the totality of all
three equations of state is equivalent to the fundamental equation.
 If only two equations of state are known, the Gibbs-Duhem relation can be integrated to
obtain the third. The fundamental equation can be obtained except for an undetermined
constant.
 Direct integration of the molar relation, when two equations of state are given, renders a
convenient method, except for an undetermined constant.
du = Tds  Pdv  u = u(s, v)

Completeness of fundamental equations

․ It is always possible to express the internal energy in terms of other parametric
combinations such as T, V, and N.
․ However, the transformed equation is not a fundamental relation and does not contain all
possible thermodynamic information.
․ The optimum information is contained in U(S, V, N) but not U(T, V, N) because T is the
derivative of the former. Thus an integration constant appears through the transformation
of the latter toward the primitive function.

Example 3.3-1: find the fundamental equation by applying the above methods.

IV. The Simple Ideal Gas and Multicomponent Simple Ideal Gases
Simple ideal gas
․ A simple ideal gas is characterized by PV = NRT and U = cNRT.
․ Examples: gases composed of noninteracting monatomic atoms (He, Ne, Ar…) at kBT  Ee
(T  104 K) and at low or moderate pressures, where c = 3/2.

Fundamental equation
․ Appropriate form in entropy representation:

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 1 cR P R
 
T u T v
 1 P
d    ud    vd  
T  T  T 
du dv
 cR R
u v
  u v
integratio
 n      cR ln  R ln
T  T 0 u0 v0

1 P 

 S   U   V    N
T  T  T 
 c 1
 U 
c
V  N   
 S  Ns 0  NR ln       where s 0  c  1R   
 U 0   V0  N 0    T 0

․ Alternative approach:
1 P
ds   du   dv
T  T 
R R
 c du   dv
u v
u v
integratio
 n  s  s0  cR ln  R ln
u0 v0

Multicomponent simple ideal gases

․ Gibbs’ Theorem: The entropy of a mixture of ideal gases is the sum of the entropies that
each gas would have if it alone were to occupy the volume V at temperature T. This is true
for all ideal gases.

S   N jsj U   N ju j
j j

  T  V 
 S   N j s j 0    N j c j  R ln   N j R ln  
N v 
j  j  T0 j  j 0 
 
U    N j c j  RT
 j 

․ Alternate interpretation

  T  V  N 
S   N j s j 0    N j c j  R ln  NR ln    R N j ln  j 
j  j  T0  Nv0  j  N 

․ The last term is known as the “entropy of mixing.” It represents the difference in entropies
between that of a mixture of gases and that of a collection of separate gases each at the

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 same temperature and the same density as the
original mixture Nj/Vj = N/V, and hence the same
pressure.
․ A thought experiment justifying Gibbs’s theorem
– Fix Nj and T.
– Separate the mixture, with TS = -WM.
– Due to equilibrium, A, = A,, B, = B,.
– Consequently, P = P = ½P. (Prob. 3.4-14)
– Total work (~ P + P –P = 0) is zero and hence
entropy is invariant. (c.f. Callen, Sec. 3.4, Fig. 3.2)

V. The Ideal Van Der Waals Fluid

For real gases
RT a
P  2
v b v
․ The correction for V is due to finite-volume
occupation of molecules while that for P is caused by the attraction of intermolecular forces.
․ While more complicated forms with five or more empirical constants have been used to
improve quantitative applications, the van der Waals equation successfully represents the
qualitative features of real fluids, including the gas-liquid phase transition.
․ Statistical mechanics provides a more quantitative and formal derivation of the van der
Waals equation. It reveals an infinite series of higher order corrections.
․ The van der Waals equation must be supplemented with a thermal equation of state to define
the system fully. This equation shall not be freely determined as that for an ideal gas since
thermodynamic formalism imposes a consistency condition.

Consistency condition of thermodynamics

P R a 1
  2
T v b v T
 f u , v 
1
T
1 P
ds   du   dv
T  T 
․ For ds to be a perfect differential, the mixed second-order partial derivatives must be equal,
i.e.

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 2s 2s

vu uv
 1  P a  1
       2  
v  T u u  T  v v u  T  v
 1  1
   a  
 1 / v   T u u  T  v
1 1 u 
~ f  
T v a
1 cR
․ Since for a simple ideal gas, 1/T = cR/u, to be consistent,  .
T ua/v
․ The van der Waals equation of state and the fundamental relation (how?) are
P R acR
  2
T v  b uv  av

S  Ns0  NR ln v  b u  a / v 
c

․ Both the fundamental equations for ideal gas and van der Waals fluid do not satisfy the
Nernst theorem, and thus they cannot be valid at very low temperatures.

VI. Electromagnetic Radiation

An example of electromagnetic system: an empty cavity maintained at T
․ This is a repository of electromagnetic energy which may be considered as a vessel
containing photons (quantum physics) or as a resonant cavity supporting electromagnetic
modes (engineering), whereas any such mechanistic models might be avoided by the
classical thermodynamicist.
․ The empirical equations of state:
U = bVT4 (Stefan-Boltzmann Law)
and P = U / (3V)
․ The fundamental equation S = S(U, V) is not a function of N because there exist no
conserved particles. 1 P
S U V
T T
1 / 4 3/ 4
1 U  P 1 1/ 4  U 
  b1 / 4    b  
T V  T 3 V 
4
 S  b1 / 4U 3 / 4V 1 / 4
3

VII. The Rubber Band

For rubber band consisting of a bundle of long-chain polymer molecules
․ The quantities of macroscopic interest: the energy U, the length L, the tension , and the

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 temperature T.
․ In addition to the analogy between L and V, and  and -P, the mole number N is similar
with the number of monomer units in the rubber band. But since that number is not
generally variable, it is taken as a constant here.
․ Qualitative observations via experiment:
 U is independent of L, for the length < the elastic limit of the rubber band (a length
corresponding to the “unkinking” or straightening of the polymer chains).
  increases with T at constant L.

Thermodynamic relations
․ U = cL0T, where L0 is the unstretched length of the rubber band ~ N.
․ For the second observation:  = bT(L  L0) / (L1  L0), L0 < L < L1.
․ The insertion of the factor T is dictated by the thermodynamic condition of consistency of
 1   
the two equations of state:     
L  T U U  T  L
1  dU L  L0
dS  dU  dL  cL0 b dL
T T U L1  L0

 S  S 0  cL0 ln
U

b
L  L0 2
U 0 2L1  L0 
․ Although this fundamental equation has been constructed on the basis only of the most
qualitative of information, it does represent empirical properties reasonably and, most
important, consistently.

VIII. Molar Heat Capacity and Other Derivatives

The second derivatives
․ The various second derivatives are descriptive of material properties, and these derivatives
often are the quantities of most direct physical interest.
․ For simple nonmagnetic systems the basic set of derivatives are just three.
․ The coefficient of thermal expansion
1  v  1  V 
     
v  T  P V  T  P
․ The isothermal compressibility
1  v  1  V 
T       
v  P T V  P T
․ The molar heat capacity at constant pressure
 s  T  S  1  dQ 
cP  T        
 T  P N  T  P N  dT  P

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․ For systems of constant mole number all other second derivatives can be expressed in terms
of these three, and they are therefore normally tabulated as functions of temperature and
pressure for a wide variety of materials.
․ Other second derivatives of interest:
1  v  1  V 
The adiabatic compressibility s       
v  P  s V  P  S
 s  T  S  1  dQ 
The molar heat capacity at constant volume cv  T        
 T v N  T V N  dT V

Tv 2 Tv 2
cv  c p   s  T 
T cp

․ Example 3.9-1: molar volume v as a function of T and P

Homework #3
․ 3.3-1
․ 3.4-2, 3.4-8, 3.4-12, 3.4-14
․ 3.5-1
․ 3.7-2
․ 3.9-1