Chemical Engineering

Thermodynamics

Recommended Books:
Smith J.M., Van Ness, Abbot M, “Chemical Engineering Thermodynamics”
7th Ed. Mcgraw-Hill international Edition.
DaubertThomas E. “Chemical Engineering Thermodynamics”, 1st Ed. 1985,
McGraw-Hill Book Company.
Sandler Stanley I. “Chemical and Engineering Thermodynamics” 3rd Ed.
John Wiley and Sons, Inc.
Cengel, Y.A., Boles, M.A., “Thermodynamics: An Engineering Approach”,
2008, Mcgraw-Hil.
 COURSE CONTENTS
 General Vapour Liquid Equilibrium (VLE) behaviour: Equilibrium Criterion
and Raoult’s Law.
 VLE Calculations – Bubble Point, Dew Point and Flash calculations.
 Partial Molar quantities; Excess Properties; Chemical potential; Fugacity
and activity coefficients; Theory and applications.
 Chemical Reaction Equilibrium and Constants; Single and Multi-Reaction
equilibria.
 Chemical and Phase Equilibrium, Phase Transitions, Gibbs Free energy,
Ideal Reacting gas mixture.
 Calculations in Phase Equilibria, Liquid-Liquid, Liquid-Solid.
Thermodynamic analysis of Chemical Processes.
 Introduction to Statistical Thermodynamics.
VAPOR/LIQUID EQUILIBRIUM

Chapter 10
 Generally, In thermodynamics and Chemical engineering
terms, Vapor Liquid Equilibrium describes the distribution of a
chemical species between vapor phase and a liquid phase.

 Vapor pressure strongly dependent upon temperature.

 Pressure of a vapor in contact with its liquid or solid form.

 In system such as distillation & absorption, if the system is not

in equilibrium, the mass transfer between system will alter
their composition.
 Chapter Outline (Smith)
Nature of Equilibrium
 Definition
 Measures of composition

VLE : Qualitative behavior

Simple Models for VLE

- Raoult’s Law
-Dewpoint & Bubblepoint Calculations with
Raoult’s Law
 THE NATURE OF EQUILIBRIUM

Equilibrium : A static condition in which no

changes occur in the macroscopic properties
of a system with time.

The T, P,
composition
reaches final
value which will
remain fixed:
equilibrium
 Measures of composition

Measures
of
composition

Molar mass for

Mass or Molar
a mixture or
mole fraction concentration
solution

mi m i xi M   xi M i
xi   Ci  i
V
m m
 VLE: QUALITATIVE BEHAVIOR
VLE: State of
coexistence of L
& V phases

Fig. 10.1 – Shows the P-T-

composition surfaces of
equilibrium states of saturated
V & saturated L of a binary
system
 Under surface- sat. V states (P-T-y1)

 Upper surface- sat. L states (P-T-x1)

 Liquid at F, reduces pressure at constant T &

composition along FG, the first bubble appear at L –
bubble point

 As pressure reduces, more & more L vaporizes until

completed at W; point where last drop of L (dew)
disappear – dew point
SIMPLE MODELS FOR VLE

Simple Models
For VLE :
Find T, P, composition

Raoult’s Law Henry’s Law

Raoult’s Law

Assumptions;
 V phase is an ideal gas
 Applicable for low to moderate pressure
 L phase is an ideal solution
 Valid only if the species are chemically similar (size, same chemical nature
e.g. isomers such as ortho-, meta- & para-xylene)
yi P  xi Pi sat
 i  1,2,..., N 
Where;
xi : L  phase mole fraction
yi : V  phase mole fraction
Pi sat : Vapor pressure of pure species i
P : Total pressure
 Dewpoint & Bubblepoint
Calculations with Raoult’s Law

FIND GIVEN
BUBL P: Calculate {yi} and P, given {xi} and T
DEW P: Calculate {xi} and P, given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P
 For binary systems to solve for
bubblepoint calculation (T is given);

y i i 1

P   xi Pi
i
sat
PP 2
sat

 P 1
sat
P
2
sat
x
1

x1 P1 sat
y1 
P
 Raoult’s law equation can be solved for xi
to solve for dewpoint calculation (T is
given)
i xi 1

P
1 1
 i i
y P sat P
i y1 / P1  y2 / P2
sat sat

y1 P
x1  sat
P1
 PHASE RULE & DUHEM’S THEORY
Equilibrium states are determined by:

Phase Rule
Duhem’s Theory
 The Phase Rule
Number of variables that may be independently fixed in a
system at equilibrium =
Difference between total number of variables that
characterize the intensive state of the system and number
of independent equation
F = 2-π+N

Where : F – degrees of freedom

π – No of phase
N – No of species
 Duhem’s Theory
• For any closed system formed initially from
given masses of prescribed chemical species,
the equilibrium state is completely determined
when any two (2) independent variables are
fixed.
 Henry’s Law

Assumptions
 For pressure low
It is so low that it can be assume as ideal gas

 Forspecies present as a very dilute solution in liquid

phase
 Henry’s Law

yi P  xi H i  i  1,2,..., N 
Where;
xi : L  phase mole fraction
yi : V  phase mole fraction
H i : Henry's constant
P : Total pressure
 Example 10.2

Assuming that carbonated water contains only CO2(1)

and H2O(2), determine the compositions of the V & L
phases in a sealed can of ‘soda’ & the P exerted on
the can at 100C. Henry’s constant for CO2 in water at
100C is about 990 bar and x1=0.01.
Henry’s law for species 1 & Raoult’s law for species 2
are written;

y1 P  x1 H1 y2 P  x P 2 2
sat

P  x1 H1  x P 2 2
sat

With H1=990 bar & P2sat = 0.01227 bar (from steam

tables at 100C)

P   0.01 990   0.99 0.01227

P  9.912 bar
 Then by Raoult’s law, for species 2;

x2 P2sat  0.99  0.01227 

y2    0.0012
P 9.912

Whence y1=1-y2=0.9988, and the vapor phase is nearly

pure CO2, as expected.
Review

 What is bubble point?

 What is dew point?
 We have previously went through the 2
simplest models for solving VLE
problems
 Raoult’s Law
 Henry’s Law
 VLE

Modified
Raoult’s Law Henry’s Law K-Values
Raoult’s Law
 VLE BY MODIFIED RAOULT’S
LAW
The 2nd assumption of Raoult’s Law is abandoned,
taking into account the deviation from solution ideality
in L phase.
Thus, activity coefficient  is introduced in Raoult’s
Law

yi P  xi i Pi sat
 i  1,2,..., N 
Activity coefficients are function of T & liquid phase
composition, x
Since;
y i i 1
P   xi i Pi sat
For bubble point
i

i xi 1
1 For dew point
P
 yi  i Pi
i
sat
BUBL P
DEW P
 BUBL T CALCULATION

BUBL T Find Ti sat

Find initial T from mole-fraction weighted average

T  x1T1sat  x2T2sat

For current T, find A,  1 ,  2 ,

P1 sat , P2sat   P1sat P2sat

Find new value for P1sat from equation 10.6;

P
P1sat 
 x1 1  x2 2  

Find new T from Antoine equation for species 1

B1
T  C1
A1  ln P1sat

NO Converge?

YES

It is the T bubble.
Find Pi sat , A and  1 &  2

Find vapor phase mole fraction

y1  x1 1 P1sat P & y 2  1  y1
 DEW T CALCULATION

DEW T Find Ti sat

Find initial T from mole-fraction weighted average

T  y1T1sat  y 2T2sat

For current T, find A, P1sat , P2sat

  P1sat P2sat

Find x1  y1 P  1 P1sat & x 2  1  x1

Calculate  1 &  2 from given correlation

Find new value for P1sat from equation 10.7;

y y 
P1sat  P 1  2  
 1  2 

Find new T from Antoine equation for species 1

B1
T  C1
A1  ln P1sat

NO Converge?

It is the T bubble.
Find Pi sat , A and  1 &  2

YES
Find vapor phase mole fraction
y1  x1 1 P1sat P & y 2  1  y1
AZEOTROPE
When x1=y1, the dew point
and bubble point curves
are tangent to the same
horizontal line
A boiling L of this
composition produce a
vapor exactly the same
composition; L does not
change in composition as it
evaporates
Relative volatility;
y1 x1
12  (10.8)
y 2 x2
sat
P exp A
12  x 0  1
sat If one limit is >1 &
1
P2 the other limit is
<1; azeotrope
sat exists.
P
12  x1 1  sat 1
P2 exp A
 VLE FROM K-VALUE CORRELATTIONS
The partition between liquid and vapor phases
of a chemical species is equilibrium ratio, Ki.
yi
Ki 
xi

This quantity is called K-value.

Serves as a measure of lightness of a constituent
species.
Ki > 1, than i exhibits higher conc. in Vapour Phase.
Ki < 0, than i exhibits higher conc. in Liquid Phase.
K-value for Raoult’s Law yi P  xi Pi sat

sat
Pi
Ki 
P
K-value for modified Raoult’s Law yi P  xi i Pi sat

 i Pisat
Ki 
P
 For binary systems to solve for bubble
point calculation;

y i i 1

Hence,
Kxi i i 1

For binary systems to solve for

dew point calculation;

x i i 1
yi
Hence,
i K  1
i
K-value
from
DePriester
chart
-Low T
range
K-value
from
DePriester
chart
-High T
range
When given a mixture of composition at certain T or
P;
Bubble point Dew point

- Insignificant L -System is almost

condensed
-The given mole -The given mole
fraction is yi fraction is xi

-Need to satisfy -Need to satisfy

equation 10.14 equation 10.13

- Composition of - Composition of
dew is xi=yi/Ki buble is yi=Ki.xi
 Flash Calculation
The most important application of VLE.

Originates from a fact that a liquid at a pressure equal to or greater that its bubble point pressure
‘flashes’ or evaporates when the pressure is reduced, producing a two-phase system of vapor and liquid
in equilibrium.
FLASH CALCULATION
Vapor, V

Liquid at P > Pbubble

V partially evaporates
Feed, F
when P is reduced,
producing 2-phase
L system of V & L in
equilibrium
Liquid, L

Find; T, P, z
In a system with one mole chemical species with an overall composition
by set of mole fraction, zi.

Li would be the moles of liquid with mol fraction xi and V be the moles of
vapor with the mol fraction of yi: z

L V  1
zi  xi L  yiV  i  1,2,.....N 
From zi  xi L  yiV

Eliminate for L gives:

zi  xi 1  V   yiV  i  1,2,.....N 
yi yi
From K-value Ki  xi 
xi Ki
Hence solving for yi,

zi K i
yi   i  1,2,.....N 
1  V  K i  1
Because y i i 1

zi K i
Hence,
 yi  1  V  K  1  1
i

(Assignment Example 10.5)