Lewis Randall Rule Problems

Problem 1:
A mixture of nitrogen and butane exists in gaseous

equilibrium at 171C and 13.79 MPa. Calculate the fugacity
of both components when nitrogen makes up 35 mass % of
the mixture.
Data:
B
N2-N2
= -1.24 * 10
-5
B
But-But
= -4.32 * 10
-5
and
figure 7.4-1
Problem 2:
The following data was collected for a gaseous mixture of compounds D and E
for the virial coefficients of a truncated eqn. of state.
Temp (C) B
DD

(m
3
/mol) B
EE

(m
3
/mol) B
DE

(m
3
/mol)
25 -1.85*10
-4
-1.69*10
-4
-2.10*10
-4
35 -1.37*10
-4
-1.27*10
-4
-1.85*10
-4
a. Calculate the fugacity of D at 27C at 500 kPa for X
D
= 0.60
b. Discuss the effect of temperature on the fugacity of D
over the range from 25C to 35C. Hint: One
additional fugacity will be sufficient.
Problem 3:
Given: P=10 bar T=373.15 K f
ET
=9.629 bar f
BU
=8.628 bar
A mixture containing 30 mol % ET and 70 mol % BU, calculate the fugacity of ET and
BU in the mixture using:
a. Lewis- Randall rule
b. Virial EOS with
B
ET-ET
= -1.15*10
-4
m
3
/mol
B
ET-BU
= -2.15*10
-4
m
3
/mol
B
BU-BU
= -4.22*10
-4
m
3
/mol
c. Compare the results of parts A and B and explain which one will be more accurate.
Problem 4
Compute the vapor fugacities of substance A and substance B in an equimolar mixture at
150C at 1 bar. State all assumptions.
(a) Using the Lewis-Randall rule.
(b) Using the Virial Equation of State.
(c) Compare results and tell which technique is more
accurate and why? At what conditions are these
techniques not accurate and give an example of more
accurate technique?
A very good problem that
looks simple but is actually
fairly complex. The statement
is a little vague and the
solution requires assumptions
that may not be completely
obvious.
As opposed to problem 1, this one
is completely straightforward but
uses the exact same equations.
Which one forces you to use more
logic? Part b is an excellent idea
but without knowing the identity of
D and E we can say very little other
than the fugacity went up or down.
Good idea of comparing between
an approximation and an EOS.
Calculations are straightforward.
YIKES! This is a grading
nightmare. Basically we are asked
to assume the pure component
fugacities for part a then merely
copy an equation for part b since
we aren't given any numbers for
virial coefficients. Part c is
impossible to do because any
Data :
at T=423.15K,
B
A-A
= m
3
/mol , B
B-B
= m
3
/mol , B
A-B
= m
3
/mol
Problem 5
A mixture of 20% CO
2 ,
35% O
2
, and 45% N
2
by mole is held in a room. The
temperature of the room is 500 K.
a) Assuming the gas obeys the given EOS for partial
molar volume, calculate the fugacity of each component
of the mixture in the room if the total pressure is 40 bar.
EOS:
) a P (
RT 3
V
i
where a= 4.0 bar

b) Then find the pure component fugacity for each
component.
c) Is your estimating in (b) a good one? What factors
would affect it?
Problem 6
One day, thermodynamic genius Stanley Sandler was
doing some recreational gas mixture experiments when he
discovered a new physical law. He found that the partial
molar volume of "gobuckeyes" in a closed system of
gobuckeye and "beatmichigan" was dependent on the total
pressure via the relationship:
P
RT
P V
g
+
Using this equation, find the fugacity of pure gobuckeyes at a temperature of 373.15K, a
pressure of 20MPa, mole fraction of gobuckeye y
g
=0.5
Problem 7
A) Assuming a mixture obeys the EOS:
P
b
P
aRT
V +
with mixing rules:

i
i i
i
i i
b x b a x a and
Derive the fugacity coefficient for a component in a binary
mixture.
B) Calculate the partial molar gibbs free energy of component
1 at 298 K and 2 bar if 0.3 moles of 1 is mixed with 1.34
moles of component 2 given the following information:
answer is justifiable based on
assumptions and we have no
numerical results to compare. This
is a FUMBLE.
Interesting idea using an
expression for partial molar
volume. I wouldn't want to be in a
room at 40 bar. In part a) how is
the result different for different
species? Seems like you'll get the
exact same answer for each
component. Part b is not very
specific. Could go the easy route
using the Lewis-Randall rule but
part a implies that there is an EOS
involved. Some of us might try to
back out phi and then pure comp.
fugacity.
Finally something besides A &
B! Question suffers from the
same ambiguity as in problem
5. Those who assume L-R will
be done in 5 minutes, those who
don't will take 30.
This is good although a
bit scary initially (mainly
because of that ugly word
"derive"). Part B is
challenging and could
have a few pitfalls along
the way if you take a
wrong path. The twist
giving U=f(T) is
interesting.
a
1
= 4.63 (mol) b
1
= 0.486 m
3
/bar
a
2
= 3.42 (mol) b
2
= 0.827 m
3
/bar
U
IG
= 2.42 + 0.324 T + 9.35 T
2
Problem 8
Components A&B mix at 20 bar, 298 K to form two gas
phases. Phase 1 is pure component A and phase 2 is
30% A and 70% B by mole. The molar Gibbs free
energy of phase 2 is 100 J/mol and the partial molar
Gibbs free energy of component B is 39 J/mol. The pure
component A molar Gibbs free energy is 120 J/mol.
Assume that pure component A behaves ideally at
system pressure. Do not assume equilibrium conditions.
a) Find the partial molar Gibbs free energy of
component A in phase 2.
b) Explain how the assumption in the problem statement
allows you to make a simplification to the problem in order to solve part c. (Hint:
What does it allow you to do with respect to fugacities?)
c) Find the fugacity of Component A in the mixture.
Problem 9
Data for two components, A & B, in a gas mixture are given below:
Property Component A Component B
Pressure = 1 bar
Temp = 373.15 K
Number of Moles 10.0 25.0
Pure comp. fugacity 0.981 bar 0.995 bar
Second virial coeff. (B
ii
) -3.21e-4 m
3
/mol -1.60e-4 m
3
/mol
Cross virial coeff (B
AB
) -2.63e-4 m
3
/mol
a) Calculate the fugacities of the two
components in a mixture by calculating pure
component fugacities with virial EOS and the
Lewis-Randall rule.
b) Calculate the fugacities of the two
components in a mixture using the truncated virial equation of state.
c) Which of these calculations would you expect to be more accurate? why?
Problem 10
Equation 7.2-13, from Sandlers Chemical and Engineering Thermodynamics, states that
Hmmm, 2 gas phases? Well let's
throw out our instincts and
continue. We are given a lot of
information but I'm worried
about the last statement
regarding equilibrium - it was
scribbled as an addendum on the
question. If the 2 phases aren't
in equilibrium I don't know if the
problem can be solved.
Back to good old A & B (they're nothing
if not reliable). Why do I have to
calculate pure component fugacities in
part a when they are given in the
problem? Am I supposed to calculate
them using the Virial Equn also?
v
P RT Z V
V N V T
i i
v
i
Z V d
N
P
N
V
RT
RT P y
y P T f
v
j
ln
1 ) , , (
ln
/
, ,
1
1
1
]
1
,
_
Compute the fugacities of ethane and butane in a

35:65 mixture at 373.15K and 10 bar. Since pressure
is relatively low, use the truncated virial equation of
state to solve for your answer.
The following are given:
Virial EOS:
V
y T B
Z
mix
mix
) , (
1+ , where
i j
ij j i mix
T B y y y T B ) ( ) , (
at 373.15 K,
B
ethane-ethane
= -1.15*10
-4
m
3
/mol
B
butane-butane
= -4.22*10
-4
m
3
/mol
B
ethane-butane
= -2.15*10
-4
m
3
/mol
Problem 11:
a) Estimate the fugacity of both gases in a mixture
of 23% napthalene and 77% isopentane at 8MPa
and 405 K using the Lewis Randall rule.
(Assuming both are gases at the given
conditions).
b) What kind of accuracy would you expect from
this model?
c) Propose an alternative model, which would be
more accurate, and OUTLINE the necessary
steps to solve the problem. DO NOT actually
solve it.
Problem 12:
Seventy-six (76) moles of methane and 90 moles of CO
2
gas are mixed in a 1 L tank at
273.15 K and 10 bar. At this temperature and pressure, the pure component fugacities of
each component are:
bar f CO
v
629 . 9
2

bar f CH
v
753 . 8
4

This problem violates both the
intent and the spirit of the exercise.
The only thing different between
this and Illustration 7.4-2 on p 408
is the composition. I expect better.
I'm docking 2 points from the quiz
score of each member of this group.
Straightforward question IF I
can find the pure component
fugacities of these species. A
little help in this regard would
be appreciated because I suspect
that naphthalene will be difficult
to get. Part c is a great level 5
question but requires a lot of
time unless we copy an idea
from the book. A modification
might be to outline the steps
using an equation of state and
discuss why it would be more
accurate.
Given the following parameters,
mol
m
B
CH CH
3
4
10 65 . 4
4 4
,
mol
m
B
CO CO
3
4
10 16 . 8
2 2
,
and
mol
m
B
CO CH
3
4
10 27 . 6
2 4

solve for the fugacities of each component using,
a) the Lewis-Randall rule.
b) the virial equation of state method.
Problem 13:
a) What is the significance of the fugacity of a gas? What does s deviation from 1
reflect about the gas? Explain >1 and <1.
b) Calculate the fugacities of pure Cl
2
and F
2
at
230 K and 15 bar, and then at 30 bar. Assume
virial EOS is valid.
mol
cm
B
Cl
3
457
2
,
mol
cm
B
F
3
32
2

c) Find the fugacities of Cl
2
and F
2
in a mixture of
100g Cl
2
and 100g F
2
at 230 K and 15 bar, and
then at 30 bar. Assume the Lewis-Randall rule
is correct.
mol
g
Cl MW 9 . 69
2
,
mol
g
F MW 38
2

Problem 14:
In a magical pressure container, I combined 17 kg of butane and 20 kg of methane. Last
night, this magical container was left in my house where ignorant roommates left the
thermostat on too high and the vessel heated up to
100C. The next morning, after waking up in a
pool of my own sweat, I thought it would be cool to
take a big whiff of the butane mixture and calculate
the fugacities of each component of the mixture at
10 bar.
a) Calculate the fugacities using the Lewis-
Randall approximation.
b) Calculate the fugacities using the Virial Equation of State.
Straightforward application of
principles used in class. Short concise
question with proper information
given. Not extremely creative but
functional. Good test of basic skills.
Very well done. Sets up the
significance of the calculation with
some discussion. There do seem to be
a lot of calculations. Seems like I'm
calculating fugacity at 2 different
pressures for no apparent reason.
Could the same thing be accomplished
by calculating at one pressure? Of
course, I'm expecting the result to give
me one >1 and one <1 to reinforce
part a but I don't know if that will
happen.
Huffing butane, now THAT's
appealing. Note how the temperature
change is only implied and by giving
only one T and P we are forced to do
the calculations assuming these are the
conditions. However, by opening the
container to smell, won't the pressure
be 1 bar? Yes, someone will ask that
very question. Be a little more
specific.
c) Are the two answers similar? Why or why not?
Necessary data:
MW(methane) = 16 g/mol
MW(butane) = 58 g/ mol
f
butane
(373.15 K, 10 bar) = 8.628 bar
f
methane
(373.15 K, 10 bar) = 9.90296 bar
B
Me-Me
= -6.6*10
-5
m
3
/mol
B
Bu-Bu
= -0.00117 m
3
/mol
B
Me-Bu
= -2.45*10
-4
m
3
/mol
Hint: You really shouldnt sniff butane.

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Problem 1:

A mixture of nitrogen and butane exists in gaseous

where a= 4.0 bar

Compute the fugacities of ethane and butane in a

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