ME 7002 (522 EM1460) Advanced Thermodynamics

Fall, 2019
Topic 2. The Conditions of Equilibrium
Instructor: Kuo-Long Pan

Contents
I. Intensive parameters
II. Equations of state
III. Entropic intensive parameters
IV. Thermodynamic equilibrium  temperature
V. Mechanical equilibrium
VI. Equilibrium with respect to matter flow
VII. Chemical equilibrium

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

I. Intensive Parameters
The fundamental equation
U  U S ,V , N1 ,, N r 
r 
 U   U  U 
dU    dS    dV    dN j
 S V , N1 ,, N r  V  S , N1 ,, N r  
j 1  N j 
      
S ,V , N ; 1,,r ,  j
  
T P
j

․ The three partial derivatives are intensive parameters, respectively defining the
temperature, negative pressure, and the electrochemical potential (or chemical potential in
brief) of the jth component. These shall be corroborated with our physical observations.
․ With constant mole numbers, TdS = dU – dWM. Compared with the definition of quasi-
static heat flux  dQ = TdS.
r
․ Quasi-static chemical work: dWc    j dN j
j 1

․ Therefore, dU = dQ + dWM + dWc = TdS  PdV + jdNj. Each term has the dimensions
of energy.

II. Equations of State

Definition
․ Since T, P, and j are derivatives of functions of S, V, N1,…, Nr, we get a set of functional

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 relationships, expressing intensive parameters in terms of the independent extensive
parameters, called equations of state:
T = T(S, V, N1,…, Nr), P = P(S, V, N1,…, Nr), j = j(S, V, N1,…, Nr).
․ The equations of state are homogeneous zero order, rendered by the fact that the
fundamental equation must be homogeneous first order, that is
T(S, V, N1,…, Nr) = T(S, V, N1,…, Nr).
․ Knowledge of all the equations of state of a system is equivalent to knowledge of the
fundamental equation and consequently is thermodynamically complete.

General forms
 U 
․ U = U(S, X1, X2,…, Xt)    T  T S , X 1 ,, X t 
 S  X1 ,, X t
t
 dU  TdS   Pj dX j  U 
   Pj  Pj S , X 1 ,, X t 
j 1  X 
 j  S ,, X k ,k  j
Molar form
․ For single-component simple systems,

u s, v  U S , V , N 
1
N
u u
du  ds  dv
s v
 u   u   U   u 
        T and     P
 s  v  s V , N  S V , N  v  s
 du  Tds  Pdv

III. Entropic Intensive Parameters

Generality
․ Considering S as dependent, then S = S(X0, X1, X2,…, Xt).
t
S t
dS   dX k   Fk dX k
k  0 X k k 0

S  U / X k S , X j  k  S   U 
  and   1  
X k U / S  X k  U  X k  S  X k
 Pk
 F0 
1
, Fk  k  1, 2, 3, ...
T T
t
․ The above results can also be obtained from the equation: TdS  dU   Pj dX j .
j 1

․ S = S(U, X1, X2,…, Xt), entropic fundamental relation with entropic extensive/intensive
parameters.

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․ U = U(S, X1, X2,…, Xt), energetic fundamental relation with energetic extensive/intensive
parameters.
․ The formal development of thermodynamics can be carried out in either the energy or
entropy representations alone, but for a particular problem one of them may prove to be
much more convenient. It is important to commit to that representation throughout the
analysis so that confusion can be avoided.

IV. Thermal Equilibrium–Temperature

Extremum principle and equilibrium condition
․ For a closed composite system internally separated by a rigid, impermeable, diathermal
wall, the conservation condition: U(1) + U(2) = constant, but the internal energy U’s are
allowed to change individually.
․ At equilibrium, dS = 0. The additivity of the entropy and virtual energy transfer lead to

   
S  S 1 U 1 , V 1 ,  , N j1 ,   S 2  U 2  , V 2  , , N j2  , 
 S 1  1  S
2 

dS   
1  dU  
 2  
 dU 2 
 U V 1 ,, N j1 ,  U V  2  ,, N j2  ,
   
1 / T 1  1/ T  2 

 
 1 / T 1  1 / T 2  dU 1  0
1 1
 1  2 
T T
․ This yields the condition of equilibrium, whereby T(1) = T(1)(U(1)) and T(2) = T(2)(U(2)) (V
and Nj are constant). Together with the conservation condition, U(1) and U(2) can be
completely determined.
․ In thermodynamic theory, we accept the existence of the fundamental equations, but we do
not assume explicit forms for them and hence we do not obtain explicit answers.
․ In practical applications the fundamental equations may be known, either by empirical
observations or on the basis of statistical mechanical calculations based on simple models.
In this way applied thermodynamics is able to lead to explicit numerical answers.
․ In energy representation: T(1) = T(2) (in terms of S, V,…)

Stability
․ In addition to dS = 0, the condition of maximum entropy needs to be satisfied for a stable
equilibrium: d2S < 0.

․ Agreement with the intuitive concept of temperature: S  1 / T 1  1 / T 2  U 1  0 
(entropy maximization).
․ The sign is consistent with the direction of heat flow.

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V. Mechanical Equilibrium
Equilibrium states
․ A closed composite system internally separated by a movable diathermal wall associated
with
 Conservation of energy: U(1) + U(2) = constant
 Closure condition: V(1) + V(2) = constant
․ At equilibrium, dS = 0. The additivity of the entropy and virtual changes of energy and
volume lead to

 S 1  1  S
1


dS   
1 

dU   1  dV 1
 U V 1 ,, N j1 ,  V U 1 ,, N j1 ,
     
1 / T 1  P 1  / T 1 
2  2 
 S   2   S 

 
2  

dU   2   dV 2 
 U V  2  ,, N j2  ,  V U  2  ,, N j2  ,
     
1/ T 2  P2  / T 2 


 dS  1 / T 1
 1/ T 2 
dU 1

 P /T 1 1

 P 2  / T 2  dV 1  0
1 1 P 1 P 2 
 1   2  
T T T 1 T 2 
1
 T  T 2  P 1  P 2 

Physical interpretation
․ The equality of the pressures is precisely the result that we would expect on the basis of
mechanics, and this corroborates the identification of the function P as the mechanical
pressure.
․ The entropic equations of state 1/T and P/T are functions of U and V, for each subsystem.
Together with the conservation equations, the four unknowns (U(1), U(2), V(1), V(2)) can be
completely solved by the four equations.
․ Thermodynamics provides the methodology, which becomes explicit when applied to a
concrete system with a definite fundamental relation, or with known equations of state.
․ Example 2.7-1: thermal and mechanical equilibrium in a system composed of three
subsystems

VI. Equilibrium with Respect to Matter Flow

Equilibrium states
․ A closed composite system internally separated by a rigid diathermal wall, permeable to
one of the species associated with
 Conservation of energy: U(1) + U(2) = constant

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  Conservation of mole numbers: N1(1) + N1(2) = constant
․ At equilibrium, dS = 0. The additivity of the entropy and virtual changes of energy and
mole number N1 lead to
 S 1  1
1  S 
dS   
1  dU   1 
 dN11
 U V 1 , N 11 ,, N j1 ,  N1 U 1 ,V 1 ,, N j1, j 1 ,
 
1 / T 1  11  / T 1 

 S 2   2   S
2 

  
2   dU  
 2  
 dN12 
 U V 2  , N 11 ,, N j2  , 
 1 U  2  ,V  2  ,, N j2, j1 ,
N
    
1 / T 2  1 2  / T  2 

 dS  1 / T 1  1 / T 2  dU 1  11 / T 1  12  / T 2  dN11  0

1 1 11 12 
 1  2  
T T T 1 T 2 
 T  T 2 
1
11  12 

Physical interpretation
․ Just as the temperature is a sort of “potential” for heat flux and the pressure is a sort of
“potential” for volume changes, the chemical potential can be looked upon as a sort of
“potential” for matter flux, with its difference providing a “generalized force” for matter
flow.
․ If we assume T(1) = T(2), the entropy variation

S   11 / T 1  12  / T 2  N11  0 
2  1
1  1
or dS  dN11  0
T
․ Thus matter tends to flow from regions of high chemical potential to regions of low
chemical potential.

VII. Chemical Equilibrium

Chemical reactions
․ In a chemical reaction the mole numbers of the system changes, some increasing at the
expense of a decrease in others. This is similar to the aforementioned diffusive systems.
․ Examples: 2H2 + O2  2H2O
2O  O2
․ A general equation of chemical reaction and the stoichiometric coefficients j
r
0   j A j
j 1

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The fundamental equation S = S(U, V, N1,…, Nr)
․ For an adiabatic and rigid “reaction vessel,” U and V are constant. Therefore,
r j dNˆ r
dS   dN j     j j
j 1 T T j 1
r
   j j  0
j 1

Here dNˆ is the factor of proportionality.

․ If the equations of state of the mixture are known, the equilibrium condition permits explicit
solution for the final mole numbers.
․ Example of a multi-reaction system: H2, O2, H2O, CO2, CO

Homework #2
․ 2.2-4, 2.2-5
․ 2.3-5
․ 2.7-1
․ 2.8-1
․ 2.9-1