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Midterm Exam
Vapor Liquid Equilibrium : RachfordRice Equation
1. Objective:
The activity aims to solve problems involving vapor liquid equilibrium.
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.
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.
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.
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.
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
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
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.
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 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
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.
Procedure Result
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
Command Window
>> vpequil
z=
K=
num =
0.5800
3 Command Window
>> vpequil(0.2)
z=
K=
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
>>
5 Editor Window
%vapor-liquid equilibrium
% using Eq. 9
function y=vpequil(v)
>> 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=
ans =
>>
%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;
Command Window
>> v=fzero(@vpequil7,0.2)
v=
0.7079
>>
%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=
ans =
>>
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.;
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
%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=
ans =
>>
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);
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
%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=
ans =
>>
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;
end
y=sum1;
Command Window
>> v=fzero(@Alarcon_le08_p10,0.5)
v=
0.8500
>>
%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=
ans =
>>
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.
I. Laboratory Skills
Members always
Manipulative Members do not Members occasionally
demonstrate needed
Skills demonstrate needed skills. demonstrate needed skills.
skills.
TOTAL SCORE
Other Comments / Observations:
RATING = ( )x 100%
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