TECHNOLOGICAL INSTITUTE OF THE PHILIPPINES MANILA

Midterm Exam
Vapor Liquid Equilibrium : RachfordRice Equation

Alarcon, Grace Dianne A.

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Laboratory Exercise No. 8

Vapor Liquid Equilibrium : RachfordRice Equation
1. Objective:
The activity aims to solve problems involving vapor liquid equilibrium.
2. Intended Learning Outcomes (ILOs):
The students shall be able to:
2.1 solve vapor-liquid equilibrium problems using matlab.
2.2 solve equations for a phase separation.
2.3 predict thermodynamic properties
3. Discussion:
Distillation towers are used to separate mixtures of chemicals into two or more streams, each a
relatively pure stream of one of the chemicals. The physical process governing that separation is
vapor-liquid equilibrium.
Take a mixture of two or more chemicals in a temperature regime where both have a
significant vapor pressure. The composition of the mixture in the vapor is different from the liquid.
By harnessing this difference, you can separate two chemicals, which is the basis of distillation. To
calculate this phenomenon, there is a need to predict thermodynamic properties such as fugacity,
and then perform mass and energy balances over the system.
Phase separation is only one part of distillation process, it is the basis for the entire process.
Vapor-liquid equilibria problems are expressed as algebraic equations.
Flash distillation (sometimes called "equilibrium distillation") is a single stage separation
technique. A liquid mixture feed is pumped through a heater to raise the temperature and enthalpy
of the mixture. It then flows through a valve and the pressure is reduced, causing the liquid to
partially vaporize. Once the mixture enters a big enough volume (the "flash drum"), the liquid and
vapor separate. Because the vapor and liquid are in such close contact up until the "flash" occurs,
the product liquid and vapor phases approach equilibrium.
Simple flash separations are very common in industry, particularly petroleum refining. Even
when some other method of separation is to be used, it is not uncommon to use a "pre-flash" to
reduce the load on the separation itself.
Flash and Phase Separation
Putting some water in an open pan on the stove, initially at room temperature. The partial
pressure of water in the air (at equilibrium) will equal the vapor pressure of water at that
temperature. Now, heat the pan. The vapor pressure increases, since it increases as the
temperature rises. If the partial pressure of water at the pan temperature exceeds the partial
pressure of water in the room temperature (usually set by humidity), the water will evaporate.
Next, imagine doing the same thing with a mixture of two chemicals in a closed vessel. The
closed vessel is one with a piston that can move so the pressure inside remains constant. The two
chemicals have different boiling points,and different vapor pressures at a given temperature. As you
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increase the temperature of the vessel, the relative amount of each chemical in the vapor changes,
because one is more volatile than the other. At temperatures below the bubble point, T bubble, the
mixture is entirely a liquid. At temperatures above the dew point, Tdew, the mixture is entirely a
vapor. At temperatures in between, both liquid and vapor co-exist. The composition of the liquid and
vapor are not the same, however. Thus, as you gradually increase the temperature from a low
value, some vapor forms, and this vapor is richer in the more volatile component. As the
temperature increases further, more and more vapor forms. Finally, as the last drop of liquid
evaporates, all the material is in the vapor phase, which has the same composition as
the original liquid. However, between the bubble point and dew point, the composition of the liquid
and vapor are changing as the temperature increases, and it is this change that there is a need to
calculate.
There is another scenario that, unfortunately, is purely imaginary. In that scenario, as the
temperature increases, chemical one evaporates completely when the temperature reaches its
boiling point. As the temperature increases further, the boiling point for the second chemical is
reached, and it all evaporates. You wish it did happen this way! Despite the fact that in real life the
separation of the two chemicals is never complete in either liquid or vapor phase, it is still a useful
phenomenon and forms the basis for
distillation.
This laboratory exercise looks first at equations governing an isothermal flash, and then shows
how
one can predict the thermodynamic quantities that is needed to solve the isothermal flash problem.
ISOTHERMAL FLASH DEVELOPMENT OF EQUATIONS
Consider the flow sheet shown in below:

Figure 1. Flash Phase Separator

Suppose you know the temperature, pressure, and overall composition of the inlet stream.
The mole fractions of the chemicals in the inlet are called {zi}. In the phase separator, however, the
liquid and vapor are separated. The mole fraction of the chemicals in the vapor phase are called {yi}
and those in the liquid
phase are called {xi}. When the vapor and liquid are in equilibrium, you can relate the mole fractions
of each chemical in the vapor and liquid by the equation:
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1
The members of the set {Ki} are called K-values, and they can be predicted from
thermodynamics.
For now, assume that their values are known.
To derive the equation governing the phenomenon, you first sum the mole fractions of vapor
and liquid over all components.
2

Then, subtract those two equations:

3

Next, substitute the equilibrium expression and rearrange to obtain:

4

Next, make a mass balance for each component over the phase separator. F is the total
molar flow rate, V is the molar flow rate of the vapor, and L is the molar flow rate of the liquid. The
mole balance is then
5

Divide by F and define v as the fraction of the feed that is vapor:

6

By using the equilibrium expression again, you can write this as

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Solve for the mole fractions in the liquid:

8

Put that expression into Eq. 4 to obtain the final equation:

9
This is called the RachfordRice equation. Notice that, if the K-values and inlet compositions
{zi} are known, this is a nonlinear equation to solve for v. Once the value of v is known, one can
calculate the value of the liquid compositions, {xi}, and vapor compositions, {yi}, using Eqs. 1 and 3.
The mole balance is then complete.

4. Resources:
Matlab
5. Procedure:
1. Suppose you have a mixture of hydrocarbons in the inlet stream. You want to find the
fraction of the stream that is vapor and the mole fraction of each chemical in the vapor and
liquid streams. Table 1 shows the flow rates and K-values at 180 o F and 70 psia, using a
basis of one mole per unit of time.
TABLE 1. Mole Fractions and K-values for VaporLiquid
Mole Fraction
Phase Equilibrium, K-value
Propane
0.1
6.8
n-Butane
0.3
2.2
n-Pentane
0.4
0.8
n-Octane
0.2
0.052
1
2. The function (filename: vpequil.m) for Procedure 1 contains:
%vapor-liquid equilibrium
% using Eq. 9
function y=vpequil(v)
z=[0.1 0.3 0.4 0.2]
K=[6.8 2.2 0.8 0.052]

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3.
4.
5.

6.
7.

sum1=0.;
for i=1:4
num=(K(i)-1)*z(i)
denom=1+(K(i)-1)*v
sum1=sum1+num/denom
end
y=sum1
Using the MATLAB command window, issue the command vpequil(0.2). Show the results.
Verify if the program is correct by using calculator. Show the results. Do they give the same
answers.
Now, add semi-colons at the end of each line of the m-file and save it. Issue fzero
command in the MATLAB command window:
>>fzero(@vpequil,0.2)
Show the results.
Determine the mole fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8)
using MATLAB by creating an m-file (filename: yourSurname_le08_p06. Show the results.
The following stream is at 100 psia and 178 oF. Calculate the fraction that is vapor by
solving the RachfordRice equation using MATLAB by creating a function file (filename:
vpequil7.m) and issuing fzero command in MATLAB command window. Determine the mole
fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by
creating an m-file (filename: yourSurname_le08_p07. Show the results. Show the results.

8. The following stream is at 126 psia and 178 oF. Calculate the fraction that is vapor by
solving the RachfordRice equation using MATLAB by creating a function file (filename:
vpequil8.m) and issuing fzero command in MATLAB command window. Determine the mole
fraction of each chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by
creating an m-file (filename: yourSurname_le08_p08.m) Show the results.
Mole Fraction
Phase Equilibrium, K-value
Methane
0.1
16
Ethane
0.2
2.65
Propane
0.7
0.762
9. A feed F is split into a vapor product V and a liquid product L in a flash tank. The feed is
50% pentane, 30% hexane and 30% cyclohexane ( all I mole %). Kpentane = 1.685 , Khexane =
0.742 and
Kcyclohexane = 0.532. Determine the fraction that is vapor by solving the Rachford-Rice
equation using MATLAB by creating a function file (filename: vpequil9.m) and issuing fzero
in MATLAB command window. Determine the mole fraction of each chemical in the vapor
(Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file
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(filename:yourSurname_le08_p09.m). Show the results.

10. The exit gas from ammonia reactor is at 250 bar and contains 61.5% H2, 20.5% N2 and
18% NH3. The gas is cooled to 25 0 C (partly condensed), and is then separated in a flash
drum into a recycled vapor stream V and a liquid product L containing most of the
ammonia. KNH3 = 0.0393,
KH2 = 60.8 and KN2 = 35.6 . Calculate the fraction that is vapor by solving the Rachford
Rice equation using MATLAB by creating a function file (filename: vpequil10.m) and issuing
fzero command in MATLAB command window. Determine the mole fraction of each
chemical in the vapor (Eq.1) and liquid stream (Eq. 8) using MATLAB by creating an m-file
(filename: yourSurname_le08_p10.m) Show the results.

Course:
Group No.:
Group Members:

Laboratory Exercise No.:

Section:
Date Performed:
Date Submitted:
Instructor:

6. Data and Results:

Procedure

Result

1
2

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=vpequil(v)
z=[0.1 0.3 0.4 0.2]
K=[6.8 2.2 0.8 0.052]
sum1=0.;
for i=1:4
num=(K(i)-1)*z(i)
denom=1+(K(i)-1)*v
sum1=sum1+num/denom
end
y=sum1

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Command Window
>> vpequil
z=
0.1000 0.3000 0.4000 0.2000
K=
6.8000 2.2000 0.8000 0.0520
num =
0.5800
3

Command Window
>> vpequil(0.2)
z=
0.1000 0.3000 0.4000 0.2000
K=
6.8000 2.2000 0.8000 0.0520
num =
0.5800
denom =
2.1600
sum1 =
0.2685
num =
0.3600
denom =

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1.2400
sum1 =
0.5588
num =
-0.0800
denom =
0.9600
sum1 =
0.4755
num =
-0.1896
denom =
0.8104
sum1 =
0.2415
y=
0.2415
ans =
0.2415
>>
4
5

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=vpequil(v)

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z=[0.1 0.3 0.4 0.2];

K=[6.8 2.2 0.8 0.052];
sum1=0.;
for i=1:4
num=(K(i)-1)*z(i);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;

Command Window
>> fzero(@vpequil,0.2)
ans =
0.4258
>>
6

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p06(v)
z=[0.1 0.3 0.4 0.2];
K=[6.8 2.2 0.8 0.052];
v=0.4258;
sum1=0.;
for i=1:4
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i)
end

Command Window
x=
0.0288 0.1985 0.4372 0.3354
ans =
0.1960 0.4368 0.3498 0.0174
>>
7

Editor Window - VPEQUIL

%vapor-liquid equilibrium
function y=vpequil7(v)
z=[20 30 50];
K=[3.7 1.4 0.6];

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sum1=0.;
for i=1:3
num=(K(i)-1)*z(i);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;

Command Window
>> v=fzero(@vpequil7,0.2)
v=
0.7079
>>
Editor Window MOLE FRACTION
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p07(v)
z=[20 30 50];
K=[3.7 1.4 0.6];
v=0.7079;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end

Command Window
x=
6.8697 23.3798 69.7506
ans =
25.4179 32.7317 41.8503
>>
8

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p08(v)
z=[0.1 0.2 0.7];
K=[1.6 2.65 0.762];
sum1=0.;

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for i=1:3
num=(K(i)-1)*z(i);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;

Command Window
>> v=fzero(@Alarcon_le08_p08,0.2)
v=
0.6767
Editor Window MOLE FRACTION
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p08(v)
z=[0.1 0.2 0.7];
K=[1.6 2.65 0.762];
v=0.6767;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end

Command Window
x=
0.0711 0.0945 0.8344
ans =
0.1138 0.2504 0.6358
>>
9

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p09(v)
z=[0.5 0.3 0.2];
K=[1.685 0.742 0.532];
sum1=0.;
for i=1:3
num=(K(i)-1)*z(i);

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denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;

Command Window
>> v=fzero(@Alarcon_le08_p09,0.2)
v=
0.6907
Editor Window MOLE FRACTION
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p08(v)
z=[0.5 0.3 0.2];
K=[1.685 0.742 0.532];
v=0.4365;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end

Command Window
x=
0.3849 0.3381 0.2513
ans =
0.6486 0.2508 0.1337
>>
10

Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p10(v)
z=[0.615 0.205 0.18];
K=[60.8 35.6 0.0393];
sum1=0.;
for i=1:3
num=(K(i)-1)*z(i);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;

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end
y=sum1;

Command Window
>> v=fzero(@Alarcon_le08_p10,0.5)
v=
0.8500
>>
Editor Window MOLE FRACTION
%vapor-liquid equilibrium
% using Eq. 9
function y=Alarcon_le08_p08(v)
z=[0.615 0.205 0.18];
K=[6.08 3.56 0.0393];
v=0.8500;
sum1=0.;
for i=1:3
x(i)=z(i)/(1+(K(i)-1)*v)
y(i)=x(i)*K(i);
end

Command Window
x=
0.1156 0.0645 0.9814
ans =
0.7031 0.2298 0.0386
>>

7. Conclusion:
I therefore conclude that Matlab also has another way of solving chemical engineering problems
specifically this type of unit operation, distillation. The same formula can be done to any problem if
and only if the corresponding distribution coefficient is applied to the proper mole fraction.

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8. Assessment (Rubric for Laboratory Performance):

CRITERIA

BEGINNER
1

ACCEPTABLE
2

PROFICIENT
3

I. Laboratory Skills
Manipulative
Skills

Members do not
demonstrate needed skills.

Members occasionally
demonstrate needed skills.

Members always
demonstrate needed
skills.

Experimental Set-up

Members are unable to setup the materials.

Members are able to set-up

the materials with supervision.

Members are able to

set-up the material with
minimum supervision.

Process Skills

Member do not
demonstrate targeted
process skills.

Members occasionally
demonstrate targeted process
skills.

Members always
demonstrate targeted
process skills.

Safety Precautions

Members do not follow

safety precautions.

Members follow safety

precautions most of the time.

Members follow safety

precautions at all times.

Time Management /
Conduct of
Experiment

Members do not finish on

time with incomplete data.

Members finish on time with

incomplete data.

Members finish ahead of

time with complete data
and time to revise data.

Cooperative and
Teamwork

Members do not know their

tasks and have no defined
responsibilities. Group
conflicts have to be settled
by the teacher.

Members have defined

responsibilities most of the
time. Group conflicts are
cooperatively managed most
of the time.

Members are on tasks

and have defined
responsibilities at all
times. Group conflicts
are cooperatively
managed at all times.

Neatness and
Orderliness

Messy workplace during

and after the experiment.

Clean and orderly workplace

with occasional mess during
and after the experiment.

Clean and orderly

workplace at all times
during and after the
experiment.

Ability to do
independent work

Members require
supervision by the teacher.

Members require occasional

supervision by the teacher.

Members do not need to

be supervised by the
teacher.

II. Work Habits

Other Comments / Observations:

TOTAL SCORE

RATING = (

Alarcon, Grace Dianne A.

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)x 100%

SCORE

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Alarcon, Grace Dianne A.

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