CHEN 6853 – Graduate ChE Thermodynamics – Fall 2016

Homework #4

Due: Start of class on Friday, October 21st

1. Derive the following expression for the partial fugacity coefficient of a mixture that adheres to the
Virial equation of state:

! !
! 𝑓! 2𝑃
𝑙𝑛 𝜙! = 𝑙𝑛 = 𝑦! 𝐵!" 𝑇 − 𝑙𝑛 𝑍!"#
𝑦! 𝑃 𝑍!"# 𝑅𝑇
!!!

Where the original equation of state and mixing rules are given below.

𝑃𝑉 𝐵!"# 𝑇, 𝑦
𝑍!"# = =1+ 𝐵!"# 𝑇, 𝑦 = 𝑦! 𝑦! 𝐵!" 𝑇
𝑅𝑇 𝑉
! !

2. A 10 m3 tank stores 1 m3 of liquid benzene at atmospheric pressure and a temperature of 30 ˚C. The
remainder of the volume of the tank is filled with air, and assume there is no air dissolved in the
benzene (i.e., xAir = 0). If the liquid benzene is in vapor-liquid equilibrium with the air, what is the
total mass of benzene in the vapor phase inside the tank? You may assume Raoult’s Law behavior.
This calculation is important to determine the amount of benzene released into the environment
because the air mixture will be released to the atmosphere once the tank is filled to capacity. (A: 4 kg
benzene)

3. Assuming ideal behavior (Raoult’s Law) please perform the follow actions for a n-hexane and n-
heptane mixture:
a. Plot a Pxy diagram (in units of kPa) at 90 ˚C.
b. Plot a Txy diagram (in units of ˚C) at 100 kPa pressure.
c. Plot a xy diagram for P = 100 kPa.
d. Determine how many equilibrium stages in a distillation column at infinite reflux are
required to create a top product consisting of a 95% n-hexane stream at the top and a 95%
n-heptane stream at the bottom? The column is operated isobarically at 100 kPa. (A:
Number of stages between 4 and 9)
e. Why was the pressure fixed in the xy diagram (part d) as opposed to the temperature fixed?
Consider the operation of a distillation column.

4. A 50:50 blend of n-hexane and n-heptane is flashed at T = 60 ˚C and P = 50 kPa.

a. What is the composition of the liquid and vapor phases? (A: xHex = 0.5, yHex = 0.7)
b. What fraction of the feed is in the vapor and liquid phases? (L = 0.8)
5. An Ethanol (1)-Benzene (2) system does not follow Raoult’s Law, and the liquid phase is highly
non-ideal. Use the van Laar equation to model the activity coefficients (alpha = 1.946, beta = 1.610).
You may assume an ideal gas vapor phase.
a. Plot a Pxy diagram (in units of kPa) at T = 70 ˚C.
b. Plot a Txy diagram (in units of ˚C) at P = 100 kPa.
c. Plot an xy diagram at a constant pressure of 100 kPa.
d. What is the azeotrope composition at P = 100 kPa? (A: x = y = 0.5)

B
ln P sat ( in kPa ) = A −
T ( in deg C) + C

Compound A B C
Ethanol 16.8958 3795.17 230.918
Benzene 13.7819 2726.81 217.572
n-Hexane 13.8193 2696.04 224.317
n-Heptane 13.8622 2910.26 216.432