10) Chapter 10 VLE - Ideal Gas - With Tutorial

Vapour Liquid Equilibrium – Ideal Gas Jan 2017
PHASE EQUILIBRIUM - FUNDAMENTALS

Learning Objectives
Student should be able to ;
i. Explain the use of phase equilibrium in chemical engineering processes

ii. Define and explain the fundamental criteria of phase equilibrium particularly
using Gibbs Free Energy.
iii. Define the concept of chemical potential and able to explain its role in defining
phase equilibria.
iv. Define the concept of fugacity and the reason for its introduction as a means
for performing calculation related to phase equilibria.
v. Perform calculation related to phase equilibria under ideal gas condition.
vi. Establish the vapour liquid equilibrium plot (P-x,y or T-x,y) for ideal mixtures.
1
Fukushima Incident
Nuclear Reactor Compartment (Ambient conditions)
Air + Water
Vapour
(containing
Iodine 131)
Seawater + Iodine 131
Nuclear Fuel Rods Given that the concentration of iodine 131 in water
vapour is 1 ppb
As a chemical engineer at Fukushima plant, you have
been requested by your superior to estimate the water
vapour present in the nuclear reactor compartment !
Incorrect estimation might cause casualty to the
technicians who enter the compartment!
2
Application of Phase Equilibrium
Phase Equilibrium is commonly encountered in Chemical Processes, eg. distillation

or even Fukushima incident!
What happen in the system ?
- equilibrium between liquid and vapour liquid
- vaporisation/condensation taking place
i.e., phase changes
To make matter more complex, system contains vapour phase changes
multi-components.
Recall on what we have learnt before ?

Thermodynamic relationships involving Free Energy function
i.e. Gibbs Free Energy in particular - homogenous fluid of pure component/const. composition.
Network of Thermodynamic Equations - Maxwell Equations
Thermodynamic calculations (enthalpy & saturation vapour pressure)
involving phase changes.
Now, these thermodynamic property relationships will be extended

to systems undergoing phase & composition changes
3
Equilibrium Criteria
Let us review the concept of thermal and mechanical equilibrium….
Under phase equilibria of pure component,
Phase a
Phase boundary
Phase b
Thermal Equilibrium Mechanical Equilibrium
Ta = Tb Pa = Pb
Driving Force DT Driving Force DP
4
Now consider a system of multi component…..
Phase a
Phase boundary
Phase b
Thermal Equilibrium Mechanical Equilibrium Another equilibrium criteria involving

composition in the two phase
Ta = Tb Pa = Pb
?a = ?b
Driving Force DT Driving Force DP
Driving Force ?
The tendency would be to say

composition difference….
5
Now consider a system of multi component…..
Phase a
Phase boundary
Phase b
If composition, then the criteria at equilibrium in addition to the pressure

and temperature should be xa = xb . But is it true ?
Air-Water system containing small amount of methanol
Will the composition of methanol in air is 0.01 too at equilibria?
Suppose the composition of methanol in water is 0.01
The answer is no. Therefore, composition is not necessary the driving force…..
We will look at this matter now … 6

Consider a closed system in terms of changes in matter but not isolated from surroundings in
terms of heat and work flow. Let us start with a pure system first….
dU = dQ + dW = dQ - Pb dV 1st law
dS = dQ/Tb + Sp 2nd law Sp - entropy production due to irreversibility
subscipt 'b' - boundary of system
W Q suppose there is an imbalance of T or P,

SYSTEM process leading to equilibrium will continue
until T and P for the system boundary equal to
surrounding by means of rejecting/accepting heat
or doing or receiving work.
combining the two eqn. will yield ;
dU = Tb dS - TbSp - Pb dV
Since, Sp > 0,
dU < T dS - P dV or dU + P dV - T dS < 0
for the above equation to be true. 7
Using the equation as the basis,

Introduce the Gibbs Free Energy

G = H - TS = U + PV - TS We know that H = U + PV
Taking the total differential from the equation, we can derive
dG = dU + P dV + V dP - T dS - S dT
At const. T and P, the eqn. becomes;
dG T,P = dU + P dV - T dS
8
Referring back to the equation,
and comparing it to
We can derive the criteria below,
dGT,P < 0
Implication : Any real process occuring spontaneously when system

is at const. T and P incurs a decrease in Gibbs Free Energy.
And the system will attain its thermodynamic equilibrium when the
Gibbs Free Energy value has attained the lowest (minimum) value.
Hence, at equilibrium we could use this basic criteria
dGT,P = 0
9
For mixtures, we could write the equation in the form below,
Gi = nia gia + nib gib + nig gig + ……. at constant T, P
a, b and g are the respective different phases and ni is the no. of moles of component i.
Taking its differential,.
dGi = d(nia gia) + d(nib gib) + d(nig gig) + ……. < 0
dGi = (nia dgia + gia dnia) + (nib dgib + gib dnib ) + (nig dgig + gig dnig) + ..
At equilibrium (const. T and P), dgi = 0. Therefore, the equation becomes..
dGi = gia dnia + gib dnib + gig dnig + ……. < 0

In a closed system and considering two phases (a and b), any mass loss in one phase will go to
the other phase. Therefore,
dnia = - dnib Substituting in the above equation

(gib - gia) dnib < 0
Since at equilibrium dGT,P = 0, therefore….
(gib - gia) = 0 and gib = gia at constant T, P 10

Also from the same equation shown earlier,
other equilibrium criteria subject to different constraint could be derived.
The other equilibrium criteria consist of ;
dSU,V = 0
dAT,V = 0
dUS,V = 0
dSH,P = 0
dHS,P = 0
but the earlier relation involving Gibbs Free

Energy is the most popularly used !
dGT,P = 0
11
Chemical Potential
The equilibrium criteria established so far seems to be very general.
Question is how can we apply such criteria in the calculation for phase equilibria ?
Need to introduce further concepts !
Consider the derivation below for pure component system!
For a constant mass system at equilibrium, we can write the following total differential
eqn. for the Gibbs Free Energy (G) Recall the total differential
dG = dU + P dV + V dP - T dS - S dT
dG = (dG/dT)P dT + (dG/dP)T dP = - S dT + V dP
(dG/dT)P = -S
(dG/dP)T = V
Now if we consider a system with variable mass, clearly there should be an additional term to
account for this.
dG = (dG/dT)P dT + (dG/dP)T dP + (dG/dn)T,P dn

= - S dT + V dP + m dn
account for changes in G with
addition/removal of material
where m = (dG/dn)T,P
We now introduce Chemical Potential (m) which is defined as the rate of changes in G with
changes in material amount in the system. 12
Chemical Potential
Following from the earlier relation for vapour-liquid equilibrium, we can then write ;
Gi = nia gia + nib gib + nig gig + …….
dG = dGa + dGb + dGg + …… = 0 at const T,P
Thus, for 2 phase system,
dGa + dGb = ma + mb =0 ma = mb
at equilibrium
dGa = Va dP – Sa dT + ma dna
for pure component system
dGb = Vb dP – Sb dT + mb dnb
mb dnb + ma dna = 0
dna = -dnb (mass transfer from phase a to b)
mb dnb - ma dnb = 0
(mb - ma ) dnb = 0 ma = mb 13
Equilibrium of Mixtures
Recall the earlier example on a system.

Air-Water system containing small amount of methanol.
Will the composition of methanol in air is 0.01 too at equilibria?
Suppose the composition of methanol in water is 0.01
The answer is no. Therefore, composition is not necessary the driving force…..
If we look carefully at the system, it contains more than one component I.e., exist in the form
of mixture.
In separation processes which forms part of a whole chemical process, often

mixtures of various components have to be separated either physically or
chemically. For a physical based separation, often the understanding of phase
equilibria for multicomponent system is important for the design and operation of
the process. Distillation, absorption, adsorption etc. are some of the examples of
the separation processes.
Earlier, the understanding of phase equilibria was developed around pure

component. Using the fundamental developed, we will now explore the multi
component system (mixtures). 14
From the earlier equation for phase equilibria for pure component system.
a b
dG + dG = ma + mb = 0 at constant T, P
Extending the same development to mixtures of components ;

a a a a b b b b
m1 dn1 + m2 dn2 + m1 dn1 + m2 dn2 = 0
a b a b
dn1 = - dn1 dn2 = - dn2 For 2
a b a b component
m1 = m1 m2 = m2
In general terms,
a b a
S ( mi - mi ) dni = 0 Basis for multi-
i
a component VLE
b
mi = mi calculation
This is comparable to the equation developed earlier,,

(gib - gia) = 0 and gib = gia at constant T, P
15
Chemical potential is an abstract concept. However, it is useful since it provides a simple
criterion for equilibria. Unfortunately, in application, it turns out that chemical potential has some
inconvenient mathematical behaviours. This has led to the introduction of fugacity.
Fugacity.
The relation between chemical potential and fugacity is described by the equation below;
Fugacity (f) - a measure of volatility of a

m = m + RT ln f component in solution
0
The above relation is derived from ;

- chemical potential value at f = unity
- function of only T dm = dg/dn = vdP - sdT at const. T
integrate ! dm = dg
T
/dn=T
vdP = RT dP/P =RT lnP
in the case of real gas, P is substituted by f
Extending the relation to mixtures ; f (fugacity) has the unit of pressure
(atm, kPa, bar etc)
0
m i = m i + RT ln f i
For ideal gas, the fugacity could be simplified to be equal to the partial pressure exerted by
the component in the mixture
fi = y i P = p i 16
Writing the eqn. for 2 different phase (a and b)
a a b 0 b
0
from equilibrium criteria ;

a
mi = mib
it can easily be seen that the following criteria also holds at equilibrium ;
a b
fi = fi
Also basis for
The fugacity of the individual component is equal for the 2 phases. multicomponent
VLE calculation
Now if we are dealing with vapour liquid equilibria, clearly the two
phases will refer to liquid and vapour !
l v
fi = fi
Fugacity is something easier to handle.

Later we will be looking at how to calculate fugacity
17
Vapour Liquid Equilibria for Ideal Mixtures

Reviewing the derivation for fugacity ….
Recall the concept of fugacity of each component in a mixture.
0
The relation was derived from
dm = dg = v dP – s dT
dmT = dgT = v dP = RT dln P
Introduce fugacity and substitute it into the equation,
m = m0 + RT ln f / f 0
Taking the f 0 at atmospheric pressure as the reference  f 0 = P = 1
and writing the equation for components in mixtures ;
0
18

Now, the fugacity of each component in a simplest liquid mixture could be calculated by ;
0 0
fi = fi xi fi - fugacity of pure liquid at T & P of mixture
At low pressure (under ideal gas condition), fi0 = Pi0
where Pi0 is the partial pressure of the pure liquid at T & P of the mixture
and under the condition where the vapour phase is an ideal gas mixture, we can write
fi = P yi
Recall the basis for equilibrium
Following the equilibrium criteria where a b
l v
fi = fi
fi = fi The fugacity of the individual component
is equal for the 2 phases.
we can derive that ;

0
yi P = Pi xi This is known as Raoult's Law
Pi0 = saturation vapour pressure for component I at specified T,P

= exp (A – B/ (T-C)) - Antoine Equation
19
Fukushima Incident
Nuclear Reactor Compartment (Ambient conditions)
Air + Water
Vapour
( containing
Iodine 131)
Seawater + Iodine 131
Nuclear Fuel Rods Given that the concentration of iodine 131 in water
vapour is 1 ppb
Can we estimate the amount of water vapour in the air
now? YES ! Provided the system in the compartment
is under equilibrium condition with the information of
temperature and pressure (assuming that air does
not dissolve in water)
20
Bubble Point Calculation & Dew Point (VLE) Calculation using Raolt’s Law
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
Bubble Point Calculation

Since
Dew Point Calculation

Since
21

Example : Find the vapour composition above a liquid mixture of 50 mol% benzene(1) and
hexane(2) at 25 C if it is assumed that both the liquid and vapour form ideal solutions. The
vapour pressure of benzene and hexane at 25 C are 93.9 and 149.2 mmHg respectively.
Using BUBL P,
Calculate for y1 and y2.
y1 = 0.5 . 93.9 / P y2 = 0.5 . 149.2 / P
P = y1 P + y2 P = x1 P10 + x2 P20 = 121.5 mmHg
The composition in vapour could then be calculated
y1 = 0.386 y2 = 0.614
22
Example : Assume Raolt’s law is valid , perform the following

calculation for benzene (1) and Toluene (2) system:
(a) Given x1 = 0.33 and T = 100C. Find y1 and P

(b) Given y1 = 0.33 and T = 100C. Find x1 and P
(c) Given x1 = 0.33 and P = 120 kPa. Find y1 and T.
(d) Given y1 = 0.33 and P = 120 kPa. Find x1 and T.
23
Henry Constant, Hi
- Applicable for gases that are very dilute solute in certain species (water)
𝑦𝑖 𝑃𝑇 = 𝑥𝑖 𝐻𝑖
Henry’s constant for gases dissolved in water at 298.15 K (25C)
Gas Hi (bar) Gas Hi (bar)

Acetylene 1350 Helium 126600
Air 72950 Hydrogen 71600
Carbon dioxide 1670 Hydrogen 550
Sulfide
Carbon monoxide 54600 Methane 41850
Ethane 30600 Nitrogen 87650
Ethylene 11550 Oxygen 44380
24
Example:
Assuming that carbonated water contains only CO2 (1) and H2O,determine the
compositions of the vapour in a sealed can of “soda” and the pressure exerted
on the can at 10°C (283.15K). Henry constant for CO2 in water at 10°C is about
990 bar. Assume x1 = 0.01.
25
PTxy Diagram
F=2–π+N
2 Phases, 2
component
F=2
26
P-x, P-y (Front View) and T-x and T-y Diagram (Plan View)
27
P-T Diagram (Side View)
28
P-T Diagram
29

The Raoults law (equation) enable a vapour liquid equilibria relation be established for an
ideal liquid/gas system mixture.
o
P1 liquid
Isothermal
P VLE diagram
vapour o
P2
For ideal mixture,

x,y
can be calculated
from : Raoult's Law
can determine x-y diagram
o
y i P = xi P i
We can also go
only need information on, directly from y
left to right ?
- Total Pressure
o
- Vapour Pressure Pi
30
x
o
T1
vapour
Isobaric
T VLE diagram
liquid o
T2
For ideal mixture,

x,y
can be calculated from :
Raoult's Law
o
can determine x-y diagram
yi = xi Pi / P
o
- have to calculate Pi
Can we go
for T value in between directly from
boiling point. left to right ?
y
Use
Antoinne
Eqn. x
31
Example : Binary system acetonitrile (1)/ nitromethane (2) conforms closely to

Raoult’s law. Vapour pressures for the pure species are given by the following
Antoine equations:
Where, P in kPa
(a) Prepare a graph showing P vs x1 and P vs y1 for a temperature of 75C (348.15K)
(a) Prepare a graph showing T vs x1 and T vs y1 for a pressure of 70kPa.
32
33
34
VLE K-Value Correlations
A value measures the

“lightness” of a constituent
species of its tendency to favor
the vapour phase
Based on Raolt’s Law
BUBL CAL
DEW CAL
35
VLE K-Value Correlations
Example : For a mixture of 10 mole % methane, 20 mole % ethane and 70 mole %

propane at 10 C (283.15K), determine the
(a) The dew point pressure

(b) The bubble point pressure
(c) Repeat your calculation using BUBL

/DEW CALCULATION given that the
Antoine Equation for methane, ethane
and Propane as follows:
36
Flash Calculation
Consider the system contain one mole of nonreacting chemical species
with overall composition represented by the set of mole fractions {zi}. L
and V is the mole of liquid and vapour , respectively.
37
Flash Calculation
Example: The system acetone (1)/ acetonitrile (2)/ nitromethane (3) at 80C
(353.15K) and 110 kPa has the overall composition, z1 = 0.45, z2 = 0.35, z3 = 0.2.
Assuming that Raolt’s law is appropriete to this sytem, determine L, V, {xi} and {yi}.
The vapour pressures of the pure species at 80C (353.15K) are:
P1sat = 195.75 kPa P2sat = 97.84 kPa P3sat = 50.32 kPa
38
Tutorial Q1 (Problem 10.1)
Assuming he validity of Raoult’s law, do the following calculations for the benzene (1)/
toluene (2) system
a) Given x1 = 0.33 and T = 100°C (373.15 K), find y1 and P.

b) Given y1 = 0.33 and T = 100°C (373.15 K), find x1 and P.
c) Given x1 = 0.33 and P = 120 kPa, find y1 and P.
d) Given y1 = 0.33 and T = 120 kPa, find x1 and P.
e) Given T = 105°C and P = 120 kPa, find x1 and y1.
g) Why is Rault’s law likely to be an excellent VLE model for this system at the stated
conditions?
39
Tutorial Q2 (Problem 10.2)
Assuming Raoult’s law to be valid, prepare a P-x-y diagram for temperature of 90C
and t-x-y diagram for a pressure of 90 kPa for Benzene (1)/ ethylbezene (2).
40
Tutorial Q3 (Problem 10.25 & 10.27)
Problem 10.25
Assuming the validity of the Dadyburjor charts, make the following VLE calculation for
the methane/ ethylene /ethane system:
- DEW T, given y1 = 0.43 y2 = 0.36 and P = 17.24 bar.
Problem 10.27
The stream from a gas well is a mixture containing 50 mol% methane, 10 mol%
ethane, 20 mole% propane and 20 mole% n-butane. This stream is fed into a partial
condenser maintained at a pressure of 17.24 bar, where its temperature is brought to
27°C Determine the molar fraction of the gas that condenses and the compositions of
the liquid and vapour phases leaving the condenser.
41
Tutorial Q4 (Problem 10.28 and 10.29)
Problem 10.29
A mixture – 25% n-pentane, 45 mole% n-hexane and 30 mole% n-heptane – is

brought to a condition of 93°C and 2 atm. What molar fraction of the system is liquid,
and what are the phase compositions?
Problem 10.28
An equimolar mixture of n-butane and n-hexane at pressure P is brought to a

temperature of 95°C, where it exists as a vapour/liquid mixture in equilibrium. If the
mole fraction of n-hexane in the liquid phase is 0.75, what is the P, what is the molar
fraction of the system that is liquid, and what is the composition of the vapour phase?
42
Conclusions and Review
The importance of phase

equilibria in Chemical Eng. Separation Processes
Fundamental of Phase Equilibria
Fundamental Relation using Gibbs Free Energy

Deriving fundamental criteria at equilibrium
dGT,P = 0 extended to mixture…
Introduce chemical potential to provide more sense…
mia = mib
And relate them through the equation involving fugacity
mi = mi0 + RT ln f
Thus allowing for the criteria to be expressed in fugacity
f ia = f i b fil = fi v
Easier to perform calculation !
43
Conclusions and Review
Demonstration on the application of the phase equilibria
Consider ideal mixture, where Raoult’s law is used to simplify

the phase equilibria complexity
yi P = xi Pi 0
Fixing the system pressure and knowing the saturation vapour
pressure at respective temperature, would allow for VLE composition to
be computed with respect to the temperature range between the two
boiling points using several approaches including Bubble/dew point
calculation, k-value and flash calculation.
x y
44
x,y

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Vapour Liquid Equilibrium – Ideal Gas Jan 2017

PHASE EQUILIBRIUM - FUNDAMENTALS

Student should be able to ;

i. Explain the use of phase equilibrium in chemical engineering processes

Nuclear Reactor Compartment (Ambient conditions)

Seawater + Iodine 131

Application of Phase Equilibrium

Phase Equilibrium is commonly encountered in Chemical Processes, eg. distillation

Recall on what we have learnt before ?

Now, these thermodynamic property relationships will be extended

Let us review the concept of thermal and mechanical equilibrium….

Under phase equilibria of pure component,

Thermal Equilibrium Mechanical Equilibrium

Driving Force DT Driving Force DP

Now consider a system of multi component…..

Thermal Equilibrium Mechanical Equilibrium Another equilibrium criteria involving

The tendency would be to say

Now consider a system of multi component…..

If composition, then the criteria at equilibrium in addition to the pressure

Will the composition of methanol in air is 0.01 too at equilibria?

Suppose the composition of methanol in water is 0.01

We will look at this matter now … 6

W Q suppose there is an imbalance of T or P,

combining the two eqn. will yield ;

Using the equation as the basis,

Introduce the Gibbs Free Energy

Taking the total differential from the equation, we can derive

At const. T and P, the eqn. becomes;

Referring back to the equation,

We can derive the criteria below,

Implication : Any real process occuring spontaneously when system

Hence, at equilibrium we could use this basic criteria

dGi = d(nia gia) + d(nib gib) + d(nig gig) + ……. < 0

At equilibrium (const. T and P), dgi = 0. Therefore, the equation becomes..

dGi = gia dnia + gib dnib + gig dnig + ……. < 0

dnia = - dnib Substituting in the above equation

(gib - gia) = 0 and gib = gia at constant T, P 10

Also from the same equation shown earlier,

other equilibrium criteria subject to different constraint could be derived.

The other equilibrium criteria consist of ;

but the earlier relation involving Gibbs Free

dG = (dG/dT)P dT + (dG/dP)T dP + (dG/dn)T,P dn

Gi = nia gia + nib gib + nig gig + …….

dG = dGa + dGb + dGg + …… = 0 at const T,P

Thus, for 2 phase system,

Recall the earlier example on a system.

Will the composition of methanol in air is 0.01 too at equilibria?

Suppose the composition of methanol in water is 0.01

In separation processes which forms part of a whole chemical process, often

Earlier, the understanding of phase equilibria was developed around pure

Extending the same development to mixtures of components ;

This is comparable to the equation developed earlier,,

Fugacity (f) - a measure of volatility of a

The above relation is derived from ;

from equilibrium criteria ;

Fugacity is something easier to handle.

Vapour Liquid Equilibria for Ideal Mixtures

Recall the concept of fugacity of each component in a mixture.

The relation was derived from

dmT = dgT = v dP = RT dln P

Introduce fugacity and substitute it into the equation,

Vapour Liquid Equilibria for Ideal Mixtures