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ChE 142: Separation Process Principles

Prof. Davis

Fall 2012 Homework 2 Solution


1. (6 points, 2 points each)
A. Why is fugacity used in place of chemical potential to determine phase equilibria?
Fugacity is used instead of chemical potential because chemical potential is not an absolute
quantity (fugacity is), the numerical values for fugacity relate to pressure and are easier to
relate, and chemical potential tends to very large negative numbers as pressure decreases.
Fugacity was invented for numerical convenience, basically.
B. Who invented fugacity?
Gilbert Lewis, who also discovered/invented the covalent bond and the Lewis dot structure
representation, invented fugacity. Apparently the name is from the Latin word for "fleetness", or
the tendency to flee or escape. Gases with higher fugacity like to boil more.
C. How does the fugacity relate to the K-value for a chemical in a mixture?
The K-value for a species in a mixture can be represented by the ratio of the partial fugacity
coefficients for that species in the liquid to that in the vapor. These partial fugacity coefficients
can be defined in terms of the partial fugacity of the species in a mixture (the fugacity is of a
pure species i), the mole fractions, and the total pressure:
iL

fiL
f
, iV iV
xi P
yi P

Its more likely that you would take data on the K-value of the mixture in order to estimate the
partial fugacity (and then the fugacity) than that you would use a fugacity to get a K-value.
2. (5 points) Problem 1.23 from Seader and Henley (p. 33) Be sure to show all work for full
credit. All the property data you need for part (b) should be available from DIPPR.
A. This mixture is notoriously difficult to separate; it is a very common
product/byproduct of catalytic reforming of naptha in petroleum refineries. The
boiling points of these four species (which all look very similar on the molecular
level) only range about 8 oC between EB (lightest, 409 K) and o-xylene (heaviest, 417
K). Even separating a mixture of only those two things would be tough, but the pand m-xylenes have a less than 1 oC difference in BP (411.5 versus 412.3 K) making
distillation nearly impossible without a column with hundreds of stages.
B. A table of properties is below; the only two properties where there is any significant
difference between these two chemicals are dipole moment and melting point:

Property
MW
VdW volume, m3/mol
VdW area, m2/mol
Acentric factor
Dipole moment, debye
Radius of gyration, m
MP, K
BP, K
T c, K
Pc, Pa

m-xylene
106.167
7.066 x 10-5
8.84 x 105
0.3265
0.30
3.937 x 10-10
225.3
412.3
617
3.541 x 106

p-xylene
106.167
7.066 x 10-5
8.84 x 105
0.3218
0.00
3.831 x 10-10
286.4
411.5
616.2
3.511 x 106

C. Because these two have a slightly different dipole moment, a mildly polar adsorbent
might work to selectively adsorb m-xylene (similarly, a non-polar sorbent might more
selectively adsorb p-xylene.) The more noticeable difference between the two is their
melting points; crystallization at low (but luckily not terribly low) temperatures
would probably be a very economical method to separate solid p-xylene crystals from
a mixture as compared to distillation near their boiling points.
3. (4 points) For the propylene/propane distillation column on p.29 of the book, find the split
fraction of propylene in the distillate, the split ratio of propane in the bottoms relative to the
top product, and the separation power of the column with propylene and the distillate as the
numerators. Does this seem like a high SP or a low one?

SF=
PY

D
nPY
157.6
=
= 0.9651
F
nPY 163.3

B
nPR
F
B
B
SFPR
nPR
nPR
nPR
107.3
SR=
=
=
=
=
= 67
PR
B
F
B
D
nPR nPR nPR nPR
1 SFPR
1.6
1 F
nPR

=
SPPY , PR SR
=
PY SRPR

0.965 ( 67 )
SFPY
=
( 67 ) = 1900
1 SFPY
1 0.965

This seems like a very high separation power, which makes sense because the distillate is nearly
pure propylene and the bottoms is nearly pure propane such a separation would require a
large column or a lot of energy (or both) and thus that unit should have a high separation power.
Separation powers near to 1.0 are the lowest; usually we specify the distillate and the light key
as the numerators so that the SP gets bigger as the unit makes a better separation.
4. (5 points) Dry air is a mixture of Nitrogen (78.084% by mole), Oxygen (20.946% by mole),
Argon (0.934% by mole), CO2 (0.039445% by mole and rising), and the rest trace gases like
Neon, Helium, Krypton, etc. Air is usually about 1% water. Using the separation heuristics
from p. 17 of Seader and Henley, construct a system of ideal distillation units for producing

nearly pure Nitrogen, Oxygen, and Argon gases from air (NOT dry air). Draw a picture of
the system and explain your reasoning. Remember that the species with the lowest boiling
points come out of the top of a distillation column.
Since the water is not valuable and would clog up a cryogenic distillation column, remove it first
by rule 1. The same argument holds for the CO2 present. Typically you would have a
desiccation/adsorption system to separate these two things, so one unit for water then another
for CO2. This leaves the other three species that you want plus the trace gases; assume that you
dont care very much about them (though you will have to make sure they dont accumulate in
the system or freeze in your column at cryogenic temperatures). This would leave (at minimum)
a system of two distillation columns in series with two options separating oxygen at the bottom
and feeding a nitrogen/argon mixture to the next column OR separating nitrogen from the top
and feeding an oxygen/argon mixture to the next column. The second choice is superior because
it obeys rule 2, rule 3, and rule 6. Since I said all products should be nearly pure, rule 5 doesnt
apply. Rule 4 doesnt apply either; the separations between nitrogen/argon and oxygen/argon
are about equally difficult. Therefore, your picture should look like this:

Desiccator

Dry air

Wet air inlet

Nitrogen
product

Argon
product

Waste CO2

Nitrogen,
Oxygen,
Argon

O2 / Ar

Oxygen
product

Note that I did not draw any pumps, compressors, heat exchangers, or reflux drums; this was not
because they wont be there (they will) but because we only care about the separators here. Of
particular note is that it will take a large and very expensive compressor to cool these gases
down to cryogenic (less than 100 K) temperatures using the Joule-Thompson effect.

5. (10 points) Problem 2.3 from Seader and Henley (p. 79) Be sure to show all work for full
credit. Note that there is a typo in the thermodynamic data; the units on Enthalpy should be
kJ/kmol (J/mol) and NOT kJ/mol.
A.
B.
C.
D.
E.

2.69 x 107 kJ/h


1.76 x 104 kJ/h/K
5.23 x 106 kJ/h
1.68 x 105 kJ/h
3.11%