Chapter 4.

Physical transformations of pure substance

Physical Chemistry
 Overview

4-1. Conditions for equilibrium between phases

4-2. Stability of phase

4-3. Thermodynamic analysis of Phase Diagram

4-4. Order of phase transition

4-5. Phase – rule : Degree of Freedom

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4-1. Conditions for equilibrium between phases
* For a system with phases  ,  maintained
at constant T, P the equilibrium condition (상평형조건)

2nd Law :

dGT ,P  0
At equilibrium :

dG = 0 (4.1)

dG = dG + dG  = 0

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4-1. Conditions for equilibrium between phases

For components i, transfer ( →)

→ dG = −   dn +   dn = 0
(Assume dni transferred from
→  =   (4.2)  → through chemical
reaction or a change in
aggregation state)
for a pure substance,
 
Gm = Gm
(  =   )
: the potential of a substance to bring about change. (physical or chemical)

Physical Chemistry
4-2. Stability of phase (상의 안정성)

For a pure substance,  = Gm : molar Gibbs energy

d = − S m dT + Vm dP (4.3)

  
  = −Sm (4.4)
 T  P
  
  = Vm (4.5)
 P T

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4-2. Stability of phase : temperature dependence

Sm, gas  Sm,liquid  Sm, solid

At given temperature, a
state with lowest chemical
potential (molar Gibbs
energy) is the most stable.

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4-2. Stability of phase : pressure dependence
  
  = Vm
 P T

Vsolid  VLiquid (most liquid) Vsolid  Vliquid (water)

Vsolid  VLiquid Vsolid  Vliquid

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4-2. Stability of phase : examples

* Examples : Phase diagram for pure substance

* water * Helium

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4-3. Thermodynamic analysis of P-T Diagram
* Phase diagram : examples (상평형도의 열역학적 해석)

* For two phases  ,  in equilibrium

 
d  = d   (6.6) ⇒ Gm = Gm

From (6.3)

− Sm dT + Vm dP = − Sm  dT + Vm  dP (4.7)

 
dP S m − S m S m
→ =   = (4.8) → Clapeyron equation
dT Vm − Vm Vm

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 4-3. Thermodynamic analysis of P-T Diagram
Since H m
S m =
T ,
Thus dP H
= m
(4.9)
dT T Vm

* For the change Liquid → Vapor

dP H v ,m
= (4.10)
dT Tb (Vg ,m − Vl ,m )

If we neglect Vl ,m (  Vg .m) and assume that V = RT

g ,m ,
P
Then dP H v ,m
=
dT RT 2 / P
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4-3. Thermodynamic analysis of P-T Diagram

→ d ln P H v ,m
= (4.11) → Clausius – Clapeyron equation
dT RT 2
d ln P H v,m
→ =−
d (1 / T ) R

If H  f (T ) , then integration from T* (P*) to T (P) gives

P = P*e −
H v ,m  1 1 
=  − *
R T T 

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 4-4. Order of phase transition : Ehrenfest classification
* First-order transition (melting, vaporization) : 1차 상전이
- usual change of state : S → L, L → V, …
- Discontinuous change of S , H , V
- First derivative of  is discontinuous

Temperature(T)

Physical Chemistry
4-4. Order of phase transition : Ehrenfest classification
* Second-order transition (2차 상전이)
- Phase transition of some metals (초전도체)
- No latent heat or density change
- Discontinuity of CP = T (S T ) P
- First derivative of  is continuous, but second
derivative is discontinuous

Temperature(T)

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 4-4. Order of phase transition : Ehrenfest classification
*  transition
- not 1st-order transition but
CP →  at transition temperature
- order-disorder transition (liquid He, 자성체)

Ex)
- order-disorder transition in alloys
- onset of ferromagnetism.
- fluid-superfluid transition of liquid He.

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 4-5. Phase – rule : Degree of Freedom (자유도)

f = C − P + 2 (4.12)
‘C’omponents, ‘P’hases,

f : number of intensive variables changeable without disturbing equilibrium state

f =
total # of intensive # of intensive variables
variables required to
describe system[1]
- that cannot be
independently varied[2]
(4.13)

[1] = PC + 2 : mole fractions, T , P (total # variables)

Physical Chemistry
 4-5. Phase – rule : Degree of Freedom

[2] = C ( P − 1) + P 1 = 1 = 1 = ... = 1 p

(# of equations) 2 = 2  = 2 = ... = 2 p

…
c = c  = c = ... = c p
f = PC + 2 − C ( P − 1) + P [equilibrium conditions]

= C − P + 2 “Gibbs phase rule’ (Gibbs 상률)

* Pure substance 순수한 물질 (C = 1, single component)

F=C–P+2=1–P+2=3–P

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