LEC 7 Appreatnt Density

Motivation: Separation processes
 In many industrial processes, chemical engineers deal with separation

processes such as:
 Purification:
Remove undesired component(s)
from a desired mixture
 Fractionation:
Separate a solution into its pure
(e.g. distillations) components
 One way to carry out separation is by equilibrium processes.
 For example, a mixture of methanol and water could be separated into its
pure components (i.e. pure methanol and pure water) using distillation which
is an equilibrium process.
Copyright Dr. Nayef M. Alsaifi, 2013

All rights reserved 2
Vapor pressure of pure components
 The vapor pressure of a liquid is the EQUILIBRIUM pressure of a vapor above its liquid
 It is the pressure of the vapor resulting from evaporation of a liquid.
 Antoine equation could be used to estimate vapor pressure of pure

components
 PHASE EQUILIBRIUM
Vapor
 e.g. : vapor & liquid @
equilibrium
 Vapor-Liquid Equilibrium (VLE)

Liquid

Vapor pressure of pure components
 Example: methanol
20 oC 50 oC 80 oC
methanol methanol methanol
Psat= 12.9 kPa Psat = 55.2 kPa Psat = 179.7 kPa
liquid
Pressure (kPa)
Vapor pressure curve

179.7 (vaporization curve)
55.2
12.9
vapor
20 50 80
All rights reserved
Temperature (°C) 4
Mixture
 In the pervious chapters, the focus was mainly on pure or fixed composition systems.
 Most industrial applications are related to mixtures.
 The thermodynamic study of mixtures is one of the main duty of chemical engineers
 A mixture is defined as a combination of two components or more.
 A system of two components is called a binary system

 A system of three components is called a ternary system
 A system of three components is called a quaternary system
 Example: water-methanol system
A mixture of
Vapor water and
methanol
Mixtures could be described by mole
fractions, mass fraction or concentrations
A mixture of
Liquid water and
Copyright Dr. Nayef M. Alsaifi, 2013 methanol
Mole fractions
 For vapor, we usually use “ yi” to indicate vapor mole fraction of component i.
 For liquid, we usually use “ xi” to indicate liquid mole fraction of component i.
 Example: binary system

mole fractions
At equilibrium
ymethanol=0.342 (34.2 %)
Vapor
Methanol(1)-water (2) ywater=0.658 (65.8%)
T= 90 oC
P= 1 atm xmethanol=0.068 (6.8 %)
Liquid
xwater=0.932 (93.2 %)
Note that:
 the sum of mole fractions of vapor or liquid equals to 1.
 the y and x values are different
Vapor pressure of benzene
 Example 10.1
Estimate the vapor pressure of benzene@ 30 oC?
Solution:
The vapor pressure could be estimated using Antoine equation:
𝐵
𝑃 𝑠𝑎𝑡 = exp⁡(𝐴 − ) Pure substance
𝑡+𝐶
benzene
A, B and C are Antoine parameters
Vapor
A=13.7819;
B=2726.81;
C=217.572;
Liquid
𝑃 𝑠𝑎𝑡 = 15.92⁡𝑘𝑃𝑎 Ans.

Vapor pressure of toluene
 Example 10.2
Estimate the vapor pressure of toluene@ 30 oC?
Solution:
The vapor pressure could be estimated using Antoine equation:
𝐵
𝑃 𝑠𝑎𝑡 = exp⁡(𝐴 − ) Pure substance
𝑡+𝐶
toluene
A, B and C are Antoine parameters
Vapor
A=13.9320;
B=3056.96;
C=217.625;
Liquid
𝑃 𝑠𝑎𝑡 = 4.888⁡𝑘𝑃𝑎 Ans.

A mixture of benzene and toluene
 What if we combine benzene and toluene @ 30 oC?
Benzene-toluene
Vapor
Liquid
 what is the total vapor pressure?
The word “total” is used because the vapor pressure is a contribution

of the vapor pressures of both benzene and toluene.

A mixture of benzene and toluene
Benzene-toluene
 Vapor pressure of pure benzene @ 30 oC

Vapor
𝑃 𝑠𝑎𝑡 = 15.92⁡𝑘𝑃𝑎
 Vapor pressure of pure toluene @ 30 oC

Liquid
𝑃 𝑠𝑎𝑡 = 4.888⁡𝑘𝑃𝑎
 Problem: What is the total vapor pressure of benzene and toluene @ 30 oC ?
 Such a question could be answered by Raoult’s law

Before one uses Raoult’s law
Let’s review the Gibbs phase rule

 Intensive variables: pressure, temperature, mole fractions (for mixtures), molar volume, etc.
 The number of intensive variables that can be varied independently in a system is

determined by the Gibbs phase rule:
𝐹 =2−𝜋+𝑁
Pure substance Mixture
water Benzene-toluene
Vapor Vapor
Liquid Liquid
𝜋=2 𝜋=2
𝑁=1 𝑁=2
𝐹=1 𝐹=2
In phase equilibrium, pressure, temperature and mole fractions (for mixtures) are
the usual intensive variables used to determine the phase 12
𝐹 =2−𝜋+𝑁
Example:
Mixture  This indicates that two intensive variables

Benzene-toluene are required.
Vapor
In phase equilibrium, pressure,
temperature and mole fractions are
the usual intensive variables used.
Liquid
 That means we need to specify two intensive variables
before we start the problem. For example, the following
𝜋=2 could be specified:
𝑁=2 • T and P.
𝐹=2 • T and xi The details of these specifications
• T and yi with Raoult’s law calculations will
• P and xi or be given later.
Copyright Dr. Nayef M. Alsaifi, 2013 • P and yi
Let’s shed light on Raoult’s law

Let’s first review partial pressure of gases
 What is partial pressure?

 If a mixture of gases is considered, the gases are assumed to be
independent and each gas exerts its own pressure.
𝑃𝑖 = 𝑦𝑖 𝑃 9.1
 The total pressure is the sum of partial pressures (Dalton’s law):
𝑃 = 𝑃1 + 𝑃2 + ⋯ + 𝑃𝑖 9.2
 Example:
In a gas mixture, the partial pressure of methane (1) is 200 kPa and the partial
pressure of ethane (2) is 350 kPa, what is the total pressure exerted by the
mixture?
 Solution:
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1 + 𝑃2 = 200 + 350 = 550⁡𝑘𝑃𝑎

Raoult’s law
 Raoult’s law:
The partial vapor pressure of a component in a mixture is given by
the vapor pressure of the pure component at that temperature
multiplied by its liquid mole fraction in the mixture.
𝑃𝑖 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 9.3
𝑃𝑖 : ⁡partial⁡pressure⁡of⁡component⁡i
𝑃𝑖𝑠𝑎𝑡 : vapor⁡pressure⁡of⁡component⁡i
𝑥𝑖 : liquid⁡mole⁡fration⁡of⁡component⁡i
 Raoult’s law states that the equilibrium partial pressure of a

component in a solution is proportional to its liquid mole fraction. François-Marie Raoult
(1830-1901)
 If equations 9.1 & 9.3 are combined, we get
𝑦𝑖 𝑃 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 9.4
 The above equation could be summed over all components to give:

𝑁
All rights reserved
𝑃= 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 9.5 16
𝑖=1
Raoult’s law
 Raoult developed his law based on two assumptions:

Ideal gas
 The vapor is ideal gas
 The liquid is ideal solution
 What is ideal solution? Ideal solution

 The solution is ideal if its molecular species are not
different in size and have similar chemical nature.
 The behavior of adjacent members of a homologous series and a

mixture of isomers could be considered as ideal solutions:
 n-hexane-n-heptane
 ethanol-propanol
 benzene-toluene
 Hexane-benzene
 Acetone-acetonitrile
 The following are not ideal solutions (non-ideal mixtures):
 Methanol-hexane
 Water-methane Why?
 Ethanol-n-pentanol 17
Raoult’s law applications and limitations
 Raoult’s law is a valid approximation for mixtures that are:
 similar in chemical nature and size (ideal solution assumption)

 at low pressure (ideal gas assumption)
 Is Raoult’s law applicable to non-ideal solutions?

 The application of Raoult’s law is limited to ideal solutions and it is not applicable to
non-ideal solutions. However, the only case that we might obtain a good
approximation from Raoult’s law to non-ideal solutions is the case when the
mole fraction of any species approaching unity and only if the vapor is an ideal gas.
 Raoult’s law is limited to species of known vapor pressure (the species must be
subcritical):
 That indicates that the Raoult’s law is not applicable above the critical
temperature

Let’s apply Raoult’s law

Dewpoint and bubblepoint calculations with Raoult’s law
 The bubble point is the point at which the first drop of a liquid mixture begins to
vaporize.
 The dew point is the point at which the first drop of a gaseous mixture begins to
condense.
bubble (vapor) Dew (liquid)
 Four classes of dewpoint and bubblepoint calculations with Raoult’s law:
1 BUBL P Given 𝑻 and 𝒙𝒊 Calculate 𝑷 and 𝒚𝒊
2 DEW P Given 𝑻 and 𝒚𝒊 Calculate 𝑷 and 𝒙𝒊
3 BUBL T Given 𝑷 and 𝒙𝒊 Calculate 𝑻 and 𝒚𝒊
4 DEW T Given 𝑷 and 𝒚𝒊 Calculate 𝑻 and 𝒙𝒊

20
Straightforward calculations
(no need for iteration)
Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒚𝒊

using
1 BUBL P
Antoine equation 𝑃=
𝑁
𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 𝑦𝑖 =
𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
𝑖=1 𝑃
Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒙𝒊
2 Dew P using 1
𝑃= 𝑦𝑖 ⁡𝑃
Antoine equation 𝑁
𝑖=1 𝑦𝑖 /⁡𝑃𝑖
𝑠𝑎𝑡 𝑥𝑖 =
𝑃𝑖𝑠𝑎𝑡

BUBL P
 Example 10.3
Calculate the pressure and vapor mole fractions of a binary system
of benzene(1)/toluene (2) at 91.96 oC and x1=0.505 ?
Solution
The vapor pressures are estimated from Antoine equation:
𝑃1𝑠𝑎𝑡 = 144.4⁡kPa
𝑁
𝑃= 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 0.505 ∗ 144.4 + 1 − 0.505 ∗ 57.84 = 101.55⁡kPa

𝑖=1
𝑥1 ⁡𝑃1𝑠𝑎𝑡 0.505⁡ ∗ 144.4

𝑦1 = = = 0.718
𝑃 101.55
𝑦2 = 1 − 𝑦1 = 1 − 0.718 = 0.282
Experimental values 𝑃 = 101.325⁡kPa 𝑦1 = 0.710

DEW P
 Example 10.4
Calculate the pressure and liquid mole fractions of a binary system
of ethanol(1)/1-propanol (2) at 40 oC and y1=0.6065 ?
Solution
The vapor pressures are estimated from Antoine equation:
1 1
𝑃= = = 11.089⁡𝑘𝑃𝑎
𝑁
𝑠𝑎𝑡 0.6065 1 − 0.6065
+
17.94 6.98
𝑦1 ⁡𝑃 0.6065 ∗ 11.089
𝑥1 = = = 0.3749
𝑃1𝑠𝑎𝑡 17.94
𝑥2 = 1 − 𝑥1 = 1 − 0.3749 = 0.6251
Experimental values 𝑃 = 11.148⁡kPa 𝑥1 = 0.374

Calculation requires iterations
 Procedure for a binary system:
Start with an initial Calculate 𝑃2𝑠𝑎𝑡 Calculate⁡𝑡2𝑠𝑎𝑡

guess for 𝛼
3 BUBL T
𝑃1𝑠𝑎𝑡 𝑃 𝐵2
𝛼 = 𝑠𝑎𝑡 𝑃2𝑠𝑎𝑡 = 𝑇= − 𝐶2
𝑃2 𝑥1 𝛼 + 𝑥2 𝐴2 − 𝑙𝑛(𝑃2𝑠𝑎𝑡 )
Find a new 𝛼⁡
Continue until T converges
𝐵1 𝐵2
𝛼 = exp⁡(𝐴1 − 𝐴2 − + )
𝑇 + 𝐶1 𝑇 + 𝐶2
𝑥2 ⁡𝑃2𝑠𝑎𝑡
Finally: 𝑦2 =
𝑃 24
BUBL T
 Example 10.5
Calculate the temperature and vapor mole fractions of a binary system of
acetonitrile(1)/nitromethane (2) at 70 kPa and x1=0.6 ?
First iteration
𝑃 70 𝐵2 oC
𝛼=2 𝑃2𝑠𝑎𝑡 = = = 43.75⁡𝑘𝑃𝑎 𝑇= − 𝐶2 = 76.12
𝑥1 𝛼 + 𝑥2 (0.6 ∗ 2 + (1 − 0.6)) 𝐴2 − 𝑙𝑛(𝑃2𝑠𝑎𝑡 )
𝐵1 𝐵2
𝛼 = exp 𝐴1 − 𝐴2 − + = 1.9733
𝑇 + 𝐶1 𝑇 + 𝐶2
Second iteration
𝛼 = 1.9733 𝑃2𝑠𝑎𝑡 = 44.19⁡𝑘𝑃𝑎 𝑇 =76.40 oC

𝛼 = 1.9712
Third iteration
𝛼 = 1.9712 𝑃2𝑠𝑎𝑡 = 44.23⁡𝑘𝑃𝑎 𝑇 = 76.42 oC 𝛼 = 1.9710
Fourth iteration
𝛼 = 1.9710 𝑃2𝑠𝑎𝑡 = 44.23⁡𝑘𝑃𝑎 𝑻 = 76.42 oC
𝑥2 ⁡𝑃2𝑠𝑎𝑡 (1 − 0.6) ∗ 44.23

𝑦2 = = = 0.2527 𝑦1 = 1 − 0.2527 = 0.7473 25
𝑃 70
4 Dew T Given 𝑷 and 𝒚𝒊 Calculate 𝑻 and 𝒙𝒊
 Procedure for a binary system:
Start with an initial Calculate 𝑃2𝑠𝑎𝑡 Calculate⁡𝑡2𝑠𝑎𝑡

guess for
4 Dew T
𝛼
𝑃1𝑠𝑎𝑡 = P(𝑦1 + 𝑦2 𝛼) 𝐵1
𝑇= − 𝐶1
𝐴1 − 𝑙𝑛(𝑃1𝑠𝑎𝑡 )
Find a new 𝛼⁡
Continue until T converges
𝐵1 𝐵2
𝛼 = exp⁡(𝐴1 − 𝐴2 − + )
𝑇 + 𝐶1 𝑇 + 𝐶2
𝑦1 ⁡𝑃
Finally: Find 𝑃1𝑠𝑎𝑡 from Antoine Eq. 𝑥1 =
𝑃1𝑠𝑎𝑡 26
BUBL T
 Example 10.6
Calculate the temperature and vapor mole fractions of a binary system of
acetonitrile(1)/nitromethane (2) at 70 kPa and y1=0.6 ?
First iteration
𝐵1 oC
𝛼=2 𝑃1𝑠𝑎𝑡 = P 𝑦1 + 𝑦2 𝛼 = 70 ∗ 0.6 + 0.4 ∗ 2 = 98⁡kPa 𝑇= − 𝐶1 = 80.05
𝐴1 − 𝑙𝑛(𝑃1𝑠𝑎𝑡 )
𝐵1 𝐵2
𝛼 = exp 𝐴1 − 𝐴2 − + = 1.9441
𝑇 + 𝐶1 𝑇 + 𝐶2
Second iteration
𝛼 = 1.9441 𝑃1𝑠𝑎𝑡 = 96.44⁡𝑘𝑃𝑎 𝑇 =79.55 oC

𝛼 = 1.9478
Third iteration
𝛼 = 1.9478 𝑃1𝑠𝑎𝑡 = 96.53⁡𝑘𝑃𝑎 𝑇 = 79.58 oC 𝛼 = 1.9476
Fourth iteration
𝛼 = 1.9476 𝑃1𝑠𝑎𝑡 = 96.53⁡𝑘𝑃𝑎 𝑻 = 79.58 oC
𝑦1 ⁡𝑃 0.6 ∗ 70
𝑥1 = = = 0.4351
𝑃1𝑠𝑎𝑡 96.53
27
Raoult’s law is not
applicable to
non-ideal solutions
but almost all
mixtures in industry
are non-ideal?
Modification of Raoult’s law
 Yes, it is correct that Raoult’s law is not applicable to non-ideal solutions but it
provides the basis that we need to study non-ideal mixtures.
 In next slides, we are going to modify Raoult’s law to make it applicable for non-
ideal mixtures and to moderate pressures.
28
VLE by modified Raoult’s law
 As previously shown, Raoult’s law is given by
𝑃𝑖 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
or
𝑦𝑖 𝑃 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
 The two main assumptions of Raoult's law:
 The vapor phase is an ideal gas

 The liquid phase is an ideal solution
 To apply the Raoult’s law up to moderate pressure conditions, the liquid phase
should be considered as non-ideal solution (not ideal solution).
 To account for the non-ideality of the liquid phase, the Raoult’s law should be
modified as follows:
All rights reserved
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 29
Modified Raoult’s Law
 The modified Raoult’s law is given by:
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
 𝛾𝑖 is called activity coefficient.
 The activity coefficient:
 is used to describe the deviation from the ideal solution.

 is a function of temperature and liquid phase compositions.
 is obtained from different thermodynamic models
 is based on experimental measurement

Modified Raoult’s Law
Raoult’s law Modified Raoult’s law
𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
𝑁 𝑁
𝑃= 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 𝑃= 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
𝑖=1 𝑖=1
1 1
𝑃= 𝑁 𝑠𝑎𝑡 𝑃= 𝑁 𝑠𝑎𝑡
𝑖=1 𝑦𝑖 /⁡𝑃𝑖 𝑖=1 𝑦𝑖 /⁡𝛾𝑖 𝑃𝑖
These equations are used in bubble point calculations
These equations are used in dew point calculations

Dewpoint and bubblepoint calculations with Modified
Raoult’s law
 If modified Raoult’s law is used, a slight modification should be done to the bubble
and dew point calculations.
bubble (vapor) Dew (liquid)
 Four classes of dewpoint and bubblepoint calculations with modified Raoult’s law:
4 DEW T Given 𝑷 and 𝒚𝒊 Calculate 𝑻 and 𝒙𝒊
32
BUBL P
Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒚𝒊

Calculate activity
using coefficients from 𝑁
𝑃= 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
Antoine equation correlating equations 𝑦𝑖 =
𝑖=1 𝑃
Activity coefficient is a function of temperature and liquid mole fractions.
In this chapter, simple activity coefficient models are considered.

33
BUBL P
 Example 10.7
Calculate the pressure and vapor mole fractions of a binary system of methanol(1)
/methyl acetate (2) at 318.15 K and x1=0.25. The activity coefficient models are given by:
𝑙𝑛𝛾1 = 𝐴𝑥22 𝑙𝑛𝛾2 = 𝐴𝑥12 𝐴 = 2.771 − 0.00523𝑇
The Antoine equations are given by:

3643.31 2665.54
𝑃1𝑠𝑎𝑡 = exp⁡(16.59158 − ) 𝑃2𝑠𝑎𝑡 = exp⁡(14.25326 − )
𝑇 − 33.424 𝑇 − 53.424
Note that T is in Kelvins and vapor pressures in kPa.
 Solution:
 At T=318.15 K, the vapor pressures are estimated from Antoine equations:
𝑃1𝑠𝑎𝑡 = 44.51⁡kPa 𝑃2𝑠𝑎𝑡 = 65.64⁡kPa
 Calculate activity coefficients:
𝐴 = 2.771 − 0.00523𝑇 = 2.771 − 0.00523 ∗ 318.15 = 1.107
𝑙𝑛𝛾1 = 𝐴𝑥22 𝛾1 = exp 𝐴𝑥22 = exp 1.107 ∗ 0.752 = 1.864
𝑙𝑛𝛾2 = 𝐴𝑥12 𝛾2 = exp 𝐴𝑥12 = exp 1.107 ∗ 0.252 = 1.072

𝑁
𝑥1 𝛾1 ⁡𝑃1𝑠𝑎𝑡
𝑃= 𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 0.25 ∗ 1.864 ∗ 44.51 + 0.75 ∗ 1.072 ∗ 65.64 = 𝟕𝟑. 𝟓𝟐⁡𝐤𝐏𝐚 𝑦1 = = 𝟎. 𝟐𝟖𝟐
𝑃 34
𝑖=1
Dew P
Calculation requires iterations because x is unknown

and activity coefficients are functions of x
Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒙𝒊

Give initial guesses
using 1
to activity coefficients 𝑃= 𝑦𝑖 ⁡𝑃
𝑁
𝑖=1 𝑦𝑖 /⁡𝛾𝑖 𝑃𝑖
𝑠𝑎𝑡 𝑥𝑖 =
Antoine equation 𝛾𝑖 = 1 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
Continue the iterations

until P converges
Calculate activity
coefficients from
correlating equations
𝑦𝑖 ⁡𝑃
 If P converges, the liquid mole fractions could be calculated from: 𝑥𝑖 =
𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
35
Dew P
 Example 10.8
Calculate the pressure and liquid mole fractions of a binary system of methanol(1) /methyl
acetate (2) at 318.15 K and y1=0.6. The activity coefficient models are given by:
𝑙𝑛𝛾1 = 𝐴𝑥22 𝑙𝑛𝛾2 = 𝐴𝑥12 𝐴 = 2.771 − 0.00523𝑇

The Antoine equations are given in example 10.7.
 Solution
 At 318.15 K, 𝑃1𝑠𝑎𝑡 = 44.51⁡kPa 𝑃2𝑠𝑎𝑡 = 65.64⁡kPa
 Assume 𝛾1 = 1 and 𝛾2 = 1
1 1
 Calculate P from 𝑃= 𝑁 𝑠𝑎𝑡 = 0.6 0.4
= 51.09⁡kPa
𝑖=1 𝑦𝑖 /⁡𝛾𝑖 𝑃𝑖 +
44.51 65.64
𝑦1 ⁡𝑃 0.6 ∗ 51.09
 Calculate liquid mole fractions: 𝑥1 = = = 0.689 𝑥2 = 0.311
𝛾1 𝑃1𝑠𝑎𝑡 1 ∗ 44.51
 Calculate activity coefficients:
𝑙𝑛𝛾1 = 𝐴𝑥22 𝛾1 = exp 𝐴𝑥22 = exp 1.107 ∗ 0.3112 = 1.113

𝑙𝑛𝛾2 = 𝐴𝑥12 𝛾2 = exp 𝐴𝑥12 = exp 1.107 ∗ 0.6892 = 1.691
 Continue in next slide for second iterations 36

Dew P
 Example 10.8
 Second iteration
1 1
 Re-calculate pressure : 𝑃= 𝑠𝑎𝑡 = = 63. 63kPa
𝑁
𝑦 /⁡𝛾 𝑃 0.6 0.4
𝑖=1 𝑖 𝑖 𝑖 +
44.51 ∗ 1.113 65.64 ∗ 1.691
𝑦1 ⁡𝑃 0.6 ∗ 63.63
 Calculate liquid mole fractions: 𝑥1 = = = 0.771 𝑥2 = 0.229
𝛾1 𝑃1𝑠𝑎𝑡 1.113 ∗ 44.51
 Third iteration
 Calculate the activity coefficients: 𝛾1 = 1.060 𝛾2 = 1.93

 Calculate the total pressure P=62.99 kPa
 Calculate liquid mole fractions x1=0.8011 & x2=0.1989
 Fourth iteration
𝛾1 = 1.0448 𝛾2 = 2.0348 P=62.90 kPa x1=0.8116 x2=0.1884
 Fifth iteration
𝛾1 = 1.0401 𝛾2 = 2.0734 P=62.89 kPa x1=0.8152 x2=0.1848
 Sixth iteration
𝛾1 = 1.0385 𝛾2 = 2.0867 P=62.89 kPa x1=0.8163 x2=0.1837 37
BUBL T
 Start with an initial estimate to temperature as follows:

𝑁
𝐵𝑖
𝑡𝑖𝑠𝑎𝑡 = − 𝐶𝑖 𝑇= 𝑥𝑖 𝑡𝑖𝑠𝑎𝑡
𝐴𝑖 − ln⁡(𝑃)
𝑖=1
Calculate 𝛾𝑖 , 𝑃1𝑠𝑎𝑡 , 𝑃2𝑠𝑎𝑡 Calculate a new 𝑃1𝑠𝑎𝑡 : Calculate a new 𝑇:

𝑃1𝑠𝑎𝑡 𝑃 𝐵1
Then, 𝛼 = 𝑠𝑎𝑡 𝑃1𝑠𝑎𝑡 = 𝑇= − 𝐶1
𝑃2 𝑥1 𝛾1 + 𝑥2 𝛾2 /𝛼 𝐴1 − ln⁡(𝑃1𝑠𝑎𝑡 )
Continue the iterations

until T converges
𝑥𝑖 𝛾𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
 The vapor mole fractions are calculated from: 𝑦𝑖 =
𝑃 38
From Slide 18
In slide 18, we
said that to use In slide
Raoult’s law, the
species must be
subcritical. What
if they are not ?
In the next slides, we are going to present a very important law, called Henry’s law.
It is very helpful to determine the solubility of gases in liquids and the gas is supercritical.

Henry’s law
If a gas is in contact with a liquid, the gas dissolves in the liquid.

The concentration of the gas in the solution is proportional to the
gas pressure above the solution.
gas
gas
William Henry
P2 > P1 1774 –1836
Liquid Liquid
P1 P2
𝑦𝑖 𝑃 = 𝑥𝑖 ⁡ℋ𝑖
𝑦𝑖 : vapor mole fraction

𝑃 : pressure
ℋ𝑖 ⁡⁡⁡ : Henry’s constant
 Henry’s law is not applicable at very high partial pressure
 If the concentration of the dissolved gas exceeds 1 %, the Henry’s law is not applicable.
40
Henry’s constant
 Henry’s constant is obtained from experiment

Henry’s law
 Example 10.7
The pressure of Co2 in equilibrium with water is 10 bar. Estimate

the mole fraction of Co2 in the solution?
 solution
𝑦𝑖 𝑃 = 𝑃𝑖 = 𝑥𝑖 ⁡ℋ𝑖
𝑃𝑖 = 𝑥𝑖 ⁡ℋ𝑖 10 = 𝑥𝑖 ⁡1670
𝑥𝑖 = 0.006

VLE from K-value correlations
 The equilibrium ratio (𝐾𝑖 ) between vapor and liquid phase is given by:
𝑦𝑖
𝐾𝑖 =
𝑥𝑖
 It is simply called K-value
 When 𝐾𝑖 > 1, species i exhibits a higher concentration in the vapor phase.

 In other words, species i is considered “light” constituent.
 When 𝐾𝑖 < 1, species i exhibits a higher concentration in the liquid phase.

 In other words, species i is considered “heavy” constituent.

𝑦𝑖
𝐾𝑖 =
𝑥𝑖
 The K-value could be given for Raoult law
𝑦𝑖 𝑃𝑖𝑠𝑎𝑡 𝑃𝑖𝑠𝑎𝑡
𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝐾𝑖 =
𝑥𝑖 𝑃 𝑃
 The K-value could be given for modified Raoult law
𝑦𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 = 𝐾𝑖 =
𝑥𝑖 𝑃 𝑃
44
𝑦𝑖
𝐾𝑖 =
𝑥𝑖
 For the bubble point calculations:
𝑁 𝑁 𝑁
𝑦𝑖 = 𝐾𝑖 𝑥𝑖 𝑦𝑖 = 𝐾𝑖 𝑥𝑖 𝐾𝑖 𝑥𝑖 = 1
𝑖=1 𝑖=1 𝑖=1
 For the dewpoint calculations:
𝑦𝑖 𝑁 𝑁
𝑦𝑖
𝑁
𝑦𝑖
𝑥𝑖 = 𝑥𝑖 = ⁡⁡ ⁡ =1
𝐾𝑖 𝐾𝑖 𝑖=1
𝐾𝑖
𝑖=1 𝑖=1
45
Flash calculations of VLE
 According to Merriam-Webster dictionary: flash means to change suddenly and

violently into vapor:
 Hot water flashing to steam under reduced pressure
 Thermodynamically, how does “flash” occur?

 If a liquid at P ≥ bubblepoint pressure, the liquid flashes (i.e. partially evaporates) when
the pressure is reduced; producing a two-phase system of vapor and liquid.
 What is the problem statement?

 If the Pressure (P), temperature (T) 𝑉
and overall composition ( 𝑧𝑖 ) are
𝑦𝑖
given, determine the liquid mole
fractions ( 𝑥𝑖 ) and vapor mole
𝐹 𝑇 𝑃
fractions (𝑦𝑖 ):
𝑧𝑖
Given: P, T, 𝑧𝑖
𝐿
𝑥𝑖
Calculate: 𝑥𝑖 , 𝑦𝑖
46
 Procedure of flash calculations:
Estimate 𝑃𝑖𝑠𝑎𝑡
Solve for V from:
Check if the two phases calculate 𝐾𝑖 from 𝑁
using Raoult’s law 𝑧𝑖 ⁡𝐾𝑖
(vapor and liquid) exist =1
1 + 𝑉⁡(𝐾𝑖 − 1)
Antoine equation 𝑖=1
HOW? Calculate 𝑦𝑖 : Calculate 𝑥𝑖 :

𝑦𝑖 ⁡
𝑧𝑖 ⁡𝐾𝑖 𝑥𝑖 =
𝑦𝑖 = 𝐾𝑖
1 + 𝑉⁡(𝐾𝑖 − 1)
𝑃𝑏𝑢𝑏𝑙 (@⁡𝑥𝑖 = 𝑧𝑖 )
Calculate
𝑃𝑑𝑒𝑤 (@⁡𝑦𝑖 = 𝑧𝑖 )
because if
𝑃𝑑𝑒𝑤 < P < 𝑃𝑏𝑢𝑏𝑙 Two phases exist
 At a given T: 𝑁
𝑃𝑏𝑢𝑏𝑙 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡
 the minimum pressure for which two phases exist is the Dew P:
𝑖=1 1
 the maximum pressure for which two phases exist is the Bubl P: 𝑃𝑑𝑒𝑤 = 𝑁 𝑠𝑎𝑡
47
Flash calculations
𝑉
𝑦𝑖
𝐹
𝑧𝑖
𝐿
𝑥𝑖
 Total mass balance:
𝐹 =𝑉+𝐿
 Species mass balance
𝑧𝑖 𝐹 = 𝑦𝑖 𝑉 + 𝑥𝑖 𝐿
𝑧𝑖 𝐹 = 𝑦𝑖 𝑉 + 𝑥𝑖 (1 − 𝑉)
48
 Example 10.9
The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80 oC and 110 kPa has the
overall composition, z1=0.45, z2=0.35, z3=0.2. Assuming that Raoult’s law is appropriate
to this system, determine L, V, xi, yi. The vapor pressure of the pure species at 80 oC are:
𝑃1𝑠𝑎𝑡 = 195.75⁡kPa 𝑃2𝑠𝑎𝑡 = 97.84⁡kPa 𝑃3𝑠𝑎𝑡 = 50.32⁡kPa
 Solution:
 Step 1: check if two phases exist
𝑁 𝑁
P=110 kPa
𝑃𝑏𝑢𝑏𝑙 = 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 𝑧𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 0.45 ∗ 97.84 + 0.35 ∗ 97.84 + 0.2 ∗ 50.32 = 132.40⁡kPa
𝑖=1 𝑖=1 𝑃𝑑𝑒𝑤 < P < 𝑃𝑏𝑢𝑏𝑙
1 1 1
𝑃𝑑𝑒𝑤 = 𝑠𝑎𝑡 = = = 101.52⁡𝑘𝑃𝑎 101.52 < P < 132.40
𝑁
𝑁
𝑖=1 𝑧𝑖 /⁡𝑃𝑖
𝑠𝑎𝑡 0.45 0.35 0.2
+ +
195.75 97.84 50.32 Therefore, two phases
 Step 2: calculate 𝐾𝑖 from Raoult’s law exist
𝑃1𝑠𝑎𝑡 195.75
𝐾1 = = = 1.7795 𝐾2 = 0.8895 𝐾3 = 0.4575
𝑃 110
 Step 3: calculate V
𝑁
𝑧𝑖 ⁡𝐾𝑖
=1 0.45⁡ ∗ 1.7795 0.35⁡ ∗ 0.8895 0.2 ∗ 0.4575
1 + 𝑉⁡(𝐾𝑖 − 1) + + =1
𝑖=1 1 + 𝑉⁡(1.7795 − 1) 1 + 𝑉⁡(0.8895 − 1) 1 + 𝑉⁡(0.4575 − 1)
We have one non-linear equation with one unknown: V=0.7364 mol 49

 Example 10.9 (cont.)
1=𝑉+𝐿 𝐿 = 1 − 𝑉 = 1 − 0.7364 = 0.2636⁡ mol
 Step 4: calculate the vapor mole fractions from:
𝑧𝑖 ⁡𝐾𝑖
𝑦𝑖 =
1 + 𝑉⁡(𝐾𝑖 − 1)
0.45 ∗ 1.7795 0.35 ∗ 0.8895

𝑦1 = = 𝟎. 𝟓𝟎𝟖𝟕 𝑦2 = = 𝟎. 𝟑𝟑𝟖𝟗
1 + 0.7364⁡(1.7795 − 1) 1 + 0.7364⁡(0.8895 − 1)
𝑦3 = 1 − 𝑦2 − 𝑦1 = 1 − 0.508 − 0.3389 = 𝟎. 𝟏𝟓𝟐𝟒
 Step 5: calculate the liquid mole fractions from:

𝑦𝑖 ⁡
𝑥𝑖 =
𝐾𝑖
0.5087⁡ 0.3389⁡
𝑥1 = = 𝟎. 𝟐𝟖𝟓𝟗 𝑥1 = = 𝟎. 𝟑𝟖𝟏𝟎 𝑥3 = 𝟎. 𝟑𝟑𝟑𝟏
1.7795 0.8895 50
VLE diagrams
 VLE data of a binary system are usually represented by :
 P-x-y (Pressure vs. x and y)

 T-x-y (Temperature vs. x and y)
Measurement at constant temperature Measurement at constant pressure
Isothermal data Isobaric data
T(K) P(kPa) x1 y1 T(K) P(kPa) x1 y1

343.15 34.71 0.000 0.000 413.59 100 0 0
343.15 32.76 0.064 0.026 411 100 0.092 0.164
343.15 32.28 0.118 0.056 409 100 0.164 0.27
343.15 30.96 0.180 0.096 407 100 0.24 0.359
343.15 28.88 0.312 0.188 404 100 0.359 0.488
343.15 27.13 0.437 0.291 402 100 0.441 0.569
343.15 25.89 0.501 0.345 400 100 0.528 0.644
343.15 23.17 0.677 0.550 397 100 0.665 0.764
343.15 21.35 0.811 0.729 395 100 0.763 0.842
343.15 19.28 0.956 0.931 393 100 0.863 0.915
343.15 18.43 1.000 1.000 390.45 100 1 1
acetic acid(1)/ diethyl ketone (2) system acetic acid(1)/ propionic acid (2) system
51
Overview P-x-y diagrams
 Different P-x-y behavior of VLE
(a) tetrahydrofuran(1)/carbon tetrachloride (2)

at 30 oC.
(b) Chlorofrom(1)/tetrahydrofuran (2)

at 30 oC.
(c) furan(1)/carbon tetrachloride (2)

at 30 oC.
(d) ethanol(1)/toluene(2) at 60 oC.
52
Overview of T-x-y diagrams
 Different T-x-y behavior of VLE
(a) tetrahydrofuran(1)/carbon tetrachloride (2)

at 1 atm.
(b) Chlorofrom(1)/tetrahydrofuran (2)

at 1 atm.
(c) furan(1)/carbon tetrachloride (2)

at 1 atm.
(d) ethanol(1)/toluene(2) at 1 atm.
53
Ethanol (1)/pentanol (2) system @ 70 oC
P-x curve (bubble-P curve) T(K) P(atm) x1 y1

348.15 0.084737 0 0
348.15 0.180789 0.1 0.5759
348.15 0.271447 0.2 0.7468
0.9 348.15 0.357105 0.3 0.8295
0.8 348.15 0.438158 0.4 0.8787

348.15 0.515132 0.5 0.912
One phase liquid
0.7 348.15 0.588684 0.6 0.9365
348.15 0.659868 0.7 0.9557
0.6
348.15 0.730263 0.8 0.9718
Pressure (atm)
0.5 348.15 0.801316 0.9 0.9862

348.15 0.875395 1 1
0.4
Two phases
0.3
0.2
0.1
One phase vapor
0
P-x relation for Raoult’s law:
𝑁
0 0.2 0.4 0.6 0.8 1
𝑃= 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 𝑥1 ⁡𝑃1𝑠𝑎𝑡 + 𝑥2 ⁡𝑃2𝑠𝑎𝑡
𝑖=1
x1, y1
P-y curve (dew-P curve)

54
Positive and negative deviations from Raoult’s law
P-x curve exhibits positive deviation P-x curve exhibits negative deviation
from Raoult’s law (𝜸𝒊 > 𝟏) from Raoult’s law (𝜸𝒊 < 𝟏)
Positive deviation occurs when Negative deviation occurs when

intermolecular forces between intermolecular forces between
similar species are stronger than different species are stronger than
those of different species those of similar species
55
Extremum on P-x-y and T-x-y diagram
 For the same binary system:
 When a maximum occurs on an isothermal P-x-y diagram, it corresponds to a minimum on the

T-x-y diagram.
 When a minimum occurs on an isothermal P-x-y diagram, it corresponds to a maximum on the

T-x-y diagram.
 For example Chlorofrom(1)/tetrahydrofuran (2) system
maximum
minimum
56
P-x-y at different isothermal data sets
57
T-x-y at different isobaric data sets
58
PT diagram of pure substances
 For pure substances, PT diagrams are not identical.
59
PT diagram of ethane-heptane system
60
Azeotropes
 Azeotropes: from Greek A (without) zeo (boil) tropes (changing):
 Therefore, azeotropes means boiling without changing
 Azeotropes means vapour and liquid phases have identical

compositions (xi=yi)
 Azeotropes causes difficulty when separating components via

distillation
61
Azeotropes
 How can you determine if a binary system has an Azeotrope?

 To determine if a binary system , a quantity called the relative volatility is helpful.
The relative volatility is given by:

𝑦1 /𝑥1
𝛼12 =
𝑦2 /𝑥2
At an azeotrope, 𝛼12 = 1
 To check if the binary system has an azetrope:
1. Find 𝛼12 (@⁡x1 = 0) If one of the values are less than 1 and the
second is greater than 1; then, the system
2. Find 𝛼12 (@⁡x1 = 1) has an azeotrope.
 Practice: Example 10.3 e page 359.
62
A look at Flash calculations on diagram
Example 10.10: Ethanol (1)/pentanol (2) system @ 70 oC

At 0.36 atm, what are liquid and vapor mole fractions if z1=0.6, z2=0.4?
0.9
0.8
0.7
0.6 Bubble pressure

Pressure (atm)
0.5
0.4
0.3
0.2
Dew pressure
0.1
x z y
0
0 0.2 0.30 0.4 0.6
0.83
0.8 1
x1, y1
Mole fractions: x1=0.30 y1=0.83

63

LEC 7 Appreatnt Density

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Motivation: Separation processes

 In many industrial processes, chemical engineers deal with separation

 One way to carry out separation is by equilibrium processes.

Copyright Dr. Nayef M. Alsaifi, 2013

 It is the pressure of the vapor resulting from evaporation of a liquid.

 Antoine equation could be used to estimate vapor pressure of pure

 Vapor-Liquid Equilibrium (VLE)

Copyright Dr. Nayef M. Alsaifi, 2013

methanol methanol methanol

Psat= 12.9 kPa Psat = 55.2 kPa Psat = 179.7 kPa

Vapor pressure curve

 Most industrial applications are related to mixtures.

 A mixture is defined as a combination of two components or more.

 A system of two components is called a binary system

 Example: water-methanol system

 Example: binary system

Estimate the vapor pressure of benzene@ 30 oC?

𝑃 𝑠𝑎𝑡 = 15.92⁡𝑘𝑃𝑎 Ans.

Copyright Dr. Nayef M. Alsaifi, 2013

Estimate the vapor pressure of toluene@ 30 oC?

𝑃 𝑠𝑎𝑡 = 4.888⁡𝑘𝑃𝑎 Ans.

Copyright Dr. Nayef M. Alsaifi, 2013

 What if we combine benzene and toluene @ 30 oC?

 what is the total vapor pressure?

The word “total” is used because the vapor pressure is a contribution

Copyright Dr. Nayef M. Alsaifi, 2013

 Vapor pressure of pure benzene @ 30 oC

 Vapor pressure of pure toluene @ 30 oC

 Problem: What is the total vapor pressure of benzene and toluene @ 30 oC ?

 Such a question could be answered by Raoult’s law

Copyright Dr. Nayef M. Alsaifi, 2013

Let’s review the Gibbs phase rule

Copyright Dr. Nayef M. Alsaifi, 2013

 The number of intensive variables that can be varied independently in a system is

Mixture  This indicates that two intensive variables

Copyright Dr. Nayef M. Alsaifi, 2013

 What is partial pressure?

 The total pressure is the sum of partial pressures (Dalton’s law):

𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1 + 𝑃2 = 200 + 350 = 550⁡𝑘𝑃𝑎

 Raoult’s law states that the equilibrium partial pressure of a

 If equations 9.1 & 9.3 are combined, we get

 The above equation could be summed over all components to give:

 Raoult developed his law based on two assumptions:

 What is ideal solution? Ideal solution

 The behavior of adjacent members of a homologous series and a

 The following are not ideal solutions (non-ideal mixtures):

 Raoult’s law is a valid approximation for mixtures that are:

 similar in chemical nature and size (ideal solution assumption)

 Is Raoult’s law applicable to non-ideal solutions?

Copyright Dr. Nayef M. Alsaifi, 2013

Copyright Dr. Nayef M. Alsaifi, 2013

bubble (vapor) Dew (liquid)

 Four classes of dewpoint and bubblepoint calculations with Raoult’s law:

1 BUBL P Given 𝑻 and 𝒙𝒊 Calculate 𝑷 and 𝒚𝒊

2 DEW P Given 𝑻 and 𝒚𝒊 Calculate 𝑷 and 𝒙𝒊

3 BUBL T Given 𝑷 and 𝒙𝒊 Calculate 𝑻 and 𝒚𝒊

4 DEW T Given 𝑷 and 𝒚𝒊 Calculate 𝑻 and 𝒙𝒊

1 BUBL P Given 𝑻 and 𝒙𝒊 Calculate 𝑷 and 𝒚𝒊

2 DEW P Given 𝑻 and 𝒚𝒊 Calculate 𝑷 and 𝒙𝒊

Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒚𝒊

Estimate 𝑃𝑖𝑠𝑎𝑡 Calculate total pressure Calculate 𝒙𝒊

Copyright Dr. Nayef M. Alsaifi, 2013

𝑃= 𝑥𝑖 ⁡𝑃𝑖𝑠𝑎𝑡 = 0.505 ∗ 144.4 + 1 − 0.505 ∗ 57.84 = 101.55⁡kPa