Lecture note for general thermodynamics, 2003

Chapter 15 Introduction to Phase and Chemical

Equilibrium
OUTLINE
• criteria for phase and chemical equilibrium
• determination of thermophysical properties
• What is the metastable equilibrium
• simultaneous reactions
• ionization

EQUILIBRIUM
No possibility that the system can do any work when it is isolated from its
surroundings

susystem1 engine susystem1

Requirements
w
A. Two subsystems have the same temperature (thermally equilibrium)
B. No unbalanced mechanical forces between the two systems (mechanical)

Establishment of general equilibrium criteria

A. Here assumes the simple compressible substances undergo chemical reactions
B. Gibbs function is very important
C. The general criteria : minimum of Gibbs function

EXAMPLE – Natural gas well problem

GOAL: 평형에 관한 정량적 관계유도

A. Uniform well temperature

B. Steady-state flows

Mass flow = 0 Ti = Te = T0 = const

Uniform temperature m i = m e
Vi 2 = Ve2
W rev = 0

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 Lecture note for general thermodynamics, 2003

 ⎛ Vi 2 ⎞ ⎛ Ve2 ⎞
Wrev = m i ⎜ h i + + gZ i − To si ⎟ − m  e ⎜ he + + gZ e − To se ⎟
⎝ 2 ⎠ ⎝ 2 ⎠
⎛ Vi 2 ⎞ ⎛ Ve2 ⎞
= m i ⎜ g i + + gZ i ⎟ − m e ⎜ g e + + gZ e ⎟
⎝ 2 ⎠ ⎝ 2 ⎠
0 = m ( g i − ge + g ( Z i − gZ e ) )
dgT + gZT = 0

No work and uniform temperature

∴ dgT = 0
dGT , P = 0

EQUILIBRIUM BETWEEN TWO PHASES AT A PURE SUBSTANCE

• pure substance at equilibrium

• Consider a control mass consisting of two phases (same P and T) – thermal and
mechanical equilibrium
• Then, how about the chemical equilibrium ?

Phase 1 : n1 and Phase : n2

Positive change of moles in phase 1 = Negative change of moles in phase 2

dn1 = − dn2 G = f (T , P , n1 , n 2 )
∂G ⎞ ∂G ⎞ ∂G ⎞ ∂G ⎞
dG = ⎟ dP + ⎟ dT + 1 ⎟
dn1
+ 2 ⎟
dn 2
∂P ⎠T ,n1 ,n2 ∂T ⎠ P ,n1 ,n2 ∂n ⎠ P ,T ,n2 ∂n ⎠ P ,T ,n1
dG = g 1dn1 + g 2dn 2 = dn1 ( g 1 − g 2 ) = 0
g1 = g 2 예) 포화증기와 포화액체의 주어진 온도에서의 값은 동일

dg f = v f dP − s f dT = dg g = v g dP − s g dT Tds = dh − vdP
dP ( v g − v f ) = dT ( s g − s f ) g g

∫ Tds = ∫ dh
dP s fg h f f
= = fg
dT v fg Tv fg Clapeyron equation g f = gg

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

WHAT IS METASTABLE EQUILIBRIUM?

• if point a is reached in the divergent section of the nozzle, no condensation

occurs until point b is reached
• At point b, abrupt condensation occurs : condensation shock
• Metastable state : a와 b사이는 증기지만 실제로 온도는 포화온도보다 낮다
• Dotted lines : possible metastable states for solid-liquid-vapor equilibrium
• Metastable state : 상변화에서 항상 존재가능성이 있음.

CHEMICAL EQUILIBRIUM (VERY IMPORTANT)

ν A A +ν BB R ν CC +ν D D homogeneous chemical reaction

dnA = −ν Ad ε ,
dGT , P = 0
dnB = −ν B d ε , decreases
dnC = +ν C d ε ,
increases
dnD = +ν D d ε
dε : change of the degree of reaction
Assumptions
- Two phases are in equilibrium at given T and P (constant)
- A small quantity of one component be transferred from one
phase to the other
- reaction process toward the right ( infinitesimal amount)

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

Evaluation of the change in the Gibbs function (process to the right in the amount d ε )

dGT , P = GC dnC + GD dnD − G AdnA − GB dnB

The partial molal dGT , P
Gibbs function = GCν C d ε + GDν D d ε − G Aν Ad ε − GBν B d ε
= ( GCν C + GDν D − G Aν A − GBν B ) d ε

For ideal gases only in this lecture G = H − TS

⎛ ∂G ⎞ ⎛ ∂H ⎞ ⎛ ∂S ⎞
⎜ ⎟ = ⎜ ⎟ − T ⎜ ⎟
⎝ ∂nA ⎠T , P ,nB ⎝ ∂nA ⎠T , P ,nB ⎝ ∂nA ⎠T , P ,nB
For compound A,

G A = H A − TS A = hATP = hATP
0
0

⎛ y P⎞
S A = s ATPA =YA P = s 0 ATP 0 − R ln ⎜ A 0 ⎟
⎝ P ⎠
⎛ yA P ⎞ ⎛ y P⎞
G A = hATP
0
0 − Ts ATP + RT ln ⎜
0 0
0 ⎟
= g 0 ATP 0 + RT ln ⎜ A 0 ⎟
⎝ P ⎠ ⎝ P ⎠

Change in Gibbs function of each component in the mixture

⎧ ⎡ 0 ⎛ yC P ⎞ ⎤ ⎡ 0 ⎛ yD P ⎞ ⎤ ⎫
ν
⎪ C⎢ C g + RT ln +
⎜ P 0 ⎟⎥ D ⎢ D ν g + RT ln ⎜ P 0 ⎟⎥ ⎪
⎪ ⎣ ⎝ ⎠⎦ ⎣ ⎝ ⎠⎦ ⎪
dGTP = ⎨ ⎬ dε
⎪ −ν ⎡ g 0 + RT ln ⎛ y A P ⎞ ⎤ − ν ⎡ g 0 + RT ln ⎛ yB P ⎞ ⎤ ⎪
⎪ A ⎣⎢ A ⎜ 0 ⎟⎥ B ⎢ B ⎜ 0 ⎟⎥
⎩ ⎝ P ⎠⎦ ⎣ ⎝ P ⎠ ⎦ ⎭⎪
∆G 0 = ν C g C0 + ν D g 0D − ν A g 0A − ν B g B0
Change in Gibbs funcion

⎧⎪ 0 ⎡ yνCC yνDD ⎛ P ⎞ν C +ν D −ν A −ν B ⎤ ⎫⎪
dGT , P = ⎨ ∆G + RT ln ⎢ ν A ν A ⎜ 0 ⎟ ⎥ ⎬ dε
⎩⎪ ⎣⎢ A A ⎝
y y P ⎠ ⎦⎥ ⎭⎪
At temperature and the standard-state pressure
Only function of temperature
Assume that the reactants are initially separated and the products are
finally separated at T and reference pressure
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 Lecture note for general thermodynamics, 2003

⎧⎪ 0 ⎡ yνCC yνDD ⎛ P ⎞ν C +ν D −ν A −ν B ⎤ ⎫⎪
dGT , P = ⎨ ∆G + RT ln ⎢ ν A ν A ⎜ 0 ⎟ ⎥ ⎬ dε
⎪⎩ ⎣⎢ A A
y y ⎝ P ⎠ ⎦⎥ ⎪⎭

Chemical equilibrium state : dGT , P = 0

⎡ yνCC yνDD ⎛ P ⎞ν C +ν D −ν A −ν B ⎤ ∆G 0
ln ⎢ ν A ν A ⎜ 0 ⎟ ⎥=− = ln K
⎢⎣ A A ⎝
y y P ⎠ ⎥⎦ RT
ν C +ν D −ν A −ν B
yνCC yνDD ⎛ P ⎞
K = νA νA ⎜ 0 ⎟
yA yA ⎝ P ⎠

Chemical equilibrium constant (화학평형상수)

Negative and large ln K leads to a very small value of K
It means the large and positive change in Gibbs function

Small K : reaction is shifted to the left (the

values of RHS are smaller than those of LHS)
K = 1 : zero change in Gibbs function

NOTE : ∆G 0
A. Effects of T on reactions − = ln K
RT
For higher T, but same shift in Gibbs function, ln K is smaller, K is closer to unity
(reaction is centered)
For lower T, the reaction is shifted toward the side with the smallest Gibbs function

B. Influence of P : only if νC + ν D − ν A − νB ≠ 0

In the case that moles of products > those of reactants

P/P0 >1 : reduces the RHS concentrations (because of a fixed K at a given T)

Arguments
A higher pressure pushes the reaction toward the side with fewer moles
A lower pressure pushes the reaction toward the side with more moles

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

Table A.11

LHS III = aLHS I + bLHS II

RHS III = aRHS I + bRHS II
∆GIII
0
= ∆GIII
0
, RHS − ∆G III , LHS = a ∆ G I + b∆ G II
0 0 0

∆GIII0
∆GI0 ∆GII0
ln K III = − = −a −b = aK I + bK II
RT RT RT
K III = K Ia K IIb

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

SIMULTANEOUS REACTIONS

• So far, it was assumed that there was only a single reaction

• Here deals with simultaneous reactions, (more than one chemical reaction)
• More general situation

• Consider a mixture of substances A,B,C,D,L,M, and N

ν A A +ν B B R ν CC +ν D D
1

ν A A +ν LL R ν M M +ν N N
2

dnA = −ν A1 d ε 1 − ν A2 d ε 2 , dnB = −ν B d ε 1 ,
dnL = −ν Ld ε 2 , dnC = +ν C d ε 1 ,
dnD = +ν D d ε 1 , dnM = +ν M d ε 2 , dnN = +ν N d ε 2 ,

Change in Gibbs function of each component in the mixture

dGT , P = ∑ Gi dni

( ) ( )
dGT , P = GCν C + G Dν D − G Aν A1 − GBν B d ε 1 + GMν M + G Nν N − G Aν A2 − GBν B d ε 1

Therefore, the partial molal Gibbs functions in terms of

⎛ yP⎞
Gi = g 0 i + RT ln ⎜ i 0 ⎟
⎝ P ⎠
The change in Gibbs function can be rewritten as

⎧⎪ 0 ⎡ yνCC yνDD ⎛ P ⎞ν C +ν D −ν A1 −ν B ⎤ ⎫⎪
dGTP = ⎨ ∆G1 + RT ln ⎢ ν A ν ⎜ 0 ⎟ ⎥ ⎬ dε 1
⎩⎪ ⎢⎣ y A yB ⎝
1 B
P ⎠ ⎥⎦ ⎭⎪
⎧⎪ 0 ⎡ yνMM yνNN ⎛ P ⎞ν M +ν N −ν A2 −ν L ⎤ ⎫⎪
+ ⎨ ∆G2 + RT ln ⎢ ν A ν ⎜ 0 ⎟ ⎥ ⎬ dε 2
⎪⎩ ⎣⎢ A L
y 2
y L
⎝ P ⎠ ⎦⎥ ⎪⎭
The standard-state change in Gibbs function for each reaction

∆G10 = ν C g 0C + ν D g 0 D − ν A1 g 0 A − ν B g 0 B
∆G20 = ν M g 0 M + ν N g 0 N − ν A2 g 0 A − ν L g 0 L

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

The change in Gibbs function of the system at constant T, P for infinitesimal degrees of
reaction of both reactions 1 and 2

⎧⎪ 0 ⎡ yνCC yνDD ⎛ P ⎞ν C +ν D −ν A1 −ν B ⎤ ⎫⎪
dGTP = ⎨ ∆G1 + RT ln ⎢ ν A ν ⎜ 0 ⎟ ⎥ ⎬ dε 1
⎪⎩ ⎢⎣ y A yB ⎝
1 B
P ⎠ ⎥⎦ ⎪⎭
⎧⎪ 0 ⎡ yνMM yνNN ⎛ P ⎞ν M +ν N −ν A2 −ν L ⎤ ⎫⎪
+ ⎨ ∆G2 + RT ln ⎢ ν A ν ⎜ 0 ⎟ ⎥ ⎬ dε 2
⎩⎪ ⎣⎢ A L
y 2
y L
⎝ P ⎠ ⎦⎥ ⎭⎪

Chemical Equilibrium Condition dGT , P = 0

Reactions 1 and 2 are independent : bracketed terms must be zero

∆G10 ∆G10
ln K 1 = − , ln K 2 = −
RT RT

ν C +ν D −ν A1 −ν B
yνCC yνDD ⎛ P ⎞
K1 = ν A ν ⎜ 0 ⎟
y A 1 yBB ⎝ P ⎠
ν M +ν N −ν A2 −ν L
yνMM yνNN ⎛ P ⎞
K2 = ν A ν ⎜ 0 ⎟
y A 2 y LL ⎝ P ⎠

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

IONIZATION
Consider the equilibrium of systems that are made of ionized gases, or plasma
Molecular dissociation at high temperature

N2 R 2N At about 3000 to 10 000 K

Free electron
N R N + + e− At higher temperature, atoms lose an electron

N + R N ++ + e − A R A+ + e −
y A + ye − ⎛ P ⎞ 1 + 1 − 1
K= ⎜ ⎟
yA ⎝ P 0 ⎠
∆G 0
ln K = −
RT
∆G = g A+ + g e0− − g 0A
0 0

School of Mechanical Engineering, ChungAng University

 Lecture note for general thermodynamics, 2003

School of Mechanical Engineering, ChungAng University