PHASE EQUILIBRIA

MODULE 1
 Content
I. Nature of Equilibrium
II. Phase Rule
III. Gibbs-Duhem Equation
IV. Criteria for Phase Equilibrium in Pure Systems
V. Criterial for Phase Equilibrium in Multicomponent
Systems
VI. Equilibrium and Stability
 Raw I. Preparation II. Reaction
Materials Phase Phase

Undesired
III. Purification Side
reactants
Phase Products
Unreacted
reactants Products

Typical Chemical Plant

Volumetric Properties
of Pure Substances
The working substance:
Fluid: substance that exists as a continuum characterized by
low resistance to flow and the tendency to assume
the shape of its container.
Ex: Steam – in steam turbines
Air – in air compressors
Air & Fuel mixture – in ICE
Water – in hydraulic turbine

Pure Substance: One that has a homogeneous &

invariable in chemical aggregation.
Compressible Substance:
• Substances whose surface effects, magnetic
effects, and electrical effects are insignificant, but
changes in volume are very important.
 Pure
Pure Substance
Simple
As Pure
◦ Ex. Pure water exists as s, l, vapor or a combination of
these  chemically homogeneous
◦ However, AIR that exists as a combination of liquid
and vapor is NOT a PURE SUBSTANCE! (air: O2 & N2)
◦ Different components of air have different condensation
temperatures at a specified pressure.
◦ The liquid air will be richer in N2 than in the vapor air.

As Simple
• Defined by 2 independent variable and intensive
thermodynamic properties
Properties and State
Properties:
Descriptive characteristics that
express the behavior of the system
• Intensive Properties – independent of mass (T, P, )
• Extensive Properties – depends on mass (VT, UT)
• Specific Properties – those of a unit mass (sp.vol.)

State: • Condition as identified through the

properties of the substance;
• Defined by particular values of any
two independent properties.
 Phases
: • Solid
• Liquid
• Vapor or gas

Melting (fusion): solid to liquid

Freezing (solidification): liquid to solid
Boiling (Vaporization): liquid to gas
Condensation: vapor to liquid
Sublimation: solid to gas or vice-versa
 Vapor-Liquid-Solid Phase
Equilibrium in a Pure Substance

Saturation Temperature: the temperature at

which the liquid will start to boil or the
temperature at which the vapor will begin to
condense at a given pressure or the
temperature at which vaporization (or
condensation) takes place at a given pressure
(saturation pressure)

H2O vapor H2O vapor

Liquid H2O Liquid H2O
Saturated Liquid: Substance existing as liquid at
the saturation temperature and pressure

Subcooled Liquid: Temperature of liquid is lower

than the saturation temperature for the existing
pressure; T < Tsatn
: Temperature is lower than the
saturation temperature for a given pressure

Compressed Liquid: Temperature of liquid is lower

than the saturation temperature for the existing
pressure;
: Pressure is greater than the
saturation pressure for a given temperature
P > Psatn
Quality (x): Ratio of the mass of vapor to the
total mass pertained to substance
existing as part liquid and part vapor at
the saturation temperature
Saturated Vapor: Substance existing as vapor at
the saturation temperature

Superheated Vapor: Vapor at a temperature

greater than the saturation temperature
: (superheated steam)
Wet mixture / wet steam: a combination of
saturated vapor and saturated liquid
Supercritical Fluids: Fluids whose T & P are
above the critical T & P
% moisture: Percentage by mass that is liquid
Critical point: The saturated liquid and
saturated vapor states are identical.
Triple point: State in which all three phases
are in equilibrium
Allotropic transformation: A transition from
one solid phase to another
Heat of fusion: Amount of heat to change the
solid to a liquid, or vice versa, to
freeze the liquid at constant pressure
Latent heat: Heat for evaporation of a saturated
liquid into a saturated vapor, or vice
versa at constant pressure
 Property Diagrams
Saturation Temperature - Saturation Pressure
For Water:
@ 99.6C, Psatn=0.1 MPa

T
Vapor pressure curve of a pure substance
Saturated Liquid and Saturated Vapor States
Critical
P point
Saturated
liquid line Saturated
vapor
Vfg Line

Vf Vg V
Vf = specific volume of saturated liquid
Vg = specific volume of saturated vapor
Vfg = difference between Vf and Vg (Vfg = Vg  Vf)
 Steam Tables
◦ Vehicle for representing thermodynamic tables.
◦ Steam is used extensively in power plants and
industrial processes.

Steam Table: Appendix F.

Procedure: pp. 712-714

F.1 – Properties of saturated steam pp. 716-721 (SI)

F.2 – Properties of superheated steam pp. 722-753 (SI)
F.3 - Properties of saturated steam pp. 754-759 (English)
F.4 – Properties of superheated steam pp. 760-778 (English)
 Saturated liquid-vapor mixture
Critical
P point
Saturated
liquid line Saturated
(x = 0) vapor
Saturated Line
mixture (x = 1)
0<x<1

V
The calculation of the properties of a saturated
mixture involves the quality, x.
 Superheated Vapor
T

Saturated
vapor P Superheated Superheat region
line vapor is a single-phase
region (vapor
phase only)
T and P are
H independent
Hg H >H
p g

Superheat vapor is characterized by:

Lower pressure (P < Psatd at a given T)
Higher temperature (T > Tsatd at a given P)
Higher specific volumes (V > Vg at a given P or T)
Higher internal energy (U > Ug at a given P or T)
Higher enthalpy (H > Hg at a given P or T)
 Compressed Liquid
In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as saturated
liquid at the given temperature.

Given: P and T
V  Vf @ T H  Hf @ T U  Uf @ T

Compressed liquid is characterized by

Higher pressure (P > Psatd at a given T)
Lower temperature (T < Tsatd at a given P)
Lower specific volumes (V < Vsatd at a given P or T)
Lower internal energy (U < Usatd at a given P or T)
Lower enthalpy (H < Hf at a given P or T)
 P-V Diagram

P Critical
C point

Compressed Superheated
Liquid Region vapor region

Saturated
A liquid-vapor
region B

V
Curve AC – saturated liquid line
Curve BC – saturated vapor line
 Critical
P point

Liquid
Solid + Liquid
Evaporation
Vapor
Solid

Liquid + Vapor
Sublimation
Solid + Vapor
V
P-V diagram of a substance that contracts on freezing.
 Solid + Liquid
P Critical
point

Liquid
Evaporation
Vapor
Solid
Liquid + Vapor

Triple Point Line

Sublimation
Solid + Vapor
V
P-V diagram of a substance that expands on freezing.
 P-V Diagram
• The boiling temperature of a pure substance increases
with pressure. Vf and Vg also change with pressure.
• The normal boiling temperature of a pure substance is
the temperature at which it boils under P = 1 atm.
• series of isobars can be plotted on a T-V diagram. If
the locus of all saturated liquid and vapor states are
connected, a dome enclosing the region of two phases
(liquid+vapor) results
• Each pure substance has one isobar that becomes
horizontal (flat) at only one point. This point coincides
with the top of the two-phase dome.
• When we include solids, we have an additional single
phase region (solid) and two additional two-phase
regions (solid+vapor) and (solid+liquid).
T T-V Diagram
Critical
point T, C
Liquid P=1 atm
200
e
Vapor
c
100
b d
20 a

V
V a-b : compressed liquid
Saturated Saturated
b-d : saturated mixture
liquid vapor d-e : superheated vapor
 T-V Diagram
• The T-V diagram contains three single phase regions (liquid,
vapor, supercritical fluid), a two-phase (liquid+vapor) region,
and two important curves - the saturated liquid and saturated
vapor curves. The number of regions and curves will
increase when we consider solids.
• The saturated liquid and vapor curves meet at the critical
point, which represents the highest temperature and pressure
in which vapor and liquid phases can coexist.
• The single phase liquid region is also called subcooled liquid
because, at a given pressure, temperature will be below the
boiling temperature.
• The single phase vapor region is also called superheated
vapor because, at a given pressure, temperature will always
be above the boiling temperature.
 P-T Diagram
Substances Substances
that expand that contract
P
on freezing on freezing

Melting Critical
point
LIQUID

SOLID Vaporization

VAPOR
Triple
Sublimation point

T
 P-T Diagram
• The triple line connects a solid, liquid and vapor state that coexist at the same
temperature and pressure. For a pure substance there will be only one such
line on the PVT surface.
• On the PT projection, two-phase regions collapse to curves.
• There is a one-to-one relationship between pressure and temperature in two-
phase regions. In the solid-vapor region, the temperature at a given pressure is
called the sublimation temperature. In the solid-liquid region it is called the
melting temperature.
• The vapor pressure curve, melting curve, and sublimation curve give the
one-to-one relationship between pressure and temperature in the vapor-liquid,
solid-liquid and solid-vapor regions respectively.
• In the vapor-liquid region at a particular pressure, the temperature is called the
boiling temperature. At a particular temperature, the pressure is called the
vapor pressure.
P-V-T Diagram

Critical

Solid-Liquid
point

Liquid
P Solid
Liquid-
Vapor

V
T
Substance that contracts on freezing.
 Critical
point

Liquid
P Solid

Solid-Vapor
V
T
Substance that expands on freezing.
OTHER THERMODYNAMIC
RELATIONS
Real Gas Behavior
&
Equations of State
Equations of State : property relations that
involve other properties of a
substance at equilibrium states.

•◦ Ideal
IdealGasGas Equation
Equation of State of State – simplest and
◦ Compressibility Factor of state for substances in the gas
best known equation
•◦ Virial
Compressibility
phase; Factorof –a gas
predicts PVT behavior
Equations a correction factor
quite accurately
within
that some
can PROPERLY
accurately SELECTED
account REGIONS.
for the deviation from ideal
•◦ Cubic
Virial Equations
Equations of State
gas behavior at a given T and P
• Cubic Equations of State
– Equations of state that◦ represent the PVT behavior
Van der Waals
of substances accurately over a larger region with
◦ Beattie Bridgemann
no limitations. ◦ Benedict-Webb-Rubin
◦ Redlick-Kwong
◦ Soave-Redlick-Kwong
◦ Peng-Robinson
◦ Etc.
 Gas and Vapor
Vapor phase – can be condensed either by
compression at constant
temperature or by cooling at
constant pressure
Gas phase – can be condensed by the reduction of
temperature and pressure
Gas – term referred when above the critical
temperature
Vapor – a gas which is not far from a state of
condensation.
Ideal gas - An imaginary substance that
obeys PV = nRT
P T 

Ex: N2, H2, O2, Ne, Kr, Ar, CO2

Dense gases
Should not be treated as ideal gases
• Property tables must be used.

Ex. Water vapor and refrigerant vapors

in steam in
power plants refrigerators
Is water vapor an ideal gas?
water vapor can be treated as
◦ AT P < 10 kPa:

ideal gas regardless of its temperature

(~0.1% error)
ideal gas assumption yields
◦ AT P > 10 kPa:

unacceptable error particularly in the

vicinity of the critical point and the
saturated vapor line.

* Ex.:
GasesWaterdeviate
Vapor from ideal gas behavior
- air conditioning: as ideal gas (P too low)
significantly at states near the saturation
- steam power plant: as real gas (P too high)
region and the critical point.
 Compressibility Factor, Z
PV
Z or PV = ZRT
RT

V RT
Z  actual where Videal 
Videal P
For Ideal Pressure and
100C is agases: Z=1
low temperature for most substances,
but Real
not for gases: <
air. Z  1 (Z > 1)
Temperature of a
substance are high or low
-N2 is well over its Tc = 147C and away from
Gases behave relative to its Tc or Pc
saturation regiondifferently
at a given T and P. But
they are normalized with P T
respect to their Tc and Pc
Pr  Tr 
P c cT
The deviation of Z from unity is a
measure of the deviation of the actual
relation from the ideal gas equation of
state.

Tc : highest T at which pure substance can exist

in V-L equilibrium
Pc : highest P at which pure substance can
exist in V-L equilibrium
 Principle of Corresponding States
(3-Parameter Theorem)
Z for all gases is approximately the same at Pr and Tr

Basis for the 2 – Parameter Theorem

of Corresponding States

Experimentally determined Z values are plotted

against Pr and Tr for several gases. By curve
fitting all the data, we obtain the generalized
compressibility chart which can be used for
all gases.
Generalized Compressibility Chart
 Observations obtained Generalized
Compressibility Chart
1. At very low pressures (Pr << 1), the gases behave as an
ideal gas regardless of temperature.
As P  0
Real gas Ideal gas

2. At high temperatures (Tr > 2), ideal gas behavior can be

assumed with good accuracy regardless of pressure
(except when Pr >> 1).

3. The deviation of a gas from ideal gas behavior is

greatest in the vicinity of the critical point. Non-ideal
gas behavior
T
Ideal gas
behavior
V
 Solving an Equation of State

If V = f (T,P) and V = V(T,P)

Volume Expansibility 1  V 
  
V  T  P

Isothermal Compressibility  1  V 
  
V  P T
 V   V 
dV    dT    dP
 T  P  P  T
dV
  dT  dP
V
 incompressible
fluids
P C

=0

Liquid
 =0 T > Tc
suggests Vapor
idealization Tc
T1 < Tc
liquid-vapor
A
B T2 < Tc

V
P-V diagram of a pure substance showing the isotherms.

ln   T2  T1    P2  P1 
V2
V1
When P & V and T & V are given instead of P & T, the generalized
compressibility chart can still be used to determine the 3rd property.

Pseudo-Reduced Specific Volume, Vr

Vactual
Vr 
RTc
Pc
where:

Vr : Definitely from Pr & Tr

: Related to Tc & Pc
instead of Vc
 Virial Equations of State
RT a(T ) b(T ) c(T ) d (T )
P  2  3  4  5  .....
V V V V V
a(T )
b(T ) Virial coefficients
c(T )
..
.
As P  0, all virial coefficients will vanish and
the equation will reduce to ideal gas equation of
state.
 All equations are applicable to gas phase only.

They must not be used for

LIQUIDS AND LIQUID-VAPOR
mixtures.

For complex equations: use digital applications

For hand calculations: use property tables or simpler
equations for convenience

All equations are implicit in V and will require

T & E approach.
Applications of the Virial Equations

All isotherms originate at the value of Z = 1 for P = 0

 Z 
   B ' 2C ' P  3 D ' P 2
 ...
 P T
From which  Z 
   B'
 P T ; P 0
Equation of tangent line: B
Z  1  B' P B' 
RT
PV B
Z  1
RT V
 B PV BP
Z  1  B' P B'  Z  1 RT  PV
RT RT RT
PV B BP B
Z  1 Z  1  1
RT V
PV V
PV B - represents PVT behavior of many vapors at
Z  1
RT V subcritical temperatures up to a P of about 5 bar

For pressures above the range of applicability but below

the Pc, the virial equation becomes truncated to 3 terms:
PV B C
Z  1  2
RT V V
Cubic Equations of State
 Van der Waals Equation of State (1873)

a & b = determined from

 a 
 P  2 V  b   RT the behavior of
substance at
 V  critical point

Effects not included in the Ideal Gas Model

 intermolecular forces of attraction
 volume occupied by molecules
themselves/unit mass
Cubic Equations of State
 Van der Waals Equation of State (1873)

 a 
 P  2 V  b   RT
 V 
In a room at atmospheric T & P, the V occupied by molecules
is 1/1000 of the room.

As P increases, V occupied by molecules becomes an

increasingly significant part of the total volume.
  P 
P C   0
 V T Tc c
Tc
2P
0
A
B V 2 T Tc  c

V
3 RTc 27 R 2Tc2 RTc PcVc 3
Vc  a b Zc  
8 Pc 64 Pc 8Pc RTc 8
Refer to Table B.1.
Properties of Pure Species on pp. 680-681.
 Beattie – Bridgeman Equation of State
(1928) : based on 5 experimentally
determined constants.
RnT  C  A
P  2 1  3 V  B   2
V  VT  V
where: * Accurate for
 a densities up to
A  Ao 1  
 V 0.8c
where
 b
B  Bo 1   c : density of
 V substance at
critical point
 Benedict-Webb-Rubin Equation of State
(1940) – extension of Beattie – Bridgeman
by raising constants to 8
• Can handle densities of up to about 2.5 c
• Strobridge further extended this equation by
raising the no. of constants to 16

RT  C  1 bR T  a
p   Bo RuT  Ao  o2  2  u 3
V  T V V
  
a c    2 
 6
 3 2 
1  2 
V 
e
V V T  V 
Ao,. Bo, Co, a, b, c, , , &   all constants for
a given liquid
 Redlich / Kwong Equation
 RT   a(T ) 
P    
 V  b   V (V  b) 

 Vapor & Vapor-Like Roots of the

Generic Equation of State Dimensionless
Quantities
RT a (T ) (V  b )
V  b bP
P P V  b V   b    RT

Z  1    q
 Z  q
a(T )
Z   Z    bRT
 Liquid & Liquid-Like Roots of
the Generic Equation of State
 RT  bP  VP 
V  b  V  b V  b  
 a(T ) 
1   Z 
Z    Z   Z  B  
 q 
bP  (T r )
 q
RT  Tr
a(T ) or
q pr
bRT  
Tr
 Theorem of Corresponding States
Acentric Factor, 
Two-Parameter Correlations:
- All fluids that are compared at the same Tr and Pr have
approximately the same compressibility factor and all
deviate from ideal-gas behavior to about the same degree.

Three-Parameter Correlations:
- All fluids having the same value of , when compared at the
same Tr and Pr, have about the same value of Z, and all
deviate from ideal gas behavior to about the same degree.

  1.0  log( Pr sat ) T 0.7

r
Example 3.9/p.98
Given that the vapor pressure of n-butane at 350K
is 9.4573 bar, find the molar volumes of
(a) saturated vapor (Vg); and
(b) saturated liquid (Vf)
n-butane at these conditions as given by the
Redlich/Kwong Equation in Table 3.1.

From Appendix B.1/pp 680-681:

Tc = 425.1 K
Vc = 255 cm3/mol
Pc = 37.96 bar
Zc = 0.274
 T 350 P 9.4573
Tr    0.8233 Pr    0.2491
Tc 425.1 Pc 37.96

For RK Eqn. from  (Tr )  (Tr ) = empirical relation that is

q  specific to the equation
Table 3.1/p.98 Tr
 0 For RK Equation:  (Tr )  (Tr )
1 / 2

  0.42748
  0.08664 (Tr ) 1/ 2
 1 q 
Tr
1 3 / 2
Zc  T 0.42748  (0.8233) 3 / 2
3 q  r   6.6048
 0.08664

Pr 0.2491
   0.08664  0.026214
Tr 0.8233
 Z 
(a) Vg (satd vapor) Z  1    q
Z    Z   
Since  0
Z  Solve by iteration taking
Z  1    q
Z Z    Z = 1 initially
1  0.026214
Z  1  0.026214  (6.6048)  0.026214
1 1  (1 0.026214)
Z  0.8619

Solve for Z repeatedly until there is convergence.

Z = 0.8619 (for Z = 1)
= 0.8372 ( = 0.8619) ZRT 0.8305  83.14  350
Vg  
= 0.8320 ( = 0.8372) P 9.4573
= 0.8308 ( = 0.8320) V g  2555.35 cm 3 / mol
= 0.8306 ( = 0.8308)
= 0.8305 ( = 0.8306)
Z = 0.8305 ( = 0.8305)
(b) Vf (satd liquid)
1   Z 
Z    Z  Z     
 q 
 1  0.026214  Z 
Z  0.026214  Z  ( Z  0.026214)   
 6.6048  (0.026214) 
Take Z =  = 0.026214
for Z = 0.026214 Calc. Z = 0.03145
= 0.03145 = 0.038026
= 0.038026 = 0.04016 ZRT 0.04324  83.14  350
= 0.04016 = 0.04140 V f  
= 0.04140 = 0.04214 P 9.4573
= 0.042159 V f  133.23 cm / mol
3
= 0.04214
= 0.042159 = 0.04286
= 0.04286 = 0.04303
= 0.04303 = 0.04320
= 0.04320 = 0.04324
Z = 0.04324 = 0.04326 
= 0.04326 = 0.07591 
Generalized Correlations for Gases
A. Pitzer Correlations for the Compressibility Factor

Z  Z 0  Z ' Z 0 & Z '  f (Tr , Pr )

Where  =0 & Z = Z0 - refer to Lee Kessler Modified
Correlation Chart form of BWR

Refer to Tables E.1 for Z0 and

f(Tr,Pr)
Tables E.2 for Z’
B. Pitzer Correlations for the
Second Virial Coefficients
BP BP  P 
Z  1  1  c  r 
RT RTc  Tr 
Pitzer’s 2nd Correlation
BPc 1.0
LK Correlation
 B 0   B' Tr
RTc VC Correlation
Z0
Pr P
Z  1 B0   B' r
Tr Tr
0 Pr
P 2.5
Z 0  1 B0 r
Tr
Pr Z0and Z1: Table E.1 – E.4
Z 1  B' pp. 696-699
Tr
• 2nd virial coefficients are f(T) only
• B0 and B’ are f(Tr) only

0.422 0.172
B 0  0.083  1.6
B'  0.139 
Tr Tr4.2

Ex. 3.10. Determine the molar volume of n-butane

at 510 K and 25 bar by each of the
following:
(a) Ideal gas equation
(b) The generalized compressibility factor
correlation
(c) The generalized virial coefficient correlation
 RT (83.14)(510)
(a) Ideal Gas Equation V   1696.1 cm3/mol
P 25

(b) Generalized Compressibility Factor Correlation

From Table B.1/p.680 T 510
Tr    1 .2
Tc 425.1
Tc = 425.1 K
P 25
Pc = 37.96 bar Pr    0.6586
Pc 37.96
Z = 0.865
From Table E.1/p.696 & Table E.2/p.697
Z’ = 0.038
Z = Z + Z’
Prsat based on Tr = 0.7
  1.0  log(Pr sat ) T 0.7
r

 = 0.2 (from Table B.1/p.680)

ZRT (0.8726)(83.14)(510)
Z = 0.865 + (0.2)(0.038) V 
P 25
= 0.8726 V  1479.98 cm3/mol
If Z = Z: Then V = 1467.09 cm3/mol
(c) Generalized Virial Coefficient Correlation
0.422
B 0  0.083  1.6
 0.2322 From Pitzer’s 2nd Correlation:
Tr
BPc
0.172
B'  0.139  4.2  0.0590
 B 0   B   0.22
Tr RTc

Pr P
Z  1  B0   B r
Tr Tr
 0.659 
Z  1  (0.220) 
 1.2 
Z  0.8792

ZRT (0.8792)(83.14)(510)
V 
P 25
V  1491.14 cm3/mol
Generalized Correlations for Liquids
Rackett Equation: for estimation of molar
volumes of saturated liquids
2
(1Tr ) 7
V sat
 Vc Z c Table B.1 for
critical constants
Pr 1 1Tr 2 7 
Z sat
 Zc  
Tr
Generalized Correlations for Liquids
Lydersen, Greenkorn, and Hougen: two-
parameter corresponding-states correlation for
liquid volume estimation
 Vc r
r   V2  V1 1

c V r 2

Tr
r 3.5
3.0
2.5

saturated
liquid
0 10
Pr
 Content
I. Nature of Equilibrium
II. Phase Rule
III. Gibbs-Duhem Equation
IV. Criteria for Phase Equilibrium in Pure Systems
V. Criterial for Phase Equilibrium in Multicomponent
Systems
VI. Equilibrium and Stability
 Realizations
 Most of the materials are not pure substances with all
atoms or molecules identical  mixtures of one type or
another
 Pure substances from which solutions are prepared are
called components, or constituents, of the solution.
 Solutions are not limited to liquids.
i.e. air – mixture of N2 and O2 ; solid solutions – Si-Ge system
 Basic Relations
I. Single Component System
 Intensive properties: depends on P and T
 Extensive Properties: depends on P, T, and amount
I. Multi-component System
 Intensive properties: depends on P, T and composition
 Extensive Properties: depends on P, T, and amount of
each component
 Properties of Solutions

 The properties of solutions, in general, are not additive properties of the pure
components
 The actual contribution to any extensive property is designated as its partial
property  used to designate the property of a component when it is in
admixture with one or more components
 Partial molar properties: partial derivatives of all thermodynamic properties
with respect to mole number/s at constant P and T
– Since most chemical, biological and geological processes occur at constant T & P.
Most Common Measures of Composition

• Mass or Mole Fraction or

For binary solution: 𝟏 𝟐 𝟏 𝟐

• Molar Concentration

• Molar Mass Concentration

 Ethanol – Water System at 20C

Molar Volumes: Volume before Mixing

Water: 18 mL/mol
Vol before mixing = +(1mol)
Ethanol: 58 mL/mol

= 76 mL

Partial Molar Volumes: Volume after Mixing

@ 50 mol% of Ethanol . .
Vol after mixing = +(1mol)
Water: 16.9 mL/mol
Ethanol: 57.4 mL/mol = 74.3 mL
Ethanol:
58 mL/mol

Water:
18 mL/mol Solution Solution Infinitely
@ xE = 0.3 @ xE = 0.1 dilute
solution
Ethanol: @ 54 mL/mole, Pure
Ethanol behaves as
58 mL/mol infinitely dilute

Water:
18 mL/mol Solution Solution Infinitely
@ xE = 0.3 @ xE = 0.1 dilute
solution
 The Phase Rule
• Applicable only to systems in equilibrium
• Gibb’s phase rule
F = 2   + N = 2 + (N  1) 

Where: F = number of degree of freedom Intensive Variables:

= the number of independent properties - T
- , and
that must be specified to determine all - (N – 1) mole fraction for any
the intensive properties of each phase phase
of the system.
No. of Variables: 2 + (N – 1)
 = the number of phase that can exist in
the system.
* phase – homogeneous quantity of the system
N = number of component in the system
 The Phase Rule: Duhem’s Theorem
• Applicable to closed systems at equilibrium wherein the
extensive and intensive states of the system are fixed

2 + (N  1)  +  = 2 + N 

Where: 2 + (N  1)  = intensive phase rule variables

 = extensive variables represented by the
masses (or mole numbers) of the phases
2 + N  = total number of variables
For a Closed System with specified amounts of chemical species present:

(  1) N + N =  N
Difference between the no. of variables & the number of equations:

2+NN =2  total no. of variables

Duhem’s Theorem
For any closed system formed initially from given masses (or moles) of
prescribed chemical species, the equilibrium state is completely
determined when any two independent variables are fixed

• The number of independent intensive variables is given by

the phase rule.
• If F = 1, at least one of the two variables must be extensive
• If F = 0, both variables must be extensive
 Gibbs Equation

For Single Component:

T
, , , , , ,

By definition:
partial molar Enthalpy
, ,
partial molar Entropy
chemical potential
For partial molar entropy:

, , ,

Therefore,

Similarly for partial molar volume,

, , ,

* The molar volume tells us how chemical potential changes with P.

(T,P) P

Analogous statement:
P
For Multicomponents:
Binary System: G(T,P,n1,n2) = µ1n1 + µ2n2 @ P = 0; T = 0

µ is just how much Gibbs energy you get from n particles.

From other differentials, =
at const T & P
, ,
Subtracting:
=

Gibbs – Duhem Equation =

True in general for multicomponent systems
Criteria for Phase Equilibrium in Pure Systems

The maximum number of phases that can

coexist in equilibrium is 3.
At this point the degree of freedom of
the system becomes zero with no independent
variable remaining.

For this system to exist there will be a definite

temperature, pressure and concentration
 Phase Rule for Multicomponent Systems
For a system of more than one substance and
more than one phase in an equilibrium state:
F=2 +Nr–
Where: F = number of different independent intensive variables that
may be changed (degree of freedom)
r = number of independent relations among intensive
variables of individual phases other than relations needed
for thermal, mechanical, and transfer equilibrium
N = number of component in the system
 = the number of phase that can exist in the system.
Criteria for Phase Equilibrium in Multicomponent Systems
At equilibrium state:
- the system has one or more phases;
- each phase contains one or more species; and
- intensive properties such as T, P, and the mole fraction of a species in a
phase have definite values.

• Starting with the system in this state, we can make changes that place the
system in a new equilibrium state having the same kinds of phases and the
same species, but different values of some of the intensive properties.
• The system remains in equilibrium if the amount of a phase is changed
without changing its T, P, or composition.  the change of an extensive
variable and not counted as a degree of freedom.
Criteria for Phase Equilibrium in Multicomponent Systems

• The different phases are not separated by adiabatic or rigid partitions, or by

semipermeable or impermeable membranes.
• The number of degrees of freedom is the maximum number of intensive
properties of the equilibrium system that may be independently vary, or fixed
at arbitrary values, without causing a change in the number and kinds of phases
and species. The value is varied only within a certain finite (sometimes quite
narrow) range before a phase disappears or a new one appears.
• The number of degrees of freedom is also the number of independent intensive
variables needed to specify the equilibrium state in all necessary completeness,
aside from the amount of each phase.
 Equilibrium and Stability
 Phase equilibria is the application of the principles of thermodynamics to the
study of equilibrium relationships within or between phases, corresponding to
homogeneous and heterogeneous phase equilibria, respectively. These phases
may be minerals within a rock, a fluid percolating through the pore space of a
sediment, or a gas, or a combination of these.
 The study of phase equilibria is used to check the stability of individual
components and mixtures of components in pressure–temperature–
composition space, to obtain estimates or evaluate conditions of pressure or
temperature of equilibration in chemical reactions, and other system activities.
 The stability of phases can be predicted by the chemical potential, with the
most stable form of the substance having the minimum chemical potential at
the given temperature and pressure.  For the overall system to be
in equilibrium, the chemical potential of the compound in each phase present
must be the same.