AECH 2122

Principles of Chemical Engineering I

Winter 2024
Assignment 4
Total Mark: 30

Assignment Rules:
For calculations, clearly show all your work step by step in an organized and logical order. Also,
show the meaning and the unit of your results.

Due Date: Sunday February 25, 2024 @ 02:00 PM in Class

Key solution
Name

Student ID
Question 6-1: Latent enthalpy of vaporization and vapor pressure calculations:
Methyl Alcohol has a vapor pressure of 0.2 bar at 301.15 K and a normal boiling point of 337.8 K.
Estimate the vapor pressure at 328.15 K using: (a) the Antoine equation; (b) the Clausius–
Clapeyron equation and (c) Latent enthalpy of vaporization, and (d) Cox charts.
Solution:
(a) Use Antoine Equation for the calculations as:
log10(P) = A − (B / (T + C)) = 5.20409 – (1581.341/(328.15-33.50)) =-0.16276
P =10^-0.16276 = 0.68745 bar

(b) Use the Clausius-Clapeyron Equation as,

^
−Δ H V
=
ln
( )
P2
P1
=
ln
0.2(
1.01325
)
=−4504 K
R 1 1 1 1
− −
T 2 T 1 301.15 337.8
Now, Calculate B as,
Δ^
HV
R 4504
B=ln ( P 1) + =ln ( 0.2 ) + =13.34656
T1 301.15
Calculate the pressure as,
Δ^HV
−
R −4504
ln P ( 328.15 K )= + B= +13.34656=−0.3789
T 328.15
P (at 318.15K) = exp (-0.3789) = 0.6846 bar

^ V ¿ (Majer∧Svoboda , 1985)
Using Δ H

^ V = A exp (−α T r ) (1−T r )

ΔH
β

Tr = T/Tc = 328.15/512.6 = 0.64

ΔH^ V =45.3 exp ( 0.31∗0.64 ) (1−0.64 )0.4241=35.817 KJ
mol
^
Δ H V 35.817∗1000
= =4308 K
R 8.314462618
Now, Calculate B as,
Δ^
HV
R 4308
B=ln ( P 1) + =ln ( 0.2 ) + =12.696
T1 301.15
Calculate the pressure as,
Δ^
HV
−
R −4308
ln P ( 328.15 K )= + B= +12.696=−0.432
T 328.15
1
P (at 328.15K) = exp (-0.432) = 0.65 bar

(c) Use Cox chart vapor pressure plot

At T =131 oF (328.15K), P = 9.5 lbf/in2, then, P =9.5* 0.0689476= 0.655 bar

(d) Use Cox-Othmer diagram for certain alcohols (shown below)

At T =55 oC (328.15K), P = 500 mm Hg, then, P =(500/760)*1.01325 = 0.6666 bar
Cox chart vapor pressure plot

500

Data: From https://webbook.nist.gov/cgi/cbook.cgi?

ID=C67561&Mask=4&Type=ANTOINE&Plot=on#ANTOINE,
Antoine Equation Parameters for Methyl Alcohol:
log10(P) = A − (B / (T + C))
P = vapor pressure (bar)
T = temperature (K)

2
For Enthalpy of vaporization (Majer and Svoboda,1985):
ΔH^ V = A exp (−α T r ) (1−T r ) β
Tr = T/Tc = 328.15/512.6 = 0.640
ΔH^ V =45.3 exp ( 0.31∗0.640 )( 1−0.640 )0.4241 =35.817 KJ
mol
^
Δ H V 35.817∗1000
= =4307.8 K
R 8.314462618
ΔH^ =Enthalpy of vaporization(at saturation pressure)( kJ / mol)
V
And Tr = reduced temperature (T / Tc)

(Majer and Svoboda, 1985)

9.5

131

Cox chart vapor pressure plots (p* vs. T)

3
Q2. Gibbs Phase Rule, Raoult's Law and Vapor-Liquid Equilibrium:
A fixed volume tank contains 1.0 mol of Benzene B (PBsat = 0.159 bar) at a pressure of 0.15 bar.
When 1.0 mol of liquid Toluene T (PTsat = 0.049 bar) is added to the tank, and the system goes to
equilibrium at the same temperature, the final pressure is 0.1018 bar. Assume ideal gas and ideal
solution for liquid phase. Determine the phase or phases present and their compositions and
number of moles. Determine the degrees of freedom for the final system at equilibrium. Specify a
feasible set of independent variables for the final system.

Solution:

Raoult's Law:
sat sat
PTotal =x B PB + x T PT =x B ¿
( 0.159−0.049 ) x B +0.049=0.1018 ⇒ x B=0.48
sat
x B P B 0.48∗0.159
yB= = =0.75
P 0.1018
Material Balance for component B: x A L+ y A V =z A ( L+V )
0.48 L+0.75 ( 2.0− L )=0.5 ( 2.0 ) ⇒ L=1.85 mol∧V =2−1.85=0.15 mol
The final system has two phase (π =2), two components (c = 2) and no reaction (r = 0).
DF = 2 + c - π – r = 2 + 2 - 2 – 0 = 2.
Two variables must be specified to fix the state of the system.

4
Q3. Vapor-Liquid Equilibrium (VLE) calculations for solutions that obey
Raoult’s law:
Calculate the bubble temperature at 100 kPa for a binary liquid with x1 = 0.35. The liquid solution
is ideal. The saturation pressures are (in °C):

Assume the first trial: T1 = 90 oC and the second trial T2 = 91 oC, and then calculate the bubble
point by interpolation to satisfy ∑ yi = 1.
Solution:
Psat
1 =exp ⁡ 14.3−
2945
T +224 ( )
Psat
2 =exp ⁡ 14.2−
2943
T +209 ( )
sat sat
x 1 P1 x 2 P2
y 1= ∧ y 2=
P P
o
First Trial (T1 = 92 C):
Psat
1 =exp 14.3− ( 2945
90+224 )
=137.14 ⇒ y 1=
0.35∗137.14
100
=0.48

sat
P2 =exp 14.2− ( 2943
90+209 )
=78.04 ⇒ y 2=
0.65∗78.04
100
=0.51

∑ y trial 1= y 1 + y 2=0.48+ 0.51=0.99

Second Trial (T2 = 93 oC):

Psat
1 =exp 14.3− ( 2945
91+224 )
=141.29 ⇒ y 1=
0.35∗141.29
100
=0.49

Psat
2 =exp 14.2− ( 2943
91+ 209 )
=80.64 ⇒ y 2=
0.65∗80.64
100
=0.52

∑ y trial 2= y 1 + y 2=0.49+ 0.52=1.02

Find TBP by interpolation:
( T 2−T 1 ) ( 91−90 )
T BP=T 2− ( ∑ ytrial 2−1 ) =91− ( 1.02−1 )=90.4 o C
( ∑ y trial 2−∑ y trial 1 ) ( 1.02−0.99 )

5
Q4. Solutions of Solids in Liquids:
Fresh feed stream flowing at 100 kg/h contains 20% by weight KNO3 (K) in H2O (W). The fresh
feed stream is combined with a recycle stream and is fed to an evaporator. The concentrated liquid
solution exited the evaporator contains 50% KNO3 is fed to a crystallizer. The crystals obtained
from the crystallizer are 96% KNO3 and 4% water. The liquid from the crystallizer constitutes the
recycle stream and contains 0.6 kg KNO3 per 1.0 kg of H2O. Calculate all stream flow rate values
and compositions.

Solution:

Known quantities: Feed flow rate and composition, cake composition.

Find: All stream values and compositions.
Analysis: The labeled process flow sheet is shown in the Figure above.

The degrees of freedom analysis is shown in the following table:

Systems
Evaporato
Crystallizer Mixer Process
r
Number of unknowns 4 4 3 2
Number of independent
2 2 2 2
equations
Number of relations 0 1 0 0
NDF 2 1 1 0

6
Since the lowest NDF is for the entire process, accordingly, we start with the overall process
system.
Basis: 100 kg/h feed.
System: Overall process
From the relation in the recycle stream, the mass fractions of K and W in the recycle stream can be
calculated:
Mass fractions of K in recycle stream:

Mass fraction of water in the recycle stream:

Overall material balance:

Component balance (K):

Substitute in the total material balance to get the value of ṁ6:

Check your answer with W balance:

7
Now the NDF for the evaporator and the mixer has been reduced to zero, and either unit could be
solved next.
System: Mixer.

Overall material balance:

Component balance (K):

8
Q5. Extraction:
Hexane is used to extract seed oil from cleaned cotton seed. Raw cotton seed consists of 15 wt%
cellulose material, 35 wt% protein meal, and 50 wt% oil. Calculate the composition of oil extract
obtained when 3 kg hexane is used per 1 kg mass raw seeds.

Solution:
Known quantities: Raw seed composition, hexane/raw seed mass ratio.
Find: Composition of oil extract.
Analysis: The process-labeled flowchart is shown in Example
Figure 3.13.1.
Basis: 100 kg of raw cotton seeds
Component balance:
Protein meal: 0.35(100 kg) = m3
Cellulose: 0.15(100 kg) = m4
Oil: 0.50 (100 kg) = xoil,5 m5
Hexane: 300 kg = (1 − xoil,5) m5
9
Total mass balance:
100 kg + 300 kg = 35 kg + 15 kg + m5

Mass of the extracted oil = m5 = 350 kg

Substitute m5 in the oil balance equation:
0.5(100 kg) = xoil,5 350  xoil,5 = 0.143

Q6-Colligative Properties:
1.60 g of naphthalene (C10H8) is dissolved in 20.0 g of benzene. The freezing point of
pure benzene is 5.5 oC, and the freezing point of the mixture is 2.8 oC. What is the molal
freezing point depression constant, Kf of benzene?

Strategy:
1. Step 1: Calculate the freezing point depression of benzene.

Tf = (Freezing point of pure solvent) - (Freezing point of solution)

(5.5 oC) - (2.8 oC) = 2.7 oC

2. Step 2 : Calculate the molal concentration of the solution.

molality = moles of solute / kg of solvent

10
 moles of naphthalene = (1.60 g) (1 mol / 128 g) = 0.0125 mol naphthalene
molality of solution = (0.0125 mol) / (0.0200 kg) = 0.625 m

3. Step 3: Calculate Kf of the solution.

Tf = (Kf) (m)

(2.7 oC) = (Kf) (0.625 m)

Kf = 4.3 oC/m

11