Institute of Petroleum Engineering

Department of Reservoir Engineering

Practical training of reservoir engineering

Submitted by :

Ahoua David Christian

Hussain Yaled

Supervised from :

Dr.-Ing. Viktor Reitenbach

Edited by :

Ahoua David Christian

Hussain Yaled

Adress :

Osterder Strae 36

Study program :

Energy and raw materials : Petroleum

engineering

Semester :

5 Semester

Matriculation number :

Ahoua David Christian : 435 668

Hussain Yaled : 434 997

Submission date :

03.04.16

Content
Introduction................................................................................................. 1
1

Vapor liquid equilibrium ....................................................................... 1

1.1

Definition ....................................................................................... 1

1.2

Applications ................................................................................... 2

Raoults law ......................................................................................... 2

2.1

Derivation (Mathematical Expression) ........................................... 3

2.2

Constraints .................................................................................... 4

Bubble and Dew Point Calculations in Matlab ..................................... 4

3.1

Bubble Point Calculation ............................................................... 6

3.2

Dew Point Calculations ............................................................... 10

Conclusion (Discussion of the Results) ............................................. 14

Bibliography / References ......................................................................... V

Annex ....................................................................................................... VI

Introduction
The main goal of the following report is to present the theory of vapor-liquidequilibrium (VLE) and apply this theory in a practical manner by calculating
the bubble point and dew point pressures at given temperatures .For this
purpose we will use Matlab as the calculating platform, and also in order to
prevent complicated equations only consider ideal vapor and liquid phase
behaviors by using the Raoults law.

1 Vapor liquid equilibrium

1.1 Definition
The vapor-liquid-equilibrium is a state at which the gas and the liquid phase
are in balance with each other, which indicates that the rate of vaporization
( liquid to vapor ) and condensation ( vapor to liquid ) are equal , that means
the amount of substance which condensate is the same amount of
substance which vaporize . In addition the chemical potential is in both
phase the same. For a clearly description of the vapor liquid equilibrium of
pure substances, only the temperature and pressure is needed. For gas
mixtures also, the composition of the vapor and liquid phases must be
known. The compositions are mostly in Mol fractions, x for the liquid phase
and y for the vapor phase. The vapor liquid equilibrium exist in the area
between the triple point and the critical point .The pressure at the vapor
liquid equilibrium is referred to as the saturated vapor pressure. Mixture
vapor liquid equilibriums are characterized by the fact that the composition
of the liquid phase differs from the composition of the vapor phase .This
effect occurs through the different volatility and therefore through the
different partial pressures of the involved substances and separation
processes in particular the rectification to separate mixtures. Pure
substances equilibrium are mostly presented in PT (pressure-temperature)
diagram, however the logarithm of the pressure is often plotted against the
reciprocal of the temperature, because this sort of presentation
approximately results in a straight line. Mixture vapor liquid equilibrium are
mostly experimentally determined at constant pressure or temperature.
Therefore Vapor liquid temperature of mixture are commonly presented as
pressure against composition at constant temperature and for the case of
1

constant pressure temperature against composition. In each case for the

liquid and vapor phase.

1.2 Applications
Vapor-liquid equilibrium (VLE) help securing the bulk of industrial separation
processes, particularly in distillation processes.
VLE informations are useful in designing columns for distillation, particularly
fractional distillation, which is a particular specialty of chemical engineers.
Distillation is a process that use the separation or partial separation of
components in a mixture with the operation of (vaporization) followed
by condensation.

Distillation

takes

advantage

of

differences

in

concentrations of components in the liquid and vapor phases.

2 Raoults law
Raoult's law is a law of thermodynamics established by French chemist
Franois-Marie Raoult in 1882. It states that the partial vapor pressure of
each component of an ideal mixture of liquids is equal to the vapor pressure
of the pure component multiplied by its mole fraction in the mixture. The
mathematical form of the Raoults law is given as: Pi = Pi*Xi (ideal solution)
or Pi = PiYi (ideal gas).
Where Pi is the partial vapor pressure of the component i in the
gaseous/solution mixture (above the solution), Pi* is the vapor pressure of
the pure component i,Pi is the liquid pressure of the pure component i and
Xi is the liquid mole fraction of the component i , Yi is the vapor mole fraction
of the component i in the mixture (in the solution).
Therefore, since the partial pressures must be equal at equilibrium, we have
the Raoult's Law equation for each component:
Raoults law for the component i :
Pi*Xi = PiYi

2.1 Derivation (Mathematical Expression)

Originally was the Raoults law found out as an idealized experimental law.
With the utilization of the Raoults law as the definition of an ideal solution,
it is possible to figure out that the chemical potential of each component of
the liquid is given by :
i = i* + RT lnxi where i* is the chemical potential of the component i in
the pure state. This equation for the chemical potential may then be used to
derive other thermodynamic properties of an ideal solution. Moreover,
supposing that the vapor mixture acts as an ideal gas, it is then possible to
re-drive Raoults law as follows. If the system is in balance (equilibrium), the
chemical potential of the component i has to be the same in the liquid
solution and the vapor above it, that means that i,liq = i,vap .
Supposing the liquid is an ideal solution, and using the formula for the
chemical potential of a gas, gives :

i,liq* + RT lnxi = i,vap + RT ln () ,

fi represents the fugacity of the vapor of i , indicates the reference state and
* indicates the pure component.
For a pure i in equilibrium with its (pure) vapor, the corresponding equation
is :

i,liq * = i,vap + RT ln ()
By subtracting both equations , the following formula is obtained :

RT lnxi = RT ln ( ) , which re-arranges to fi = xifi* .

The fugacities can be replaced by simple pressures if the vapor of the

solution behaves ideally :
pi = xipi* which is Raoults law .
To summarize, it is to notice that, for the application of Raoults law , an
ideal behavior of the solution must be assumed, this assumption comes
3

from the fact that intermolecular forces between different molecules are
equal to those between similar molecules which is the condition for an ideal
solution.

2.2 Constraints
1. In case of the solution of an electrolyte this law is not applicable.
2 .Raoults law is not applicable in case of volatile solvent.
3 .Raoults law is applicable only in case of an ideal solution
4- Intermolecular forces between the components in the solution should be
similar to those intermolecular forces between individual molecules.
If we have a solution of A and B forces between A-A = B-B = A-B
5-The gaseous phase are assumed to be act as an ideal gas where we can
use ideal gas law.

3 Bubble and Dew Point Calculations in Matlab

In this notes we will explain how to perform Bubble and Dew point
calculations in Matlab.
Vapor (saturated) Pressure
First of all we need the Antoine coefficients of the components which we
can get either from the task or from the internet. In the following we assume
the units to be in mmHg for pressure, and degrees C for temperature. In
Matlab, we must first declare the Antoine coefficients and the mole fractions
of the components.

all clear
=0.15; =0.2; =0.25; =0.1; =0.15; =0.15;
=6.87024;

=6.84130;

=6.89385;

=6.85390;

=6.90940; =6.93440;
=1168.7200;

=1201.53100;

=1264.37000;

=1331.5700; =1349.8200; =1429.4600;

=224.2100; =222.64700; =216.63600; =216.3600;
=209.38500; =201.8200;

To calculate the saturated (vapor) pressures of the components we need to

implement Antoines equation. To return pressure in bar the units are
converted by dividing the equation with 750.

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750;

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750;

= @(T) 10( /(T+ )))/750 ;

To plot the Saturated (vapor) pressures against the temperatures we need

the following code.
T = linspace(57,92,2);

Plot(T, arrayfun(
, T), T, arrayfun(
, T), T, arrayfun(
, T),

T, arrayfun(
, T), T, arrayfun(
, T), T, arrayfun(
, T));

xlabel(Temperature [deg C]);

5

ylabel(Pressure [bar]);
title(Saturation (Vapor) Pressure);
legend(Hexane, Cyclohexane, Heptane, Cycloheptane, Octane, Nonane, Location, Best);
grid;

3.1

Bubble Point Calculation

At given pressure:
We begin the bubble point calculation by solving the following equation
()

1=0

f = @(, , ) (
+

()
()
()
+
+

()
()
()
+
+
)1

If we have given the pressure P and x, the bubble point temperature is then
the value of T at which
f(, , ) = 0

= 100;
=0.15;
=0.2;
=0.25;
=0.1;
=0.15;
=0.15;

= (@()(, , ),360);

After the bubble point temperature is calculated, we can determine the

vapor composition by Raoults law.
=

( )

( )

=
=

( )

( )

 =
=

( )

( )

( )

To visualize the results, the following code must be typed in.

disp([Pressure: , P, bar]);
disp([Bubble Point Temperature , Tbub, degree C]);
disp([Liquid Phase Composition: ]);
disp(x);
disp([Vapor Phase Composition: ]);
disp(y);

At given temperature:
If we have given the temperature T and x, then the bubble point pressure is
the value at which

() =

The goal here is to find a p that satisfies this equation. After calculating the
vapor (saturated) pressure of every component, we can then determine the
partial pressure of each component. The sum of these partial pressures is
then the bubble point pressure of the mixture.

T = 57
=0.15;
=0.2;
=0.25;
=0.1;
=0.15;
=0.15;

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750;

= @(T) 10( /(T+ )))/750 ;

= @(T) 10( /(T+ )))/750;

= @(T) 10( /(T+ )))/750 ;

 = + + + + +

=
=

disp([ < Temperature: , T, degree C]);

disp([Bubble Point Pressure , , bar]);
disp([Liquid Phase Composition: ]);
disp(x);
disp([Vapor Phase Composition: ]);
disp(y);

3.2 Dew Point Calculations

At given pressure:
To calculate the dew point at given pressure, we must first solve the
following equation

()

1=0

10

 = @ (, , ) (
+

() + () + () + ()

() + () ) 1;

At given Pressure P and vapor mole fractions y, the dew point temperature
is the value for which
(, , ) = 0

= 100;
= 0,15;
= 0,2;
= 0,25;
= 0,1;
= 0,15;
= 0,15;
= (@() (, , ), 360);
( );
();

After we calculating the dew point temperature, we can determine the liquid
phase composition from Raoults law as follows
=

( )

= (

( )

11

= (

;
( )

= (

= (

To show the results the following code must be typed in

( : , , );
( , , );
( : );
();
( : );
();

At given temperature:
If we have given the temperature T and y, then the dew point pressure
is the value at which

()

The goal here is to find a p that satisfies these equation. With the given
temperature we can therefore calculate the dew point pressure. After that
the calculation of the liquid phase composition can be easily done as follows
= 57;
= 0,15;
= 0,2;
= 0,25;
12

 = 0,1;
= 0,15;
= 0,15;
1
=

+ + +
+
+

=
=

=
=

( : , , );
( , , );
( : );
();
( : );
();

13

4 Conclusion (Discussion of the Results)

We have calculated the bubble point and dew point pressures of the mixture
at the given temperature range 57-92 C as well as the compositions of the
vapor and liquid phases at bubble point and dew point pressures .As you
can see, the compositions of the liquid and vapor phases differentiate from
each other as stated before in the theory . It is Obvious that at the same
temperature, the dew point pressures are smaller than the bubble point
pressures which indicates that to reach the dew point curve, it is necessary
to increase the pressure, while on the contrary for the bubble point the
pressure must be decreased .However these results are only valid for ideal
mixtures where Raoults law is applicable. But in reality most mixtures dont
behave ideally and therefore we can conclude that Raoults law cannot be
often applied for VLE calculations without further modifications.

14

Bibliography / References
http://www.nt.ntnu.no/users/skoge/septek/lectures/flash_from_skogestad_
book.pdf (01.04.2016)
http://vlecalc.com/compound_properties.html?Comp1=33&numOfC=1&co
mpnames=1 (31.03.2016)
http://www.mycheme.com/calculating-bubble-dew-points-for-idealmixtures/ (30.03.2016)
http://jckantor.github.io/CBE20255/pdf/Bubble_and_Dew_Point_Calculatio
ns.pdf (02.04.2016)
http://matlab.cheme.cmu.edu/2011/09/15/calculating-a-bubble-pointpressure/#1 (31.03.2016)
https://en.wikipedia.org/wiki/Vaporliquid_equilibrium (01.04.2016)
http://chemwiki.ucdavis.edu/Core/Physical_Chemistry/Physical_Properties
_of_Matter/Solutions_and_Mixtures/Ideal_Solutions/Changes_In_Vapor_P
ressure%2C_Raoult's_Law (03.04.2016)
https://en.wikibooks.org/wiki/Introduction_to_Chemical_Engineering_Proc
esses/Vapor-Liquid_equilibrium (03.04.2016)
Reservoir Engineering II Lectures by Prof.L.Ganzer
Thermodynamics: An Engineering Approach" by Yunus A. engel,
Michael A. Boles, p. 65

Annex
EXPLANATION
We hereby assure that we have written this work independently and that no
other than the stated sources and tools were used, and in addition that all
references of work that were literally or in essence taken from other sources,
are identified, and that the work in same or similar form has not yet been
submitted under an examination of any authority. We confirm my
agreement, with the review of this work in terms of this information through
an information-technical verification test.
Clausthal-Zellerfeld, 3. April 2016
Ahoua David , Hussain Yaled

VI