ChBE 3110-001

Estimate the vapor pressure and the composition of the vapor in equilibrium with
a liquid that is 80 mole % benzene and 20 % toluene at 20 C. Use the Antoine
equation to calculate the vapor pressure of the pure components.
a) Write the chemical structure of benzene and toluene. Comment on the validity
of Raoults Law for these two chemicals.

b) Use Raoults law to determine the composition of the vapor phase?

ChBE 3110-002
A divers blood is saturated with air at a total pressure of 500 kPa absolute, and
the mole fraction for the nitrogen gas is 0.79. The diver comes to the surface
quickly, not allowing time for the dissolved nitrogen to equilibrate slowly as the
pressure is reduced. At the surface, the pressure is 100 kPa. Given the following:
divers body mass is 55 kg, and that 75 % is water
divers temperature is 37 C.
Assume that the fluids in the body are similar to water
The Henrys law constant for water at 37 C is 1.005x107 kPa,
How much Nitrogen is released? Convert the number to liters at STP. This
condition is known as the bends and can be a serious and fatal problem.

ChBE 3110-003
1. Equilibrium data for acetone and water are provided below. The mole fractions
are for acetone. Plot the mole fraction of acetone in the vapor (y, ordinate)
against the mole fraction of acetone in the liquid (x, abscissa).
Write the chemical structure of acetone
Calculate the K values or factors and the relative volatility for the composition of
x=0.05.
Make a plot of K and vs. mole fraction of acetone in the liquid. Use a log scale
for the K and .
Boiling Temperature, C
100
74.8
68.53
65.26
63.59
61.87
60.75
59.95
59.12
58.29
57.49
56.68
56.3
56.15

Mole fraction in liquid, x

0
0.05
0.10
0.15
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.95
1

Mole fraction in vapor, y

0
0.6381
0.7301
0.7716
0.7916
0.8124
0.8269
0.8387
0.8532
0.8712
0.8950
0.9335
0.9627
1

ChBE 3110-004
Air in a room is saturated with mercury vapor. The vapor pressure of mercury
(Hg) at 20 C 0.16 Pa. Using Raoults law
a) what is the mole fraction of Hg in the air?
b) express this mole fraction in g/m3 ?
c) The threshold limit value (TLV) is the permissible concentration to which
workers can be exposed for an 8 hour shift. For Hg the TLV is 25 g/m3.
d) The average adult male inhales about 15 kg/day of air. How much Hg would
an adult inhale in 8 hours in this room?

ChBE 3110-005
Beginning with a liquid mixture of acetone and chloroform at ambient pressure
(100 kPa), and
the mole fraction of acetone in the liquid, x A = 0.7 ,
activity coefficients for the liquid phase
A = 0.95

B = 0.71
a) estimate the bubble point temperature and the composition of the vapor in
equilibrium with this liquid.

ChBE 3110-006
Use EES to create a Txy diagram for the iso-propanol-water system at 100 kPa
absolute pressure. The activity coefficients of iso-propanol is given by
log g a =

B 2 Axb2
( Axa + Bxb )2

and for water

A2 Bxa2
log g b =
( Axa + Bxb )2
A=1.0728
B=0.4750
Label the Txy plot to identify:
regions of vapor, liquid, and two phases
bubble point
dew point
normal boiling points
azeotrope

ChBE 3110-007
A mixture of 40 % by mole toluene and 60 % benzene are heated at a constant
pressure of 230 kPa to 120 C. Data for the Antoine correlation of vapor pressure
are provided below.

a) assuming ideal gas behavior for the vapor and ideal solution behavior for the
liquid,
What are the compositions of the vapor and liquid at equilibrium?
What fraction (by moles) exist in each phase?

b) 2 % hydrogen is added to the original mixture (39 % toluene, 59 percent

benzene). The critical temperature of hydrogen is 33 K, therefore you may
assume that it does not dissolve in the benzene or toluene and follows ideal gas
behavior.
What is the mole fraction of the mixture that ends up in the vapor phase?

c) Benzene and toluene are often cited as examples of an ideal solution. From
the experimental data below calculate the activity coefficient of benzene and
toluene at 199.3 kPa. The temperature is 120 C.

Pressure, kPa
149.0
174.1
174.8

Mole fraction benzene in Mole fraction benzene in

liquid
vapor
0.117
0.220
0.264
0.453
0.258
0.425

199.3

0.440

0.639

245.6

0.682

0.842

Antoine correlation

ln p vap kPa = A

B
T ( C) + C
A

Benzene
A=13.7819

B=2726.81

C=217.572

Toluene
A=13.9320

B=3056.96

C=217.625

ChBE 3110R

Summer 2012

ChBE 3110-008
Cp
p
Show that
.
=
T s TV p

The isobaric coefficient of thermal expansion is p =

1 V

.
V T p

Start by expressing entropy as a function of p and T, that is, S = S ( p, T ) , and then

writing the total differential dS. Use Maxwell and other thermodynamic
relationships given below.
1
S

= CV
T V T
1
S

= Cp
T p T

ChBE 3110-009
We developed an expression for chemical potential in terms of the Gibbs energy
G. The analogous result for U is shown below. Find the equivalent expressions
using A and H. Show your work.

(nG )

(nU )

i = Gi =
=
=?=?

ni T , p , n ni S ,V , n
j

ChBE 3110-010
For a particular fluid, the equation of state (EOS) is given by

Where C is a constant, in this case C=1.2 x 106 (K3m3mol-1)

Estimate the fugacity of this vapor at a pressure of 6.5 kPa and 400 K.
a. Estimate the fugacity of this vapor at a pressure of 6.5 kPa and 400 K. Recall that the
fugacity coefficient is expressed by
.
b. 6.5 kPa is also the saturation pressure of the fluid at this temperature, what is the
fugacity of the saturated liquid in equilibrium with this vapor?

ChBE 3110-011
Propane is at 105 C and 3.4 MPa
a) Estimate the fugacity from the generalized correlation provided below and
p

ln = (Z 1)
o

dp
p

Z = Z o + Z '

Zo =1+

Z '=

pr
0.422
0.083 1.6
Tr
Tr

pr
0.172
0.139 4.2
Tr
Tr

b. Plot the state on the graph below generated in EES. Also include a point assuming
ideal gas behavior and the calculation of fugacity from EES.

ChBE 3110-012
A. The cartoon below represents vapor-liquid equilibrium between phases
and . For each of the quantities in the box below, indicate whether these
are equal (=) or not equal () at equilibrium. Identify the name of each of
the 8 quantities on the right.

B. For the binary system shown below. If a vapor with a composition of y A =0.4 at
a temperature of 100 C is cooled at constant pressure. Sketch the process on
the chart below.
1. What is the composition of the liquid when the first drop condenses?
2. If a liquid mixture (x A =0.4) is heated from 75 C, what is the temperature and
vapor composition of the first bubbles that form?
3. Which (A or B) is more volatile?

ChBE 3110

ChBE 3110-012
C.
1. Describe partial molar quantities, use Gibbs energy as an example.

2. Explain the summation principle for partial molar quantities. Use volume as an
application

3. What is an ideal solution?

ChBE 3110

ChBE 3110-013
A. Explain conceptually how fugacity coefficients for mixtures are calculated.

B. Compare and contrast the concept of an ideal solution and an ideal gas. How
are these connected to residual and excess properties as well as fugacity and
activity coefficients?

C. Given the equation for residual Gibbs energy

nG R
d
RT

nV R
nH R
=
dp
dT + ln i dni , how does the fugacity coefficient
2
RT
RT

ln i
=?
change with pressure, i.e.,

T , x

ChBE 3110

ChBE 3110-014
An equimolar mixture of n-pentane and n-hexane are cooled to 20 C.
a. Justify the use Raoults law for this system.

b. What pressure is required so that 33 mole percent is vapor and 67% is liquid?

c. What is the composition of each phase?

Antoine correlation

ln p vap kPa = A

B
T ( C) + C
A

n-pentane
A=13.7667

B=2451.88

C=232.014

n-hexane
A=13.8193

B=2696.04

C=224.317

ChBE 3110

ChBE 3110-015
Ethane is at 5 MPa and 25 C. Using the generalized Pitzer correlations.

A. What is the fugacity of ethane at these conditions?

B. What is the fugacity coefficient of ethane?
C. What is the 2nd virial coefficient, (include units) explain physically the sign of this
coefficient.
Useful equations

ln i = (Z i 1)
0

Z =1+

dp
.
p

Bp
+.
RT

Bpc
= B 0 + B 1
B =
RTc
0.422
B 0 = 0.083 1.6
Tr
0.172
B1 = 0.139 4.2
Tr

Critical data for ethane

Tc=305.3 K
Pc=4.872 MPa
=0.09952

ChBE 3110

ChBE 3110-016
A liquid mixture of 10 % by mole ethanol and 90 % n-hexane are at high pressure
and 80 C. Holding the temperature constant, the pressure is reduced until a
vapor phase begins to form. Data for the Antoine correlation of vapor pressure
are provided below.

a) assuming ideal gas behavior for the vapor and ideal solution behavior for the
liquid, i.e. Raoults law
What is the composition of the vapor and at equilibrium when the first
vapor starts to form (bubble point)?

What is the pressure?

b) Experimental data report the composition of the vapor as 0.37 mole fraction
ethanol and the pressure as 203 kPa. Explain the difference between these
results and your calculations.

Antoine correlation

ln p vap kPa = A

B
T ( C) + C
A

Ethanol
A=16.8958

B=3795.17

C=230.918

n-hexane
A=13.8193

B=2696.04

C=224.317

ChBE 3110

ChBE 3110-017
The truncated virial equation of state describes the vapor phases of hydrogen and
carbon monoxide.
Z =1+

Bp
RT

a. At a pressure of 3 MPa and -50 C, the compressibility factors for pure components
are measured to be

Z H 2 = 1.021
Z CO = 0.9541

Calculate the fugacity, fugacity coefficient, and the second virial coefficient for each of
the pure components

b. A mixture of hydrogen and carbon monoxide consists of 0.3 mole fraction hydrogen
with the balance CO. The cross coefficient, BH 2 CO , is -1 cm3/mol. What are the fugacity
coefficients of hydrogen and CO in the mixture?

Recall that the fugacity coefficient for a pure component is given by

p
dp
ln = (Z 1) .
p
0
For a binary mixture, the fugacity coefficient of the mixture, , is expressed as
i

p
B11 + y 22 12 .
ln 1 =
RT

where

p
B22 + y12 12 ,
ln 2 =
RT

12 = (2 B12 B22 B11 ) .

ChBE 3110

ChBE 3110-018
1.

a. What are residual properties? How are they related to fugacity coefficients?

b. What are partial properties?

c. A fundamental residual property relationship is provided below. From this

equation show that the fugacity coefficient is a partial property with respect to
GR
.
RT

nG R
d
RT

nV R
nH R
=
dp
dT + ln i dni
2
RT
i
RT

ChBE 3110

ChBE 3110-019
(7000 kg/h of n-hexane are flashed isothermally with a smaller amount of toluene
at 95 C and 150 kPa pressure. The vapor fraction out of the flash tank is 0.9.
a. Calculate the amount of toluene in the feed assuming Raoults law applies.

Molecular weights
hexane
toluene

86.177 g/mol
92.141 g/mol

Antoine correlations
ln ( p[kPa]) = A
A
B
C

n-hexane
13.8193
2696.04
224.317

B
T ( C) + C
toluene
13.932
3056.96
217.625
A

b. Comment on the validity of Raoults law here. Would you expect the feed to
contain more or less toluene if deviations from ideal behavior were considered?

Exam # 1

ChBE 3110R

Summer 2012

ChBE 3110-020
2. (25 pts) Calculate the fugacity coefficient and 2nd virial coefficient for ethylene at 100
C and 3 MPa. Critical property data for ethylene are provided below.
Tc
Pc

Vc

282.3 K
5.04 MPa
0.087
131 cm3/mol

Exam # 1

ChBE 3110R

Summer 2012

ChBE 3110-021
(25 pts) For the two systems at 27 C, experimentally determined activity
coefficients are provided.
i. label the curve corresponding to each component.
ii. identify whether the deviations are positive or negative
iii. for each mixture indicate whether the pressure predicted for an ideal
solution would be higher or lower than the pressure for the real mixtures.
iv. use molecular interactions to explain your answers for ii and iii.
dichloroethan/tetrahdrofuran

1.5

1.1

1.4

activity coefficient

activity coefficient

acetonitrile/dichloroethane

1.3

1.2

1.1

0.8

0.7

0.6

0.9
0

0.9

0.2

0.4

0.6

0.8

Exam # 1

0.2

0.4

0.6

xa tetrahydrofuran

xa, acetonitrile

Acetonitrile

0.5
0

dichloroethane

tetrahydrofuran

ChBE 3110R

Summer 2012

0.8

ChBE 3110-022
You are exploring vapor-liquid equilibria at very high pressures. Develop an
expression for the fugacity coefficient for a vapor based on the truncated virial
equation of state using the 2nd and 3rd virial coefficients,
Z = 1 + B' p + C ' p2 .
where
B' =

B
,
RT

and

C' =

C B2
(RT )2

What are the physical interpretations of the 2nd the 3rd virial coefficients?

Exam # 1

ChBE 3110R

Summer 2012

ChBE 3110-023
a. From the data for the vapor pressure of water above sugar (C 12 H 22 O 11 )
solutions taken from the International Critical Tables and summarized
below for 25 C, determine the activity coefficients of water.

Molarity

xC12 H 22 O11

Vapor
pressure, kPa

3.12579

0.1

0.00180

3.12026

0.4

0.00715

3.10329

1.0

0.01770

3.06605

2.0

0.03478

2.99500

3.0

0.05127

2.91658

4.0

0.06722

2.83171

5.0

0.08263

2.74289

6.0

0.09755

2.65789

6.18 (sat)

0.10018

2.64211

2O

12 H 22 O11

Infinite dilution
reference

12 H 22 O11

Solid sugar
reference

Whereas there is only one logical choice for the reference for the water, the
sugar is a different story. Clearly, we cant use the vapor pressure or fugacity of
the pure sugar.
b. Determine the activity coefficient of the sugar. Here, take the activity
coefficient of an infinitely dilute solution as unity.

c. Repeat part b, but now use the solid sugar as the reference. Take the
activity of the solid as unity, and since the fugacity of the sugar in the
saturated solution is equal to that of pure solid, the activity coefficient for
the saturated solution is

Csat H
12

22 O11

1
sat
C12 H 22 O11

ChBE 3110-024
Estimate the mole fraction and concentration (mol m-3) of benzene in air that is
saturated with benzene at 20 C. The total system pressure is atmospheric, 100
kPa.

ChBe 3110-025
Your colleague provides you with data for the ethanol-chloroform system.
Comment on the suitability of these data?
Mole fraction chloroform
Mole fraction chloroform
Measured pressure (kPa)
in liquid phase
in vapor phase
0.01
0.02
0.05
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
0.95

0.0414
0.0832
0.2000
0.3588
0.5754
0.6844
0.7466
0.7858
0.799
0.852
0.901
0.950
0.975

13.97
14.45
16.0
18.85
25.03
30.12
33.84
36.44
40.13
37.50
37.89
38.55
39.47

a) do they agree with the pure component data from the Antoine equation?
b) are they consistent with the Gibbs-Duhem equation?
c) do you suspect that any of the data points are in error? How effective is the
integral test in identifying this point?

ChBE 3130-026
Problem 13.33 from Smith and VanNess

ChBE 3110-027
The following reaction occurs in the gas phase.

2NOBr 2NO + Br2

9.24x10-4 moles of NOBr is placed in a 573 cm3 reactor. The following data are
measured at equilibrium
Temperature, K
298
323

Pressure, kPa
4.984
5.637

a) What is the extent of reaction? (moles NOBr reacted/moles NOBr initially

charged in vessel)
b) Calculate the equilibrium constant and G o for the reaction at 298 K
c) Estimate the heat of formation for the reaction, H o

ChBE_3110_028

Gas insulated substations (GIS) use sulfur hexafluoride in place of air in phase-tophase and phase-to-ground insulators because of its superior dielectric properties.
Typically the pressure of the gas can range from 600-1600 kPa absolute.
One concern is the condensation of the gas or even worse condensation of water
during periods of cold temperature. Your assignment is to provide a specification of
the maximum water content of the SF 6 gas to the supplier. As a reference, the PV
diagram is provided. Also the vapor pressure of the SF 6 is given by
.

The design team has chosen the

pressure to be 1000 kPa and estimates
the minimum temperature will be 0 C.
What is your recommendation for the
maximum allowable moisture content of
the gas?

Ideally you want SF 6 to condense first,

how would you revise your specification
for the moisture content to ensure SF 6
condenses first if the temperature went
below 0 C?
Treat the vapor as an ideal gas and liquid water and sulfur hexafluoride are
practically immiscible.

ChBE 3110-029
Calculate the vapor pressure of solvent above a solution made from 1 mole of
LiTFSI (MW=287.09 g/mol) dissolved in 1 kg of acetonitrile. How would the
answer change if LiTFSI completely dissociated into Li+ and TFSI- ions?

ChBE 3110-030
Use the Antoine equation in the back of the book to estimate the vapor pressure
of water at -5 C. Compare this with the vapor pressure of gas above the solid
using EES, that is p1=p_sat(water, t=-5[C]).
a.
First try +5 C, you should get essentially the same answer for both
methods.
b.
At -5C, which vapor pressure is larger? Think of the vapor pressure
below 0 C calculated with the Antoine equation as the vapor pressure above a
subcooled liquid. Explain why one is larger than the other in terms of fugacity
and Gibbs energy.

ChBE 3110-031
Effect of osmotic pressure on cells.
a) The salt concentration inside of a cell is approximated as 7 g NaCl dissolved in
1 L of water, and further assume the salt is completely dissociated. That is two
moles of solute are created for each mole of NaCl. What is the osmotic pressure
on the cell when placed in pure water? Why cant cells be placed in a hypotonic
solution, one with a lower salt concentration than in normal cells of the body and
the blood, without destroying them?
b) before the advent of refrigeration, one key method of preserving foods was
salting or adding sugar. How does this method work to control the growth of
yeasts and bacteria?

ChBE 3110-032
Estimate the value of K f (the cryoscopic constant) for water that describes the
freezing point depression, T f = K f m .
Determine the freezing point depression of water as the result of the addition of
0.01 g/cm3 of a) methanol and b) a protein with a molecular weight of 60,000.

ChBE_3110_033
As simple and intuitive as the solubility parameter approach is, it does not work
well for polar solvents like water. Use the solubility parameter approach to
estimate the infinite dilution activity coefficients of a water/isopropanol mixture.
Compare with data in the figure provided for 25 C.

Substance

Molar volume

Solubility Parameter

Isopropanol
Water

76.8 cm3/mol
18 cm3/mol

23.52 (MPa)
47.3 (MPa)

ChBE 3310_034

Tungsten oxide is reduced with hydrogen according to the reaction.

WO 2 ( s ) + 2H 2 W(s) + 2H 2O
The data below provide the ratio of water and hydrogen partial pressures as a
function of temperature. The pressure is atmospheric.
What is the enthalpy (heat) of reaction at 900 C?
Temperature, C
734
800
828
865
900
941
1000
1036

pH 2 O

pH 2

0.45
0.53
0.65
0.75
0.82
1.01
1.16
1.29

ChBE 3110-035
In 20 minutes you are scheduled to go into a meeting with your boss to discuss
thermodynamic data for the propane, n-butane system. Your colleague was taking the
lead in measuring the data, but he missed the train from Prague. Still your boss doesnt
want to wait for him. You quickly gather the data together taken at 50 C, which are
shown below, a Pxy diagram and activity coefficients.

a) Explain whether you expect activity coefficients calculated from the solubility
parameter approach to be useful here? What data can you add to the above plots from
the data below? Sketch any additional data on the plot above.
b) Comment on the activity coefficients, particularly with regards to the Gibbs-Duhem
relationship.
c) The activity coefficients were calculated from

. What are potential sources

of error?
Quantity
Molar volume, cm3/mol
Solubility Parameter, MPa
Vapor pressure at 323.15 K, MPa
Critical Temperature, K
Critical Pressure, MPa
Compressibility, Zc

Exam # 2

ChBE 3110R

Propane
98.31
12.3
1.719
369.8
4.248
0.276

Butane
107.2
13.7
0.4986
425.1
3.796
0.274

Summer 2009

ChBE_3110_36
Two liquids A and B are combined. Data for three different systems, (1 and 2
Gibbs energy for the mixture, and 3 activity coefficients as a function of
composition) are shown below. For each one, indicate if phase separation will
occur and explain your answer.

__________________________________________

__________________________________________

__________________________________________

ChBE_3110_36
B. Explain the concept of a random fluid and local composition

C. What are the differences between chemical and physical adsorption?

D. Calculate the osmotic pressure of a solution that contains 5 g of sucrose per

1000 g of water. The molecular weight of sucrose is 180 g. Why is osmotic
pressure considered a colligative property.

ChBE 3110-037
Ammonia is produced from a stoichiometric mixture of nitrogen and hydrogen. The
reaction occurs in the gas phase, which may be assumed to be ideal.
3
1
N 2 + H 2 = NH 3 .
2
2
a) What is the equilibrium constant at 230 C? Use a reference state of 100 kPa and an
ideal gas; the enthalpy of the reaction may be assumed constant.
b) If the pressure is atmospheric, what is the equilibrium composition (mole fractions of
each of the three species) exiting the reactor at 230 C?
c) At what pressure does the equilibrium mole fraction of ammonia equal 0.5?

The standard enthalpies and Gibbs energy of formation are provided below. The
reference state is pure component, ideal gas at 100 kPa and 298.15 K
Species
NH 3

Exam # 2

H kJ/mol
-46.110

G kJ/mol
-16.450

ChBE 3110R

Summer 2012

ChBE 3110-038
2. (40 pts) Butadiene is produced by the dehydrogenation of n-butane at 650 C
and 100 kPa. A large amount of steam is added along with the butane, but steam
is not involved in the reaction.
C 4 H10 CH 2 CH = CHCH 2 + 2H 2
At equilibrium, the mole fraction of butadiene leaving the reactor is 0.12.
What are the mole fractions of hydrogen, butane, and steam in the product?

For each mole of butane, how many moles of steam are required?

Compound
n-butane
butadiene

Final

H of J/mol

-125,790
109,240

ChBE 3110R

G of J/mol

-16,570
149,795

Summer 2009

ChBE_3110_039
Recall the summability relationship for partial molar properties, M = M i xi ,
i

(nM )

where M i
. Analogous properties similar to partial molar quantities
ni T , p , n j
can be useful. One such thermodynamic property holds T, V constant rather than
T, p. This is defined as
~ (nM )

M i
ni T ,V , n

~
Show that this property also satisfies the summability relation, M = M i xi
i

Start with M = M (T ,V , ni ) ; because ni = xi n , the following relations apply and will

be useful.
dni = xi dn + ndxi
d (nM ) = ndM + Mdn

ChBE 3110-040
A. (50 pts) Sulfur dioxide is oxidized in air according to the reaction
1
SO 2 + O 2 = SO 3 .
2
This is accomplished in a catalytic reactor that is operating at 425 C and atmospheric
pressure. Air is added to the sulfur dioxide so that there is a 50 % excess of oxygen.
a) What is the equilibrium constant at 25 C?
b) Is the reaction exothermic or endothermic?
c) Estimate the equilibrium constant at 425 C. You may assume that the heat of
d (ln K ) H o
.
reaction is constant. Recall that
=
dT
RT 2
d) What is the equilibrium composition (mole fractions of each of the four species)
exiting the reactor? Remember the reaction is carried out with air (21 % oxygen balance
N 2 ) not pure oxygen.

Air
SO2

SO3
SO2
N2
O2

Catalytic reactor
425 C
100 kPa

The standard enthalpies and Gibbs energy of formation are provided below. The
reference state is pure component ideal gas at 100 kPa and 298 K
Species
SO 2
SO 3

Exam # 2

H kJ/mol
-296.83
-395.72

ChBE 3110A

G kJ/mol
-300.194
-371.060

Spring 2009

ChBE 3110-041
50 kg of toluene (C 7 H 8 ) have been spilled and leaked into the soil contaminating
the groundwater. The two fluids are practically immiscible.

Toluene with smll

mount of wter

Wter with smll

mount of toluene

a. Using the solubility data below, estimate 1) the activity coefficient of water in
the toluene phase, and 2) the activity coefficient of toluene in the water phase.

b. If the water is saturated with toluene (to the solubility limit below), how many
kg of water could be contaminated with the 50 kg of water?

Solubility of toluene in water

1.1 x 10-4 (mole fraction)

Solubility of water in toluene

1.7 x 10-3 (mole fraction)

Exam # 2

ChBE 3110A

Spring 2009

ChBE_3110_042
Carbon monoxide is chemisorbed on the surface of a platinum catalyst. The CO
is removed by adding 10 cm3 (100 kPa, 273 K) of oxygen to form carbon dioxide.
The process is similar to a titration.
1
CO + O 2 CO 2
2

The catalysts contains one gram of Platinum with as surface area of 90 m2/g. Its
capacity to adsorb CO is 2.2 x 10-9 moles/cm2 of platinum. What is the fractional
coverage of CO on the surface, ?

ChBE 3110-043
A chemist dissolves 0.233 g of an unknown substance into 0.8923 kg of water.
The osmotic pressure at 298 K is found to be 1.605 kPa, what is the molecular
weight of the solute?

Final

ChBE 3110A

Spring 2010

ChBE_3110_044
The following empirical expression has been proposed for the activity
coefficients. The system is isothermal, binary one where the standard states are
the pure components at the same temperature and pressure as the solution.
Critique the acceptability of this suggestion.

1 = 1 + Ax2
2 = 1 + Bx1

ChBE_3110_045
The standard Gibbs energy change for the reduction of chromium oxide by hydrogen is
given by
Cr2 O 3(s) + 3H 2(g) = 2Cr(s) + 3H 2 O (g)
G o (T ) = 408,568 119.7T , J/mol
Where the temperature is in Kelvin, and the reference state is the pure components at
100 kPa.
a) If the vapor is a mixture of water and hydrogen, determine the corresponding
mole fractions at 1500 K and 100 kPa.
b) Is the oxidation of chromium by water vapor exothermic or endothermic?
Estimate H of at 1500 K.

ChBE 3110-046
Ullage is used in industrial and marine settings to
describe the empty space in large tanks or holds used
to store or carry liquids. This idea is illustrated with a
picture of a barrel wine of wine, which by the way is
the origin of the word, deriving from the French
ouillage, meaning to fill up a cask.

For our purposes we are concerned with the fuel tank of an airliner. In 1996
TWA flight 800, exploded and crashed shortly after takeoff. The cause of the
incident was an explosion of the fuel tank i For simplicity, the jet fuel is
assumed to be a binary mixture of n-nonane and hexadecane with the mole
fraction of hexadecane equal to 0.65 and 0.35 for n-nonane. There is no
special effort to evacuate tanks when they are filled, so there will always be
some air present.
Assuming a tank volume of 1 m3, a pressure of 100 kPa, and a temperature of
30 C, what is the composition of the vapor as fuel is added? We may further
assume that the filling is done slowly so that vapor liquid equilibrium exists at
all times. At the temperatures of interest the vapor pressure of hexadecane is
negligible; and as a first approximation, assume ideal gas and ideal solution
behavior. The lower flammability limit is 0.03 (ratio of mass of fuel/mass of air)
in the ullage, what impact does increasing temperature have?
Molecular weight of nonane is 128.2 g/mol, Antoine data for n-nonane
A1=13.9854
B1=3311.19
C1=202.694
ln(psat(kPa))=A1-B1/(T(C)+c1)

A four-year NTSB investigation concluded that the probable cause of the accident was an explosion of
flammable fuel/air vapors in a fuel tank. As a result of the investigation, new requirements were
developed for aircraft to prevent future fuel tank explosions.

ChBE 3110R

2012

ChBE 3110-047
a. What is the Gibbs-Duhem relationship? Explain how it is applied to activity coefficient
data.

b. Which (if any) of the following data are clearly incorrect based on the Gibbs-Duhem
equation?

Exam # 2

ChBE 3110R

Summer 2012

ChBE_3110_048
a. Use the solubility parameter approach to calculate the infinite dilution
activity coefficients of a 1-pentene, benzene mixture at 25 C.
1-pentene

benzene

Substance

Molar volume

Solubility Parameter

Benzene
1-pentene

89.0 cm3/mol
109.6 cm3/mol

18.78 (MPa)
14.44 (MPa)

b. Sketch the activity coefficients as a function of mole fraction of benzene.

c. What are limitations of the solubility parameter approach?

ChBE 3110-049
a. A rough rule of thumb for polymer solution theory is that a 4 molar
aqueous polymer solution will have an osmotic pressure of about 100 bar.
Explain this rule of thumb.

b. Albumin is essential for maintaining the osmotic pressure needed for

proper distribution of body fluids between intravascular compartments and
body tissues. An osmometer (see figure) is a simple device used to
.The following data have been
measure the osmotic pressure,
reported for the osmotic pressure of serum albumin in water at 25 C.

i.

Calculate the molecular weight of the protein.

ii.

In this case, the data are nearly linear with concentration. What would
non-linear behavior represent?

Albumin Concentration g/dL

0.78
1.25
2.79
3.38
4.18
8.98
12.45

Exam # 2

Osmotic pressure, cm H 2 O
2.39
4.01
8.53
10.80
13.01
27.84
37.69

ChBE 3110R

Summer 2012

ChBE_3110_050
You are trying to produce of a solution of Cu+ ions. The approach is to react copper(I)
oxide with hot dilute sulfuric acid.

Cu 2 O + H 2SO4
You were expecting to get Cu+ and water, yet each time you end up with a solid brown
precipitate and a blue solution that appears to be Cu(II) sulfate.
Your colleague suggests that perhaps Cu+ is disproportioning. Evaluate the merits of this
hypothesis.

ChBE 3110-051
Consider the electrochemical cell below.

Zn(s)

ZnCl2(aq)

HCl(aq)

CuCl2(aq)

Cu(s)

The two reactions are

Zn Zn 2+ + 2e
Cu 2+ + 2e Cu

Find an expression for FU.

Is the reaction spontaneous under standard conditions?

Final

ChBE 3110R

Summer 2012

ChBE 3110-052
Carbon black is produced from the reaction of methane

CH 4(g) = C (s) + 2H 2(g)

If pure methane is fed to the reactor, what is the composition of the gas exiting
the reactor if it is in equilibrium at 650 C and atmospheric pressure?

Under the same conditions an equi-molar mixture of methane and nitrogen are
added to the reactor, what is the composition of the gas at equilibrium?

Would you recommend increasing the pressure of the reactor to increase the
formation of carbon?

Compound
methane

Final

H of J/mol

G of J/mol

-74,520

-50,460

ChBE 3110R

Summer 2012

ChBE_3130_053
Develop and expression of the equilibrium potential of the H2/B2 fuel cell. U is not in
the handout, but is available on the electrochemistry notes in t-square. The value
calculated above was at 25 C; estimate the standard potential at 200 C.

ChBE_3130_054
The two reactions for the silver zinc battery are
Ag 2 O + H2 O + 2e 2Ag + 2OH
Zn + 2OH H2 O + 2e + ZnO

(0.340 V)

(7-4)

(-1.251 V)

(7-5)

The Gibbs energy of formation of Ag2O is -11,210 J/mole. Calculate the Gibbs
energy of formation for ZnO

ChBE_3110_055
An ethanol water mixture with xaF = 0.126 is flashed at 92 C. At what pressure will
the mole fraction of ethanol in the liquid phase equal 0.02? What fraction of the feed
is vapor? Use the activity correlations from HW 3.

ChBE 3110-056
Air is separated into oxygen and nitrogen in a cryogenic process where liquid and
vapor are in equilibrium. The pressure on a liquid mixture containing 0.3 mole
fraction of oxygen at -190 C is reduced. Determine the bubble point pressure
and the composition of the vapor phase.

What is the relative volatility? Would distillation be an effective method of

separation?

Antoine correlation

ln p vap kPa = A

B
T ( C) + C
A

oxygen
A=13.38

B=734.6

C=266.697

nitrogen
A=12.93

B=588.7

C=266.550

Final

ChBE 3110R

Summer 2012

ChBE 3110-057
Youre working on getting accurate thermodynamic data for the propane, nbutane system. One hypothesis of why the activity coefficient data didnt satisfy
the Gibbs-Duhem equation is that the vapor phase is not ideal. Originally the
yp
activity coefficients were calculated from i = i vap rather than the more general
xi pi
expression: x f = y f p .
i i i

i i

Quantity
Critical Temperature, K
Critical Pressure, MPa
Compressibility, Z c
Acentric factor
Critical volume, V c cm3/mol

Propane
369.8
4.247
0.2764
0.1524
201.8

Butane
425.1
3.796
0.274
0.200
255.1

Hint: First calculate the 2nd Virial coefficients for the pure components from the
generalized compressibility-factor correlation, then use combining rules to
estimate B 12 , lastly use the mixing rules for the Virial equation of state. The
Bp
.
truncated Virial equation is Z = 1 +
RT

Final

ChBE 3110R

Summer 2012

ChBE 3110-058
a. (13 pts) At little bit of water in the gas tank of your automobile can be
disastrous in really cold weather because the water is not miscible and can
freeze in the fuel lines. Consequently, refiners and distributors work very hard to
eliminate water from gasoline. It has been standard practice to add ethanol to
gasoline for emissions. Comment on the whether this will make the problem of
freezing fuel lines worse or better.

b) (14 pts) The simplest model for activity coefficients is the symmetric model.

ln a = Axb2
ln b = Axa2
Show that this model is consistent with the Gibbs-Duhem equation.

c. (13 pts). Explain positive and negative deviation for activity coefficients in
terms of molecular interactions.

Final

ChBE 3110R

Summer 2012

ChBE_3110_059
You are exploring separating methyl acetate from water. The activity coefficients for
this binary system are given by
ln a =

A xa

1 +
x
B
b

and
ln b =

B
B xb

1 +
A xa

A=2.99
B=1.89
a) Create a plot of activity coefficients vs. composition, what type of behavior
is observed? Explain this in terms of interactions between water and
methyl acetate
b) Plot the relative volatility, , for this system at 80 C. For what values of
composition will distillation be an effective separation method?

ChBE 3110-060
Methane is synthesized from the reaction
2CO + 2H 2 = CH 4 + CO 2

At 1000 K and 5 MPa from a feed containing 0.4 moles of hydrogen and 0.6
moles of carbon monoxide, 0.1904 moles of methane are produced. Assuming
that the reaction above is at equilibrium, estimate the standard enthalpy of this
reaction.

Data for the Gibbs energy of formation for a standard state of 25 C and 100 kPa
are provided below.
G of

J/mol

CO
Hydrogen
Methane
CO 2

-137,169
0
-50,460
-394,356

Exam # 2

ChBE 3110A

Spring 2008

ChBE 3110-061
Vapor liquid equilibrium data at 35 C for the ethanol-chloroform system are as follows.
Mole fraction
Mole fraction
Total
a
b
chloroform in
chloroform in
Pressure,
liquid
vapor
kPa
0.0000
0.0000
13.5237
0.0100
0.0414
13.9737
0.0200
0.0832
14.4513
0.0500
0.2000
15.9974
0.1000
0.3588
18.8461
0.2000
0.5754
25.0250
0.3000
0.6844
30.1158
0.4000
0.7466
33.8382
0.5000
0.7858
36.4447
A. Assuming the vapor phase is ideal, estimate the activity coefficients for ethanol and
chloroform. The vapor pressure of pure chloroform, CHCl 3 , is 38.83 kPa.

B. Estimate the activity coefficient for ethanol at infinite dilution. Three approaches are
suggested
i. use of Gibbs-Duhem equation
ii. treat the system as a regular solution. One definition for a regular solution is
that

G
= Axa xb , where A is a constant.
RT

iii. Solubility parameters. The density of chloroform is 1.483 g/cm3 and the
molecular weight is 119.38 g/mol. The density of ethanol is 0.789 g/cm3 and the
molecular weight is 46.07 g/mol. The solubility parameters are
CHCL 3 = 18.7 MPa

EtOH = 26.2 MPa

C. Comment on the validity of the three approaches in part B.

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_062
(10 pts) Explain the concept of local composition. Why is this important in
developing models for activity coefficients.

(5 pts) In general what two constraints are put on any model for activity
coefficients?

(10 pts) For the system shown in the figure below, if the mole fraction of a is 0.3,
what are the compositions of the two phases? (a highly accurate estimate is not
needed, but provide details on how precisely you came to this answer).
100

The quantity plotted

ordinate is G xi Gi

on

the
0

-100
-200
-300
-400
-500
-600
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

xa

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_063
Assuming ideal gas behavior, what are the changes for internal energy, Gibbs
energy, and entropy when 79 moles of N 2 are mixed with 21 moles of O 2 . The
temperature is 25 C, the pressure is 100 kPa.
U mix = ?
Gmix = ?
S mix = ?

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_064
Calculate the fugacity coefficient for n-butane at 373.15 K and 100, 1000, and 1500 kPa
from the 2nd virial coefficient. Compare with values obtained from EES. Propose an
explanation for any differenceshint: at what pressure does n-butane condense?
B=-4.22x10-4 m3/mol

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_065
Coke (essentially carbon) is burned in air (0.21 O 2 and 0.79 N 2 ) to produce heat
for in the main boiler of a large power plant. The gases leaving the combustion
chamber are at 620 C and atmospheric pressure (100 kPa). The chemical
equations shown below are known to occur and may be assumed to be in
equilibrium.

1
O 2 CO
2
1
CO + O 2 CO 2
2
CO 2 + C s 2CO
Cs +

(1)
(2)
(3)

a) Show that only two of these three equations are independent.

b) Use the property change of formation data provided below to calculate the
equilibrium constant for each of the reactions at 298.15 K.

c) The equilibrium constants at 620 C are

K1 = 2.2 1011
K 2 = 2.0 1012
K 3 = 0.22
Calculate the equilibrium mole fraction of CO and CO 2 exiting the combustion
chamber. Assume that a stoichiometric amount of air is added to completely
oxidize the coke to carbon dioxide. [Hint, since the equilibrium constant is not
infinite, there will always be some solid carbon present]

Partial credit will be given for setting up the problem correctly.

Carbon monoxide
Carbon dioxide

H of (J/mol)
-110525
-393509

Standard changes are from standard states at 25 C.

G of (J/mol)
-137169
-394359

ChBE 3110_066
Calculate the fugacity coefficients for isobutane 1 and isopentane 2 for the
following mixture. You may assume the interaction parameters are zero, kij = 0 .
Mole fraction of isobutane
Temperature
Pressure

0.70
400 K
1500 kPa

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_067
The activity coefficient for species 1 in a binary mixture is given by
ln 1 = ax22 + bx23 + cx24
What is the expression for ln 2 ?

Exam # 2

ChBE 3110A

Spring 2010

ChBE 3110_068
Nitrogen and carbon tetrachloride are in equilibrium.
The system is at a total pressure of 100 kPa and 25 C.
The vapor pressure of carbon tetrachloride is 15.02 kPa
at 298 K.

a) Can Raoults law be used to describe the equilibrium

of the carbon tetrachloride between phases? What
about nitrogen? In both cases, explain your reasoning.

Nitrogen gas and

CCl4 vapor

Carbon
tetrachloride and
small amount of
Nitrogen

b) Using the Henrys law constant for nitrogen, 1.7x108 Pa, estimate the mole
fraction of nitrogen in the phase.

c) Assuming that Henrys constant remains unchanged, what effect would

dissolving a nonvolatile substance into the liquid carbon tetrachloride have on the
amount of nitrogen dissolved in the liquid? The temperature and total pressure
remain at 100 kPa and 25 C. Explain your reasoning.

ChBE 3130_069
The freezing point depression of a solution can be described as a chemical
reaction.
M solid M solution

The equilibrium constant for this

reaction is related to the relative
activities,

Solution:
solvent, 1
solute, 2

K = ai i .
i

a) starting with the above equation,

and assuming the heat of reaction
(same as the heat of fusion here),
develop a general expression for
ln (a1 ) = ?

{recall the general thermodynamic relationship,

Solid, pure component 1

d G

RT = H }
dT
RT 2

From the relationship for activity developed above, the final expression for
freezing point depression of a dilute solution is

M 1 RT 2
m,
H f 1000
where M 1 is the molecular weight of the solvent, and m is the molality of the
solution.
T f =

b) when 1.32 g of solute are added to 1 kg of carbon tetrachloride, the freezing

point is reduced by 0.89 C. What is the molecular weight of the solute?

For carbon tetrachloride

the heat of fusion, H f , is 2500 J/mol.
the normal freezing point is 250.3 K
molecular weight, 153.82 g/mol

FINAL

ChBE 3110A

Spring 2009

ChBE_3110_070
Consider the electrochemical cell below. Iron corrodes to form Fe2+. Find an
expression for FU.

Pt(s), H2(g)

HCl(aq)

Fe

Pt(s)

The standard electrode potential for Fe Fe2 + + 2e is U = 0.440 . Youll also note
that this reaction does not appear in Table 2.2. Suggest what the form of FU .

ChBE_3110_071

Calcium oxide, or quick lime CaO, is made by the calcination of limestone, CaCO 3 .
CaCO3 heat
CaO + CO 2
At what temperature is the pressure of carbon dioxide equal to 70 kPa. Typical
production of lime uses temperatures above 800 C.

ChBE_3110_072

Consider the electrochemical cell shown below. The two reactions are
Zn Zn 2+ + 2e
Hg 2Cl 2 + 2e 2Cl + 2Hg
a) What is the overall chemical reaction?

b) Develop an expression for U, the equilibrium potential of the cell.

c) What is the standard Gibbs energy of formation of the aqueous ZnCl 2 ? Hg 2 Cl 2

The following standard electrode potentials are provided.

Reaction
Zn Zn 2+ + 2e

2Hg + 2Cl Hg 2Cl 2 + 2e

FU

o
1 H* 1 Zn
1 RT ln lZn 2+
+
2 2
2
2

lH +

( )

o
o
1 H* Hg
+ 1 Hg
RT n H + C
2 C 2
2 2
2

-0.7618 V

0.26808 V

ChBE 3130_073
Vapor liquid equilibrium experimental data for the ethanol benzene system are
shown below in the Pxy plot. The data were collected at a constant temperature
of 45 C.
a) Identify what the curves labeled with A and B as well as the point C represent.
b) For this ethanol benzene system, would you expect positive deviations, ideal
solution behavior, or negative deviations. Support your answer in terms of
molecular interactions and the experimental data shown in the plot.
c) Assuming the vapor behaves ideally, what are the activity coefficients for
benzene and ethanol at 27 kPa?
d) Describe (calculation not needed) how you could check the data for
thermodynamic consistency.

Antoine correlation

ln p vap [kPa ] = A

B
T ( C) + C
A

Benzene
A=13.7819

B=2726.81

C=217.572

Ethanol
A=16.8958

B=3795.17

C=230.918

FINAL

ChBE 3110A

Spring 2009