Physical chemistry

Nghiem Thi Thuong

School of Chemical Engineering, HUST
Chapter 1. Aspects of Thermodynamics

Phase equilibria: pure substance

- Definition and concepts
 Chapter 1. Aspects of Thermodynamics

Definition of phase
solid, gas, liquid

A phase is a form of matter that is uniform throughout in chemical composition and

physical state/properties

Homogeneous Heterogeneous
system system
 Chapter 1. Aspects of Thermodynamics

Number of phase (P)

a mixture of gases is one phase

ü Miscible liquid: 1 phase

ü Immiscible liquid: >2 phases
ü Partially miscible liquids: 1, 2 or more phases
depending on composition and temperature

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 Chapter 1. Aspects of Thermodynamics

Number of phase (P)

Allotropy (allotropes): form of an element

Polymorph (polymorphs): one of a few solid phases of an
element or compound
 Chapter 1. Aspects of Thermodynamics

Definition of component
ü A component is a chemically independent constituent of a system

ü The number of components (C) in a system is the minimum number of independent

constituents necessary to define the composition of all the phases present in the
system
Examples:

System Number of
Components
(1) Water system consists of the equilibrium 1
ice ⇌ water ⇌ vapour
(2) Mixture of gases N2, O2 2
(3) Mixture of HCl, NH3 (same number of moles) in a closed 1
vessel: NH3 (k) + HCl (k) ⇌ NH4Cl (r)
(4) Decomposition of CaCO3, CaCO3(r) ⇌ CaO(r) + CO2(k) 2
 Chapter 1. Aspects of Thermodynamics

Degree of freedom (F)

"Degree of freedom is the least number of variable factors (concentration, pressure and
temperature) which must be specified so that the remaining variables are fixed
automatically, and the system is completely defined"

F = 0 → nonvariant or no degree of freedom.

F = 1 → univariant or one degree of freedom.
F = 2 → bivariant or two degrees of freedom.
Examples:

(1) For a pure gas, F = 2. For a given sample of any pure gas PV = RT. If the values of
pressure (P) and temperature (T) be specified, volume (V) can have only one definite
value, or that the volume (the third variable) is fixed automatically.

(2) For a mixture of gases, F = 3. A system containing a mixture of two or more gases is
completely defined when its composition, temperature and pressure are specified. Since
it is necessary to specify three variables to define the system completely.
 Chapter 1. Aspects of Thermodynamics

Degree of freedom (F)

Examples:

(3) For water ⇌ water vapour, F = 1. The system water in equilibrium with water vapour,
has two variables temperature and pressure. At a definite temperature the vapour
pressure of water can have only one fixed value. Thus, if one variable (temperature or
pressure) is specified, the other is fixed automatically.

(4) For saturated NaCl solution, F = 1. The saturated solution of sodium chloride in
equilibrium with solid sodium chloride and water vapour.
NaCl solid ⇌ NaCl solution ⇌ water vapour
Thus, the system is completely defined if we specify temperature only. The other two
variables i.e,. the composition of NaCl-solution (solubility) and vapour pressure have a
definite value at a fixed temperature.

Meaning of degree of freedom

The number of variables which must be arbitrarily fixed in order to define
the system completely.
 Chapter 1. Aspects of Thermodynamics

Phase transition
First-order phase transition

Second-order phase transition

Temperature
 Chapter 1. Aspects of Thermodynamics

Condition of phase equilibrium

phase 1 ⇌ phase 2 ⇌ phase 3 … … . ⇌ phase f

1,2,3 … 𝑘 1,2,3 … 𝑘 1,2,3 … 𝑘 1,2,3 … 𝑘

3 conditions must be satisfied at the equilibrium

• Thermo-equilibrium
• Mechanical-equilibrium
• Chemical-equilibrium
T1 = T2 = T3 = ... = Tf
P1 = P2 = P3 = ... = P f
µ11 = µ12 = µ13 = ... = µ1f
µ12 = µ 22 = µ 32 = ... = µ 2f
µ1k = µ k2 = µ k3 = ... = µ kf
 Chapter 1. Aspects of Thermodynamics

Phase rule
F: degree of freedom
F = C -P + 2 P: number of phases
C: number of components

If either T or P is constant F = C -P + 1 (Reduced phase rule)

If T, P and one other factor

affect the equilibrium F = C -P + 3

Do it at home: Derivation of the phase rule

 Chapter 1. Aspects of Thermodynamics

Phase diagrams
A phase diagram is a plot showing the conditions of pressure and temperature under which
two or more physical states can exist together in a state of dynamic equilibrium.

The diagram consists of :

(a) the Regions or Areas (AOC, OCB, BOA) F=2
(b) the Lines or Curves (OA, OB, OC, OD.. F =1
(c) the Triple point (O); F= 0

OA': metastable equilibrium

supercooled liquid ⇌ vapour

The vapour pressure of the metastable phase is always

higher than that of the stable phase at the same temperature.
 Chapter 1. Aspects of Thermodynamics

Phase diagrams
2-component system

A M1! M2 B

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1 xB→
0 10 20 30 40 50 60 70 80 90 100 %yB→
3-component system A (100%) !
Pa
%A = %
%B h
b
h %A Pb
c
P %B = %
h
Pc
B (100%) C (100%) %C = %
a H h
%C !
 Chapter 1. Aspects of Thermodynamics

Phase diagrams A tie line rule

Continuous rule System H = phase H1 + phase H2

P T
!
liquid
Lỏng
H1 H H2
liquid== Hơi
Lỏng vapour
(1) (2) Hơi
vapour

V
A x1 x x2 B
!
Lever rule
g1 x 2 − x HH2 g1: mass of phase H1
= =
g2 x − x1 HH1 g2: mass of phase H2
Chapter 1. Aspects of Thermodynamics

Phase equilibria: pure substance

- Phase transition of pure substance.
- Clapeyron equation and its derivatives
Chapter 1. Aspects of Thermodynamics

One component system: C=1

Degree of freedom F=C-F+2=1-F+2=3-F ≥0
→ F ≤3 → maxium three phases can coexist at the equilibrium

If F=3 → F =3-3=0 → T and P were fixed

If F=2 → F=3-2=1 → T or P can vary → T = f(P) or P=f(T)

Determine the
relationship between
T and P at phase
equilibrium
Chapter 1. Aspects of Thermodynamics

Effect of pressure on the phase transition temperature

If two phases, α and β, are in equilibrium at a pressure P and temperature T, their chemical
potentials must be equal:

µ α, P, T = µ(β, P, T)

−S! α dT + V! α dP = −S! β dT + V! β dP

−S! α dT + V! α dP = −S! β dT + V! β dP

dP S! β − S! α ∆S!
= = (Clapeyron equation)
dT V! β − V! α ∆V!

dP
is a slope of the phase boundary curve in phase diagram
dT
Chapter 1. Aspects of Thermodynamics

Effect of pressure on the phase transition temperature

Solid ⇌ Liquid equilibrium

dT V! liquid − V! solid ∆V"#$%&' T. ∆V"#$%&'

= = =
dP S! liquid − S! solid ∆S"#$%&' ∆H"#$%&'

Water system (or Bi or Ge): ∆𝑉!"#$%& <0, ∆𝐻!"#$%& >0 → Tfusion decreases as P
increases

Other systems: ∆𝑉!"#$%& >0, ∆𝐻!"#$%& >0 → Tfusion increases as P increases

Liquid ⇌ Vapour equilibrium

∆𝑉'()* > 0, ∆𝐻!"#$%& >0 → Tb increases as P increases

Chapter 1. Aspects of Thermodynamics

Effect of temperature on the saturated pressure

dP ∆H()*+ ∆H()*+ ∆H()*+ . P
= = =
dT T. ∆V()*+ T. V)*+&#, RT -
Vapor
dP ∆H()*+ . dT dlnP ∆H()*+ Clapeyron-
= → = Clausius equation
P RT - dT RT -
Liquid/solid
dP
Since ∆H()*+ > 0 → > 0 → P increases as T increases
dT

Quantitatively determine of P at different T ln P ∆H()*+

tgα = −
∆H()*+ R
lnP = − + const
RT
P- ∆H()*+ 1 1
ln = ( − )
P. RT T. T-
1/T
 Chapter 1. Aspects of Thermodynamics

Determine boiling temperature of a liquid

Normal boiling temperature of a liquid is the temperature at which the saturated vapour
pressure of the liquid equals to pressure of atmosphere outside

ln P ∆𝐻0123
𝑡𝑔𝛼 = −
𝑅
∆H()*+
lnP(atmosphere) = − + const
RT/

1/T

Standard boiling temperature a liquid is the temperature at which the saturated

vapour pressure of the liquid equals to 1 bar
Chapter 1. Aspects of Thermodynamics

Phase equilibria: pure substance

- Phase diagrams of typical materials
 Chapter 1. Aspects of Thermodynamics

Water system
∆H()*+
OA curve: lnP = − + const
RT
∆:!"#$
8
P)*+&#,/5%6#%7 = K. e ;<

∆H$#/5%!
OB curve: lnP = − + const
RT
∆:%&'()*
8
P)*+&#,/$&5%7 = K′. e ;<

dT T. ∆V"#$%&'
OC curve: =
dP ∆H"#$%&'

Triple point O: no degree of freedom what is OA' curve?

- supercooling curves

Case study: What is freeze drying? How was it applied practically?

 Chapter 1. Aspects of Thermodynamics

CO2 system

Supercritical CO2
 Chapter 1. Aspects of Thermodynamics

Carbon system
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