Laboratory Exercise No.

5
Vapor –Liquid Equilibrium : Rachford–Rice Equation

1. Objective:
The activity aims to solve problems involving vapor – liquid equilibrium.

2. Intended Learning Outcomes (ILOs):

The students shall be able to:
2.1solve vapor-liquid equilibrium problems using matlab.
2.2solve equations for a phase separation.
2.3predict 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 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, Tbubble, 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:

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.

Then, subtract those two equations:

Next, substitute the equilibrium expression and rearrange to obtain:

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

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

Solve for the mole fractions in the liquid:

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

9
This is called the Rachford–Rice 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 Vapor–Liquid
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]
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
3. Using the MATLAB command window, issue the command vpequil(0.2). Show
the results in Table .
4. Verify if the program is correct by using calculator. Show the results. Do they
give the same answers.
5. 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.
6. 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.
7. The following stream is at 100 psia and 178 oF. Calculate the fraction that is
vapor by solving the Rachford–Rice 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.

8. The following stream is at 126 psia and 178 oF. Calculate the fraction that is
vapor by solving the Rachford–Rice 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 (filename:yourSurname_le08_p09.m). Show the results.

10.The exit gas from ammonia reactor is at 250 bar and contains 61.5% H 2, 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: CHE 508 Laboratory Exercise No.: 5
Group No.: Section: CH51FC2
Group Members: Date Performed: 1/11/2019
AQUINO, AIRAH DS. Date Submitted: 1/11/2019
Instructor: ENGR. MARANAN

6. Data and Results:

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

Matlab command:
>>vpequil
>>vpequil(0.2)

Matlab output:
z = 0.1000 0.3000 0.4000 0.2000
K = 6.8000 2.2000 0.8000 0.0520
num =0.5800

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 = 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 Calculator computation is the same with matlab answer.
5 Contents of m-file with some changes:
%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;

Matlab command:
>>fzero(@vpequil,0.2)

Matlab output:
ans = 0.4258

6 Contents of AQUINO_le08_p06:
%vapor-liquid equilibrium
% using Eq. 9
function y=Aquino_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

Matlab command:
>>AQUINO_le08_p06

Matlab output:
x = 0.0288
y = 0.1960
x = 0.0288 0.1985
y = 0.1960 0.4368
x = 0.0288 0.1985 0.4372
y = 0.1960 0.4368 0.3498
 x = 0.0288 0.1985 0.4372 0.3354
y = 0.1960 0.4368 0.3498 0.0174
ans = 0.1960 0.4368 0.3498 0.0174

7 Contents of vpequil7.m:
%vapor-liquid equilibrium
function y=vpequil7(v)
z=[20 30 50];
K=[3.7 1.4 0.6];
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;

Matlab command:
>>fzero(@vpequil7,0.2)

Matlab output:
0.7079

Contents of AQUINO_le08_p07:
%vapor-liquid equilibrium
% using Eq. 9
function y=Aquino_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

Matlab command:
>>Aquino_le08_p07

Matlab output:
x = 6.8697
x = 6.8697 23.3798
x = 6.8697 23.3798 69.7506
ans =25.4179 32.7317 41.8503
8 Contents of vpequil8.m:
%vapor-liquid equilibrium
 % using Eq. 9
function y=Aquino_le08_p08(v)
z=[0.1 0.2 0.7];
K=[1.6 2.65 0.762];
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;

Matlab command:
>>v=fzero(@Aquino_le08_p08,0.2)

Matlab output:
v = 0.6767

Contents of AQUINO_le08_p08:
%vapor-liquid equilibrium

% using Eq. 9
function y=Aquino_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

Matlab command:
>>Aquino_le08_p08

Matlab output:
x = 0.0711
x = 0.0711 0.0945
x = 0.0711 0.0945 0.8344
ans = 0.1138 0.2504 0.6358

9 Contents of vpequil9.m:
%vapor-liquid equilibrium

% using Eq. 9
function y=Aquino_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);
denom=1+(K(i)-1)*v;
sum1=sum1+num/denom;
end
y=sum1;

Matlab command:
>>v=fzero(@Aquino_le08_p09,0.2)

Matlab output:
x=
0.3849
x=
0.3849 0.3381
x=
0.3849 0.3381 0.2513

Contents of AQUINO_le08_p09:
%vapor-liquid equilibrium

% using Eq. 9
function y=Aquino_le08_p09(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

Matlab command:
>>Aquino_le08_p09
Matlab output:
x = 0.3849
x = 0.3849 0.3381
x = 0.3849 0.3381 0.2513
ans = 0.6486 0.2508 0.1337
10 Contents of vpequil10.m:
%vapor-liquid equilibrium

% using Eq. 9
 function y=Aquino_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;
end
y=sum1;

Matlab command:
>>v=fzero(@Aquino_le08_p10,0.5)

Matlab output:
v =0.8500

Contents of AQUINO_le08_p10
%vapor-liquid equilibrium

% using Eq. 9
function y=Aquino_le08_p10(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

Matlab command:
>>Aquino_le08_p10

Matlab output:
x = 0.1156
x = 0.1156 0.0645
x = 0.1156 0.0645 0.9814
ans = 0.7031 0.2298 0.0386

7. Conclusion:
I therefore conclude that Matlab can solve vapor-liquid equilibrium problems, equa-
tions for a phase separation and it can also predict thermodynamic properties of the
system. It makes the computation faster and can optimize the time of working with
thermodynamic problems.