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Midterm Exam
Vapor Liquid Equilibrium : RachfordRice Equation
170
171
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:
172
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
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
173
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]
174
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
Alarcon, Grace Dianne A.
175
Course:
Group No.:
Group Members:
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
176
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 =
177
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)
178
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
179
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.;
180
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);
181
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;
182
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.
183
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
Process Skills
Member do not
demonstrate targeted
process skills.
Members occasionally
demonstrate targeted process
skills.
Members always
demonstrate targeted
process skills.
Safety Precautions
Time Management /
Conduct of
Experiment
Cooperative and
Teamwork
Neatness and
Orderliness
Ability to do
independent work
Members require
supervision by the teacher.
TOTAL SCORE
RATING = (
24
)x 100%
SCORE
184
185
186