Department of Chemical Engineering

University of San Carlos Technological Center

Nasipit, Talamban, Cebu City

ChE 411N
Phase and Chemical Equilibria of Mixtures

Vapour-Liquid Equilibrium Diagrams

(Methyl tert-butyl ether and Methanol binary system)

A project submitted to
Engr. Luis K. Cabatingan
Instructor, ChE 411N

By
Ugoy, Marc Dennis Angelo B.

October 19, 2013

Abstract
In separation process of binary mixture the vapour liquid equilibrium diagram is integral to
design the separation apparatus. This project objective is to construct the x-y diagram for MTBEMethanol binary mixture system at constant temperature and to construct vapour liquid
equilibrium diagram for the same binary mixture system at various temperatures which is at
constant pressure and at various pressures which is at constant temperature. The other objective
is to determine the Azeotropic point in which the MTBE-Methanol binary mixture formed at
certain point that posed problems in separation processes. The separation process encountered
problems during the Azeotropic point which vapour and liquid fraction are equal. A predictive
activity coefficient model which is the UNIFAC model was used to determine the activity
coefficients of both components in a binary mixture. The vapour pressure equation used was the
Wagner 3,6 equation. The total pressure and the vapour composition of MTBE which was used
to plot x-y and P-xy diagram was determined using the Raoults law equation for non-ideal
solutions. The various temperatures which were used to construct the T-xy diagram were
determined by iteration using Wagner 3,6 equation and the Raoults law equation for non-ideal
solutions. This was done using the solver add-ins in Microsoft Excel. The x-y, P-xy and T-xy
diagram were constructed using the data that was processed. The result, MTBE fraction of x
vapor fraction and y liquid fraction formed Azeotropic point at 0.7000~0.7250 in which x=y and
T=313.15K.

TABLE OF CONTENTS
Chapter

Title

Page

Abstract ---------------------------------------------------------------------------------------------------

Nomenclature ---------------------------------------------------------------------------------------------

ii

List of Tables ---------------------------------------------------------------------------------------------

iv

List of Figures --------------------------------------------------------------------------------------------

I.

Introduction ---------------------------------------------------------------------------------- 1
Rationale of the Project ---------------------------------------------------------------- 1
Related Literature ----------------------------------------------------------------------- 4
Binary mixture of MTBE and Methanol ------------------------------------- 4
Conventional production of MTBE ------------------------------------------- 4
Importance of Vapour-Liquid Equilibrium Diagram ----------------------- 5
Theory of Vapour-Liquid Equilibrium Diagram ---------------------------- 6
Raoults Law --------------------------------------------------------------------- 9

Activity coefficient model UNIFAC equation -----------------------------10

Wagner vapour pressure equation ---------------------------------------------12
Azeotrope -------------------------------------------------------------------------13
II.

The Problem ----------------------------------------------------------------------------------- 15

Statement of the Problem --------------------------------------------------------------- 15
Objective ---------------------------------------------------------------------------------- 16
Scope of Project -------------------------------------------------------------------------- 16
Significance of Project ------------------------------------------------------------------ 16

III.

IV.

Methodology --------------------------------------------------------------------------------- 17
Tools used -------------------------------------------------------------------------------- 17
Procedure ---------------------------------------------------------------------------------- 17
Determining of activity coefficients of MTBE and Methanol ------------ 17
Constructing xy and P-xy diagram -------------------------------------------- 17
Constructing T-xy diagram ---------------------------------------------------- 18
Results and Analysis ------------------------------------------------------------------------- 19
Conclusion -------------------------------------------------------------------------------- 21

V.
VI.

References ------------------------------------------------------------------------------------- 22
Appendix -------------------------------------------------------------------------------------- 23
Appendix A:UNIFAC model constant and parameters for MTBE-Methanol binary
mixture ------------------------------------------------------------------------------------- 23
Appendix B: Data for constructing xy, P-xy and T-xy diagram for MTBEMethanol binary mixture -----------------------------------------------------------------24

Appendix C: Data for determination of vapour pressure as a function of

temperature -------------------------------------------------------------------------------- 28

NOMENCLATURE
y = Vapour mole fraction
x = Liquid mole fraction
Pvap = Vapour pressure
1 = MTBE (Methyl tert-butyl ether)
2 = MeOH (Methanol)
P = Equilibrium pressure [bar]
T = Equilibrium temperature [K]
Pc = Critical pressure [bar]
Tc = Critical temperature [K]
A , B , C , D = Wagner equation parameters of a specific component
= Activity coefficient
= Molecular weighted segment
= Area fractional components
L = Compound parameter r and z
r = Volume parameter
q = Surface area parameter

Umn = Energy of interaction between groups m and n

z = Average coordination number which is taken by 10
k = Activity of an isolated group in a solution
R = Group volume parameters
Q = Group surface area parameters
m = Summation of the area fraction of group m
mn = Group interaction parameter
Xn = Group mole fraction of number of group n
R* = Ideal gas constant, 83.14 cc-bar/mol-K
amn = Net energy interaction between groups m and n
vk = Summation of occurrence of the functional group

LIST OF TABLES
Figure number

Title

Page

1.
2.
3.
4.

UNIFAC definition of components MTBE and EtOH ---------------------------------- 23

UNIFAC Rk and Qk values for each subgroup -------------------------------------------- 23
UNIFAC Main group interaction parameters, amn in Kelvin ---------------------------- 23
Activity Coefficients at varying composition of liquid MTBE, x1 at
constant temperature of 313.15K determined using Modified UNIFAC model ----- 24
5. P and y1 data at constant temperature of 313.15K ---------------------------------------- 25
6. T and y1 data at constant pressure of 0.6677 bar ------------------------------------------ 26
7. Data for determination of Vapour Pressure as a function of temperature ------------- 28

LIST OF FIGURES
Figure number

Title

Page

1. Schematic diagram of the production of MTBE ----------------------------------------- 5

4

2.
3.
4.
5.

VLE Diagram of Binary Mixture ----------------------------------------------------------- 7

x-y diagram for the MTBE-Methanol system at a fixed temperature of 313.15K --- 19
The x-y diagram for MTBE-Methanol system at a fixed pressure of 0.6677 bar. --- 19
The Pressure-composition diagram for the MTBE-Methanol system at
fixed temperature of 313.15K -------------------------------------------------------------- 20
6. The Temperature-composition diagram for the MTBE-Methanol system at fixed
pressure of 0.6677 bar. ---------------------------------------------------------------------- 20

THE PROBLEM AND ITS SCOPE

INTRODUCTION

Rationale of the Project

The separation process depends heavily on both chemical and physical properties of
the material needed to be separated. These properties determined the type of separation
process. Separation process in the bigger picture was used to transform a mixture of
substances into two or more distinct product and because the fundamental part of separation
process is manipulating both chemical and physical properties of the elements aimed to be
separated and the separated product could differ in chemical properties or physical properties
such as size, boiling point and other properties. Bear in mind that almost every element or
compound is found to be naturally in an impure state such as mixture of two or more
components. Separation applications in the fields of chemical engineering are very important.
Separation processes can be essentially be defined as mass transfer that occurs in
distillation,

absorption,

drying,

liquid-liquid

extraction,

adsorption,

ion-exchange,

crystallization, and membrane processes (Geankoplis, 2003). Mass transfer is important in

many areas of science and engineering that occurs when a component in mixture migrates in
the same phase or from phase to phase because of difference in certain properties such as
boiling point, concentration or component size this justify why separation process manipulate
either chemical or physical properties as mentioned above (Geankoplis, 2003)The
classification can be based on the mean of separation, mechanical or chemical. The choice of
separation depends on the pros and cons of each. Mechanical separations are usually

favoured if possible due to the lower cost of the operations as compared to chemical
separations. Systems that cannot be separated by purely mechanical means (e.g. crude oil),
chemical separation is the remaining solution. The mixture at hand could exist as a
combination of any two or more states: solid-solid, solid-liquid, solid-gas, liquid-liquid,
liquid-gas, gas-gas, solid-liquid-gas mixture, etc.
Distillation is a unit operation or a physical separation process and not a chemical
reaction. Commercially distillation has a number of applications. It used to separate crude oil
into more fractions, other example is the distillation process used to distillate water to
remove its impurities. Distillation process can be divided into two main types of distillation
which is batch distillation and continuous distillation. Batch distillation refers to the use of
distillation in batches, meaning that a mixture is distilled to separate it into its component
fractions before the distillation still is again charged with more mixture and the process is
repeated. This is in contrast with continuous distillation where the feedstock is added and the
distillate drawn off without interruption. Batch distillation has always been an important part
of the production of seasonal or low capacity and high-purity chemicals. It is a very frequent
separation process in the pharmaceutical industry and in wastewater treatment units. And
continuous distillation is an ongoing separation in which a mixture is continuously (without
interruption) fed into the process and separated fractions are removed continuously as output
streams as time passes during the operation.
The distillation process operated by manipulating the physical properties based on the
volatility of the component in the mixture, the boiling point differences of the components in
the mixture, using the boiling point is a way to separate the components from mixture is
through heating process, by heating the mixture it will evaporate the components that have
2

lower boiling point in comparison with the other components. This will leave behind the
component that have higher boiling point that is still in liquid form. And to recover the
evaporated components the condenser will be used condense the vapour back into liquid
form. This is roughly the basic ideas behind distillation process. In much more complex
system of distillation column the vapour liquid equilibrium principles were used as
guidelines in the distillation process. In industrial level each of the binary or ternary mixture
contains a set vapour liquid equilibrium data that helps engineer to perform separation
process. Vapour Liquid Equilibrium data are the reason this study is conducted.
The applications of distillations can be roughly divided in few groups, laboratory
scale, and industrial distillation. The main difference between laboratory scale distillation and
industrial is that laboratory scale is often performed batch-wise, whereas industrial
distillation often occurs continuously.
However azeotropic phenomena limit the separation achievable by ordinary
distillation. Complete separation of azeotropic mixtures requires either the coupling the
distillation columns with other separation methods such as adsorption, membranes, and
extraction or the use of more complex distillation schemes based on a modification of the
equilibrium to effect the complete separation. Although many new separation techniques are
being developed, distillation will remain the method of choice for large-scale separation of
non-ideal mixtures including azeotropic mixtures. Separation of such mixtures is achieved by
use of one of the enhanced distillation methods. These include extractive distillation, salt
distillation, pressure-swing distillation, reactive distillation, and azeotropic distillation. The
latter method involves the use of entrainers to alter the relative volatility of the components

and break the azeotrope. The choice of separation method depends on the specific system and
economics (Silva, 2006).
Related Literature
Binary Mixture of MTBE and Methanol
MTBE also known as methyl tertiary butyl ether and MTBE is a chemical compound
with molecular formula (CH3)3CH3CO. MTBE is a volatile, flammable and colourless liquid
that is immiscible with water. MTBE has a minty odour vaguely reminiscent of diethyl ether,
leading to unpleasant taste and odour in water. MTBE is a gasoline additive, used as
oxygenate and to rise the octane number, although its use has declined in the United States in
response to environmental and health concerns. The production of MTBE is from the
chemical reaction of Isobutylene and Methanol but in this reaction not all the reactants turn
to MTBE, Methanol still exist in the final product of this reaction which the Methanol is the
undesired product so it is important to separate the undesired and the desired product.
Conventional production of MTBE
Methyl tertiary butyl ether is a high octane fuel additive and non-toxic as well as none
polluting in contrast to lead alkyl additives. The high number of process licensors and plant
under operation underline the economical importance of MTBE. The demand is predicted to
increase from 8 to 32 million tons in the year 2000 making it worthwhile to improve existing
production facilities. (Hommerich, 1998)
Figure 1 shows a schematic subdivision into three parts. In the reactor cascade, ibutene, which is available in C4 - Raffinate from a steam cracking or catalytic cracking

processes. Therefore, the effluent from the cascade consists mainly of MTBE, linear butenes
(n-butenes) and excess methanol. Particularly the azeotrope formation of methanol with both
MTBE and C4 poses difficulties on the subsequent product purification. In column 1
operated at 6 bar, the reactor effluent is separated into and n-C 4/methanol distillate with
azeotropic composition and a bottom product containing approximation of 97 wt% MTBE
and 3 wt% methanol. The distillate is fed to third process part where high selectivity of the
etherification is used for producing pure n-C 4 hydrocarbons. The MTBE /methanol stream of
column 1 is fed to third process part where high selectivity of the etherification is used for
producing pure n-C4 hydrocarbons. The MTBE/methanol stream of column 1 is fed to a
second distillation at 12 bars in order to achieve the final product quality of over 99 wt% for
MTBE. The MTBE/methanol azeotrope at the top of column 2 has to be recycled into the
reaction zone, since an economical separation is not feasible because of the small amount
(approx. 4% of the reactor effluent) (Hommerich, 1998).

Column
MTBE
Column

MeOH

Figure 1. Schematic diagram of the production of MTBE (Hommerich, 1998)

Importance of Vapour-Liquid Equilibrium Diagram

VLE is a set of data necessary especially for engineer in separation process. This
data is importance in chemical industries. Most industries handle two type of distillation
which is continuous and batch distillation, and VLE is at the heart of the process as it
provides guidance at how to design of the distillation equipments itself.VLE is especially
important to continuous distillation or fractional distillation. In distillation it is
importance to have a boiling diagram of the binary mixture. The diagram provide the
information of the mixture in terms of which components is more volatile (boiling point)
and which is less volatile (higher boiling point).In the boiling point diagram it also show
the fraction of the mixture at different temperature and pressure. This information is
paramount to conduct any distillation process. Once the data acquired this will provide
the engineer at what temperature and at what pressure should the distillation process be
proceeds and provide how much distillate will be resulted from distillation and how much
condensate will be obtained and this much more importance particularly for the
continuous distillation process.
Theory of Vapour-Liquid Equilibrium
As in gas-liquid systems the equilibrium in vapour liquid system is restricted by
the phase rule. For two components system and two phases there are four variables which
are temperature, pressure and compositions y of which is the fraction mixture in vapour
condition and x which is in liquid conditions. In the mixture of two components let say
MTBE and Methanol the mixture is in two phase, vapour and liquid. VLE is a set of data
obtained experimentally to provide ways for engineer to separate the mixture effectively.

VLE is a condition where a liquid and its vapour (gas phase) are in equilibrium with each
other, a condition or state where the rate of evaporation (liquid changing to vapour)
equals the rate of condensation (vapour changing to liquid) on a molecular level such that
there is no net (overall) vapour-liquid interconversion. Although in theory equilibrium
takes forever to reach, such an equilibrium is practically reached in a relatively closed
location if a liquid and its vapour are allowed to stand in contact with each other long
enough with no interference or only gradual interference from the outside. There are
many types of VLE. vapour and liquid. .VLE is a set of data obtained experimentally to
provide ways for engineer to separate the mixture effectively. VLE is a condition where a
liquid and its vapour (gas phase) are in equilibrium with each other, a condition or state
where the rate of evaporation (liquid changing to vapour) equals the rate of condensation
(vapour changing to liquid) on a molecular level such that there is no net (overall)
vapour-liquid interconversion. Although in theory equilibrium takes forever to reach,
such an equilibrium is practically reached in a relatively closed location if a liquid and its
vapour are allowed to stand in contact with each other long enough with no interference
or only gradual interference from the outside. There are many types of VLE. VLE can be
of one component and or more than one. VLE that comprise more than one component
were called binary mixture (two components) of ternary for three components. It said that
the more components we have in VLE the more complicated it will be (Geankoplis,
2003).

Figure 2. VLE Diagram of Binary Mixture

Figure 2 the binary mixture of two components. Often the VLE relations for a
binary mixture let say A(MTBE) and B(Methanol) are given as a boiling point diagram as
shown above. The upper line is the saturated vapour line (or the dew point line) and the
lower line is the saturated liquid line (the bubble point line).The region between those
lines is the area which vapour and liquid are in mixture. In other word the mixture is
between those line is a two phase region. The concentration of a vapour in contact with
its liquid, especially at equilibrium, is often given in terms of vapour pressure, which
could be a partial pressure (part of the total gas pressure) if any other gas are present with
the vapour. The equilibrium vapour pressure of a liquid is usually very dependent on
temperature. At vapour-liquid equilibrium, a liquid with individual components
(compounds) in certain concentrations will have an equilibrium vapour in which the

concentrations or partial pressures of the vapour components will have certain set values
depending on all of the liquid component concentrations and the temperature. It also
means that if a vapour with components at certain concentrations or partial pressures is in
vapour-liquid equilibrium with its liquid, then the component concentrations in the liquid
will be set dependent on the vapour concentrations, again also depending on the
temperature.
The equilibrium concentration of each component in the liquid phase is often
different from its concentration (or vapour pressure) in the vapour phase, but there is a
correlation. Such VLE concentration data is often known or can be determined
experimentally for vapour-liquid mixtures with various components. In certain cases such
VLE data can be determined or approximated with the help of certain theories such as
Raoult's Law, Dalton's Law, and/or Henry's Law (Geankoplis, 2003).
Raoults Law
The law was established by by Franois-Marie Raoult`s. Raoult's law which states
that for binary mixture the total pressure of an non-ideal solution is dependent on the
vapour pressure of each chemical component P ivap, the mole fraction of the component x i
and yi present in the solution and its activity coefficient i which in mathematical is
expressed as:

x1 1 P1vap x2 2 P2vap P
xi i Pi vap yi P
[1 &2]

Equation 1 is also known as Vapour-Liquid Equilibrium equation which is only

applicable for a system with low pressure. P is the total pressure vapour pressure of all
the components exist in the mixture consequently, as the number of components in
solution increases, the individual vapour pressures decrease, since the mole fraction of
each component decreases with each additional component. The non-ideality in the
equation is the introduction of the activity coefficient which is a factor used
in thermodynamics to

account

for

deviations

from

ideal

behaviour

in

a mixture of chemical substances. In an ideal mixture, the interactions between each pair
of chemical species are the same (or more formally, the enthalpy change of solution is
zero) and, as a result, properties of the mixtures can be expressed directly in terms of
simple concentrations or partial pressures of the substances present e.g. Raoult's law for
ideal solution. Deviations from ideality are accommodated by modifying the
concentration by an activity coefficient. Analogously, expressions involving gases can be
adjusted for non-ideality by scaling partial pressures by a fugacity coefficient. So for the
mixture to be ideal the activity coefficient must be equal to 1.
Activity Coefficient Model UNIFAC equation
The UNIFAC model (UNIQUAC Functional-group Activity Coefficients) was
first published in 1975 by Fredenslund, Jones and Prausnitz, a group of chemical
engineering researchers from the University of California. It is a semi-empirical system
for the prediction of non-electrolyte activity in non-ideal mixtures. UNIFAC uses
the functional groups present on the molecules that make up the liquid mixture to
calculate activity coefficients. It attempts to break down the problem of predicting
interactions between molecules by describing molecular interactions based upon the
10

functional groups attached to the molecule. This is done in order to reduce the sheer
number of binary interactions that would be needed to be measured to predict the state of
the system. Equipped with the activity coefficients and a knowledge of the constituents
and their relative amounts, phenomena such as phase separation and vapour-liquid
equilibria can be calculated. UNIFAC attempts to be a general model for the successful
prediction of activity coefficients. It is mathematically expressed as for binary mixture:
n
1* z
1
r1
*
ln 1 ln
q1 ln * 2 l1 l2 v1k ln k ln k1
x1 2
1
r2
k

n
*2 z
2
r2
*
ln 2 ln
q2 ln * 2 l2 l1 vk2 ln k ln k2
x2 2
2
r1
k

[3]

[4]

m km
ln k Qk 1 ln m mk

m
m n nm

Where:

Qm X m
Qn X n
n

[5]

[12]

11

mn exp
Xm

amn
T
vm2 x2

2
1
k 1

v x v
n

2
k 2

r1 v1k Rk1
k 1
n

r2 vk2 Rk2
k 1
n

q1 v1k Qk1
k 1
n

q2 vk2Qk2
k 1

[6]
[13]
[7]

1*

x1r1
x1r1 x2 r2

*2

x2 r2
x1r1 x2 r2

x1q1
1'
x1q1 x2 q2

x2 q 2
2'
x1q1 x2 q2
[14]
[8]

[9]

[15]

[16]

12

z
r1 q1 r1 1
2
z
l2 r2 q2 r2 1
2
l1

[10]
[17]
[11]

[18]

The UNIFAC model splits up the activity coefficient for each species in the
system into two components; a combinatorial
the

and a residual component

. For

molecule, the activity coefficients are broken down as per the following equation:

ln i ln i ln ir
c

[19]

*i z

r
ln ln
qi ln i* *j li i l j

xi 2
i
r j

c
i

For Equation 3 and 4,

[20]

ln ir vki ln k ln ki
k

[21]

In the UNIFAC model, there are three main parameters required to determine the
activity for each molecule in the system. Firstly there are the group surface area

and
13

volume contributions

obtained from the Van der Waals surface area and volumes.

These parameters depend purely upon the individual functional groups on the host
molecules. Finally there is the binary interaction parameter
interaction energy

, which is related to the

of molecular pairs (equation in "residual" section). These

parameters must be obtained either through experiments, via data fitting or molecular
simulation.
Wagner Vapor Pressure Equation
The Wagner vapor pressure equation is the best equation for correlation. It is
expressed as:

t 1

T
At Bt 1.5 Ct 3 Dt 6
ln Pr
Tic
1 t

[22]

Pi vap
Pr
Pic
Where

[22]

[23]

The A, B, C and D are characteristics constants for the fluid under study, and P vap
is the vapour (saturation) pressure. If parameters A, B, C, and D are available for a pure
hydrocarbon, the equation predicts vapour pressures within the acceptable accuracy down
to a reduced temperature of 0.5 which is more accurate than other vapour pressure
estimation equation (DDBSP, 2009).
Azeotrope

14

Departures of the Raoult`s Law frequently manifest themselves in the formation

of azeotropes particularly mixtures of close boiling species of different chemical types
whose liquid solutions are non ideal. azeotropes are formed by liquid mixtures exhibiting
maximum and minimum boiling point. These represent, respectively negative or positive
deviations from Raoult`s Law. Vapour and liquid compositions are identical at the
azeotropic compositions thus all the K values are 1 and no separation can take place.
There are types of azeotropes that are commonly encountered with the binary mixture.
The most common type by far is the minimum boiling homogenous azeotrope.
Heterogeneous azeotrope is always minimum boiling point mixture because activity
coefficient must be significantly greater than 1 to cause the splitting into two liquid
phases. This is true for the MTBE Methanol mixture which showed minimum azeotrope
position. azeotropes limit the separation achievable by ordinary distillation. It is possible
to shift the equilibrium by changing the pressure sufficiently to break azeotrope or move
it away from the region where required separation must take place (Seaders, 1998)

15

THE PROBLEM

Statement of the Problem

Binary mixture of MTBE-Methanol have been subject of numerous investigations
in recent years because of their anti knock properties. However azeotropic phenomena
limit the separation of this mixture achievable by ordinary distillation. Complete
separation of azeotropic mixtures requires either the coupling the distillation columns
with other separation methods such as adsorption, membranes, and extraction or the use
of more complex distillation schemes based on a modification of the equilibrium to effect
the complete separation. Although many new separation techniques are being developed,
distillation will remain the method of choice for large-scale separation of non-ideal
16

mixtures including azeotropic mixtures. Separation of such mixtures is achieved by use

of one of the enhanced distillation methods. These include extractive distillation, salt
distillation, pressure-swing distillation, reactive distillation, and azeotropic distillation.
The latter method involves the use of entrainers to alter the relative volatility of the
components and break the azeotrope. The choice of separation method depends on the
specific system and economics (Silva, 2006).
The final steps in the synthesis process of MTBE are the separations of the
compound from the methanol via azeotropic distillations. The study of Vapour Liquid of
the mixture is of great interest to supplement the design of the distillation processes,
because the mixture showed deviations from Raoult`s Law that is positive azeotropic,
positive or negative azeotrope will influence separations in terms of its efficiencies.
Initial step in studying azeotropes is study on Vapour Liquid Equilibrium Diagram.
Objective
The objective of the project is to obtain a Vapour-Liquid diagram for MTBEMethanol Binary mixture as a function of pressure, temperature and composition.
Scope of Project
I.

To construct x-y, P-xy, and T-xy diagram for MTBE-Methanol mixture.

II.

Determine azeotropic point of MTBE-Methanol mixture.

Significance of the Project

Azeotrope has limits the separation achievable by ordinary distillation. It is
possible to shift or break the azeotropic point by applying entrainer in separation process.
17

To research on what type of entrainer that would work in enhancing separation process,
the research on the Vapour Liquid Equilibrium of the mixture must be completed first.
The significant of study into the Vapour Liquid Equilibrium is that it can provide data
such as temperature, pressure and vapour/liquid fraction compositions that can be
simplified in a diagram that could help the study of finding the entrainer.

METHODOLOGY

Tools used:
1. Microsoft Excel 2007
2. Modified UNIFAC Program from Sandler
Procedure:
Determining activity coefficients of MTBE and Methanol
Modified UNIFAC program developed by Sandler was used in determining
activity coefficients of MTBE and Methanol. This was done by supplying first the
number of components (2), name of the components (MTBE and Methanol), and the

18

number of groups in each molecule from the menu of UNIFAC groups. MTBE has 3
groups which are CH3, C, and CH3O and on the other hand, Methanol has only 1 group
which is CH3OH. A temperature was also supplied in the program which is 40C or
313.15K. From this temperature, vapour pressure was then calculated and used by the
program to determined the activity coefficients and the equation model used in
determining the vapour pressure is the Wagner 3,6 model. G ex-xy diagram was chosen
and activity coefficients at varying compositions from 0-1 with an increment of 0.025
was displayed in the display area in the program (located lower left).
Constructing x-y and P-xy diagram
Activity coefficients with its accompanying liquid MTBE composition obtained
from the Modified UNIFAC program was tabulated in the Excel Spreadsheet also with
activity coefficients of MTBE and Methanol. Equation 1 and 2 was used in determining P
and y, respectively, at varying composition of liquid MTBE and at constant temperature
of 313.15 where Equation 22 was used in determining the vapour pressure of MTBE and
Methanol at the same temperature. This was tabulated in the Excel Spreadsheet. An x-y
diagram was constructed using the data in the spreadsheet. This was done by plotting the
column containing x1 vs columns containing y1 then columns containing x1 vs with the
same column that contains x1 in one Scatter graph with smooth lines. Also, P-xy diagram
was constructed using the same data in the spreadsheet. This was done by plotting the
column that contains P vs column containing x 1 and vs column containing y1 in one
Scatter graph with smooth lines.
Constructing T-xy diagram

19

This required iterative method in determining T at varying composition of liquid

MTBE and constant pressure which chosen to be close to azeotrope located in the P-xy
and x-y diagram. 10 columns was created which are named alphabetically from A-J.
Column A contains x1, column B and C contains 1 and 2, column D contains chosen
temperature which are all 300K, column E and F contains t1 and t2, column G and H
contains vapour pressure of MTBE and Methanol, column I contains total pressure P, and
column J containing y1. Equation 1, 2, 22, and 23 were used in column I, J, G and H, and
E and F, respectively. Solver add-ins was used for iteration in which the set target cells
are column I that must be equal to chosen constant pressure and the changing column is
column D. A T-xy diagram was constructed using the resulting data in the spreadsheet.
This was done by plotting column D vs column A and vs column J.
RESULTS AND ANALYSIS
1.0000
0.8000
0.6000
mole fraction of vapour MTBE, y1

0.4000
0.2000
0.0000
0.0000 0.5000 1.0000

mole fraction of liquid MTBE, x1

Figure 3. The x-y diagram for the MTBE-Methanol system at a fixed temperature of 313.15K
20

1.0000
0.8000
0.6000
mole fraction of vapour MTBE, y1

0.4000
0.2000
0.0000
0.0000 0.5000 1.0000

mole fraction of liquid MTBE, x1

Figure 4. The x-y diagram for MTBE-Methanol system at a fixed pressure of 0.6677 bar.

0.6500

0.5500
Equilibrium Pressure, P [bar]
0.4500

0.3500
0.0000

0.5000

1.0000

mole fraction of liquid MTBE, x1

Figure 5. The Pressure-composition diagram for the MTBE-Methanol system at fixed

temperature of 313.15K

21

327.5000
322.5000
317.5000
Equilibrium Temperature, T [K]

312.5000
307.5000
302.5000
0.0000 0.5000 1.0000

mole fraction of liquid MTBE, x1

Figure 6. The Temperature-composition diagram for the MTBE-Methanol system at fixed

pressure of 0.6677 bar.

It can be be verified in figure 3 6 in which it shows nonlinear function of mole

fraction that non-ideal solutions such as MTBE-Methanol exhibits deviation from
Raoults law.
Also From Figure 3-6 it showed that MTBE-Methanol mixture formed azeotropic
point at 313.15K in figure 6 and at 0.6677 bar in figure 3-5 which are all at composition
approximately 0.7175. At this point the Azeotropic formed the minimum boiling point or
positive azeotrope highlighting that this is the positive deviation of Raoult`s Law. This is
also because that the activity coefficient of at least one of the species Methanol or MTBE
in the mixture is greater than unity which is > 0.
As presented Figure 3 and 4, below the azeotropic point it has a greater difference
between the x-y curve (blue curve) of the mixture and the x = y line (red line). This tells
22

us that there is larger difference in composition between the liquid and the vapour phase
and thus it is easier to separate the MTBE and Methanol by distillation (Sandler, 1999).
In figure 6, it was assumed that the small variations of temperature do not greatly
affect the activity coefficients because the temperature dependence of activity coefficient
is small compared to the variation of the vapour pressure (Sandler, 1999).
Conclusion:

Vapour-Liquid Equilibrium diagram of MTBE-Methanol binary mixture were

obtained by constructing its x-y and P-xy at constant temperature of 313.15K and
T-xy diagram at constant pressure of 0.6677 bars in which exhibits deviation from

Raoults law.
Azeotropic point was determined at composition approximately 0.7175 and a
pressure of 0.6677 bar for P-xy diagram and a temperature of 313.15K for T-xy
diagram.

References:
DDBPS. (2009). Pure components Equations. OldenBurg
Geankopolis, G.J. (2003). Principles of Transport Processes and Separation
Processes. New Jersey. Pearson Education, Inc.
Hommerich U., Rauterbach R.D. (1998) Design and Optimization of
Combined Pervaporation/Distillation process for the production of MTBE. Journal of
Membrane Science.
23

Ishak, M.A. (2010). Effects of Temperature on Vapour-Liquid Equilibrium of

MTBE-Methanol Mixtures. Malaysia. University of Malaysia Pahang.
Sandler, S.I. (1999). Chemical and Engineering Thermodynamics. 3rd edition.
New York. John Wiley and Sons and Technology.
Seaders, J.D. (1998). Separation process principles. John Wiley and Sons
Publishing Inc.
Silva, E.A.B., Rodrigues, A.E. (2008) Design Methodology and Performance
Analysis of a Pseudo-Simulated Moving Bed for Ternary Separation. Separation Science
and Technology.

24

APPENDIX
Appendix A. UNIFAC model constants and parameters for MTBE-Methanol binary mixture
Table 1. UNIFAC definition of components MTBE and EtOH
components

Subgroup

no.

CH3

CH3O

CH3OH

MTBE (1)

MeOH (2)

Table 2. UNIFAC Rk and Qk values for each

subgroup
Subgroup
C
main group
CH3
CH2
CH3O
CH3O
CH3OH
CH3OH

R
0.2195

qi

li

vk

4.3757

4.032

-1.6572

1.4311

1.432

-0.4356

Table 3. UNIFAC
Main group
interaction
parameters, amn
in Kelvin

0.0000
CH3O
0.9011
0.8480
0
251.5
1.1450
1.0880
83.36
0
1.4311
1.4320
16.51
-128.6
CH2

ri

CH3OH
697.2
238.4
0

25

Appendix B. Data for constructing x-y, P-xy and T-xy diagram for MTBE-Methanol binary mixture system

Table 4. Activity Coefficients at varying composition of liquid MTBE, x 1 at constant temperature of 313.15K determined
using Modified UNIFAC model
x1

x1

x1

x1

0.0000

3.7651

1.0000

0.2750

1.8674

1.1012

0.5250

1.3470

1.3697

0.7750

1.0854

2.0640

0.0250

3.3863

1.0013

0.3000

1.7957

1.1188

0.5500

1.3122

1.4121

0.8000

1.0687

2.1859

0.0500

3.0922

1.0048

0.3250

1.7298

1.1379

0.5750

1.2795

1.4587

0.8250

1.0537

2.3241

0.0750

2.8565

1.0101

0.3500

1.6691

1.1589

0.6000

1.2489

1.5099

0.8500

1.0404

2.4820

0.1000

2.6623

1.0170

0.3750

1.6128

1.1817

0.6250

1.2202

1.5663

0.8750

1.0287

2.6635

0.1250

2.4988

1.0252

0.4000

1.5605

1.2066

0.6500

1.1934

1.6287

0.9000

1.0189

2.8734

0.1500

2.3586

1.0346

0.4250

1.5119

1.2337

0.6750

1.1684

1.6978

0.9250

1.0110

3.1181

0.1750

2.2365

1.0454

0.4500

1.4664

1.2633

0.7000

1.1452

1.7746

0.9500

1.0050

3.4060

0.2000

2.1287

1.0573

0.4750

1.4240

1.2957

0.7250

1.1236

1.8603

0.9750

1.0013

3.7480

0.2250

2.0326

1.0706

0.5000

1.3842

1.3310

0.7500

1.1037

1.9562

1.0000

1.0000

4.1585

0.2500

1.9460

1.0852

26

Table 5. P and y1 data at constant temperature of 313.15K

x1

y1

P[bar]

x1

y1

P[bar]

x1

y1

P[bar]

x1

y1

P[bar]

0.0000

0.0000

0.3548

0.2750

0.5198

0.5899

0.5250

0.6465

0.6531

0.7750

0.7530

0.6670

0.0250

0.1274

0.3969

0.3000

0.5365

0.5995

0.5500

0.6565

0.6564

0.8000

0.7670

0.6656

0.0500

0.2142

0.4310

0.3250

0.5519

0.6082

0.5750

0.6664

0.6593

0.8250

0.7825

0.6634

0.0750

0.2784

0.4594

0.3500

0.5662

0.6161

0.6000

0.6762

0.6617

0.8500

0.7999

0.6601

0.1000

0.3286

0.4837

0.3750

0.5795

0.6232

0.6250

0.6860

0.6638

0.8750

0.8198

0.6556

0.1250

0.3695

0.5048

0.4000

0.5920

0.6296

0.6500

0.6961

0.6654

0.9000

0.8430

0.6495

0.1500

0.4037

0.5233

0.4250

0.6039

0.6354

0.6750

0.7063

0.6667

0.9250

0.8706

0.6414

0.1750

0.4330

0.5397

0.4500

0.6151

0.6405

0.7000

0.7170

0.6675

0.9500

0.9042

0.6305

0.2000

0.4586

0.5543

0.4750

0.6259

0.6452

0.7250

0.7282

0.6679

0.9750

0.9460

0.6162

0.2250

0.4812

0.5675

0.5000

0.6364

0.6494

0.7500

0.7402

0.6678

1.0000

1.0000

0.5971

0.2500

0.5015

0.5793

27

Table 6. T and y1 data at constant pressure of 0.6677 bar

Appendix
Vapour
function of

x1

y1

T [K]

t1

t2

P1vap

P2vap

0.0000

0.0000

327.4139

0.3404

0.3613

0.9823

0.6677

0.6677

0.0250

0.1153

325.0982

0.3451

0.3658

0.9092

0.6051

0.6677

0.0500

0.1983

323.3343

0.3486

0.3692

0.8564

0.5608

0.6677

0.0750

0.2619

321.9305

0.3515

0.3720

0.8161

0.5275

0.6677

0.1000

0.3127

320.7770

0.3538

0.3742

0.7842

0.5014

0.6677

0.1250

0.3546

319.8089

0.3557

0.3761

0.7581

0.4804

0.6677

0.1500

0.3902

318.9827

0.3574

0.3777

0.7364

0.4630

0.6677

0.1750

0.4209

318.2655

0.3589

0.3791

0.7180

0.4483

0.6677

0.2000

0.4478

317.6409

0.3601

0.3803

0.7023

0.4359

0.6677

0.2250

0.4717

317.0892

0.3612

0.3814

0.6886

0.4252

0.6677

0.2500

0.4931

316.6018

0.3622

0.3824

0.6767

0.4159

0.6677

0.2750

0.5125

316.1689

0.3631

0.3832

0.6663

0.4077

0.6677

0.3000

0.5301

315.7813

0.3639

0.3840

0.6571

0.4006

0.6677

0.3250

0.5464

315.4365

0.3646

0.3846

0.6489

0.3943

0.6677

0.3500

0.5614

315.1258

0.3652

0.3852

0.6417

0.3887

0.6677

0.3750

0.5754

314.8490

0.3657

0.3858

0.6353

0.3838

0.6677

0.4000

0.5886

314.6007

0.3662

0.3863

0.6296

0.3795

0.6677

0.4250

0.6010

314.3777

0.3667

0.3867

0.6245

0.3756

0.6677

0.4500

0.6127

314.1793

0.3671

0.3871

0.6200

0.3721

0.6677

0.4750

0.6240

314.0003

0.3674

0.3874

0.6160

0.3691

0.6677

0.5000

0.6348

313.8428

0.3678

0.3877

0.6124

0.3664

0.6677

0.5250

0.6453

313.7020

0.3680

0.3880

0.6093

0.3640

0.6677

0.5500

0.6556

313.5773

0.3683

0.3883

0.6065

0.3619

0.6677

0.5750

0.6657

313.4693

0.3685

0.3885

0.6041

0.3601

0.6677

0.6000

0.6757

313.3765

0.3687

0.3887

0.6021

0.3585

0.6677

C. Data for
determination of
Pressure as a
temperature
28

Table 7. Wagner 3,6 parameters, Tc and Pc

data
Pvap constants

component
1

-7.8252

-8.5480

2.9549

0.7698

-6.9408

-3.1085

12.1742

1.5448

Tc

496.4000

512.6000

Pc

33.7000

80.9000

29