NATIONAL INSTITUTE OF TECHNOLOGY CALICUT

Department of Chemical Engineering

5th Semester B. Tech., Assignment-5, Monsoon Semester, 2024-25

CH3001D CHEMICAL ENGINEERING THERMODYNAMICS-II

Answer All Questions

Submission deadline: 20th November, 2024

Instructions
Use Appendix Tables from Introduction to Chemical Engineering Thermodynamics (8th ed.)
by Smith and Van Ness
Assume and clearly state the missing data

Q. No. Question
1 Assuming the validity of Raoult’s law, do the following calculations for the
benzene(1)/toluene(2) system:

a) Given x1 = 0.33 and T = 100°C, find y1 and P.

b) Given y1 = 0.33 and T = 100°C, find x1 and P.
c) Given x1 = 0.33 and P = 120 kPa, find y1 and T.
d) Given y1 = 0.33 and P = 120 kPa, find x1 and T.
e) Given T = 105°C and P = 120 kPa, find x1 and y1.
f) For part (e), if the overall mole fraction of benzene is z 1 = 0.33, what molar fraction of
the two-phase system is vapor?

2 A mixture containing equimolar amounts of benzene(1), toluene(2), and ethylbenzene(3)

is flash vaporized at 110°C and 100 kPa. Determine the equilibrium mole fractions {x i}
and {yi} of the liquid and vapor phases formed and the molar fraction of the vapor (V)
formed. Assume that Raoult’s law applies.

3 A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium at
temperature T. The overall mole fraction of species 1 in the system is z 1 = 0.65. At
2 2 sat sat
temperature T, ln ( γ 1 ) =0.67 x 2; ln ( γ 2 ) =0.67 x 1; P 1 =32.27 kPa; and P 2 =73.14 kPa.
Assuming the validity of Modified Raoult’s law,

a) Over what range of pressures can this system exist as two phases at the given T and z1?
b) For a liquid-phase mole fraction x1 = 0.75, what is the pressure P and what molar
fraction of the system is vapor?
c) Show whether or not the system exhibits an azeotrope.
2
4 For the system ethyl ethanoate(1)/n-heptane(2) at 343.15 K, ln ( γ 1 ) =0.95 x 2;
ln ( γ 2 ) =0.95 x 12; P 1sat =79.80 kPa; and P 2sat =40.50 kPa. Assuming the validity of
Modified Raoult’s law,

a) Make a BUBL P calculation for T = 343.15 K, x1 = 0.05.

b) Make a DEW P calculation for T = 343.15 K, y1 = 0.05.
c) What are the azeotrope composition and pressure at T = 343.15 K?

5 The following expressions have been reported for the activity coefficients of species
1 and 2 in a binary liquid mixture at given T and P:

ln ( γ 1 ) =x 22 ( 0.273+0.096 x 1 ) and ln ( γ 2 ) =x 12 ( 0.273 − 0.096 x 2 )

 a) Determine the implied expression for G E / RT .
b) Generate expressions for ln γ 1 and ln γ 2 from the result of part (a).
c) Compare the results of part (b) with the reported expressions for ln γ 1 and ln γ 2.
Discuss any discrepancy. Can the reported expressions possibly be correct?

6 Consider the following model for G E / RT of a binary mixture:

GE k 1/ k
=( x 1 A 21 )
k
+ x 2 A 12
x 1 x 2 RT

This equation in fact represents a family of two-parameter expressions for G E / RT ;

specification of k leaves A12 and A21 as the free parameters.

a) Find general expressions for ln γ 1 and ln γ 2, for any k.

∞ ∞
b) Show that ln γ 1 = A 12 and ln γ 2 = A 21, for any k.
c) Specialize the model to the cases where k equals −∞, −1, 0, +1, and +∞. Two of the
cases should generate familiar results. What are they?

7 The excess Gibbs energy for the system chloroform(1)/ethanol(2) at 55°C is well
E
represented by the Margules equation, G / RT = ( 1.42 x 1 +0.59 x 2 ) x 1 x 2. The vapor
sat sat
pressures of chloroform and ethanol at 55°C are P 1 =82.37 and P 2 =37.31 kPa.

Assuming the validity of Modified Raoult’s law, make BUBL P calculations at 55°C for
a)
liquid-phase mole fractions of 0.25, 0.50, and 0.75.

For comparison, repeat the calculations using gamma/phi formulation of VLE with
b)
virial coefficients: B11 = -963, B22 = -1523, and B12 = 52 cm3.mol−1. Assume the Poynting
factor as one for both the species.

8 a) The system n-pentane(1)/n-hexane(2)/n-heptane(3) forms an ideal solution. Calculate

the dew temperature and the liquid-phase composition at 760 Torr if y1 = 0.5, y2 = 0.3
and y3 = 0.2. Consider that 1 atm = 760 Torr.

b) The system acetone(1)/cyclohexane(2) forms an azeotrope at x1 = 0.7390 at 25°C and

262 Torr. Estimate the van Laar constants for the system and calculate the activity
coefficients at x1 = 0.5.

9 Develop expressions for the mole fractions of reacting species as functions of the
reaction coordinate for:

a) A system initially containing 2 mol NH3 and 5 mol O2 and undergoing the reaction:

4 NH 3 ( g ) +5 O 2 ( g ) → 4 NO ( g ) +6 H 2 O ( g )

b) A system initially containing 3 mol H2S and 5 mol O2 and undergoing the reaction:

2 H 2 S ( g ) +3 O 2 ( g ) → 2 H 2 O ( g ) +2 SO 2 ( g )

10 The following reaction reaches equilibrium at 500°C and 2 bar:

4 HCl ( g ) +O 2 ( g ) → 2 H 2 O ( g ) +2Cl 2 ( g )
 If the system initially contains 5 mol HCl for each mole of oxygen, what is the
composition of the system at equilibrium? Assume ideal gases.

11 The gas stream from a sulfur burner is composed of 15 mol% SO 2, 20 mol% O2, and 65
mol% N2. This gas stream at 1 bar and 480°C enters a catalytic converter, where the SO 2
is further oxidized to SO3. Assuming that the reaction reaches equilibrium, how much
heat must be removed from the converter to maintain isothermal conditions? Base your
answer on 1 mol of entering gas.

12 For the ammonia synthesis reaction,

1 3
N ( g ) + H 2 ( g ) → NH 3 ( g )
2 2 2

the equilibrium conversion to ammonia is large at 300 K, but it decreases rapidly with
increasing T. However, reaction rates become appreciable only at higher temperatures.
For a feed mixture of hydrogen and nitrogen in the stoichiometric proportions,

a) What is the equilibrium mole fraction of ammonia at 1 bar and 300 K?

b) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a
pressure of 1 bar?
c) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal gas?
d) At what temperature does the equilibrium mole fraction of ammonia equal 0.50 for a
pressure of 100 bar, assuming the equilibrium mixture is an ideal solution of gases?

13 Limestone (CaCO3) decomposes upon heating to yield quicklime (CaO) and carbon
dioxide. At what temperature is the decomposition pressure of limestone 1(atm)?

CaCO 3 ( s ) →CaO ( s ) +CO 2 ( g )

14 The following isomerization reaction occurs in the liquid phase: A → B , where A and B
E 0
are miscible liquids for which: G / RT =0.1 x A x B . If Δ G 298 =− 1000 J, what is the
equilibrium composition of the mixture at 25°C? How much error is introduced if one
assumes that A and B form an ideal solution?

15 Cracking propane is a route to light olefin production. Suppose that two cracking
reactions occur in a steady-flow reactor:

C 3 H 8 ( g ) →C 3 H 6 ( g ) + H 2 ( g )

C 3 H 8 ( g ) →C 2 H 4 ( g ) +CH 4 ( g )

Calculate the product composition if both reactions go to equilibrium at 1.2 bar and
1000 K.