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:
2.1 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 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.
 2

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:

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 %). K pentane = 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. K NH3 = 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
functiony=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, equations 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.