ChemE 101 – 12.

4 Worksheet Department of Chemical Engineering

1st Semester AY 2020-2021 University of the Philippines Diliman
Material Balance Calculations of VLE Systems

Name ChemE 101 Section

Instructions: Fill in any missing information in the provided solution to each problem. You may print this worksheet, or, in the absence of a
printer, write the complete solution on another sheet of paper.

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PROBLEM 1
Consider a binary mixture of benzene(1) and ethylbenzene(2).
1. A vapor mixture of benzene and ethylbenzene with a composition y1 = 0.63 is in equilibrium with a liquid phase at 50 kPa. What is
the temperature of the system and the liquid phase composition?
2. At what temperature will a 55-mole% benzene mixture with ethylbenzene begin to boil at 90 kPa?
3. An equimolar mixture of benzene and ethylbenzene is fed to a vapor/liquid separator at 45 kPa and 88.96°C.
a. Show that the system will separate into vapor and liquid phases in the separator.
b. What are the compositions of the vapor and liquid phases?
c. What fraction of the feed exits the separator as vapor?
4. At what pressure will a gas mixture of 10 mole% benzene, 20 mole% ethylbenzene, and 70% nitrogen condense at 75°C? What will
be the composition of the initial condensate?
Additional Information:
B
ln P sat [kPa ]= A -
T [°C]+ C
Component A B C

Benzene 13.7819 2726.81 217.572

Ethylbenzene 13.9726 3259.93 212.30

Solution:
For item (1):
Given: y1 and P
Required: x1 and T
Type of calculation: Dew T calculation

Solving for the temperature and composition:

y1 y2 1
Working equation: sat
+ sat =
P1 P2 P

Solving for the initial guess T0:

2726.81
T1sat = - 217.572 = 58.7040°C
13.7819 - ln (50 )
3259.93
T1sat = - 212.3 = 111.7301°C
13.9726 - ln (50 )
T0 = 0.63 (58.7040 )+ 0.37 (111.7301) = 78.3237°C

Solving for the bubble temperature:

0.63 0.37 1
+ =
æ 2726.81 ÷ ö æ 3259.93 ÷ö 50
exp ççç13.7819 - ÷
÷ exp ççç13.9726 - ÷
÷
è T + 217.572 ø è T + 212.3 ø
® Tdew = 89.8040°C

Computing for the composition:

y1P 0.63 (50 kPa )
x1 = = = 0.2321
P1sat æ 2726.81 ö÷
exp çç13.7819 -
ç ÷
è 89.8040 + 217.572 ø÷
x 2 = 1 - x1 = 0.7679
T = 89.8040 °C, Composition: 0.2321 benzene, 0.7679 ethylbenzene
For item (2):
Given: x1 and P
Required: T
Type of calculation: Bubble T calculation
Solving for the temperature:
Working equation: x 1P1sat + x 2P2sat = P

Solving for the initial guess T0:

2726.81
T1sat = - 217.572 = 58.7040°C
13.7819 - ln (50 )
3259.93
T1sat = - 212.3 = 111.7301°C
13.9726 - ln (50 )
T0 = 0.63 (58.7040 )+ 0.37 (111.7301) = 78.3237°C

Solving for the dew temperature:

æ 2726.81 ö÷ æ
çç13.9726 - 3259.93 ÷
ö
0.55 exp çç13.7819 - ÷ + 0.45 exp ÷ = 90
èç T + 217.572 ø÷ èç T + 212.3 ø÷
T = 91.5423°C

For item (3):

To determine the state of the system, we can determine the bubble and dew pressures at the given temperature (88.96°C) and then
compare the computed range to the system pressure indicated (45 kPa). We use the overall composition as our x1 or y1, depending on
the type of calculation.

Computing for the saturation pressures:

æ 2726.81 ö÷
P1sat = exp ççç13.7819 - ÷ = 132.4522 kPa
è 88.96 + 217.572 ø÷
æ 3259.93 ö÷
P2sat = exp çç13.9726 - ÷ = 23.3738 kPa
çè 88.96 + 212.3 ø÷

Bubble P calculation
Working equation: x 1P1sat + x 2P2sat = P

Computing for the bubble pressure:

Pbubble = 0.5 (132.4522) + 0.5 (23.3738) = 77.9130 kPa

Dew P calculation
y1 y2 1
Working equation: sat
+ sat =
P1 P2 P

Computing for the dew pressure:

1
Pdew = = 39.7355 kPa
0.5 0.5
+
132.4522 23.3738

Based on the bubble and dew pressures, the state of the system is a two-phase mixture.

We now perform a flash calculation to determine the compositions of the liquid and vapor phases:
Working equation: x 1P1sat + (1 - x 1 )P2sat = P
We use the saturation pressures determined from the system temperature. Solving for the liquid composition using Raoult’s Law for the
binary mixture:
x1 (132.4522) + (1 - x 1 )(23.3738) = 45

x1 = 0.1983, x 2 = 0.8017

Solving for the vapor composition using Raoult’s Law:

y1 = 0.5836, y2 = 0.4164

To determine the fraction of the feed that leaves as vapor, we use the material balance for the L and V phases:
L+V = F
x1L + y1V = z 1F

Solving for the V/F fraction:

V z - x1 0.5 - 0.1983
= 1 = = 0.7831
F y1 - x 1 0.5836 - 0.1983

For item (4):

Given: y1 and T
Required: x1 and P
Type of calculation: Dew P calculation

Take note that Raoult’s Law only applies to condensable species. Hence, the equilibrium relationships only hold true for benzene and
ethylbenzene.

Solving for the pressure and composition:

y1 y2 1
Working equation: sat
+ sat =
P1 P2 P

Solving for the dew pressure:

æ 2726.81 ÷ ö
P1sat = exp ççç13.7819 - ÷
÷ = 86.6405 kPa
è 75 + 217.572 ø
æ 3259.93 ö÷
P2sat = exp çç13.9726 - ÷ = 13.8159 kPa
çè 75 + 212.3 ø÷
0.1 0.2 1
+ = ® Pdew = 63.9784 kPa
86.6405 13.8159 P

The composition is computed using Raoult’s Law:

P = 63.9784 kPa, Composition of condensate: 0.0738 benzene, 0.9262 ethylbenzene

PROBLEM 2
The feed to a distillation column is a 45.0 mol % n-pentane(1) – 55
mol % n-hexane(2) liquid mixture. The vapor stream leaving the top
of the column which contains 98.0 mol % pentane and the balance
hexane, goes to a total condenser (in which all of the vapor is
condensed). Half of the liquid condensate is returned to the top of
the column as reflux and the rest is withdrawn as overhead product
(distillate) at a rate of 85.0 kmol/h. The distillate contains 95.0% of
the pentane fed to the column. The liquid stream leaving the
bottom of the column goes to a reboiler. Part of the stream is
vaporized. The vapor is recycled to the bottom of the column as
boil-up and the residual liquid is withdrawn as bottoms product.
1. Calculate the molar flow rate of the feed stream and the molar
flow rate and the composition of the bottom product stream.
2. Estimate the temperature of the vapor entering the condenser,
assuming it is saturated at an absolute pressure of 1 atm and
that Raoult’s Law applies to both pentane and hexane.
Estimate the volumetric flow rates of the vapor stream leaving
the column.
3. Estimate the temperature of the reboiler and the composition of
the vapor boil-up, again assuming operation at 1 atm.

Additional information:
1060.793 1175.817
log P1sat [mmHg ]= 6.84471 - log P2sat [mmHg ]= 6.88555 -
T [°C]+ 231.541 T [°C]+ 224.867
Notes;
Solution:
For item (1):
The molar flowrate of the feed stream and the molar flow rate and composition of the bottoms stream is obtained by material balances:

Assume: steady-state
Basis: 1 h

c
Since 95% of the entering pentane exits as a distillate:
0.95(0.45)F = 0.98(85)
Overall OMB: 194.854 = 85 + B ®
Overall pentane bal: 0.45(194.853) = x1 (109.854) + 0.98(85)

F = 194.854 kmol/h, B = 109.854 kmol/h, x1 (in B) = 0.040, x 2 (in B) = 0.960

For item (2):
The liquid leaving the total condenser will have the same composition as the saturated vapor entering it. This is because all of the vapor
condensed into liquid. Both reflux and distillate streams will have the same composition. Assuming that the vapor entering the total
condenser is at its dew point, and that the pressure is 1 atm, we perform a Dew T calculation for this mixture:
1060.793
6.84471-
P1sat = 10 T + 231.541

1175.817
6.88555-
sat
P 2 = 10 T + 224.867
c
1
760 =
0.98 0.02
1060.793
+ 1175.817
6.84471- 6.88555-
10 T + 231.541
10 T + 224.867

T = 37.313°C
The distillate is half of the stream exiting the total condenser. The entering stream to the condenser should have a molar flow rate twice
that of the distillate stream.
V (molar flowrate of vapor) = 2(85) = 170 kmol/h
c

Since this is a gas, we can use the ideal gas law to determine the volumetric flow rate:
æ L atm ö÷
(170, 000 mol/h)ççç0.08206 ÷(37.313 + 273.15 K)
nRT
& è mol Kc ø÷
V = = = 4.331 ´ 106 L/h = 4331 m 3 /h
P 1 atm

For item (3):

For the reboiler system, the liquid leaving the bottom part of the column is being partially vaporized by the reboiler. The two streams
leaving the reboiler is composed of the boil-up, which is the vapor stream, and the bottoms, which is the liquid stream. Both streams are
in equilibrium with each other. This is a Bubble T Calculation. Raoult’s law may be used for this problem:
1060.793
6.84471-
P1sat = 10 T + 231.541

1175.817
6.88555-
sat
P 2 = 10 T + 224.867

sat c
xP1 1 x P sat
+ 2 2 = 1
P P
æ 6.84471- 1060.793 ÷ ö æ 1175.817 ö

(0.040)ççç10 T + 231.541 ÷
+ (0.960) çç10 6.88555- T + 224.867 ÷
÷ = 760 ®
çè ÷
÷ ççè ÷
÷
ø ø
T = 66.632°C

Using Raoult’s Law to determine the composition of the vapor:

1060.793
6.84471-
P1sat = 10 T + 231.541
= 1936.696 mm Hg
sat
xP 1 1(0.040)(1936.696) c
y1 = = = 0.102
P 760
y2 = 1 - y1 = 0.898

y1 = 0.102, y2 = 0.898

6
PROBLEM 3
A mixture of hydrocarbons with equal amounts of propane and butane exists at a pressure of 100 psia and is all in the vapor phase.
1. What is the minimum temperature (°F) at which it could be a vapor?
2. What mole % of the vapor is condensed if the mixture is cooled to 90°F? What would be the liquid phase and vapor phase
compositions at this temperature?
3. What temperature is required to condense 100% of the vapor?
Additional Information:
B
log10 P sat [bar ]= A -
T [K ]+ C
Component A B C

Propane 4.53678 1149.36 24.906

Butane 4.3281 1132.108 0.918

Solution:
For item (1):
The minimum temperature at which the gas mixture could be a vapor is the temperature where the first drop of liquid appears. Hence,
this is a Dew T calculation.

Computing for the dew temperature:

1.01325 bar
P = 100 psia ´ = 6.8929 bar
14.7 psia
1149.36
T1sat = - 24.906 = 285.8678 K
4.53678 - log (6.8929)
1132.108
T2sat = - 0.918 = 323.4961 K
4.3281 - log (6.8929)
T0 = 0.5 (285.8678) + 0.5 (323.4961) = 304.6820 K
y1 y2 1
Working equation: sat
+ sat =
P1 P2 P
0.5 0.5 1
1149.36
+ 1132.108
=
4.53678- 4.3281- 6.8929
10 T + 24.906
10 T + 0.918

Tdew = 309.2013 K = 96.8924°F

For item (2):

This is a flash calculation. Given a temperature and pressure, we determine the liquid and vapor compositions of the liquid and vapor
phases formed. We use the given temperature to determine the saturation pressures:
1K
T = 90 + 459.67°R ´ = 305.3722 K
1.8°R
1149.36
4.53678-
P1sat = 10 305.3722+ 24.906
= 11.3974 bar
1132.108
4.3281-
P2sat = 10 305.3722+ 0.918
= 4.2846 bar

7
Using Raoult’s Law, we compute for the liquid and vapor compositions:

x1 = 0.3667, y1 = 0.6063
Using material balances to compute for fraction of the feed that condenses:

L+V = F
x1L + y1V = z 1F

L
= 0.4438
F

For item (3):

If all of the vapor is condensed, then the temperature also corresponds to the point where the last bubble condenses. This is also the
temperature where the first bubble forms. Hence, this is a Bubble T calculation. We set the given composition to be the liquid
composition, and we determine the bubble temperature:
1.01325 bar
P = 100 psia ´ = 6.8929 bar
14.7 psia
1149.36
T1sat = - 24.906 = 285.8678 K
4.53678 - log (6.8929)
1132.108
T2sat = - 0.918 = 323.4961 K
4.3281 - log (6.8929)
T0 = 0.5 (285.8678) + 0.5 (323.4961) = 304.6820 K

Working equation: x 1P1sat + x 2P2sat = P

æ 4.53678- T1149.36 ö÷ æ 4.3281- 1132.108 ö÷
0.5 çç1010
+ 24.906
0.5 çç10
÷ = 6.8929
T + 0.918 ÷
÷+
÷ ç
çè ø÷ ç
è ø÷
T = 300.3414 K = 80.9445°F

8
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