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2001
Chapter 1. Course Introduction
WHAT ARE "UNIT OPERATIONS"?
A typical process which a chemical engineer might work with is the production oI gasoline
Irom crude oil
process ÷ sequence oI 'unit operations¨ (physical changes) ¹ chemical reactors
Any process can be subdivided into a number oI steps which are perIormed in sequence to go
Irom some initial starting material (crude oil. in this case) to some Iinal material (gasoline). Eor
example. we might start by heating the crude oil to lower its viscosity. then pump the oil to the
distillation column. where we then separate various components oI the crude. A unit operation is
one oI the steps oI this sequence. Usually the term reIers to steps intended primarily to perIorm
some physical transIormation (as opposed to chemical transIormation) oI the input stream.
Examples oI unit operations:
 heat exchange (change temperature oI a stream)
 Iluid Ilow (transportation)
 distillation (separation oI mixture into multiple streams which are richer in some components
that original)
 evaporation (remove water Irom liquid)
 humidiIication (increase water content oI gas)
 gas absorption (remove one component oI a gas mixture)
 sedimentation (separate solid Irom liquid)
 classiIication (divide mixture oI particles into diIIerent "classes" on the basis oI size)
In this course. we will apply the principles learned in the engineering science courses you have
had the last three semester to the design oI equipment Ior physical transIormations. We might
divide up the courses in the curriculum as Iollows:
06361 page 2 Spring. 2001
Course Objective Scale
Thermo 1) conservation oI energy
2) criteria Ior phase/chemical equilibria
molecular
Iluids. heat/mass
transIer
rates oI physical processes microscopic
unit operations design equipment Ior physical transIormations macroscopic
kinetics 1) rate oI chemical processes
2) design equipment Ior chemical
transIormations
molecular
macroscopic
process design divide process into sequence oI steps
(synthesize Ilowsheet)
supramacro
06361 page 3 Spring. 2001
Chapter 2. Heat Exchange Equipment
DOUBLEPIPE HXER
One particularly simple heatexchange
device is the doublepipe heat exchanger.
shown in the Iigure at right. It is called this
because the basic component is constructed
Irom two pipes. one inside the other. One Iluid
(Eluid B) Ilows inside the inner pipe while the
second Iluid (Eluid A) Ilows in the annular
space between the two pipes. OI course. one
Iluid is hotter than the other and heat Ilows
through the wall oI the inner pipe Irom the hot
Iluid to the cold Iluid. To obtain larger heat
exchange area. several pipes are arranged sidebyside and Iittings are attached to allow the Iluids
to contact the pipes in series so the overall Ilow is the same as iI only one very long pipe were
used rather than several shorter ones.
SHELLANDTUBE HXER
II very large heat exchange areas are required. the doublepipe heat exchanger design
becomes impractical. Instead. the shellandtube heat exchanger design is used.
Shown above is a bundle oI smalldiameter tubes which are arranged parallel to each other and
reside inside a much largerdiameter tube called the 'shell¨. much like strands oI uncooked
spagetti come in a tubeshaped container. The tubes are all maniIolded together at either end so
06361 page 4 Spring. 2001
that the 'tube Iluid¨ enters the leIt side and is distributed equally among all the tubes. At the
right side. the Iluid exits Irom each tube. is mixed together in a second maniIold. then leaves as a
single stream. The second Iluid. called the 'shell Iluid¨. Ilows in the space in between the
outside oI tubes. BaIIle plates inside the shell Iorce the shell Iluid to Ilow across the tubes
repeatedly as the Iluid moves along the length oI the shell.
In the design above (called a 11 hxer). the Ilow is Irom leIt to right inside the tubes and Irom
right to leIt Ior the shellside Iluid. Another common design is shown below (called a 12 hxer).
HalI oI the tubes have Ilow Irom leIt to right while the other halI have Ilow in the opposite
direction.
06361 page 5 Spring. 2001
Chapter 3. Fundamentals of Heat Transfer: Review
LOGMEAN DRIVING FORCE
The design equation used Ior sizing heat exchangers generally takes the Iorm oI
q U A T = A (1)
where q is the heat duty oI the exchanger (rate oI energy transIer) U is some heattransIer
coeIIicient. A is the area oI the heat exchange surIace. and AT is the driving Iorce Ior heat
transIer.
In any real heat exchanger. the local driving
Iorce AT will vary along the length oI the
exchanger: say it varies between AT
1
at one end
oI the exchanger to AT
2
at the other end. Then
the question arises: which value oI AT do you
use in (1)? The answer turns out to be: use the
log mean oI AT
1
and AT
2
:
A
A A
A
A
T
T T
T
T
L
=
÷
1 2
1
2
ln
This turns out to be correct in nearly every
situation. We will prove it now Ior one particular
case and leave some other cases to be proved in
the homework (HWK #1. Probl. 1)
Proof: When the driving Iorce varies with position along
the exchanger. the usual approach to math modelling is
to divide the length oI the hxer (L) into a large number
oI thin slices. such that the thickness oI each slice is thin
enough so that the temperature oI either stream is
essentially constant over the slice. leaving the driving
Iorce constant over the slice:
AT ÷ T´(x) T(x)
Depending on which x we choose. we get a diIIerent driving Iorce. The rate oI heat transIer Irom
the hot Iluid to the cold Iluid in any slice is given by a local heat transfer coefficient U(x):
dq ÷ U(x) AT(x) dA (2)
2
2
1
1
A
x÷0 x
x¹dx
x÷L
one slice
06361 page 6 Spring. 2001
where q(x) is the rate oI heat transIerred Irom the hot Iluid to the cold Iluid in the length oI hxer
Irom x÷0 and x÷x; and dq is
q(x¹dx) ÷ q(x) ¹ dq
and dA is the heat exchange area in this slice oI length dx. II the inner pipe (oI a doublepipe
hxer) is a cylinder oI diameter D. then the heat exchange area oI this slice is
dA ÷ tD dx
Integrating (2) as a Iunction oI x is diIIicult since
we`d have to predict AT(x). There is a easier way
(but a 'trick¨ is required). Consider steadystate
countercurrent Ilow through a doublepipe heat
exchanger (shown at right). A steadystate energy
balance on the hot Iluid gives
1
rate in rate out
m H m H q
=
' ' ' ' = +
(3)
A similar balance on the cold Iluid gives
1
rate in rate out
mH q mH
=
+ =
(4)
Solving (3) and (4) Ior q:
1 1
rate of energy rate of energy
gained by lost by
cold stream hot stream
( ) m H x H q x m H x H ' ' ' ÷ = = ÷
. .
(5)
where m is the mass Ilowrate oI the stream (units are Kg/sec). H is the enthalpy per unit mass
(units are J/Kg). the subscripts and primes have the Iollowing meaning:
 unprimed reIers to the cold stream.
 prime reIers to the hot stream.
 '1¨ reIers to the leIt end oI hxer. and
 '2¨ reIers to the right end oI hxer.
Now. let`s try to relate each enthalpy to the appropriate temperature. In general. enthalpy
changes can have both latent heat (caused by change in phase) and sensible heat (caused by
change in temperature) contributions.
x÷0 x÷x x÷L
pipe wall
hot Iluid
cold Iluid
q x ( )
T´
1
T´ T´
2
T
1
T T
2
06361 page 7 Spring. 2001
dH c dT dv
p
= +
sensible
heat
latent
heat
.
ì
where
 dH is the change in enthalpy (energy/mass)
 c
p
is the heat capacity (energy/mass/degree) oI the Iluid. also known as 'speciIic heat¨
 dT is the change in temperature (degree)
 ì is the heat oI vaporization (energy/mass)
 dv is the mass Iraction oI Iluid vaporized
When the Iluid consists oI two phases (liquid and vapor). which have diIIerent heat capacities
c
pL
and c
pJ
. we use weighed average oI the two heat capacities
c
p
÷ (1v)c
pL
¹ v c
pJ
where v is the mass Iraction oI vapor present and 1v is the mass Iraction oI liquid present. Eor
the time being. let`s assume:
Assumption #1: no phase changes occur in either Iluid
Now we only have to worry about contributions Irom changes in the temperature (sensible heat):
dH ÷ c
p
dT
Integrating over the temperature change allows us to evaluate the change in enthalpy
AH c dT c T T
p
T
T
p b a
a
b
= = ÷
using
assumption
#1
using
assumption
#2
In general. the speciIic heat (c
p
) depends on temperature. But iI the temperature change is not too
large say 1020° then the speciIic heat doesn't change too much. Let's assume we can
neglect these small changes:
Assumption #2: constant speciIic heat Ior both streams
Then we can Iactor c
p
out oI the integral and the integration becomes trivial:
AH ÷ c
p
AT
06361 page 8 Spring. 2001
In particular. HH
1
÷ c
p
(TT
1
)
and ' ÷ ' = ' ' ÷ ' H H c T T
p 1 1
where c
p
and c
p
are the speciIic heats oI the cold and hot streams. Thus (5) can be rewritten as:
at x÷x: mc T x T m c T x T q x
p p
( )
÷ = ' ' '
( )
÷ ' =
( )
1 1
(6)
Eor example.
at x÷0: mc T T m c T T q
p p 1 1 1 1
0 0 ÷ = ' ' ' ÷ ' =
( )
=
In particular. we are interested in the total rate oI heat transIer over the entire length L oI the
exchanger:
at x÷L: mc T T m c T T q L q
p p T 2 1 2 1
÷ = ' ' ' ÷ ' =
( )
÷
Now let me show you the "trick": using (6). I can show that the temperature oI either stream i.e.
T(x) or T(x) is a linear Iunction oI the amount oI
heat transIered. q(x):
T x T
mc
q x
p
( )
= +
( )
1
1
'
( )
= ' +
' '
( )
T x T
m c
q x
p
1
1
Since both temperatures are linear Iunctions oI q.
their diIIerence is also a linear Iunction oI q. A
straight line has the very nice property that its slope
is the same at every point:
d T
dq
T T
q
T
A A A
= =
÷
÷
const
2 1
0
(7)
I can easily evaluate the driving Iorce (AT) at the two ends oI the heat exchanger. and I know the
total heat duty (q
T
). so I can calculate this slope. The dq and d(AT) which appear in (7) represent
the incremental rate oI heat transIer and the change in driving Iorce AT which occurred over a
diIIerent length dx oI the heat exchanger(Irom x to x¹dx). They are related by
dq ÷ U dA AT (8)
where dA is the heat exchange area in that slice oI the heat exchanger Irom x to x¹dx. Treating
the heat exchange surIace as a cylinder oI radius R:
06361 page 9 Spring. 2001
dA ÷ 2tR dx
(8) into (7):
d T
U T dA
T T
q
T
A
A
A A
=
÷
2 1
or
d T
T
T T
q
U dA
T
A
A
A A
=
÷
2 1
Next. we integrate over the length oI the heat exchanger Irom x÷0 (where AT ÷ AT
1
) to x÷L
(where AT ÷ AT
2
):
d T
T
T T
q
U x Rdx
T
T
T
x
x L
dA
A
A
A A
A
A
1
2
2 1
0
2
=
÷
=
=
t
.
The integral on the righthandside becomes trivial to evaluate iI we can make one additional
assumption:
Assumption #3: U is constant
Then we can Iactor U outside the integral and integrate the remainder:
2 2 2
0 0
t t t Rdx R dx RL A
x
x L L
T
=
=
= = =
which is iust the total heat exchange area. Thus we have
ln
A
A
A A T
T
T T
q
UA
T
T
2
1
2 1
=
÷
Solving Ior the total heat duty q UA
T T
T
T
T T
=
÷ A A
A
A
2 1
2
1
ln
or q UA T
1 1 L
= A where A
A A
A
A
T
T T
T
T
L
=
÷
2 1
2
1
ln
is called the logmean temperature difference (LMTD). It represents the average driving Iorce
Ior heat transIer. This result provides us with the main design equation Ior heat exchangers.
06361 page 10 Spring. 2001
Summary oI assumptions:
 U and c
p
's are constant
 AH oI neither stream has contributions Irom both sensible and latent heats (i.e. AH
is either all sensible heat or all latent heat)
Actually. we assumed in the analysis above that AH was all sensible heat Ior both streams. In the
homework. you will show that AH can also be all latent heat and the LMTD is still the
appropriate average driving Iorce. Eor example. iI you use condensing steam as your hot Iluid. as
long as the steam remains saturated:
Ior saturated steam: T(x) ÷ const ÷ T
bp
We also assumed in the analysis above.
that the Ilow was countercurrent. You
will also show in the Iirst homework
problem that the same design equation
applies to cocurrent Ilow.
RESISTANCES IN SERIES
Consider heat transIer through the
inner pipe oI a doublepipe heat
exchanger. Let`s take a slice out oI the
heat exchanger and examine the
temperature proIile along a radius to the
pipe at one particular axial position.
oblique view
of slice
06361 page 11 Spring. 2001
One can identiIy three regions in which the temperature varies sharply. These correspond to
the three resistances to heat transIer: the pipe wall itselI. the Iluid Iilm inside the pipe and the
Iluid Iilm outside the pipe. These resistances act in series. The total resistance is related to the
resistance oI each Iilm by:
1 1
1
U h
x
k
D
D
h
D
D
o o
w
w
o
L
i
o
i
total
resistance
resistance of
outer film
resistance of
pipe wall
resistance of
inner film
= +
+
.
.
That resistances add in this way is a very
important concept. so I`m going to take
the time to prove it to you again. This
will also give us an opportunity to
review the deIinitions oI the quantities.
Consider the temperature proIile
along some line drawn perpendicular to
the pipe wall through the center oI the
pipe. These temperature variations drive
heat transIer down the temperature hill.
The rate dq oI heat transIered through
some small element oI the inner surIace
oI the pipe having area dA
i
is
dq h dA T T
i i
D dL
h wh
i
= ÷
t
(9)
where h
i
is a singlephase heattransfer coefficient Ior the inner Iilm oI
Iluid next to the pipe and dL is the length oI the pipe segment. At steadystate. this same rate oI
heat transIer must occur through the liquid Iilm outside the pipe:
dq h dA T T
o o
D dL
wc c
o
= ÷
t
(10)
At steadystate. this same rate oI heat transIer must also occur through the pipe wall itselI:
dq
k
x
d A T T
w
w
L wh wc
= ÷ (11)
D
i
D
o
T
a
T
c
T
g
T
h
T
wh
T
wc
end view
oI slice
r
r
i
r
o
r
r
e
s
i
s
t
a
n
c
e
#
1
r
e
s
i
s
t
a
n
c
e
#
2
r
e
s
i
s
t
a
n
c
e
#
3
dq
D
i
D
o
06361 page 12 Spring. 2001
where k
w
is the thermal conductivity oI the pipe wall and x
w
is the wall thickness. Since the
inner and outer areas are somewhat diIIerent. we use an average oI them in (11):
where d A
dA dA
dA
dA
D D dL
D
D
D dL
L
o i
o
i
o i
o
i
L
=
÷
=
÷
=
ln ln
t
t
is the logmean oI dA
o
and dA
i
. Now we deIine the overall heattransfer coefficient U
o
as
dq U dA T T
o o h c
÷ ÷ (12)
This is called 'overall¨ because we are using the overall driving Iorce in the deIinition. Solving
(12) Ior the overall temperature diIIerence. then writing this overall as the sum oI the individual
temperature diIIerences
dq
U dA
T T T T T T T T
o o
h c h hw
dq
h dA
hw cw
dq
k
x
d A
cw c
dq
h dA
i i w
w
L
o o
= ÷ = ÷ + ÷ + ÷
. . .
Substituting (9). (10). and (11):
dq
U dA
dq
h dA
dq
k
x
d A
dq
h dA
o o i i
w
w
L
o o
= + +
Dividing through by dq dA
o
leaves:
1 1 1
U h
D
D
x
k
D
D h
o i
o
i
w
w
o
L
o
= + +
aIter substituting the expressions relating the dA`s to D`s and dL.
Heat transIer coeIIicients (either U or h) are like conductances in electricity: the heat Ilux is
proportional to them (like electrical current through a resistor is proportional to its conductance).
The reciprocal oI the heat transIer coeIIicients (1/U or 1/h) is like an electrical resistance. The
Iormula above (relating 1/U to 1/h´s) is like that relating the overall resistance oI a circuit
composed oI three resistors in series: the total resistance is the sum oI each oI the three
individual resistances.
06361 page 13 Spring. 2001
FOULING FACTORS
The useIulness oI analogies is that we can extend our knowledge in one area using
knowledge in other. Eor example. iI there are additional layers through which heat must be
conducted. then we can iust add their resistances to get the total. A situation involving additional
layers is:
fouling deposition oI dirt. scale or any solid deposit on one or both sides oI the tube
Eouling generally reduces heat transIer by imposing an additional resistance. It's eIIect is
accounted Ior by use oI
Iouling Iactors: h
k
x
d
d
d
=
There may be a Iouling Iactor Ior both the inside and the outside oI the pipe. Adding these
resistances to the others:
1 1 1 1 1
U h h
x
k
D
D h
D
D h
D
D
o o do
w
w
o
L di
o
i i
o
i
= + + + +
fouling
outside pipe
fouling
inside pipe
.
By means oI the electrical analogy. we are able to guess the Iorm oI the correction without
having to go through the analysis.
CORRELATIONS TO ESTIMATE `S
In all the problems we have worked so Iar. we have been given the values oI the 1phase heat
transIer coeIIicients (the h
i
and h
o
). Now we are going to turn our attention to how these can be
estimated iI they are not otherwise known. The empirical correlations appropriate Ior a given
situation usually depend on three questions:
1. What is the geometry? (e.g Ilow inside pipe. Ilow across bank oI tubes. Ilow around sphere)
06361 page 14 Spring. 2001
2. Is the Ilow turbulent or laminar?
3. Does a phase change occur?
Our book presents a number oI common correlations which cover the most common situations:
Sect. 4.5. 4.6  without phase change
laminar Ilow inside tubes p238 (not covered in class)
turbulent Ilow inside tubes 239244+
Sect. 4.8  with phase change (not covered in class)
Eor Ilow inside long tubes. the criteria Ior turbulent Ilow is simple: iust calculate the
Revnolds number:
N
v D GD
i i
Re
= =
p
u u
where p ÷ Iluid density
u ÷ Iluid viscosity
v is the crosssectional average Iluid velocity
The latter quantity is deIined as
i
Q
v
S
=
where Q ÷ volumetric Ilowrate through tube (units oI volume per time)
S
i
÷ tD
i
2
/4 ÷ crosssection area oI tube
Another term which is sometimes used to calculate Reynolds number is the mass velocitv:
i i
Q m
G v
S S
p
÷ p = =
`
(units oI mass per area per time)
The mass velocity is oIten used in problems involving gas Ilow where both density and velocity
depend on pressure. but their product is independent oI pressure (since it represents mass
Ilowrate and at steady state. a mass balance requires the mass Ilowrate to be the same at all axial
positions). However Reynolds number is calculated. the criteria Ior turbulent Ilow is as Iollows:
N
Re
~ 6000 ¬ Ilow is turbulent
N
Re
· 2100 ¬ Ilow is laminar
2100 · N
Re
· 6000 ¬ Ilow is in transition
+
You should make a special effort to read these pages before working the HWK problems. since I don`t have time
in class to present all the details.
06361 page 15 Spring. 2001
h
for 1urbulent Flow In Long Pipes
Eor turbulent heat transIer in long pipes. the individual Iilm coeIIicient inside a pipe can be
estimated using the Sieder1ate equation eq. (4.58) in G:
+
h D
k
v D
c
k
i i
N
i
N
p
N
w
Nu
=
0 023
0 8 1 3 014
.
Re Pr
. / .
p
u
u
u
u
. .
where k ÷ thermal conductivity oI Iluid inside tube
c
p
÷ heat capacity (speciIic heat) oI Iluid inside tube
u ÷ viscosity oI Iluid inside tube
Unless speciIically indicated. all Iluid properties are evaluated at the mixingcup temperature oI
the Iluid:
u. k. c
p
evaluated at T
The subscript 'w¨ indicates the property is to evaluated at the wall temperature:
u
w
evaluated at T
w
Experimentally. one Iinds that heat transIer coeIIicients can be diIIerent Ior heating and cooling
over the same temperature range. The reason. is that the viscosity at the wall is very important in
determining transport and u
w
can be very diIIerent Irom u. This is accounted Ior in the u/u
w
Iactor.
Which 1 do you use for property evaluations?
When the inlet and outlet Ts diIIer. what T do you use to evaluate the properties at? Use
arithmetic mean values Ior T and T
w
:
T
T T
a b
=
+
2
and T
T T
w
wa wb
=
+
2
where the subscript 'a¨ reIers to the inlet and 'b¨ reIers to the outlet. Since the outlet T and the
outlet T
w
depend on the heat transIer coeIIicient. this makes the determination oI h a trialand
error (see Example 4.52).
+
The coefficient of 0.023 in this equation is the value which appears in McCabe. Smith & Harriott. Geankoplis
gives a value of 0.027 instead. In homeworks and exam. you can use either value. The Notes use 0.023 because
most of the homework problems using this equation were taken from MS&H.
06361 page 16 Spring. 2001
Chapter 4. ShellandTube Heat Exchangers
The value oI h
o
Ior shellandtube heat exchangers depends on arrangement oI tubes and
baIIles inside the shell. We will Iirst describe typical arrangements and then give a common
correlation Ior h
o
.
TUBE PITCH
The bundle oI tubes in a shellandtube heat exchanger can be stacked in one oI two diIIerent
ways
The use oI triangular pitch allows the tubes to be more tightly packed  more tubes and thereIore
more area per unit volume oI shell. This makes the shell cheaper.
On the other hand. the square pitch has the advantage that it is easier to clean. You can get a
long brush in between two rows or between two columns. OI course. the shell has to be pulled
oII oI the tube bundle beIore you can get at it in either
case.
Regardless oI which geometry is used. the centerto
center distances between adiacent tubes is called the
tube pitch.
BAFFLES
To some extent. it is advantageous to reduce the
crosssectional area available Ior Ilow. Eor the same
volumetric Ilowrate. this will increase the mass Ilux or the mass velocity oI the Iluid Ilow. which
will increase h
o
. OI course. this also increases the pressure drop and the pumping cost.
06361 page 17 Spring. 2001
A common technique Ior thus increasing h
o
is to
install baIIle plates. which partially block the
crosssectional area on the shell side. A baIIle
plate is a disk whose diameter is the inside
diameter oI the shell:
D
s
÷ diameter oI shell
with holes drilled through it Ior the tubes to pass
through. Part oI the disk is cut oII to Iorm what is
called the baffle window. which is the cross
section available to the shellside oI the Iluid.
When the height oI the window is 1/4 oI the shell
diameter. we call the plate a 25" baffle.
A number oI these plates is placed along the length oI the exchanger with the location oI the
baIIle window alternating between the top and bottom oI the plate.
A second advantage oI these plates is that they prevent the Iormation oI large stagnant regions
(having low heat transIer rates) which usually accompany 'channelling¨ oI the Iluid in a direction
path connecting inlet to outlet. The spacing between the baIIle plates is called the baffle pitch:
P ÷ baIIle pitch
Typical baIIle pitch is a Iraction oI the shell diameter:
0.2 · P/D
s
· 1
Besides reducing the area available Ior Ilow on the shell side. the baIIles also Iorce the Iluid
across all oI the tubes. which normally will enhance the heat transIer coeIIicient.
FOR SHELLANDTUBE EXCHANGER
ReIerence: McCabe. Smith & Harriott. 5
th
ed.. p432436
06361 page 18 Spring. 2001
An approximate but generally useIul correlation Ior estimating the shellside coeIIicient in a
shellandtube heat exchanger is the Donohue equation:
h D
k
D G
c
k
o o o e
p
w
=
0 2
0 6
0 33 014
.
.
. .
u
u
u
u
(13)
where u. k and c
p
are properties oI the shellside
Iluid. The Iorm oI this equation is very similar
to the SiederTate equation. except the
exponents and coeIIicient are diIIerent. Another
diIIerence is that the mass velocity G
e
is a
weighted average
G G G
e b c
= (geometric mean)
oI the mass velocity through the baIIle window
G
m
S
b
b
=
`
and the mass velocity Ior crossIlow perpendicular to the tubes
G
m
S
c
c
=
`
where S
b
is the area available Ior Ilow oI the shellside Iluid through the baIIle window and S
c
is
the intersticial area available Ior crossIlow perpendicular to the bank oI tubes at the widest point
in the shell.
S f
D
N
D
b b
s
b
o
area of
blue region
=
÷
t t
2 2
4 4
(14)
where D
s
÷ diameter oI entire shell
N
b
÷ number oI tubes in baIIle window
f
b
÷ area Iraction oI baIIle plate that is window
Eor a 25° baIIle plate. we have
f
b
÷ 0.1955 (15)
The second area is calculated Irom
06361 page 19 Spring. 2001
S PD
D
p
c s
o
= ÷
1
p ÷ tube pitch
P ÷ baIIle pitch
Appendix: Derivation for S
and S
In case you are curious as to how these Iormulas we obtained. I have put their derivation in
this appendix.
D
o D
s
p
P
widest
row oI
tubes
area Ior
crossIlow
(shaded)
S
c
is the area open to Iluid Ilow across the widest row oI tubes in the shell and between two
adiacent baIIle plates. Eirst the total area (ignoring tubes) is
total area ÷ PD
s
where P is the baIIle pitch. To calculate the Iraction oI PD
s
which is open. let's subdivide D
s
into repeating unit cells:
length oI unit cell ÷ p (tube pitch)
length which is open ÷ pD
o
Iraction open ÷ (pD
o
)/p ÷ 1  D
o
/p
Multiplying this Iraction by the total area gives the area open:
S PD
D
p
c s
o
= ÷
1 (16)
06361 page 20 Spring. 2001
OI course. we have ignored some end eIIects which could be signiIicant iI the number oI tubes is
not large.
Likewise the open area oI a baIIle window is the total area oI the window minus the area blocked
oII by tubes:
S f
D
N
D
b b
s
b
o
=
÷
t t
2 2
4 4
where f
b
÷ 0.1955 (Ior a 25° baIIle)
and N
b
÷ no. oI tubes thru window
To get this value oI f
b
. we have to do a little
geometry. Eirst. recall that the area oI a circle oI
radius r is tr
2
.
A r
circle
= t
2
A 'sector¨ is a portion oI a circle (see Iigure at
right):
A r
sector
=
1
2
2
2u
total angle
subtended
by sector
where 2u is the total angle subtended by the arc oI the sector. Note that iI we substitute 2t Ior
the 2u. we get the A
sector
÷ A
circle
. The area oI the triangle whose sides are x.v. and r equals
A bh xv
triangle
= =
1
2
1
2
Einally. the area oI the segment is calculated Irom
A
segment
÷ A
sector
 2A
triangle
Eor a 25° baIIle. the height oI the segment. rx. will be 25° oI the diameter  or 50° oI the
radius:
x
r
v r x r = ¬ = = ° = ¬ = ÷ =
÷
05 05 60
3
3
2
1 2 2
. cos . u
t
A
r
r r r
triangle
=
= =
1
2 2
3
2
3
8
0 217
2 2
.
06361 page 21 Spring. 2001
A r r
tor sec
= = u
t
2 2
3
A r r r r
segment
= ÷
= ÷
=
t t
3
2
3
8 3
3
4
0 61418
2 2 2 2
.
Now f
b
is the Iraction oI the total area oI the circle which is represented by this segment:
f
A
A
r
r
b
segment
circle
= =
÷
= =
t
t
3
3
4
0 61418
31416
01955
2
2
.
.
.
MULTIPASS CONSTRUCTION
Just as we can improve the heat transIer coeIIicient on the shell side by reducing the baIIle
pitch. we can improve the heat transIer coeIIicient on the tube side by restricting the Ilow to halI
oI the tubes. Both have the eIIect oI reducing the area available Ior Ilow. thereby increasing the
Iluid velocity and the heat
transIer coeIIicient.
Suppose we partition the
maniIold in such a way
that the inlet Iluid can only
enter halI oI the tubes.
The other halI oI the tubes
are used Ior return Ilow.
We say that such an
exchanger has two tube
passes.
Although two tube passes
improves h
i
. one oI the passes
will be cocurrent. A 24
exchanger improves both h
i
and h
o
. and in addition. the
Ilow is more nearly
countercurrent. We could also
partition the shell side with a
horizontal baIIle in addition to
the vertical baIIles. producing
two shell passes.
The most commonly used
designs are:
shellside Ilow
tube
side
Ilow
tube sheets
shellside Ilow
tube
side
Ilow
tube sheets
06361 page 22 Spring. 2001
 12 exchanger
 24 exchanger
where the Iirst number is the number oI shell passes and the second number is the number oI tube
passes.
An even number oI tube passes is desireable because then input and output oI the tubeside Iluid
occur on the same end oI the exchanger. This allows the other end oI the exchanger to "Iloat" in
response to thermal expansion oI the metal. which can otherwise be a serious problem when the
shell changes temperature during startup or shutdown.
"TRUE" MEAN TEMPERATURE DIFFERENCE
Eor multipass construction. the Ilow is neither countercurrent nor cocurrent. As a consequence.
the average driving Iorce is no longer the LMTD. As it turns out. what is called the true mean
temperature difference (MTD) is somewhat less than the logmean:
AT
m
÷ F
T
AT
L
(17)
This is the AT. which when multiplied by UA gives the total rate oI heat transIer Ior a shelland
tube exchanger:
q
T
÷ U
o
A
o
AT
m
F
T
is a correction Iactor which is unity Ior pure cocurrent or pure countercurrent Ilow:
F
T
÷ 1
Eor pure crossIlow to a bank oI tubes. or Ior a mixture oI crossIlow and countercurrent Ilow. the
Iactor is less than unity:
F
T
÷ F
T
(Y. Z. type oI Ilow) s 1
where Y and Z are ratios oI temperature diIIerences:
Y
T T
T T
cb ca
ha cb
=
÷
÷
and Z
T T
T T
ha hb
cb ca
=
÷
÷
where the subscript 'c¨ reIers to the cold Iluid while the subscript 'h¨ reIers to the hot Iluid and
the subscript 'a¨ reIers to the inlet while 'b¨ reIers to the outlet.
06361 page 23 Spring. 2001
F
T
is usually plotted as a Iunction oI Y Ior diIIerent
values oI Z. Such a plot is sketched at right. More
accurate plots can be Iound in Geankoplis`s book:
12 HX ÷ Eig. 4.94a
24 HX ÷ Eig. 4.94b
Note that as Z÷0. F
T
÷ 1 over the entire range oI
Y·1. This special case is applicable Ior condensing
vapors. As long as the vapor is condensing. its
temperature stays at the boiling point:
T
ha
÷ T
hb
÷ T
bp
so that Z ÷ 0 and F
T
÷ 1
Ior condensing steam as the hot Iluid. Similarly iI we have boiling water as the 'cold¨ Iluid. its
temperature doesn`t change (i.e. T
ca
÷ T
cb
÷ T
bp
) and then we have
Y ÷ 0 and F
T
÷ 1
Although the Ilow in the exchanger is complex. we calculate AT
L
in (17) as iI the Ilow were
countercurrent. The deviation caused by not being countercurrent is included in the values oI
the empirical correction Iactor F
T
.
Example: A steel mill is considering whether a spare heatexchanger will be able to cool oI 3000
gal/hr oI a dilute acid Irom 250°E to 180°E using 5000 gal/hr oI 80°E river water. You are asked
to estimate: a) the truemean driving Iorce. AT
m
. and b) the shellside coeIIicient. h
o
.
Description of available heat exchanger:
type: 12
tubes: 158 1inch. 14BWG stainless tubes. 16 It long. stacked in 1¼ inch square
pitch
baIIles: 25° with 6 inch pitch
shell: 20 inch inside diameter. mild steel
Solution: Eirst we have to determine the outlet temperature oI the cold stream. The rate oI
energy lost by the hot stream is the rate oI energy gained by the cold stream
q m c T T m c T T
T h ph ha hb c pc cb ca
= ÷ = ÷ ` `
06361 page 24 Spring. 2001
Assuming the physical properties oI dilute acid and river water are the same as pure water. we
can take c
ph
÷ c
pc
so that heat capacity can be cancelled out oI the second equation above.
leaving
T T
T T
m c
m c
m
m
cb ca
ha hb
h ph
c pc
h
c
÷
÷
= ~ = =
`
`
`
`
.
3000
5000
0 6
gal hr
gal hr
(18)
Erom the problem statement we have
T
ha
÷ 250°E T
hb
÷ 180°E T
ca
÷ 80°E
Substituting these into (18) and solving Ior T
cb
. we obtain
T
cb
÷ 122°E
+
Next. we calculate the two quantities needed to evaluate the truemean driving Iorce:
Z
T T
T T
ha hb
cb ca
=
÷
÷
= =
1
0 6
167
.
. and Y
T T
T T
cb ca
ha ca
=
÷
÷
= 0 247 .
Since this is a 12 exchanger. we read F
T
Irom Eig. Eig. 4.94a:
F
T
÷ 0.97
Although the Ilow in the exchanger is complex. we calculate AT
L
as iI the Ilow were counter
current:
AT
1
÷ T
ha
T
cb
÷ 128°E and AT
2
÷ T
hb
T
ca
÷ 100°E
A
A A
A
A
T
T T
T
T
L
=
÷
= °
1 2
1
2
113
ln
E
Einally 110 E
L
m 1
T F T A = A = °
The shellside coeIIicient (h
o
) can be estimated using Donohue`s correlation (13). Since acid is
corrosive. we would be welladvised to place it inside the stainless tubes. leaving river water on
the shell side (which is mild steel). With this choice. the mass Ilowrate is
+
Such a high temperature in the river could be harmful to fish and other wildlife. Engineers need to be mindful of
the impact of their designs on the environment as well as on the health and safety of people in the vicinity. Eaced
with this result. the engineer should suggest altering the design (e.g. increase the flowrate of cooling water to obtain a
lower increase in temperatue). Eor the purpose of this academic example. we will ignore this obiection and proceed
through the analysis.
06361 page 25 Spring. 2001
` . . m =
= × 5000 8 34 417 10
4
gal
hr
lb
gal
lb
hr
Eor crossIlow. the maximum available area Ior Ilow can be calculated Irom (16):
S PD
D
p
c s
o
= ÷
= 1 0167 . It
2
using P ÷ 6 inch. D
s
÷ 20 inch. D
o
÷ 1 inch (see Appendix A.52). and p ÷ 1.25 inch. The mass
velocity Ior crossIlow is
G
m
S
c
c
= = ×
`
. 2 5 10
5
lb
It  hr
2
Let`s assume that the Iraction oI tubes which pass through the baIIle window equals the Iraction
oI the shell crosssection represented by the baIIle window. In other words:
N
b
÷ f
b
×158 ÷ 0.1955×158 ÷ 30.8
where 158 was given as the total number oI tubes in the shell and f
b
÷ 0.1955 applies Ior 25°
baIIle windows (see (15) and Appendix on page 20). Now everything in (14) is known:
S f
D
N
D
b b
s
b
o
=
÷
=
t t
2 2
4 4
0 258 . It
2
The mass velocity through the baIIle window is
G
m
S
b
b
= = ×
`
. 162 10
5
lb
It  hr
2
and the eIIective mass velocity is
G G G
e b c
= = × 2 01 10
5
.
lb
It  hr
2
BeIore we can estimate h
o
Irom (13). we need some Iluid properties. Since we have no idea
what the wall temperature is. let`s iust get a rough estimate oI h
o
by setting u/u
w
÷ 1. The other
properties (besides u
w
) are evaluated at the average temperature oI the shellside Iluid T ÷
0.5(80°E ¹ 122°E) ÷ 101°E (38.3°C). Using Appendix A.2:
u ÷ 0.681 cP. k ÷ 0.363 BTU/Ithr°E. p ÷ 62.0 lb/It
3
. c
p
÷ 0.999 BTU/lb°E
(13) yields h
o
÷ 363 BTU/It
2
hr°E
06361 page 26 Spring. 2001
Once we have h
o
and h
i
we can estimate T
w
and iterate until the area required no longer changes.
06361 page 27 Spring. 2001
Chapter 5. Evaporation
evaporation  concentrating a solution containing a nonvolatile solute by boiling away the
solvent (usually water)
Examples:
 production oI orange iuice concentrate
 production oI concentrated H
2
SO
4
 production oI distilled water
Usually the product is a concentrated solution (called the
'liquor¨) and the vapor is condensed and discarded.
liquor  the concentrated solution
An important exception is the production oI distilled
water Irom tap water. Here the condensed vapor is the product and the more concentrated
solution oI minerals or (in the case oI desalination) salts is discarded.
Evaporation is not the only unit operation that involves boiling. Some others that involve boiling
include:
 distillation  involves two or more volatile components (evaporation has iust one)
 drying  product is a solid (in evaporation. product is usually a more concentrated liquid
solution)
 crystallization  product is a slurry oI crystals precipitated Irom solution (not a simple
solution)
Usually these diIIerences are suIIicient to require diIIerent equipment to perIorm the operation.
EQUIPMENT FOR EVAPORATION
There are several types oI evaporators. but they all have the Iollowing parts:
Part #1: HX (Ior adding the latent heat oI vaporization to the liquid Ieed). Usually HX is a
shellandtube with condensing steam as the hot Iluid on the shell side (because steam
is Iree oI minerals which Iorm scale).
Part #2: vapor space or vapor head (larger chamber in which liquid. entrained in the vapor as
droplets or Ioam. can be separated Irom the vapor. usually by impinging stream onto a
plate.)
You also need something to move the liquid through the heat exchanger. Sometimes a pump is
used and sometimes it's iust leIt to gravity. either in the Iorm oI a Ialling Iilm on the outside oI
the HX tubes or the entrainment oI liquid by rising bubbles.
06361 page 28 Spring. 2001
Part #3: liquid mover
 pump
 gravity  Ialling Iilm
 gravity  entrainment by rising bubbles
Long1ube Jertical Evaporator
When the heat exchanger tubes are oriented vertically. the bubbles produced by boiling rise
and carry liquid with them. Tubes are typically 1 or 2 inches in diameter and 12 to 32 Ieet in
length. The liquid entrained in the vapor coming out oI the HX is richer in solute than that
entering the HX. Vapor and Iine liquid droplets are separated in the vapor head by placing a
baffle plate in the path oI the twophase Iluid coming out oI the HXer.
Notice the vent at the top oI the shellside oI the HX. Usually a very small Iraction oI the steam
Ilow is allowed to bleed out oI the shell. This is done to allow air which is oIten mixed with the
steam to escape. Otherwise noncondensable gases will accumulate in the shell. causing the
pressure to rise and decreasing the steam Ilowrate.
Longtube vertical evaporators are especially eIIective in concentrating liquids that tend to Ioam.
Eoam is broken when the twophase mixture hits the baIIle plate.
06361 page 29 Spring. 2001
ForcedCirculation Evaporator
Many concentrated solutions are highly
viscous. Eor example. a concentrated sugar
solution can have a viscosity that is 10
6
times larger than water. II the concentrated
solution is highly viscous. the velocity oI
rising bubbles will be very small and the
heat transIer coeIIicient will also suIIer.
Eor very viscous liquids. a pump is oIten
used to improve the circulation. OI course a
pump also raises the pressure signiIicantly
which can prevent the liquid Irom boiling.
In a Iorcedcirculation evaporator. boiling
usually occurs near the end oI the HX where the pressure is lower or in the pipe leading Irom the
HX to the vapor space.
HX tubes are now oriented horizontally so they are easier to clean. Again a baIIle plate is used to
separate vapor Irom entrained liquid.
EVAPORATOR PERFORMANCE
Regardless oI which type oI evaporator we use. there are two standard measures oI perIormance:
capacitv pounds water evaporated per hour
economv lb water evaporated per lb steam used (usually somewhat less than unity)
EXAMPLE: SIMPLE
EVAPORATOR PROBLEM
Suppose we are trying to
concentrate a solution oI orange iuice
Irom 10wt° solids to 50wt° in a
longtube vertical evaporator. Our
past experience has shown that a
reasonable heat transIer coeI. is
Given: U ÷ 500 Btu/hIt
2
°E
To keep the boiling T low enough.
we keep the vapor space under vacuum:
p ÷ 4 inHg
06361 page 30 Spring. 2001
II the Ieed is 55.000lb/hr at 70°E. what area oI heat exchanger is required and what Ilowrate oI
15 psig steam?
Eind: ` m
s
. A
Eirst we do a mass balance to determine the Ilowrates. A mass balance on the solids yields:
10°(55.000 lb/hr) ÷ 50°( ` m)
so ` m ÷ 11.000 lb/hr (liquor)
is the Ilowrate oI the liquor. The corresponding Ilowrate oI the vapor must be (Irom an total
mass balance):
` m
f
 ` m ÷ 44.000 lb/hr (vapor)
The heat duty oI the HXer is iust the heat gained by the Ieed. In terms oI enthalpies oI the
streams:
q ÷ vapor ¹ liquor  Ieed
q ÷ ( ` m
f
 ` m)H
v
¹ ` mH  ` m
f
H
f
(19)
Eor highmolecularweight substances like orange iuice and other 'organic colloids¨
v
we can
neglect boilingpoint elevation and heat of dilution. Then the enthalpies oI the Ieed and the
liquor are essentially the properties oI pure water under those conditions. The enthalpy oI liquid
water and water vapor can be read Irom the Steam Tables Iound in Appendices A.29 and A.210
(pages 857861).
+
v
'Organic colloids¨ are solutions of high molecularweight polymers or dispersions of fine particles. Then the
molar concentration of these solutions is negligibly small and their properties are close to that of pure water: see
example on page 35. An example of an organic colloid is orange iuice.
+
Eor consistency with later examples in which heat of dilution effects are important. we read all the enthapies from
the steam tables. which have a reference state (where H is defined to be zero btu/lb) corresponding to saturated liquid
water at its freezing point. In Example 8.41 on p498. Geankoplis works a very similar problem in which all
enthalpies are calculated using the conditions of the liquor as the reference state. Then (by definition) H in (19) is
zero; the enthalpy of the feed H
f
differs from that of the liquor iust in sensible heat. which can be estimated as (8.4
9); and the enthalpy of the vapor H
v
differs from that of the liquor iust in latent heat (i.e. H
v
is iust the heat of
vaporization at the T.p of the vapor space). See the discussion on 'steam economy¨ on page 33. Try reworking
Example 8.41 evaluating the enthalpies appearing in (8.47) using the steam tables (as above): you should get very
nearly the same answer.
06361 page 31 Spring. 2001
at 70 °E:
+
H
f
÷ 38.09 btu/lb
m
But what is the temperature oI the liquor? Well. since the liquor is in equilibrium with the vapor.
their temperature and pressure should be the same. Since the vapor is iust saturated steam at 4
inHg. we look up its properties in the steam table:
p
v
÷ 4 inHg ÷ 1.97 psia
Irom App. A.29 (p858): T ÷ 125.1 °E
Interpolating the tables.
+
we obtain
at 125.1 °E: H
v
÷ 1115.7 btu/lb
m
and H ÷ 93.1 btu/lb
m
Substituting back into (19):
q
lb
hr
btu
lb
lb
hr
btu
lb
lb
hr
btu
lb
btu
hr
=
+
÷
= × + × ÷ × = ×
44 000 11157 11 000 931 55 000 38 09
491 10 010 10 0 21 10 480 10
7 7 7 7
. . . . . .
. . . .
Now. using the design equation. we can calculate the required area:
q ÷ UAAT
m
(20)
In a typical evaporator problem. steam is condensing on the shell side while water is evaporating
on the tube side. When a phase change occurs with a single component (water in this case). the
temperature stays at the boiling point. Thus the driving Iorce AT is practically constant along the
length oI the heat exchanger.
+
Strictly speaking. the enthalpies tabulated in A.29 are for saturated liquid. meaning that the pressure on the liquid
equals the vapor pressure. Here the pressure on the feed is probably 1 atm (or 14.7 psia) rather than 0.3622 psia (the
vapor pressure). Pressure has a very weak effect on the enthalpy of liquid water and the effect of pressure usually
neglected. Eor example. the effect of a change on pressure equal to 1atm on the enthapy of liquid water can be
estimated as
cm btu
1 atm 1 0.044
lb
H p J
g
 
A = A ~ =
]
\ ¹
which is equivalent to a change in temperature of only 0.044 °E. As long as we are dealing with much larger sensible
temperature changes. we can neglect the effect of pressure on the enthalpy of liquid water.
+
In working the homework assignments. you will have frequent need to perform this interpolation. A Mathcad
document has been prepared to assist you: http://www.andrew.cmu.edu/course/06202/Steamtab.mcd This file reads
the steam table from http://www.andrew.cmu.edu/course/06202/STEAMTAB.PRN. Links to both files can be
found at our homepage.
06361 page 32 Spring. 2001
However. some changes might still occur at either end
oI the heat exchanger. Eor example. steam might enter
superheated. meaning that it`s temperature is above the
boiling point. Until the temperature drops to the
boiling point. condensation does not occur. Similarly.
so much heat might be removed Irom the steam. that it
completely condenses and is then subcooled below the
boiling point. Einally. the Ieed solution has to be
heated up to its boiling point beIore evaporation
occurs.
v
The temperature proIile at right illustrates the
most general situation.
Eor a preliminarv design (which is all we will do in
this course). it is customary to approximate the 'true mean¨ MDT as:
AT
m
~ T
s
 T
where T
s
÷ T oI sat`d steam at p in steam chest
T ÷ T
bp
oI conc'd liquor at p in vapor space
Knowing the pressure oI the steam. we can Iind its temperature in the steam tables:
at 15 psig ÷ 29.7 psia: T
s
÷ 250°E
The heat oI vaporization ì
s
is the diIIerence between the enthalpy oI saturated vapor H
s
and the
enthalpy oI the condensate H
c
leaving (assumed here to be saturated liquid):
ì
s
÷ H
s
H
c
÷ 1164.2 btu/lb  218.6 btu/lb ÷ 945.6 btu/lb
The driving Iorce Ior heat transIer is the diIIerence in temperature oI saturated steam and
saturated vapor:
AT
m
~ T
s
T ÷ 250125 ÷ 125°E
Now everything in (20) is known except Ior A:
4 77 10 500 125
7
. × =
÷ ÷°
°
Btu
h
Btu
h It E
E
2
A
v
The heat required to preheat the feed from 70°E (the feed conditions) to 125°E (the boiling point at the pressure in
the vapor space) is
lb btu btu btu
55000 93.1 38.09 0.30 10
hr lb lb hr
  
÷ = ×
] ]
\ ¹\ ¹
This is only 6.3° of the heat duty q. We are willing to tolerate this size of error in our preliminary design.
0
Position in Hxer
L
T
e
m
p
e
r
a
t
u
r
e
Steam enters
superheated
Steam leaves
subcooled
Eeed solution
enters subcooled
T
s
T
06361 page 33 Spring. 2001
or A ÷ 768 It
2
The amount oI steam required is iust the heat duty divided by the latent heat oI the steam:
7
Btu
4.80 10
lb
h
50. 800
Btu
hr
945.6
lb
s
s
q
m
×
= = =
ì
`
Recall that our two main perIormance indicators were 'capacity¨ and 'economy¨. Capacity is
iust the rate oI evaporation. which will be the Ilowrate oI the vapor. Eor this example.
capacity = ` m
lb
hr
f
The economy is the mass oI vapor produced per mass oI steam consumed:
economy =
÷
= =
` `
`
.
.
.
m m
m
lb
hr
lb
hr
f
s
44 000
50 800
087
Steam Economv
Why is the economy less than one? The answer becomes clear. iI (instead oI looking up the
enthalpies oI water and its vapor in a table) we estimate them as sensible and latent heat. Eirst.
let`s select the liquor as the reIerence state Ior the calculations oI the enthalpies. Then
choose liquor as reIerence: H ÷ 0
The vapor is at the same temperature as the liquor so there are not sensible heat changes. but the
vapor has a much higher enthalpy owing to its heat oI vaporization:
H
v
÷ ì
Since the Ieed is also a liquid (like the liquor). its enthalpy diIIers Irom the liquor only in sensible
heat:
H
f
÷ c
p
(T
f
 T)
Substituting these enthalpies in (21):
f f p f s s
m m m c T T m ÷ ì ÷ ÷ = ì ` ` ` `
06361 page 34 Spring. 2001
or
1
f f
s
p f
s s
m m m
c T T
m m
<
÷
ì
= ÷ ÷
ì
` ` `
` `
Generally the heat oI vaporization oI water decreases with increases in temperature. Since the
steam must be hotter than the water being boiled. this means that ì
s
· ì. So the Iirst term in the
equation Ior economy is already less than one. The second term decreases it Iurther; this term
represents the energy required to preheat the Ieed up to the temperature oI the liquor where
boiling occurs. So a pound oI steam boils less than one pound oI water because some oI the
energy oI the steam is required to preheat the Ieed. However. even iI the Ieed were at the same
temperature as the liquor. a pound oI steam would boil less than one pound oI water because the
latent heat oI the hot steam is less than the latent heat oI the water being boiled.
OVERVIEW OF EVAPORATOR DESIGN
The design equation Ior evaporators can be summarized as
heat duty: ` ` ` ` ` m m H m H mH q m H H
f v f f s s c
÷ ÷ + = = ÷
vapor feed
liquor
steam
. .
.
(21)
HXer area: q ÷ U A AT
m
Eor preliminary designs. we can approximate
AT
m
~ const. ÷ T
s
 T
where T is the boiling point oI the liquor at the pressure in the vapor space. This is approximate
when there is signiIicant BPE because T will vary along the length oI the heat exchanger tube as
the concentration oI solute also changes.
 Evaluation oI enthalpies with negligible BPE and negligible heat oI dilution (example on
page 29 and also Example 8.41 on p498). Assuming the solvent is water. we can read the
enthalpies oI all three streams Irom the steam tables.
read T. T
s
. H. H
f
and H
v
Irom steam tables
 Evaluation oI enthalpies with complications (Example 8.43 on p501):
read H. H
f
Irom special table or chart
read T Irom Dühring chart; T
s
. H
v
Irom steam tables
+
+
Since enthalpies are being taken from more than one source. we should take care that the reference state is the
same for all tables and charts used in a given problem. The steam tables in Geankoplis use saturated liquid water at
32°E and 1 atm as the reference state. The enthalpy chart for NaOH solutions in Geankoplis also use 0 wt° NaOH
at 32°E and 1 atm as the reference state.
06361 page 35 Spring. 2001
COMPLICATIONS
BoilingPoint Elevation
Some complications arise in other evaporator problems because the enthalpy and partial
pressure oI a liquid more generally depends on its concentration as well as its temperature.
Whenever a solute is added to water. the partial pressure oI the water is reduced. Recall Raoult's
law Irom thermodynamics.
Roault`s law: p
i
(x
i
.T ) ÷ x
i
p
i
o
(T )
where p
i
÷ partial pressure oI component i
x
i
÷ mole Iraction component i
p
i
o
÷ vapor pressure oI pure i at some T
Note that adding any solute with water causes x
w
·1 so that
p
w
· p
w
o
In general. this implies that I must heat the solution up to a higher temperature (i.e. higher than
the b.p. oI pure solvent) beIore it will boil. This increase in boiling point due to addition oI
solute is called
boilingpoint elevation (BPE)  increase in b.p. due to addition oI solute
This eIIect can be quite signiIicant Ior concentrated solutions oI inorganic salts. Eor example. Ior
at a pressure oI 1 atm. the boiling point oI pure water is
1 atm. 0° NaOH in water: T
bp
÷ 212°E
II the pressure is other than 1 atm. the temperature can be read Irom the steam tables. Given this
boiling point Ior pure water. we can look up the boiling point oI solutions oI NaOH Irom a
Dühring chart (see p500 oI Geonkoplis):
50wt° NaOH in water: T
bp
÷ 283°E at 1atm
Note that the boiling point oI the solution is signiIicantly greater than the boiling point oI pure
solvent. BPE is a colligative property. which means
colligative propertv  depends on molar (not mass) concentration
Example: Use Raoult`s law to estimate the partial pressure oI water at 100°C oI a) a 50wt°
NaOH solution and b) a 50wt° suspension oI 'organic colloids¨ (use MW
average
÷ 1000 g/mol).
Estimate the BPE Ior each.
06361 page 36 Spring. 2001
Solution: To calculate the mole Iraction oI water in the solution. take 1 gram oI solution as a
basis. This 1 gram mixture consists oI 0.5 g oI water (MW ÷ 18) and 0.5 g oI NaOH (MW ÷ 40).
We calculate the corresponding number oI moles oI each and the mole Iraction:
NaOH (MW÷40) Organic Colloids
(MW÷1000)
x
w
05
05 05
0 690
.
. .
.
g
18
g
mol
g
18
g
mol
g
40
g
mol
+
=
05
05 05
1000
0 982
.
. .
.
g
18
g
mol
g
18
g
mol
g
g
mol
+
=
At 100°C (the b.p. oI pure water). the vapor pressure oI pure water is 1 atm (÷ p
w
o
). Using
Raoult`s law. the partial pressure is estimated as
p
w
0.690(1 atm) ÷ 0.690 atm 0.982(1 atm) ÷ 0.982 atm
To cause the solution to boil. the partial pressure must be raised to 1 atm. Eor the same mole
Iraction oI NaOH. this means raising the vapor pressure to
p
w
o
1
1450
atm
0.690
atm = .
1
1018
atm
0.982
atm = .
Using the steam tables (Appendix A.29). we Iind that the temperature has to be
T 110.0°C 100.8°C
Thus using Raoult`s law. the BPE is estimated to be
BPE Irom
Raoult`s law
110.0°C  100°C ÷ 10.0°C 100.8°C  100°C ÷ 0.8°C
OI course. this is only an estimate. Raoult`s law is only asymptotically correct as x
w
÷1. The
actual BPE is 39°C.
BPE
determined
Irom Eig.
8.42
283°E  212°E ÷ 71°E ÷
39°C
Although BPE is signiIicant Ior a lowmolecularweight solute like NaOH. the same 50wt°
concentration oI an "organic colloid" (e.g. orange iuice) may have a negligible BPE because the
molecular weight is much higher. Thus the same wt° gives a much smaller molar concentration
oI a highmolecularweight solute and thereIore a much smaller BPE.
06361 page 37 Spring. 2001
Heat of Dilution
II you dilute concentrated sulIuric acid by adding water. large quantities oI heat can be
released. II the mixing is adiabatic and both Iluids are initially at room temperature. the Iinal
temperature aIter mixing can by high enough to causing boiling. You were probably warned to
use great caution when diluting sulIuric acid in chemistry lab. The problem is that the enthalpy
oI a solution depends not only on its temperature. but also on its concentration:
H ÷ H(T.c)
which means you might need more than iust a heat capacity to calculate sensible heat changes.
Eig. 8.43 gives the enthalpyconcentration diagram Ior NaOH solutions.
Example: Suppose we dilute 1lb oI 50wt° NaOH solution at 70°E with 1lb oI pure water. also
at 70°E. What is the Iinal temperature iI the mixing is adiabatic?
Solution: read the enthapies oI the two solutions Irom 8.43:
H(50°. 70°E) ÷ 123 BTU/lb
H(0°. 70°E) ÷ 40 BTU/lb
Multiplying each by the corresponding weight and adding. we obtain the Iinal enthalpy oI the
mixture ('adiabatic¨ iust means that no energy is lost during mixing):
(123 BTU/lb)(1 lb) ¹ (40 BTU/lb)(1 lb) ÷ 163 BTU
Dividing by the mass oI the Iinal mixture. we obtain the enthalpy per pound:
163
815 25°.
BTU
2 lb
BTU
lb
= = = . ? H T
This represents the speciIic enthalpy oI the Iinal mixture. which we also know is 25wt°. Again
using Eig. 8.43. to get this H. we need to choose the temperature as
T ÷ 123°E
Thus the Iinal solution is warmer than the two initial solutions. due to the 'heat oI dilution.¨
Question: when diluting sulIuric acid (which also exhibits a signiIicant heat oI dilution). why is
is wiser to add (concentrated) acid to water. rather than water to (concentrated) acid?
We will now look at two methods to improve steam economy oI an evaporator:
1. multiple 'eIIects¨
2. vapor recompression
06361 page 38 Spring. 2001
MULTIPLE EFFECTS
In the simple evaporators we have dealt with so Iar. one
oI the product streams is water vapor also known as
steam. Why can`t this vapor be used in place oI steam? The
answer is simple: iI the vapor replaced the steam. there
would be no driving Iorce Ior heat transIer because the
'steam¨ and the vapor would have the same temperature. To
get a driving Iorce in the right direction. we have to use
steam with a higher pressure. One method oI making use oI
the latent heat oI the vapor is the compress it. We will look
at that option below. but Iirst let`s examine another option.
One way to improve economy is to divide the heat duty
among several evaporators which are piped together in such a way that the vapor produced by
one can be used to boil the liquid in another. This reduces the steam usage and improves
economy.
You can have any number oI evaporators connnected together in this way. Each evaporator in
this sequence is called an effect. and the entire sequence is called a multipleeffect evaporator.
In the Iigure above. we show a doubleeIIect evaporator. In order to maintain a driving Iorce Ior
heat transIer in each eIIect. we must have
T
2
· T
1
· T
s
This can be accomplished by having
+
p
2
· p
1
· p
s
This requires a vacuum pump or compressor:
+
Assuming we have saturated liquid and vapor in each effect. the pressure in any effect is iust the vapor pressure at
the temperature for that effect. Recall that vapor pressure increases with temperature.
J
L
06361 page 39 Spring. 2001
p
2
· p
1
+
AT
2
÷ T
1
 T
2
~ 0
q
2
÷ U
2
A
2
AT
2
(22)
OI course. we still have to supply steam to the Iirst eIIect
AT
1
÷ T
s
 T
1
~ 0
q
1
÷ U
1
A
1
AT
1
(23)
Eor simple designs where BPE and AH
dil
are negligible and where the sensible heat needed to
preheat the Ieed up to its boiling point is negligible. the same latent heat added to the vapor in the
Iirst eIIect is recovered by condensing in the second eIIect:
q
1
~ q
2
(24)
Usually the pressure in the last eIIect and the pressure oI the steam are known. Using the steam
tables. we can convert these pressures into temperatures. The unknowns are the temperatures
and pressure in the other eIIects.
Example: given T
s
and T
2
. Iind T
1
. Solution: (22) and (23) into (24) yields
U
1
A
1
(T
s
T
1
) ÷ U
2
A
2
(T
1
T
2
)
This represents one equation in one unknown (T
1
). assuming that the U`s and A`s are known.
II instead. we have N eIIects. the analog oI (22). (23) and (24) yield N1 equations in N1
unknowns. These equations are strongly coupled. A simpler approach is to try and solve Ior the
AT
i
`s instead oI the T
i
`s. We will illustrate this by resolving the last example. Erom (22) and
(23). we have
AT
q
U A
1
1
1 1
= (25)
and AT
q
U A
2
2
2 2
= (26)
Adding (14) and (26): AT
q
U A
q
U A
i
i =
= +
1
2
1
1 1
2
2 2
(27)
Dividing (25) by (27):
+
The expression for T which follows assumes that the vapor produced in the first effect condenses in the steam
chest of the second effect at the same temperature at which it boiled. If BPE is significant. the vapor will condense
at a lower temperature than it boiled (even if the pressure is the same). Why?
06361 page 40 Spring. 2001
A
A
T
T
q
U A
q
U A
q
U A
U A
U A U A
q q
1
1
1 1
1
1 1
2
2 2
1 1
1 1 2 2
1 2
1
1 1
=
+
¬
+
=
(28)
Since LAT can be easily calculated Irom the inIo given in the problem statement:
A A A T T T T T T T T T
s s
= + = ÷ + ÷ = ÷
1 2 1 1 2 2
(29)
we can easily calculate AT
1
Irom (28):
AT
U A
U A U A
T T
s 1
1 1
1 1 2 2
2
1
1 1
=
+
÷
The analog oI (24)  (29) Ior N eIIects are
(25): AT
q
U A
i
i
i i
= Ior i ÷ 1.2. ... N (30)
A
A
T
T
q
U A
q
U A
q
U A
q
U A
i
i
i i
N
N N
=
+ + +
1
1 1
2
2 2
.
Applying the analog oI (24) (q
1
÷ q
2
÷ ... ÷ q
N
÷ q). we can cancel out the q
i
. leaving:
A
A
T
T
U A
U A U A U A
i i i
N N
=
+ + +
1
1 1 1
1 1 2 2
.
(31)
Now the sum oI the driving Iorces can also be expressed as
A A A A T T T T
T T T T T T T T
T T
N
s N N N N
s N
= + + +
= ÷ + ÷ + + ÷ + ÷
= ÷
÷ ÷ ÷
1 2
1 1 2 2 1 1
.
. (32)
(32) into (31):
AT T T
U A
U A U A U A
i s N
i i
N N
= ÷
+ + +
1
1 1 1
1 1 2 2
.
Ior i ÷ 1.2. ... N
06361 page 41 Spring. 2001
In the simple case in which all the A`s are equal and all the U `s are equal. this last result reduces
to
AT
N
T T
i s N
= ÷
1
Ior i ÷ 1.2. ... N
In short. the total driving Iorce is divided equally among each oI the N eIIects.
Performance
Each eIIect results in the evaporation oI water at a rate equal to q/ì
i
. Summing the rate oI
evaporation in each eIIect. we obtain the total rate oI evaporation:
` m
q
J
i
i
i
N
=
=
ì
1
Steam is used only in the Iirst eIIect. The rate oI steam consumption in the Iirst eIIect is
` m
q
s
s
=
1
ì
The steam economy can then be calculated as
`
`
m
m
q
q
N
J
s
i
i
i
N
s
q q q
s
i
i
N
N
= ¬ ~
=
= = =
=
ì
ì
ì
ì
1
1
1
1 2
1
II we neglect changes in the latent heat with temperature and pressure. then all the ì`s are equal
and the sum reduces to N. II changes in the latent heat with temperature are considered. the sum
will be less than N.
Summary: Eor the same capacity. steam requirements are signiIicantly less Ior multipleeIIect
evaporators. than Ior singleeIIect evaporators: generally. the economy increases with the number
oI eIIects. The price that is paid Ior this increased steam economy is greater equipment costs:
generally the cost oI the equipment is proportional to the number oI eIIects.
Eor a single eIIect: economy · 1
Eor N eIIects: economy · N
The reason that the economy increased is that we need to supply steam only to the Iirst eIIect.
The source oI heat Ior 2
nd
. 3
rd
. ... N
th
eIIects is supplied by condensing the vapor produced in the
previous eIIect.
06361 page 42 Spring. 2001
VAPOR RECOMPRESSION
Multiple eIIects recover some oI the latent heat oI
the overhead vapor by using it in place oI steam to boil
the liquor in downstream eIIects. Is there any way we
can use the vapor in place oI steam in a singleeIIect
evaporator? The problem with using the vapor in place
oI steam is that the temperature oI the vapor is the
same as the temperature oI the liquor: the liquor and
vapor leaving the same eIIect are already in thermal
equilibrium with each other. In other words. there is no
driving Iorce Ior heat transIer.
without compression: AT ÷ T
s
 T ÷ 0
One way to increase the temperature oI the
vapor is to compress it. Eig. 1 shows how
adiabatic compression oI water vapor
(treated as an ideal gas) increases its
temperature.
+
Note that the temperature
rises Iaster with increases in pressure than
the boiling point increases. Thus adiabatic
compression oI a saturated vapor nearly
always produces a superheated vapor.
When heat is removed Irom this
compressed vapor. it will eventually
condense at its boiling point Ior that
pressure.
Increasing the pressure oI the vapor also
increases its boiling point. so that as the
vapor condenses. it stays at a high
temperature T
s
so we always have some
driving Iorce.
With compression: AT ÷ T
s
 T ~ 0
UnIortunately. raising the temperature and
pressure oI the vapor actually lowers its latent heat per pound
ì
s
· ì (because T
s
~ T)
+
Temperatures calculated from (7.30) in Smith & van Ness (4
ed.. p237).
Pressure (psia)
1 10 100
T
e
m
p
e
r
a
t
u
r
e
(
d
e
g
R
)
1000
Boiling Point
Fig. 1
Colored curves show how temperature
increases with adiabatic compression,
starting with saturated vapor at 1 psia
(green), 14.7 psia (red) or 400 psia
(yellow). For comparison, the boiling
point is shown by the black curve.
06361 page 43 Spring. 2001
so the vapor no longer has enough latent heat to boil the same mass oI liquid. Thus makeup
steam is required. although generally much less steam is needed than iI the vapor`s latent heat is
not recycled.
The reduction in steam is not without cost. We still have to pay the utilities (electricity or
steam turbine) to operate the compressor. Generally. compressors are expensive to buy.
maintain. and operate; so you have to do some economic calculations to see iI using a
compressor is economical. At the usual conditions oI an evaporator. the vapor can be treated as
an ideal gas. Then the work required Ior adiabatic compression can be estimated Irom
+
W
p p
p
pr
in
in
out
in
=
÷
÷
=
÷
¸
¸ p
1
1
1
1
 
Btu
lb
(33)
where 'out¨ and 'in¨ reIer to the outlet and inlet oI the compressor and where ¸ is the heat
capacity ratio. which is
for ideal gas
1.324
p p
v
p
c c
R
c
c
M
¸ ÷ = ~
÷
.
Ior water vapor using
c
p
÷ 0.45 Btu/lb°E.
R ÷ ideal gas constant ÷ 1.986 Btu/lbmolR ÷ 1.986 cal/molK
M ÷ mol. wgt. ÷ 18 lb/lbmol ÷ 18 g/mol
Now (33) gives the work needed to compress a unit mass oI gas. under ideal conditions (no
irreversible losses oI energy). To get the power requirements. we must multiply by the mass Ilow
rate and divide by the mechanical eIIiciency (n) oI the compressor:
P
m m W
f pr
=
÷
=
` `
 
n
÷
Btu
hr
kW
By compressing the vapor to raise its temperature. we are lowering its latent heat oI vaporization.
This means that. even iI we completely condense all the vapor. we still won`t have enough latent
heat to boil the liquor at its lower temperature. The diIIerence must come Irom makeup steam.
To estimate the makeup steam requirements. let`s return to the design equation (19) Ior the total
heat duty:
+
See Smith & van Ness. 4
ed.. footnote on page 238.
06361 page 44 Spring. 2001
q m m H m H mH
f v f f
= ÷ ÷ + ` ` ` `
vapor feed
liquor
.
.
In the simple case where BPE and AH
dil
are negligible (i.e. Ior inorganic colloids). H
f
and H
diIIer Irom the enthalpy oI saturated liquid only in sensible heat. To the extent that sensible heat
is negligible.
+
we can substitute the enthalpy oI saturated liquid Ior H
f
and H:
q m m H m H mH
m m H m m H
m m H H
m m
f v f L L
f v f L
f v L
f
= ÷ ÷ +
~ ÷ ÷ ÷
= ÷ ÷
= ÷
` ` ` `
` ` ` `
` `
` `
ì
heat to boil vapor: q m m
f
~ ÷ ` `
ì (34)
This heat duty is partially oIIset by the latent heat recovered by condensing the compressed
vapor. The remainder comes Irom make up steam:
q m m m
f s s s
= ÷ + ` ` `
ì ì
compressed vapor
make up steam
.
.
(35)
where we are assuming we are compressing the vapor to the same pressure as the makeup steam.
Eliminating q between (34) and (35). we can solve Ior the steam requirements:
` ` ` m m m
s f
s
~ ÷ ÷
ì
ì
1
Notice that any compression allows us to recover all the latent heat oI the vapor. thus
signiIicantly reducing steam consumption without compression. However greater compression
actually increases steam consumption (because ì
s
decreases with pressure). Rearranging this
expression. we can calculate the economy:
1
f
s
s s
m m
m
÷
ì
~ >>
ì ÷ ì
` `
`
+
Sensible heat is often negligible compared to latent heat. To see why. note that the latent heat of vaporization of
water at 1atm. 212°E is 970.3 btu/lb. where 1 btu is the amount of sensible heat required to raise the temperature of
one lb of water 1°E. This means that. for sensible heat to equal latent heat. I need to raise the temperature of water
970°E. A temperature rise of only 30°E. say. represents a sensible heat change of 30/970 or 3° of the latent heat of
water. This is an estimate of the relative error made in this estimate of
m .
06361 page 45 Spring. 2001
which is now very much greater than unity. However. this way oI computing economy is unIair
because the reduction in steam consumption is at the cost oI operating the compressor. In
computing the 'economy¨ Ior an evaporator with vapor recompression. it is customary to add an
equivalent steam rate Ior the compressor to the makeup steam rate beIore dividing into the
capacity.
 II the plant uses a steampowered turbine or iI the plant uses steam generators to make its
own electricity. then the apparent steam usage is
btu hr lb
   
btu lb hr
s s
app
s s
P
m m = + = =
' ì n
` `
where P is the electrical power supplied to the compressor.
s
' ì is the latent heat oI the steam
used (the prime is added because the pressure oI the steam used here might be diIIerent Irom
that used in the evaporator) and n
s
is the eIIiciency oI electricity generation Irom steam
(typically 0.35).
 On the other hand. iI electricity is purchased Irom a utility to drive the compressor. then it
makes sense to convert the electricity usage into an equivalent amount oI steam (on a
Iinancial basis):
` `
$
m m P
s
app
s
= + ×
$
kW hr
lb oI stm
II P is in kW then the last term yields lb/hr oI steam.
Regardless oI which method oI converting the power usage is appropriate. the economy is
computed as:
economy ÷
÷ ` `
`
m m
m
f
s
app
In Hwk #3. Prob. 5. we will consider the trade oII
oI operating costs (direct steam usage plus
electricity Ior compressor) and capital costs (heat
exchanger area) as a Iunction oI the output
pressure oI the compressor. The results are
summarized in the graph at right. which shows
that an optimum pressure exists at which total
costs are minimized. Notice that both power
requirements Ior the compressor as well as steam
usage increase with pressure. Only when the cost
oI the heat exchangers is considered does an optimum exit.
$0
$50,000
$100,000
$150,000
$200,000
$250,000
$300,000
15 20 25 30
Pressure of compressed vapor
(psia)
C
o
s
t
s
(
$
/
y
e
a
r
)
Hxer area
electricity
steam
total
06361 page 46 Spring. 2001
Chapter 6. VaporLiquid Equilibrium
ReIerence: Smith & Van Ness. 4th Ed.. Sect. 10.5
Today we switch Irom heattransIer operations (heat exchange. evaporation. condensation) to
masstransIer operations (distillation. extraction. absorption. humidiIication). Instead oI sizing
equipment to exchange heat between two phases we will size equipment to exchange mass
between two phases.
NO. OF PHASES PRESENT
Suppose I have an apparatus like that shown in the Iigure
at right in which I can place an arbitrary mixture oI
components and control the temperature and pressure. How
many phases will be present at equilibrium?
One Component
Eor example. suppose I put iust water in the piston at 1
atm and room temperature (say 70 °E) Just one component
no air! Is the water liquid. solid. or vapor? We know Irom
our own experience that water is a liquid near room
temperature. Thus we have iust one phase present at equilibrium.
+
II I repeated this experiment at 250 °E. we would have the water present as all vapor again
I have iust one phase present. Only iI the temperature corresponds to the boiling point (212 °E)
will I have two phases present. II I repeated the experiment at some other pressure there will be
only one temperature at which two phases are present.
The relationship between temperature and
pressure Ior which two phases coexist at equilibrium
is called the vapor pressure curve. This diagram
summarizes all the vaporliquid phase behavior Ior a
onecomponent system.
1wo Components
Now suppose I put two components in the pot:
let`s say a mixture oI nheptane (C
7
) and noctane
+
If air were present as a second component. we would also have a gas phase.
06361 page 47 Spring. 2001
(C
8
). which are important components in gasoline. The vaporliquid phase behavior oI two
component systems is a little more complicated. because I have an additional variable
composition as well as T and P. Instead oI a single temperature at which both liquid and
vapor can coexist. there is a range oI temperatures.
At a given pressure. we can summarize the phase
behavior by means oI a Txv diagram like that shown at right.
To understand the meaning oI this diagram. consider what
happens iI we charge the piston with a mixture oI heptane
and octane having a particular composition. II the
temperature is low enough. we will have iust one phase:
liquid.
As we heat this mixture to the temperature corresponding
to the lower curve. we would begin to see bubbles oI vapor
Iormed in the liquid as more heat is added. This temperature
at which the bubbles Iirst Iorm is called the
bubble point when heating a subcooled liquid. the
temperature at which the Iirst bubble Iorms
The composition oI this Iirst bubble can also be read Irom
the Txy diagram. In general. the vapor will be richer than
the liquid in one component and leaner in the other. This
diIIerence in composition oI the vapor and liquid can serve
as the basis Ior separating two or more components oI a
mixture. By completely condensing the vapor. I produce a
liquid which is richer in one component than the original
liquid. Thus I have achieved a degree oI separation oI the
two components.
Eor a binary system having two phases. we denote the composition oI the liquid and vapor using
x and v:
x ÷ mole Iraction oI more volatile component
+
in liquid phase
v ÷ mole Iraction oI more volatile component in vapor phase
Keep in mind that liquid and vapor must have the same temperature at equilibrium. The line
connecting the two points representing vapor and liquid is called a tie line. It`s horizontal on a
Txy diagram.
+
By 'more volatile component¨ we mean that component which has either 1) the higher vapor pressure at a given
temperature. or 2) the lower boiling point for a given pressure. Example: for a mixture of C
7
(heptane) and C
8
(octane). heptane has the lower normal boiling point and so heptane is the more volatile component.
06361 page 48 Spring. 2001
As we continue to heat the mixture. the liquid becomes less
rich in the more volatile component since the more oI the
more volatile component is leaving Ior the vapor phase. The
compositions oI the liquid and vapor move along the heavy
solid line shown in the Iigure at right. The highest
temperature at which liquid remains is called the
dew point when cooling a superheated vapor. the
temperature at which the Iirst drop oI dew
Iorms
Eventually. as we continue to heat. all the mixture ends up in
the vapor.
+
IDEAL SOLUTIONS OBEY RAOULT`S LAW
ReIerence: Smith & Van Ness. Example 10.1 (p305)
Now let`s try to predict the Txy diagram Ior the simplest case: an ideal
solution in equilibrium with an ideal gas. So let`s suppose we are at some
temperature Ior which both phases coexist at equilibrium.
Let P
i
´ ÷ vapor pressure oI pure i
P ÷ total pressure
x
i
.v
i
÷ mole Iractions in liq or vapor at equil.
p
i
÷ v
i
P ÷ partial pressure oI component i
Raoult's law: p
i
÷ x
i
P
i
´
IDEAL BINARY MIXTURES
What we have said so Iar about ideal solutions applies to any number oI components. Let's now
restrict our attention to systems with only two components. which we will call A and B.
The mole Iractions must sum to one Ior each phase. so we can express the mole Iraction oI B in
terms oI that Ior A:
x
B
÷ 1x
A
+
The vertical line in left margin indicates that this material was not covered during class. I do however expect you
to read it and you will be responsible for this material on the exams.
v
i
x
i
06361 page 49 Spring. 2001
v
B
÷ 1v
A
Applying Raoult's law to each component:
p
A
÷ v
A
P ÷ x
A
P
A
´ (36)
p
B
÷ (1v
A
)P ÷ (1x
A
)P
B
´ (37)
Adding the partial pressures Irom (36) and (37) we obtain the total pressure:
P ÷ p
A
¹ p
B
÷ x
A
P
A
´(T) ¹ (1x
A
)P
B
´(T)
Solving Ior the mole Iraction x
A
: x
A
÷ (PP
B
´)/(P
A
´P
B
´) (38)
Irom (36): v
A
÷ x
A
P
A
´/P (39)
Keep in might that the vapor pressures in these equations depend on temperature. So iI you
speciIy a T and P. I can determine the vapor pressures and calculate the composition oI the vapor
and liquid which will be at equilibrium.
Given: T.P
Look up: P
A
´(T) and P
B
´(T)
Calculate: x
A
.v
A
Irom (38) and (39)
Thus I can construct a complete phase diagram Ior the mixture using only vaporpressure data Ior
the pure components.
Example.
v
nheptane and noctane Iorm a nearly ideal mixture. Use Raoult's law to construct a
phase diagram at constant pressure (1 atm).
Solution. We Iirst look up the normal boiling points oI the two pure components.
component 1
bp
(° °° °C) denoted by
nheptane 98.4 A
noctane 125.6 B
v
Illustration 9.1 from Treybal. A similar example is 10.1 from S&VN (p305).
06361 page 50 Spring. 2001
We choose the "low boiler" as
component A since it has the larger
vapor pressure over this range oI
temperatures. Next. we choose a
temperature between the two boiling
points. look up vapor pressures oI the
pure components and substitute into (38)
and (39). The results are summarized in
the table at right and the graph below.
98
100
102
104
106
108
110
112
114
116
118
120
122
124
126
0 0.2 0.4 0.6 0.8 1
mole fraction of heptane
T
e
m
p
e
r
a
t
u
r
e
(
d
e
g
C
)
Liquid
Vapor
L&V
1 (°C) P'
(mmHg)
P'
(mmHg)
x v o oo o
98.4 760 333 1.000 1.000 2.28
105 940 417 0.656 0.811 2.25
110 1050 484 0.488 0.674 2.17
115 1200 561 0.311 0.492 2.14
120 1350 650 0.157 0.279 2.08
125.6 1540 760 0.000 0.000 2.03
06361 page 51 Spring. 2001
XY AND TXY DIAGRAMS
The Txy diagram is a convenient graphical method
Ior summarizing vaporliquid equilibrium (VLE) data at
a particular pressure. Eor binary mixtures. we usually
denote the mole Iraction oI the more volatile component
as x in the liquid phase as as v in the vapor phase. Eor
this particular choice oI x and v. the Txy diagram will
always slope downward as shown at right.
Erom the Txy diagram. one can construct an 'xy¨
diagram. which is the one we will use in distillation
calculations. The xy diagram is shown at right. Eor xy
diagrams which resemble is one. the relationship
between x and v can be sometimes be represented by a
single number: the relative volatilitv. which is deIined as
i
ii
i
K
K
o ÷
where the K `s are called the distribution coefficient.
which in turn are deIined as:
i
i
i
v
K
x
÷
Since this term is also useIul in mixtures having more than two components. we will use
subscripts to denote components. Generally the most volatile component will have the largest
distribution coeIIicient and will have its concentration increased (in the vapor compared to the
liquid) by the largest percentage. The ratio oI the distribution coeIIicients oI two components is
the relative volatility.
T
mole Iraction oI A
T
bp,A
T
bp,B
x
x
v
v
06361 page 52 Spring. 2001
NONIDEAL BEHAVIOR
Fig. 2. Txy and xy diagrams for nonideal systems. On left is carbon disulfide in acetone at
one atmosphere pressure. On right is acetone in chloroform. Taken from Treybal, 2
ed.,
pages 290 and 295.
Examples Txy and xy diagrams Ior binary mixtures which display signiIicant nonideal behavior
are illustrated in Eig. 2. In particular notice that the curve on the xydiagram can cross the 45°
line. This point oI crossing is called an azeotrope:
azeotrope  vapor and liquid have the exactly the same composition at equilibrium (i.e. v ÷ x)
The occurance oI azeotropes can pose diIIiculty Ior distillation since producing a new phase by
condensation or by evaporation produces no separation oI components.
06361 page 53 Spring. 2001
Chapter 7. Flash Distillation
Now let`s apply these concepts about vaporliquid
equilibria to distillation. The simplest device Ior continuous
distillation oI some liquid Ieed is the 'Ilash unit.¨ This is
iust a HXer to add enthapy oI the Ieed and a chamber to
allow the vapor and liquid to separate. The schematic at
right is the same as that used Ior evaporation. however the
vapor now contains all oI the components not iust the
'solvent¨.
Given the Ieed composition and the amount oI heat
added to the Ieed. we would like to determine the
composition and Ilowrates oI the distillate and bottoms
products.
Given: F. x
F
and q
Eind: D. B. v
D
and x
B
The mole and enthalpy balances are: F ÷ D ¹ B (40)
x
F
F ÷ v
D
D ¹ x
B
B (41)
H
F
F ¹ q ÷ H
D
D ¹ H
B
B (42)
where F.D.B are total molar Ilowrates oI each stream and x and v are mole Iractions oI the more
volatile component. The remaining equation comes Irom requiring the vapor and liquid products
to be at equilibrium:
(x
B
. v
D
) lies on equil.curve (43)
(40)(43) represent Iour equations in the Iour unknowns.
APPROXIMATE SOLUTION
The solution to these Iour equations can be obtained in a number oI ways. Let's start with the
simplest method. In many cases. the molar heat oI vaporization is nearly the same Ior both
components.
(Eor this reason. we tend to solve all distillation problems using mole Iraction
rather than mass Iractions. and express enthalpies per unit mole rather than enthalpy per unit
mass.) II you can assume that the molar heat oI vaporization oI the mixture is completely
independent oI its composition. then solution is quite easy:
 Assume H
D
H
B
÷ const. say AH
v
÷ Btu/mol (independent oI v
D
)
 neglect sensible heat compared to latent heat
J
L F
F
x
H
D
D
x
H
B
B
x
H
q
06361 page 54 Spring. 2001
Let's choose saturated liquid having the composition oI the Ieed as our reIerence state Ior
enthalpies. Then
H
F
÷ H
B
÷ 0
and H
D
÷ AH
v
Even iI the liquid is not saturated liquid. its enthapy diIIers Irom that oI saturated liquid only
through sensible heat. which is neglected here. The Iirst equality is the result oI neglecting
sensible heats
Then (42) reduces to: q ~ AH
v
D (44)
Now we can deIine and solve Ior the Iraction oI the Ieed that is vaporized:
f
D
F
q
H F
v
÷ ~
A
which can be considered known. We will now express the molar Ilowrates in terms oI this f:
Dividing (40) by F and rearranging:
B
F
D
F
f = ÷ = ÷ 1 1 (45)
Dividing (41) by F: x v f x f
F D B
= + ÷ 1 (46)
Solving Ior v
D
: v
f
f
x
x
f
D B
F
=
÷
+
1
(47)
which is a straight line on the xv diagram. To
plot this line. we need to know the slope and one
point which lies on the line.
slope ÷
f
f
÷1
To obtain one point. we can substitute an
arbitrary value in Ior x
B
. say we substitute
x
B
÷x
F
. Then (47) becomes
v
f
f
x
x
f
x
D F
F
F
=
÷
+ =
1
Thus one point on the line given by (47) is
one point: (x
B
. v
D
) ÷ (x
F
. x
F
)
06361 page 55 Spring. 2001
Knowing one point and the slope. we can draw the line. In eIIect. this line represents the
relationship between v
D
and x
B
which is imposed by the mass and energy balances Ior a given q
(or a given f) and Ior the given assumptions on calculating enthalpy. We call this line the
operating line: relationship between v
D
and x
B
which is imposed by the mass and
energy balances
To Iind which point on this line is the solution Ior a given q. we need also to satisIy (43). which
represents phase equilibrium. This relationship is a curve on the xv diagram. known as the
equilibrium curve: relationship between v
D
and x
B
which is imposed by vapor
liquid equilibria
The intersection oI operating line and the equilibrium curve satisIies all Iour oI the original
equations and yields the answer.
Inverse LeverArm Rule on 1xv Diagram
There is also a simple graphical procedure Ior estimating the
Iraction vaporized on a Txy diagram. Suppose you are given a
Ieed composition and (instead oI speciIying the Iraction evaporat
ed) the Iinal temperature oI the mixture at equilibrium. Then you
can locate a point (x
F
. T) on the Txy diagram. A horizontal line
through this point intersects the vapor and liquid curves at the
composition oI those phases: (x
B
. T) and (v
D
. T).
As it turns out. the amount oI vapor produced is inversely
proportional to the distance between the Ieed point (x
F
. T) and the
vapor point (v
D
. T). Similarly. the amount oI liquid remaining is
inversely proportional to the distance between the Ieed point (x
F
. T) and the liquid point (x
B
. T).
More precisely. the ratio oI vapor D to liquid B Ilowrates in an continuous Ilash unit is given by
D
B
x x
v x
F B
D F
=
÷
÷
(48)
where D. B and F are proportional to the distances
indicated on the Txy diagram above. Because oI the
inverse nature oI this relationship. this is called the
inverse leverarm rule. As a useIul analogy. think oI
the Ilowrates as being like masses being balanced on a
beam. resting on a Iulcrum (see sketch at right). The
Iurther the mass is Irom the pivot. the small the mass
can be. At (mechanical) equilibruim:
T
x
B
v
D
x
F
D
B
F
l
1
l
2
M
1
M
2
06361 page 56 Spring. 2001
1 1 2 2
M l M l = or
1 2
2 1
M l
M l
=
Notice the inverse relationship between the mass and the distance Irom the pivot. Now we will
try to prove (48):
Proof:
Solving (46) Ior f: f
D
F
x x
v x
F B
D B
÷ =
÷
÷
(49)
Substituting into (45):
B
F
D
F
x x
v x
v x
v x
F B
D B
D F
D B
= ÷ = ÷
÷
÷
=
÷
÷
1 1 (50)
Dividing (49) by (50). we obtain (48).
RIGOROUS SOLUTION
Although the approximate solution works reasonable well Ior some mixtures. Ior others it
might not be good enough. Then you will need a lot more thermodynamic data besides latent
heat and heat capacity. You will need an Hxv
diagram.
An Hxv diagram is at least superIicially
similar to a Txv diagram in that it gives you
some idea oI the thermal condition oI the
mixture as a Iunction oI composition. except
that instead oI T on the vaxis. we have H.
At right we show the Hxv diagram which
would apply iI 1) the molar heats oI
vaporization oI the two components are equal.
and 2) sensible heat is negligible compared to
the latent heat: two parallel. horizontal lines.
Below it is an Hxv diagram Ior a real mixture.
Unlike a Txv diagram. the saturated liquid and
saturated vapor curves do not connect at the ends or
at any other composition. The vertical distance
between these two curves represents the latent heat
oI vaporization at a particular composition. which
is usually substantial Ior all compositions. Unlike
temperature. enthalpy oI liquid and vapor will be
quite diIIerent. so the tie lines are not horizontal
l I ti A
B
enthalpy
per mole
A B
ideal case
sat`d vapor
sat`d liquid
v
06361 page 57 Spring. 2001
like on a Txy diagram. In Iact. tie lines tend to be more nearly vertical.
As we shall soon see. we will need to determine the tie line through a particular point. No matter
how many tie lines your graph has. it would be a real stroke oI luck iI one passes through the
particular point speciIied. So we need some way to interpolate tie lines. This is accomplished by
means oI:
auxiliarv line  a curve on an Hxy diagram Ior interpolating tie lines
II we Iorm a right triangle out oI each tie line. then the locus oI the points where the right angle is
located is the auxiliary line. OI course. the ends oI the auxiliary line coincides with the ends oI
the saturated vapor line. By reversing this procedure. we can locate more tie lines.
Now let's see how this diagram can be use do solve our Ilash distillation problems. Eirst. I will
give you the receipe and then later I will show why
the receipe works.
receipe:
 locate the Ieed point (x
F
.H
F
)
 locate a second point q/F above the Ieed point
(x
F
.H
F
¹q/F)
 Iind the tie line which passes through this
second point
 ends oI the tie line are (x
B
.H
B
) and (v
D
.H
D
).
 f can be determined with the help oI (49):
f
z x
v x
F B
D B
=
÷
÷
Proof: now let's show that this procedure really works.
The main idea which we need to prove is that the point (x
F
. H
F
¹q/F) call this point 'E¨ lies on
the tie line. We know that (x
B
. H
B
) call this point 'B¨ and (x
D
. H
D
) call this point 'D¨ lie on
the tie line since the two streams leaving the Ilash unit must be in phase equilibrium with each
other. Our approach will be show that the slope oI the line drawn Irom B to E is the same as the
slope oI the tie line drawn Irom E to D.
Substituting (40) into (41): x
F
(D¹B) ÷ v
D
D ¹ x
B
B
Dividing by D and solve Ior B/D:
B
D
v x
x x
D F
F B
=
÷
÷
(51)
06361 page 58 Spring. 2001
Divide (42) by F: H
q
F
D
F
H
B
F
H
F D B
+ = +
Using (40) to eliminate D:
H
q
F
B
F
H
B
F
H H
B
F
H H
F D B D D B
+ = ÷
+ = ÷ ÷ 1
Solving Ior B/F:
B
F
H H
q
F
H H
D F
D B
=
÷ +
÷
(52)
II instead. we had used (40) to eliminate B:
D
F
H
q
F
H
H H
F B
D B
=
+
÷
÷
(53)
(52) ÷ (53):
B
D
H H
q
F
H
q
F
H
D F
F B
=
÷ +
+
÷
(54)
Equating (51) and (54). we could show that:
H H
q
F
v x
H
q
F
H
x x
D F
D F
F B
F B
÷ +
÷
=
+
÷
÷
Note that both sides oI this equation have the Iorm oI rise/run on an Hxv diagram; thus each side
represents the slope oI a line drawn between two points on an Hxv diagram. These two slopes
involve three distinct points:
(x
B
.H
B
); (x
F
.H
F
¹q/F); and (v
D
.H
D
)
The equality oI these two slopes means that these three points must lie on the same line. That
line connecting B and D must be a tie line. The conclusion is that
(x
F
.H
F
¹q/F) lies on tie line
This is the basis Ior the receipe.
06361 page 59 Spring. 2001
Inverse LeverArm Rule on Hxv Diagram
(54) provides a basis Ior an inverse leverarm rule
which is similar to (48). The total diIIerence in
enthalpy between saturated vapor and saturated liquid
is H
D
H
B
.
+
This diIIerence can be partitioned into
(H
F
¹q/F)  H
B
and H
D
 (H
F
¹q/F). Thus the red tie
line can be divided into two parts which are
proportional to this diIIerence in enthalpies. (54) says
that ratio oI the lengths oI these two parts oI the tie
line equal the molar Ilowrate ratio B/D.
BATCH (DIFFERENTIAL) DISTILLATION
The oldest device Ior distillation consisted oI a
kettle into which a liquid mixture was placed. By heating
the kettle either by Iire or steam or electrically. the liquid
is partially vaporized. AIter condensing the vapor. you
have a product which is richer in one oI the components.
II both oI the components are volatile (e.g. ethanol and
water). it wouldn't make sense to vaporize all oI the
liquid in the kettle. A mass balance can tell you that. iI
you vaporize the entire charge. the cumulative condensate
composition will be essentially the same as the initial
charge. Oh. perhaps you have removed some nonvolatile
minerals which might have been in the water. but you
won't enrich the ethanol concentration in this way. And
enriching the composition oI the more volatile component is the obiective oI distillation.
The solution is to evaporate only partially. because the Iirst vapors which come oII will be the
richest in the more volatile component. Vapors produced later will only dilute the condensate.
This process is called batch distillation because we process one batch at a time rather than
continously processing as with Ilash distillation.
Let's now try to predict how the composition oI the liquid and vapor change as we evaporate
more and more oI the charge.
Let n
A
(t). n
B
(t) ÷ moles oI component A or component B leIt in liq.
n(t) ÷ n
A
(t) ¹ n
B
(t) ÷ total moles oI liq. leIt in kettle at time t
+
H
D
H
B
is not the 'heat of vaporization¨. which is the heat to totally vaporize one mole of feed. On the Hxy
diagram. heat of vaporization is the length of a vertical line between the two curves.
steam
kettle
(still)
condenser
condensate
collector
cooling
water
n. n . x
A
v
cond
x
06361 page 60 Spring. 2001
A
n t
x t
n t
= ÷ mole Iraction oI A in liq. remaining (55)
v(t) ÷ instantaneous mole Iraction oI vapor produced
Suppose we evaporate a small amount oI liquid at time t over a time interval dt:
n(t¹dt)  n(t) ÷ dn · 0
dn ÷ total moles evaporated in time dt
A Iraction oI this is component A:
dn
A
÷ v(dn) (56)
(55) into (56): d(xn) ÷ v(dn)
xdn ¹ ndx ÷ vdn
ndx ÷ (vx)dn
dn
n
dx
v x
=
÷
Integrating Irom t÷0. at which time x.n have their initial values:
x(0) ÷ x
0
and n(0) ÷ n
0
to some later time. at which time x.n have values:
x(t) and n(t)
we obtain
dn
n
dx
v x
n
n t
x
x t
0 0
( ) ( )
=
÷
Integrating: ln
n
n t
dx
v x
x t
x
0
0
( )
=
÷
( )
Solving Ior n(t):
0
0
exp
x
x t
dx
n t n
v x
= ÷
÷
06361 page 61 Spring. 2001
which is called Ravleigh's equation. This serves as the design equation
Ior batch distillation. To use this equation. we must recall that the vapor
coming out oI the kettle at any time is in equilibrium with the remaining
liquid:
at equilibrium: v ÷ f(x)
Eor each x between x(0) and x(t). we can look up the
corresponding v(t) and compute the integrand in
Rayleigh's equation 1/(vx). The integral is the area
under the curve between these two limits.
Example: A 50mol° mixture oI heptane and octane
is placed in a batch and heated. Plot the composition
oI the remaining liquid as a Iunction oI the Iraction oI
the initial charge which remains. At the pressure in
the still. the vaporliquid equilibrium can be
reasonably represented by a constant relative
volatility oI o ÷ 1.7 (Ior a discussion on when this might arise. see p105).
Solution: Eor binary solutions. it's customary to deIine x and v to be the mole Iraction oI the
more volatile component (heptane in this case); this choice yields relative volatilities greater than
unity.
We will have to guess values oI x(t). Below we go through the procedure Ior one particular
guess. say x÷0.2.
Step 1:Guess x. We expect the vapor to be richer in the more volatile component
Step 2:Calculate the corresponding v. Recalling the deIinition oI relative volatility (see page
51):
v
x
1
v x
x t ( )
x
0
dx
v x
x t
x
06361 page 62 Spring. 2001
1 1
i i i
ii
i i i
K v x v x
K v x v x
o = = =
÷ ÷
Dropping the subscripts and solving Ior v:
1 1
x
v
x
o
=
o ÷ +
This Iunction is evaluated Ior o÷1.7 and plotted in the
Iigure at right. Eor x÷0.2. this yields. v÷0.298.
Step 3:We evaluate n/n
0
Irom Rayleigh's equation:
0.5
0
0.2
exp
n t dx
n v x
= ÷
÷
The integral is evaluated by assuming x's between 0.2 ·
x · 0.5. The integrand is plotted in the Iigure at right.
The area under the curve between the two dotted lines
is
0.5
0.2
2.45
dx
v x
=
÷
Rayleigh's equation yields
0.5
0
0.2
exp 0.086
n t dx
n v x
= ÷ =
÷
This represents the Iraction oI the initial charge which remains in the still as liquid. The Iraction
oI the initial charge which has been distilled is iust unity minus this
0
1 0.914
n t
n
÷ =
0 0.5 1
0
0.5
1
x
1.7
0 0.5 1
0
5
10
15
1
y
i
x
i
0.2 0.5
x
i
06361 page 63 Spring. 2001
Step 4:Calculate the condensate concentration
II all the condensate is collected in a container
and mixed together. the average concentration oI
the condensate will be
0 0
0
moles oI A depleted
total moles depleted
0.528
cond
x
x n xn
n n
=
÷
= =
÷
The graph at right shows what typically happens
as the initial liquid is more and more distilled.
Notice that the vapor is initially richer than the
liquid. Since the leaving vapor is richer. the
remaining liquid becomes leaner. Thus both x
and v become leaner as distillation proceeds.
0 0.5 1
0
0.2
0.4
0.6
0.8
x(t)
y(t)
xbarcondensate
x(0)
fraction of initial charge distilled =
[n(0)n(t)]/n(0)
06361 page 64 Spring. 2001
Chapter 8. Multistage Operations
In both batch distillation and Ilash distillation. the separation oI the two components is limited by
equilibrium. Eor example. suppose I have a 5050 mixture oI hexane and octane. II I vaporize
halI oI this mixture. I produce a vapor having:
x
F
÷0.5. f÷D/E÷0.5 ÷ v
D
÷0.55. x
B
÷0.45
which we read oII oI an xy diagram. Suppose you want a 95°
pure product? II I vaporized a smaller Iraction oI the Ieed.
that would increase the composition oI the distillate. but the
best I can do is:
x
F
÷0.5. f~0 ÷ v
D
÷0.58. x
B
÷0.5
This helps a little but it's still a long way Irom 0.95 and you
don't generate much product with such a small Iraction
vaporized.
One solution is to take the distillate product oI the Iirst Ilash
and partially condense it. This will produce a liquid phase which will be leaner in the more
volatile component. leaving the remaining vapor richer.
This could be repeated many times until the vapor composition reaches or exceeds the desired
value. Although we have produced a stream oI the desired composition. it turns out that we are
"throwing out" alot oI the desired component in the "waste" streams  the bottoms.
Erom the Iirst Ilash unit alone. we are losing 25° oI component A in the initial Ieed (1f)x
1
~
0.25. II this component A is valuable. we don't want to throw it away.
 success at achieving high v
D
. but low recovery (recovery is ° oI A in Ieed which
ends up on Iinal product)
06361 page 65 Spring. 2001
 requires n¹1 HX'ers
Another problem is that each Ilash unit requires a heat exchanger and then we will need one
additional heat exchanger to condense the product Irom the Iinal Ilash unit.
COUNTERCURRENT CASCADE
Both oI these drawbacks can be removed by a slight modiIication: we recycle the bottoms oI
one Ilash unit into the Ieed oI the previous Ilash unit.
Instead oI n¹1 HXers. we now need only two. To condense the vapor. we need to transIer some
oI its latent heat to the liquid recycled Irom upstream. Eor this to work. the temperature oI the
vapor must be greater than that oI the liquid. Let`s see: generally. the vapor will get richer in the
more volatile component as we move leIt to right:
v
1
· v
2
· ... · v
N
Assuming that the vapor and liquid streams leaving each Ilash
are in equilibrium. then the corresponding inequalities Ior
temperature can be deduced Irom the typical Txy diagram at
right:
T
1
~ T
2
~ ... ~ T
N
So the recycled liquid will be cooler than the vapor it's mixed
with. Thus the liquid will absorb some oI the heat oI the vapor.
This condenses some oI the vapor and vaporizes some oI the
liquid. Now that we have shown that the heat exchangers
might be eliminated. let`s return to a discussion oI the countercurrent cascade.
The product recovery Ior a countercurrent cascade is much better than Ior the series oI Ilash
units without recycle. Eirst. we have only one waste stream (B)  instead oI one Irom each Ilash.
Second. the composition oI this waste stream will usually turn out to be leaner in the valuable
component  because we are enriching the Ieed to the Iirst Ilash by recycling Irom upstream.
06361 page 66 Spring. 2001
Note that we also recycled some oI the product liquid to condense the vapor Ieed to the last stage.
This recycling oI the product is called
reflux  that part oI the product stream recycled to the cascade
reflux ratio  L
a
/D (ratio oI molar Ilowrates)
stage  one unit oI a cascade (e.g. one Ilash unit)
ideal stage  a stage whose exit streams are at equilibrium
06361 page 67 Spring. 2001
Chapter 9. Equipment for Tray Towers
In our schematic oI a countercurrent cascade. we had the streams moving horizontally.
Generally. a pump would then be required between each stage to overcome Iriction. With vapor
and liquid. the density diIIerence is suIIiciently large. that we can use gravity to move the Iluids
iI we stack the stages vertically rather than horizontally. A vertical stack oI stages is called a trav
tower.
At right we see a schematic oI a typical trav tower
(Treybal. p129). Each stage or Ilash unit is
represented by one tray. Eive trays are evident in
Eig. 3. Liquid Ilows down Irom the tray above and
Ilows across the tray where in comes into contact
with vapor Ilowing upward Irom the tray below.
AIter mixing. the liquid and vapor are separated.
with the new liquid Ilow down to the tray below and
the vapor Ilowing to the tray above. Through the
act oI mixing. the composition oI the liquid and
vapor streams has changed.
Fig. 4. An expanded view of a single
°bubble cap¨
The contacting oI vapor and liquid on any given tray
is Iacilitated by bubble caps. one oI which is shown
in more detail in Eig. 4. Each tray contains many
bubble caps arranged in a array covering the central
region oI the tray (see Eig. 5).
Fig. 3. A typical tray tower.
06361 page 68 Spring. 2001
In this particular design shown in Eig. 4. vapor
penetrates the tray through a circular hole 2.47
inches in diameter. upward through a 3inch
length oI pipe beIore being diverted downward by
the cap and Iorced through the liquid outside the
pipe.
The Ilow pattern under both normal and abnormal
operation is shown in Eig. 6.
Fig. 6. Flow patterns under normal and abnormal operating of a bubble cap
Fig. 5. Top view of arrangement of bubble caps on
a tray.
06361 page 69 Spring. 2001
An alternative tray design is the sieveplate tray (see
Eig. 7). Sieveplate trays are much cheaper to Iabricate
compared to bubblecap trays since the tray consists oI
a circular plate with holes drilled through Ior the
passage oI vapor. These holes are generally much
smaller in diameter than the bubble caps.
A disadvantage oI sieve plates is that they are much
more prone to weaping and Ilooding (conditions
corresponding to poor contact oI liquid and vapor).
Fig. 7. Side view of a °sieve plate¨ tray.
06361 page 70 Spring. 2001
Chapter 10. Performance of a CC Cascade
ANALYSIS OF A CC CASCADE
At right is a schematic representation oI a countercurrent cascade. It
ignores some oI the details oI plumbing inside the stages and. oI course. in
reality there are no pipes to carry the liquid and vapor between the
adiacent stages. But these are unimportant details as Iar as mass and
energy balances are concerned. The schematic preserves the essential
Ieature  which is that the Ilow oI liquid and vapor occurs
countercurrently.
Since we have so many streams to deal with. some convention Ior
numbering the stages and labelling the streams will be helpIul. McCabe.
Smith & Harriott use the Iollowing conventions:
tray numbers: increase in direction oI liquid Ilow (1>i>N)
stream labels: subscripts denote stream
 L
i
. J
i
are molar Ilowrates oI total (A¹B) liquid and vapor leaving the
ith stage.
 L
a
. J
a
÷ J
1
are the Ilowrates at the top oI the cascade while L
N
. J
b
are
the Ilows at the bottom oI the cascade ("b" Ior bottom).
*
 x
i
. v
i
are the mole Iraction oI the more volatile component in the liquid and vapor leaving the
ith stage.
Suppose we know everything about the two input streams: their Ilowrate. composition. and
enthalpy. Suppose we also have all the thermodynamic data: Hxv diagram and xv diagram.
Given: L
a
.x
a
.J
b
.v
b
; Hxv and xv diagrams
We want to determine the Ilowrate. composition and enthalpy oI the two output streams and oI
all the intermediate streams:
Eind: L
i
.x
i
.J
i
.v
i
Ior i÷1.....N ( ÷ 4N unknowns)
I haven't bothered to list the enthalpies or temperatures here. because iI I know the mole Iraction
and pressure. I can look up the enthalpy and temperature oI saturated liquid or vapor.
*
In heat transfer. the subscripts "a" and "b" were used for entering and leaving streams. respectively. That
convention is abandoned here.
06361 page 71 Spring. 2001
As our system. let's select the Iirst "i" stages. An overall mole balance Ior this system
requires:
total: L
a
¹ J
i¹1
÷ L
i
¹ J
a
. (57)
while a mole balance on the more volatile component requires:
component A: L
a
x
a
¹ J
i¹1
v
i¹1
÷ L
i
x
i
¹ J
a
v
a
. (58)
Einally. we can also perIorm an enthalpy balance:
enthalpy: L
a
H
x.a
¹ J
i¹1
H
v.i¹1
÷ L
i
H
x.i
¹ J
a
H
v.a
. (59)
Do I have enough inIormation to calculate the result? How many independent equations do I
have?
equations: (57).(58).(59) × N ( ÷ 3N eqns)
x
i
and v
i
at equil. ( ÷ N eqns)
So. at least when I am dealing with ideal stages. I have as many equations as unknowns.
Many distillation towers have N÷20 stages or more. so I could easily be talking about 80
equations  a Iormidible problem. Eortunately. there are assumptions which can make this
problem tractable so that it can be solved easily with pencil and paper.
CONSTANT MOLAL OVERFLOW
In our discussion oI Ilash distillation. we noted that many pure
components have the same heat oI vaporization per mole. II you can
assume that the molar heat oI vaporization oI the mixture is completely
independent oI its composition. then solution is greatly simpliIied.
Assumptions:
1) H
v.i
H
x.i
÷ ì Ior all i.
2) neglect sensible heat compared to latent heat
Let's choose saturated liquid having the composition oI the Ieed as our
reIerence state Ior enthalpies. Since the only diIIerence between the
various liquid streams is sensible heat. we take them all to be equal 
equal to zero:
H
x.a
÷ H
x.i
÷ 0 Ior all i
and H
v.i¹1
÷ H
v.a
÷ ì
06361 page 72 Spring. 2001
With these assumptions. the enthalpy balance about the top i stages
L
a
H
x.a
¹ J
i¹1
H
v.i¹1
÷ L
i
H
x.i
¹ J
a
H
v.a
(60)
simpliIies to: J
i¹1
÷ J
a
Ior all i (61)
and the total mole balance about the top i stages
L
a
¹ J
i¹1
÷ L
i
¹ J
a
(62)
Subtracting (16) Irom (15): L
a
÷ L
i
Ior all i
In other words. all oI the vapor streams have the same molar Ilowrate within the cascade
(although their composition and mass Ilowrate will change) and all the liquid streams have the
same molar Ilowrate:
J
a
÷J
1
÷J
2
÷...÷J
N
÷J
b
( ÷ J. say)
L
a
÷L
1
÷L
2
÷...÷L
N
÷L
b
( ÷ L. say)
which is called the state oI constant molal overflow. Since the input Ilowrates are known. we
know all the Ilowrates. Thus we have iust halved the number oI unknowns Irom 4N to 2N. We
can then drop the subscripts on the Ilowrates and Iorget the enthalpy balance (60) and the total
mole balance (62). This leaves iust the component mole balance
L
a
x
a
¹ J
i¹1
v
i¹1
÷ L
i
x
i
¹ J
a
v
a
.
which can be rearranged to: v
L
J
x v
L
J
x
i i a a +
= + ÷
1
(63)
or v
i¹1
÷ mx
i
¹ b
which is a straight line on an xv diagram. This line is called the:
operating line v
i¹1
vs. x
i
; a graphical representation oI the mass balance.
Another important curve on an xv diagram is the:
equilibrium curve v
i
vs. x
i
; a graphical representation oI VLE
In the next section. we will see how these two curves can be used to determine the number oI
equilibrium stages required to achieve some desired degree oI separation.
06361 page 73 Spring. 2001
A RECTIFYING CASCADE
In a typical distillation tower. the liquid Ied to
the top oI the enriching cascade is a portion oI the
vapor product which has been condensed and
reIluxed back into the tower. as shown at right.
The ratio oI the amount reIluxed to the amount not
reIluxed is called the reflux ratio
L
R
D
÷ (64)
Since all oI the vapor stream leaving the top oI the
cascade is condensed to Iorm the distillate product
and the liquid Ied to the top. the three streams must
have the same composition:
x
D
÷ x
a
÷ v
a
(65)
Then the operating line (63) can be simpliIied to
+
v
L
J
x
L
J
x
L
J
x
D
J
x
i i
J L
J
D
J
D i D +
÷
=
= + ÷
= +
1
1
.
(66)
The ratio oI the Ilowrates can be expressed in terms oI the reIlux ratio R using (64):
L
J
L
L D
RD
RD D
R
R
=
+
=
+
=
+1
(67)
1
1
D D D
J L D RD D R
= = =
+ + +
The operating line (66) can be rewritten as
1
1
1 1
i i D
R
v x x
R R
+
= +
+ +
(68)
Thus the slope oI the operating line (a plot oI v
i¹1
versus x
i
) is R/(R¹1).
+
Alternatively. we could 'start over¨ and perform a component mole balance on the top i stages of the cascade
(indicated by the blue line in the sketch).
L.x
a
D.x
D
÷0.95
F.x
F
÷0.5
L.x
1
L.x
N1
L.x
2
B÷L.x ÷x
N b
J.v ÷v
1 a
J.v
2
J.v
N
J.v
3
J.v
b
1
2
N
06361 page 74 Spring. 2001
Now. one point on the operating line is x
i
÷ v
i¹1
÷ x
D
. In other
words. iI we substitute x
D
Ior both x
i
and v
i¹1
. (68) is
automatically satisIied.
Example. Suppose I have a Ieed stream containing 50°
alcohol in water which I want to enrich to 95° alcohol. How
many stages do I need iI I use a reIlux ratio oI unity and what
will be the Ilowrate oI this product?
Given: x
F
. x
D
. F and R
Eind: N and D
Solution: The Iirst step is to draw the operating line on the xy
diagram. One point is (x
D
.x
D
) or (0.95. 0.95). And the slope is
R R +
( )
1 ÷ 1/2 Ior R÷1. Armed with one point and the slope. we could draw the line. But it is
usually easier to construct a line iI we know two points. A second convenient point corresponds
to the yintercept. Substituting x
i
÷ 0 into (68) yields
x
i
÷ 0:
1
1
D
i
x
v
R
+
=
+
which can be conveniently calculated Irom what`s given. Thus
0
1
.
x
R
D
+
is a second point on our operating line. Knowing the
slope and one point. or two points. we can draw the operating
line.
*
Once the operating line is plotted on the xv diagram
(which is the equilibrium curve). we can determine the
composition oI other streams as Iollows.
The two streams leaving a given ideal stage are at equilibrium.
thus the compositions of the two streams leaving a given stage must lie on the equil. curve.
Since we already know the composition oI the vapor stream leaving stage 1 (v
1
÷ x
D
÷ 0.95). we
can determine x
1
by moving horizontally Irom one point on the operating line (x
D
. x
D
) to one
point on the equilibrium curve and then read oII the value oI x
1
:
(x
1
.v
1
) on equil. curve: gives x
1
*
The point (x
D
.x
D
) and slope of 1/2 are not drawn to scale in the sketches. Eor that matter. neither is the
equilibrium curve. However. given the equilibrium curve and operating line as drawn. the method of stepping off the
number of stages is correct.
x
D
x
D
x
R
D
1
06361 page 75 Spring. 2001
On the other hand. the operating line represents a component
mole balance about an arbitrary number oI stages measured Irom
the top. In particular. Ior iust the top stage. the operating line
(66) gives me a relationship between x
1
and v
2
:
(x
1
.v
2
) on oper. line: gives v
2
Knowing x
1
. I can determine v
2
. In general. the compositions of
the two streams between a given pair of adjacent stages must
lie on the operating line. Now
I can repeat the process:
(x
2
.v
2
) on equil. curve: gives x
2
(x
2
.v
3
) on oper. line: gives v
3
and so on. Continuing to
step oII stages in this manner
until the vapor mole Iraction
equals or drops below x
F
÷
v
b
. requires Iour steps:
answer: N ÷ 4
Comment #1: Although the Ieed might be a liquid. it`s the
vapor mole Iraction which must be at or below the Ieed
composition. because the actual Ieed to be bottom oI the
cascade is a vapor (see stream whose composition is labelled
v
b
in the Ilowsheet on page 73). The horizontal line v ÷ x
F
(÷ v
b
) on the xydiagram is called the feed line.
Comment #2: AIter taking 4 steps (or any integer number). we
don`t end up exactly at the Ieed composition (except by some extreme stroke oI luck). Instead
we end up stepping below the Ieed composition. II the trays really are perIectly ideal. and the
Ieed composition is 0.5. the distillate composition would turn out to be slightly richer than 0.95.
Although any real column has an integer number oI trays. it is customary to report the answer as
a Iraction; Ior example. to go Irom a Ieed oI 0.50 to a distillate oI 0.95. we require 3.7 ideal
stages (or 3 ¹ 0.7. where 0.7 is the Iraction oI the last step which corresponds to the Ieed
composition) in the current problem.
Comment #3: Suppose that our Ieed composition had been a little lower. say v
b
´. No matter how
many steps we took. we could never get a vapor composition lower than that at the intersection
oI the operating and equilibrium curves. In that case. any solution Ior the speciIied reIlux ratio is
impossible. Instead the reIlux ratio would have to be increased. which will rotate the operating
line counterclockwise about the speciIied point. This will lower the composition at the
intersection point and make the separation possible. It turns out there exists a minimum value oI
x
a
x
F
v
b
v´
b
v
a
1
2
3
4
Ieed line Ior sat`d vapor
06361 page 76 Spring. 2001
the reIlux ratio which allows a particular distillate composition x
D
to be produced Irom a given
Ieed composition x
F
. This called the minimum reflux ratio.
Let`s Iinish this problem by calculating the Ilowrates. Since the vapor Ilowrate leaving each
tray is the same. and because we are creating the vapor to the Iirst tray by completely vaporizing
the Ieed. we can say that
J ÷ F
The ratio oI liquid to vapor Ilowrate inside the cascade is given in terms oI the known reIlux ratio
by (67):
L
J
R
R
R
=
+
=
=
1
1
2
1
or L J F = =
1
2
1
2
Since the bottoms stream B is one oI the liquid streams
B L F = =
1
2
Einally. the distillate Ilowrate can be calculated Irom the deIinition oI the reIlux ratio: recall (64):
D
L
R
L F
R
= = =
=1
1
2
A STRIPPING CASCADE
Use oI a single cascade with 3.7 stages allows us to convert
a Ieed oI 50mol° alcohol into one containing 95mol°. But a
signiIicant amount oI the alcohol is being lost in the second
product stream. It`s possible to strip the alcohol Irom this
stream by Ieeding it to a second cascade.
In a stripping cascade. liquid is Ied into the top. Liquid out
the bottom oI the cascade is partially vaporized and the vapor is
recycled into the bottom oI the cascade. The vapor stream at
the top represents the second product stream.
Because the bottoms product is only partially vaporized to Iorm
the vapor stream which is recycled to the cascade. its
composition is not the same as the bottoms product. In other
words
x
N
= v
N¹1
= x
B
So no analogy can be made to (65). However we still have a
L.x
a
B.x
B
F.x
F
÷0.5
L.x
1
L.x
N1
L.x
2
L.x
N
J.v ÷v
1 a
J.v
2
J.v
N
J.v
3
J.v
N¹1
1
2
N
06361 page 77 Spring. 2001
operatingline relationship like (63) or (66) which is imposed by mole balances. Erom a balance
over the entire stripping cascade on the more volatile component. we know that
Lx Fx Bx Jv
a F B a
= = +
in out
. .
so Jv
a
 Lx
a
÷ Bx
B
Substituting this result into (63). the operating line Ior a stripping
cascade becomes
+
v
L
J
x
B
J
x
i i B +
= ÷
1
(69)
Like all the operating lines we`ve encountered so Iar. this one has
a slope oI L/J. One point on this operating line is (x
B
.x
B
) since
substituting v
i¹1
÷ x
i
÷ x
B
automatically satisIies (69) provided L
 B ÷ J which is always true since this represents a total mole
balance. Another point is (x
F
.v
1
) iI we happen to know or can
somehow calculate v
1
. Then we have two points and can draw
the operating line. Otherwise. we use one point and the slope.
Example. Suppose I have a Ieed stream containing 50° alcohol
in water which I want to strip the alcohol Irom to produce a stream containing only 5° alcohol.
How many stages do I need iI I boil halI oI the liquid leaving the bottom oI the cascade and
return it as vapor?
Given: x
F
. x
B
and J/L
Eind: N
Solution: Once again. vapor and liquid streams leaving the
same stage are assumed to at equilibrium; thus (x
i
.v
i
) lies on
the equilibrium curve. On the other hand. the composition oI
adiacent streams (x
i
.v
i¹1
) lies on an operating line Ior this
cascade. One point on this operating line is x
i
÷ v
i¹1
÷ x
B
. II
we 'boil halI the liquid leaving the bottom oI the cascade and
return it as vapor¨ we know that J ÷ L/2. so the slope oI the
operating line is:
L/J ÷ 2
Knowing the slope and one point. we can immediately draw
+
Alternatively. we could 'start over¨ and perform a component mole balance on the bottom Ni stages of the
cascade (indicated by the blue line in the sketch).
x
B
x
B
x
F
v
1
L
J
x
B
x
N
v
N¹1
06361 page 78 Spring. 2001
the operating line. The liquid product being drawn oII at x
B
is in equilibrium with the vapor
being sent back into the cascade; thus (x
B
. v
N¹1
) lies on the equibrium curve. On the other hand.
(x
N
. v
N¹1
) are adiacent streams in the cascade and so their compositions must lie on the operating
line.
Similarly. (x
N
. v
N
) lies on the equilibrium curve. while (x
N1
.
v
N
) lies on the operating line.
We continue to step oII stages in this manner until we step past
a liquid composition equal to the Ieed x
F
; in other words. we
continue stepping until we cross the blue vertical Ieed line. In
this case. three steps are required. But one oI these steps is the
reboiler; only two additional equilibrium trays are required:
answer: N ÷2 plus reboiler
Comment #1: Notice that the 'Ieed line¨ Ior a stripping
cascade is vertical. whereas the Ieed line Ior a rectiIying
cascade was horizontal (see page 75). This is because the Ieed
into the bottom oI a rectiIying cascade is a vapor. whereas the Ieed to a stripping cascade is a
liquid.
Comment #2: Suppose that our Ieed composition had been a little higher. say x
F
´. No matter how
many steps we took. we could never get a liquid composition higher than that at the intersection
oI the operating and equilibrium curves. In that case. any solution Ior the speciIied L/J ratio is
impossible. Instead the L/J ratio would have to be decreased. which will rotate the operating line
clockwise about the speciIied point. This will raise the liquid composition at the intersection
point and make the separation possible. It turns out there exists maximum L/J. or a minimum
vapor rate J which allows a particular bottoms composition x
B
to be produced Irom a given Ieed
composition x
F
and liquid Ilowrate L. This minimum J/L is called the minimum boilup ratio.
Let's Iinish the problem by determining the Ilowrates. Once again. all the Ilowrates can be
deduced Irom the equimolal overIlow assumption and the reboil Iraction. All the liquid
Ilowrates correspond to the Ilowrate oI the liquid Ied to the top:
L ÷ F
Since I`m reboiling halI oI this liquid to return to the cascade as vapor. all the vapor Ilowrates are
J ÷ L/2 ÷ F/2
The bottoms Ilowrate is what remains aIter halI oI the liquid to the reboiler is boiled:
B ÷ L J ÷ F/2
x
B
x
N
x
F
x
F
x
N1
v
N¹1
v
N
1
2
3
Ieed line Ior a sat`d liq
06361 page 79 Spring. 2001
STEAM DISTILLATION
Instead oI using a heat exchanger to partially boil the liquid
stream leaving the bottom stage to produce the vapor entering the
bottom stage. we could directly iniect steam as the vapor. This
has the advantage that it avoids the cost oI a heat exchanger and
you are getting direct contact between the hot and cold Iluids.
OI course. use oI steam as the vapor is only useIul iI water is
one oI the two components being separated (e.g. alcohol/water)
and Iurther. it must be the less volatile component. II instead you
are trying to separate heptane Irom octane. iniecting steam would
be produce a second liquid phase (since oil and water are not
miscible).
This produces the operating line shown at right. Note that
one point on the operating line is (x
B
. 0) since the 'vapor¨
entering the bottom is pure steam (water). OI course. part oI the
operating line lies below the 45° line (x÷v). But there are no
restrictions that v must be larger than x. As with the stripping
cascade. we continue to step oII stages between the operating line
and the equilibrium curve until our liquid composition exceeds
x
F
.
Comment: Suppose that our Ieed composition had been a little
higher. say x
F
´. No matter how many steps we took. we could
never get a liquid composition higher than that at the intersection
oI the operating and equilibrium curves. In that case. any solution Ior the speciIied L/J ratio is
impossible. Instead the L/J ratio would have to be decreased. which will rotate the operating line
clockwise about the speciIied point. This will raise the composition at the intersection point and
make the separation possible. It turns out there exists maximum L/J. or a minimum steam rate J
which allows a particular bottoms composition x
B
to be produced Irom a given Ieed composition
x
F
and liquid Ilowrate L.
÷0.5
÷ 0
(live steam
1
2
x
B
x
F
v
1
L
J
0
x
F
06361 page 80 Spring. 2001
Chapter 11. McCabeThiele Method
A typical distillation tower will consist oI at least two
cascades  one to enrich the Ieed in the more volatile
component and a second one to strip the more volatile
component out oI the bottoms stream beIore disposing oI
it.
rectification  enrichment oI vapor by contact with liquid
reIlux
With enough trays. we can usually make D as pure as we
like (an exception occurs Ior an azeotropic mixture).
However. the liquid stream at the bottom oI the cascade
might still contain a signiIicant Iraction oI the more
volatile component. This is where a second cascade is
useIul:
stripping  removal oI the more volatile component Irom
a liquid by contact with reboled bottoms (or direct
iniection oI steam)
A typical problem in designing a distillation column is the
Iollowing:
Given: z
F
.x
D
.x
B
.L/D.H
F
Eind: N and N
where N and N are the number oI stages in enriching and stripping sections. Having two
cascades is a little tricker than one. so let me Iirst tell you how to solve the problem by giving
you the receipe. and later we will rationalize some oI the steps in this receipe.
This receipe is called the McCabe1hiele Method and it works when you have only two
components and you can assume equal molal overIlow.
Step 1) Plot equilibrium data on an xv diagram.
Step 2) Locate x
B
.z
F
. and x
D
on 45° line
We use "z
F
" to denote the mole Iraction ignoring which phase the Ieed is in:
z
F
÷
moles oI A in liquid ¹ vapor
total moles in liquid ¹ vapor
condenser
F
z
H
F
F
D
x
H
D
D
B
x
B
L
L
J
J
enriching
cascade
stripping
cascade
Ieed tray
06361 page 81 Spring. 2001
Step 3) Calculate q (a dimensionless variable representing the
thermal condition oI the Ieed):
J F
J L
H H
q
H H
÷
÷
÷
where H
F
÷ enthalpy oI Ieed
H
J
÷ H oI sat'd vapor with v÷z
F
H
L
÷ H oI sat'd liq. with x÷z
F
Step 4) Plot qline. which is a line given by the Iollowing
equation (Q.L.):
v
q
q
x
z
q
F
=
÷
+
÷ 1 1
OI course. the name "qline" is given because this line
depends on q the thermal condition oI the Ieed. Eor
example. suppose the Ieed is ...
superheated vapor:
H
F
~H
J
÷ q·0 ÷ 0 1
1
q
q
< <
÷
sat'd vapor:
H
F
÷H
J
÷ q÷0 ÷ 0
1
q
q
=
÷
(horizontal line)
2phases mixture: H
L
·H
F
·H
J
÷ 0·q·1 ÷ 0
1
q
q
<
÷
In this case. q represents the Iraction oI the Ieed which is liquid.
sat'd liquid: H
F
÷H
L
÷ q÷1 ÷
1
q
q
= ·
÷
(vertical line)
subcooled liquid: H
F
·H
L
÷ q~1 ÷ 1
1
q
q
< < +·
÷
As it turns out. the two operating lines Ior the two cascades intersect somewhere along this line.
sat`d L L&V
sat`d V
subcooled
superheated
z
F
06361 page 82 Spring. 2001
one point: (z
F
.z
F
)
slope: q/(q1)
Stop 5) Plot the operating line Ior the rectiIication section (R.O.L.):
v
R
R
x
x
R
D
=
+
+
+ 1 1
one point: (x
D
.x
D
)
another point: (0.x
D
/(R¹1))
Step ô) Plot the operating line Ior the stripping section (S.O.L):
B
Bx L
v x
J J
= ÷
one point: (x
B
.x
B
)
another point: intersection oI R.O.L. and Q.L.
Step 7) Step oII stages
You could start at either end (x÷v÷x
D
or x÷v÷x
B
). although it is customary to start at the top. In
stepping oII the stages. you eventually have a choice as to which operating line to drop down to.
LOCATION OF FEED PLATE
At some point during the stepping process. you will have a choice oI either operating line to
step down to. Either operating line can be used. but once you switch operating lines. you cannot
go back to the original line: switching operating lines corresponds to switching Irom one cascade
to the other. The stage at which we switch operating lines is the
feed plate: stage at which you switch operating lines
06361 page 83 Spring. 2001
Either oI the two stepping schemes above is OK. but one scheme leads to Iewer total trays than
the other.
optimum feed plate: to get the Iewest number oI total stages. you switch operating lines when
that allows you to take larger steps
In other words. iI you have a choice oI which operating line to use. use that one which takes you
Iurthest Irom the equilibrium curve. This choice gives the biggest step and Iewest total stages.
CONVERGENCE OF OPERATING LINE AND EQUILIBRIUM CURVE
In some oI the homework problems. the distance between the operating line and equilibrium
curve becomes very small near the point oI their intersection. When this happens. a very large
number oI steps might be required to make any progress on separation.
Rule: an infinite number oI steps is required to get to an intersection oI the operating line and
equilibrium curve.
Proof: when the size oI your steps are no longer large compared to the width oI the pen or pencil
you are using to draw them. you should "blow up" the drawing to reduce drawing errors.
To demonstrate this graphically. let me present the results oI stepping oII stages in a particular
example:
Example: given the xydiagram Ior ethanol and water at 1 atm pressure (has an azeotrope at x ÷ v
÷ 0.8). step oII stages Ior the Iollowing conditions:
Given: z
F
÷ 0.25. x
D
÷ 0.7999. x
B
÷ 0.01. q ÷ 0.3
Eind: N and N Ior the optimum Ieed location
06361 page 84 Spring. 2001
0 0.2 0.4 0.6 0.8
0
0.2
0.4
0.6
0.8
equilibrium curve
y÷x line
Rectifying section oper. line
Q line
Stripping section oper. line
stepping off stages
yprime
xprime
Enter values:
1 Murphree plate efficiency
x
D
0.7999 Mol frac in distillate
x
E
0.25 Mol frac in feed
x
B
0.01 Mol frac in bottoms
q 0.3 Thermal conditions of
feed (liquid fraction)
R 8.618 Reflux ratio (to
obtain total reflux,
use R=0)
R
min
4.483
After N steps, this is actual xB:
xB
calc
5.57 10
3
Nrect 60 Feed tray
N 67 Total number of
stages
Solution: This is a particularly diIIicult separation because the distillation composition x
D
÷
0.7999 is very close to the azeotrope. We anticipate a large number oI steps. Available online is
a Mathcad document McCabeThiele (Pro).mcd  which steps oII stages automatically using the
optimum Ieed location.
The results are shown in the Iigure at right. The program reports (not shown) the total number oI
steps and the Ieed location. In this Iigure. there are a total oI 67 steps with the Ieed introduced on
the 60
th
Irom the top. In the upper right corner. the steps are becoming so small as to be
invisible.
The below on the leIt is a blowup oI the region Irom 0.7 to 0.8. Even on this blowup the steps
are becoming invisible in the upper right corner. So the second graph below on the right is
another blowup: this Irom 0.79 to 0.80. Still the steps are becoming vanishingly small.
The red (equilibrium) curve does not show up on the second graph below on the right.
However. the equilibrium curve is iust the locus oI points Irom the upperleIt corner oI each step.
Similarly. the lower right corner oI each step is the operating line. Notice that in these blowups.
both the equilibrium curve and the operating line very linear.
06361 page 85 Spring. 2001
0.7 0.72 0.74 0.76 0.78
0.7
0.72
0.74
0.76
0.78
0.79 0.792 0.794 0.796 0.798
0.79
0.792
0.794
0.796
0.798
Over a narrow range. any continuous curve becomes virtually linear. When both the operating
line and equilibrium curve are straight lines. an analytic expression exists Ior calculating the
number oI steps:
N
v v
v v
v v
v v
a a
b b
a b
a b
=
÷
÷
÷
÷
log
log
*
*
* *
(70)
which is called Kremser's equation. The subscripts a and b
denote streams at the top and bottom oI the cascade. respectively; the v* are vapor compositions
in equilibrium with the liquid at the top and bottom oI the cascade.
Proof: the linear equilibrium curve can be expressed as
v
i
÷ mx
i
¹ b (71)
A mole balance about the top i stages oI the cascade yields
x
b
x
a
v
b
v
a
v *
b
v *
a
E
C
O
L
06361 page 86 Spring. 2001
1 i i a a
L L
v x v x
J J
+
 
= + ÷

\ .
Using (71) to eliminate x
i
:
1
i
i a a
v b L L
v v x
J m J
+
÷
 
= + ÷

\ .
Now we deIine a new parameter. which represents the ratio oI the slope
oI the operating line (L/J) to the slope oI the equilibrium curve (m):
L
A
mJ
÷
In terms oI A. our mole balance becomes
1
*
a
i i a a i a a
v
v A v b v Amx Av v A mx b
+
= ÷ + ÷ = + ÷ +
.
Erom (71). we see that mx
a
¹b is iust the vapor concentration in equilibrium with liquid at
concentration x
a
. which we denote at v
a
*. AIter minor rearrangement. the above equation
becomes
1
*
i i a a
v Av Av v
+
= ÷ + (72)
This serves as a recursion Iormula. which we can applied repeatedly to obtain the concentration
on successive stages. starting at the top. Eor i÷1. recalling v
1
÷ v
a
. (72) yields
i ÷ 1:
2 1
* 1 *
a
a a a a
v
v A v Av v v A Av = ÷ + = + ÷
i ÷ 2:
3 2
2 2
* 1 * *
1 *
a a a a a a
a a
v Av Av v A v A Av Av v
v A A v A A
= ÷ + = + ÷ ÷ +
= + + ÷ +
where the second equality above results Irom substituting v
2
Irom the previous step. Now we
begin to see a pattern developing:
i ÷ n:
2 2
1
1 *
n n
n a a
v v A A A v A A A
+
= + + + + ÷ + + + . . (73)
The sums represent partial sums oI geometric series. whose sum is known analytically:
1
2
i
i¹1
N
x
a
x
i
x ÷x
N b
v v
÷
a
v
i
v v
N b
÷
06361 page 87 Spring. 2001
1
2
1
1
1
n
n
A
A A A
A
+
÷
+ + + + =
÷
.
Substituting this result into (73):
1
1
1 1
*
1 1
n n
n a a
A A
v v v A
A A
+
+
÷ ÷
= ÷
÷ ÷
Eor the bottom stage oI the cascade. n÷N and v
N¹1
÷ v
b
:
1
1 1
*
1 1
N N
b a a
A A
v v v A
A A
+
÷ ÷
= ÷
÷ ÷
Multiplying through by 1A and collecting terms multiplied by A or by A
N¹1
:
1
* *
N
b a a b a a
v v A v v A v v
+
÷ + ÷ = ÷ (74)
This can be simpliIied. Recall that A is deIined as the ratio oI the slopes oI the operating line to
the equilibrium curve. This ratio can be calculated Irom the concentration deIined on the xy
diagram above:
slope oI OL
* * slope oI EC * *
a b
a b
a b
a b a b
a b
v v
x x
v v
A
v v v v
x x
÷
÷
÷
÷ = =
÷ ÷
÷
(75)
We can use this result to obtain v
a
 v
b
÷ A(v
a
*v
b
*). which will now be substituted into (74):
1
* * * *
* * * *
b a a b b b
N
b a a b a a
A v v v v A v v
A v v A v v A v v
+
÷ + ÷ = ÷
÷ + ÷ = ÷
.
AIter dividing through by A and solving Ior A
N
:
*
*
N b b
a a
v v
A
v v
÷
=
÷
or
*
log
*
log
b b
a a
v v
v v
N
A
  ÷

÷
\ .
=
Taking the log oI both sides. recalling that log(A
N
) ÷ N logA. then solving Ior N we obtain the
second expression above. To obtain the Iorm oI Kremser's equation given as (70). we substitute
(75) Ior A.
Comment #1: In the xydiagram shown next to (70). the equilibrium curve lies above the
operating line. In other words. v
a
* ~ v
a
and v
b
* ~ v
b
. To obtain N~0. you must have v
a
~ v
b
. II
06361 page 88 Spring. 2001
you inadvertently (but consistently) interchange the subscripts a and b. you will obtain negative
values Ior N. Kremser's equation can also be applied to situations in which the operating line lies
above the equilibrium curve; then to obtain N~0. the inequalities above must be reversed.
Comment #2: II the operating line and equilibrium curve should cross (which is physically
impossible). when evaluating (70) you will Iind yourselI trying evaluate the log oI a negative
number.
Comment #3: The situation in which the operating line and equilibrium curve are parallel (i.e.
A ÷ 1) is a special case: (70) becomes indeterminant. However. since the driving Iorce v*v is
constant. the number oI steps is iust the total change in concentration divided by the driving
Iorce:
Ior A ÷ 1:
* *
a b
a b
v v
N
v v
÷
=
÷
Now we will return to discuss the motivation Ior Kremser's equation: approaching the
intersection oI OL and EC:
Notice that. as x
b
approaches the point oI intersection (see Iigure on p83). v v
b b
*
÷ and
N =
=
·
÷ ·
log
log
log
log
0
Thus vou can never reach the point of intersection Ior any Iinite number oI steps. In particular. a
very large number oI stages is required as we increase the purity oI either oI our two product
streams. Eor example. as x
D
÷1. the endpoint (x
D
. x
D
) oI our operating line approaches (1.1).
which is always one point on the equilibrium curve: as x
D
÷1. N÷·.
CHOOSING THE REFLUX RATIO
An important part oI the design oI any distillation column is the choice oI reIlux ratio. There
are a Iew qualitative considerations which must be kept in mind.
06361 page 89 Spring. 2001
1) Existence of R
The Iirst thing you should know is that there is a minimum
value that the reIlux can assume and still achieve the desired
separation. Recall that the slope oI the ROL is
slope oI ROL ÷
R
R +1
Notice that. as R is reduced. the intersection oI the ROL and the
Qline moves toward the equilibrium curve. As it does so. the
minimum number oI stages required approaches inIinity Ior the
reasons mentioned above: you can never get to the intersection oI
the operating line and the equilibrium curve.
Usually this minimum reflux ratio can be determined using the
point oI intersection between the qline and the equilibrium curve.
On some peculiar xv diagrams the R.O.L. or S.O.L. constructed in
this way might cross the equilibrium curve at points other than
where the Qline crosses. Then the reIlux ratio must be increased
until neither operating line crosses equilibrium curve beIore
reaching the qline. OI course. the operating line can be tangent
to the equilibrium curve.
This point oI tangency is called a pinch point. In stepping oII the
stages. it will take an inIinite number iust to reach the pinch. but iI
the reIlux ratio is increased every so slightly. then the separation can be achieved. although the
number oI stages might be large.
minimum reflux ratio  smallest value oI R Ior which the desired separation can be achieved
with a Iinite number oI stages.
The pinch point might also occur on the S.O.L. as shown at right.
Regardless oI where the pinch occurs. once you have drawn the q
line and operating lines. the minimum reIlux ratio (thus determined
graphically) can be calculated Irom (11.424) in Geankoplis:
R
x v
v x
D
min
=
÷ '
' ÷ '
(76)
where (x´.v´) is any point on the R.O.L. (x´.v´) can be chosen Ior
convenience: Ior example. you might want to choose the yintercept.
06361 page 90 Spring. 2001
To determine the minimum reIlux ratio using the McCabe
Thiele method. we might imagine drawing the ROL and SOL
on the xvdiagram starting with a high reIlux ratio (where ROL
and SOL coincide with 45° line) and then decrease the reIlux
ratio until any one oI three things happens:
1. the ROL becomes tangent to the equilibrium curve
2. the SOL becomes tangent to the equilibrium curve
3. the intersection oI the ROL and SOL occurs on the
equilibrium curve
An important thing to notice about the minimum reIlux ratio is
that. as we approach it. the number oI stages approaches inIinity:
as R ÷ R
min
. N ÷ ·
Clearly you don't want to operate near the minimum reIlux ratio because it would cost too much
to build a column with so many stages. Generally as you increase the reIlux ratio. both operating
lines move away Irom the equilibrium curve so that the steps become larger. Then Iewer stages
will be needed.
as R. N
2) 1otal Reflux: R÷ ÷÷ ÷· ·· · gives Minimum Stages
In the limit that R approaches inIinity. the vintercept oI the R.O.L. becomes zero. The
R.O.L. becomes the 45° line. OI course. the S.O.L. and R.O.L. always intersect along the qline.
which means that the S.O.L. also becomes the 45° line. This is the Iurthest the operating lines
can ever be Irom the equilibrium curve. so this condition gives the minimum number oI stages:
as R÷·: R.O.L. ÷ S.O.L. ÷ 45°line
and N N
min
Although it might appear that this is the best value oI the reIlux ratio. it turns out that there is a
"dark side" to this solution. The problem is what is happening to Ilowrates inside the column.
Recall R L/D
Now to get inIinite reIlux ratio. one oI two things has to happen:
R ÷ ·: L÷· or D÷0
06361 page 91 Spring. 2001
In most designs. you are interested in processing a Iixed amount oI material. this implies that
F.D. and B are Iixed. which eliminates the second alternative above. A simple mass balance
about the split oI L and D tells us that the vapor Ilowrate must also get very large:
L ÷ ·: J ÷ ·. q
c
÷ ·. q
r
÷ ·. tower diameter ÷ ·
This means that the heat exchanger Ior both the condenser and the reboiler are getting very large
as are the cost oI utilities (steam and cooling
water).
Thus the costs oI building the tower becomes
large either near the minumum reIlux ratio
(where the height oI the tower becomes large)
or near total reIlux (where the diameter oI the
column becomes large). The costs oI utilities
increase about linearly with reIlux ratio.
The total costs will experience a minimum at
some reIlux ratio. which we call the
optimum reflux ratio: minimizes total
costs/year
Typically the optimum occurs Ior:
1.1 · R
opt
/R
min
· 1.5
However most plants actually operate at slightly larger R since the additional cost is not very
much and it buys you Ilexibility in case you decide later you want to change x
D
or in case the
Ieed composition changes. you have some room to maneuver:
1.2 · R/R
min
· 2.0
$
vear
06361 page 92 Spring. 2001
CALCULATING FLOWRATES AND CONDENSER/REBOILER HEAT DUTIES
To compute the heat duties oI the condenser and reboiler. we will need to know the Ilowrates
in various parts oI the column. We will start at the top oI the
column and work our way down. Eirst we use the deIinition
oI reIlux ratio:
L ÷ RD and J ÷ (R¹1)D (77)
Given F or D and the composition oI the three streams (x
D
.
z
F
and x
B
). we can determine the two unknown Ilowrates
iust by doing a total mole balance and a component mole
balance over the entire distillation column (the blue system
in and Iigure at right).
F ÷ D ¹ B
z
F
F ÷ x
D
D ¹ x
B
B
Solving these two equations Ior the two unknown Ilowrates.
we obtain
F
x x
z x
D
D B
F B
=
÷
÷
(78)
and B
x x
x x
F
x x
z x
D
D F
D B
D F
F B
=
÷
÷
=
÷
÷
(79)
Given F. x
D
. z
F
and x
B
. we can thus calculate D. J and L. In a total condenser. we are
condensing all oI the overhead vapor. Assuming the condenser output is a saturated liquid. the
condenser heat duty is iust
q J
c
= ì
To calculate the reboiler heat duty. we need to evaluate
J . A look at the streams entering the Ieed plate (see
Iigure at right). we realize that we have at least two
unknowns L and J . A total mole balance gives:
J F L J L + + = +
which represents only one relationship in two
unknowns. The remaining relationship is obtained Irom an enthalpy balance about the Ieed tray:
F L J L J
FH LH JH LH JH + + = +
06361 page 93 Spring. 2001
Our analysis oI countercurrent cascades is based on the equimolar overIlow assumption. which
contains some assumptions about enthalpy: see "Constant Molar OverIlow" on p71. In
particular. we neglect sensible heat and assume that all components have the same latent heat oI
vaporization. then we can evaluate the enthalpies oI all saturated liquid or saturated vapor
streams as:
H
L
÷ 0. H
J
÷ ì
Recall the deIinition oI q Irom p81. This allows us to express the enthalpy oI the Ieed in terms oI
q:
J F F
J L
H H H
q
H H
÷ ì ÷
÷ =
÷ ì
or H
F
÷ (1q)ì
Substituting the values Ior enthalpy into the enthalpy balance about the Ieed plate gives:
F(1q)ì ¹ J ì ÷ Jì or
1
J J
q
F
÷
= ÷
(80)
Substituting this into the total mole balance and dividing by F:
1
1
q
L L J J
F F
÷
÷ ÷
= +
.
or
L L
q
F
÷
=
(81)
Thus introducing the Ieed onto a plate causes a discontinuity in the Ilowrates oI liquid and vapor
in the column. Although the Ilowrates are the same Ior each stage in the cascade above the Ieed.
and the same Ior each stage in the cascade below the Ieed. the Ilowrates are diIIerent in the two
cascades. Eor example. Ior a saturated liquid Ieed. q÷1. and the liquid leaving the Ieed tray has a
higher Ilowrate than than entering by an amount equal to the Ieed Ilow rate:
Ior q÷1: L L ÷ qF ÷ F and JJ ÷ (1q)F ÷ 0
whereas the vapor Ilow is unchanged. On the hand. iI the Ieed is saturated vapor. then the vapor
Ilowrate leaving the stage will be higher than than entering by an amount equal to the Ieed rate.
Ior q÷0: L L ÷ 0 and JJ ÷ F
The Ilows Ior other thermal conditions oI the Ieed are summarized graphically below:
06361 page 94 Spring. 2001
Knowing all the Ilowrates. we can now calculated the reboiler heat duty. The reboiler has to boil
all the vapor send into the bottom cascade. Eor a partial reboiler (where the bottoms product is
withdrawn Irom the liquid remaining in the kettle). there can be no superheating oI the vapor (it
must be a saturated vapor). Then the reboiler heat duty is
q J
r
= ì
ROLE OF QLINE
Recall (see 'Step 4¨ on p81) that we said one point oI the
SOL is the intersection oI the qline (QL) and the ROL. In
this section. we present the arguments supporting this claim.
The equations oI the operating lines are obtained by
perIorming a mole balance on component A between some
pair oI streams in the middle oI the column and the end oI the
column away Irom the Ieed (balances use the systems denoted
by the yellow lines):
R.O.L.: Jv ÷ Lx ¹ Dx
D
(82)
S.O.L.: J v ÷ L x  Bx
B
(83)
We claim that the qline represents the intersection oI these
two lines. Think oI these as two equations in two unknowns
(x.v). The point oI intersection oI these two lines is that point
(x.v) which simultaneously satisIies both equations.
Now we are not going to try to solve these two equations Ior (x.v). But we can Iind other linear
relationships between x and v by combining these two equations. One linear combination is
particularly convenient in that it yields an equation which we can plot without knowing any oI
the Ilowrates that appear in (82) and (83):
06361 page 95 Spring. 2001
(83) minus (82): (J J)v ÷ ( L L)x  (Bx
B
¹Dx
D
)
Notice that the last term in this equation represents the total rate oI
component A leaving the tower. This must equal the total rate at
which A enters the tower. So the above becomes:
(J J)v ÷ ( L L)x  Fz
F
Dividing by F gives:
1
F
q
q
J J L L
v x z
F F
÷
÷ ÷
= ÷
.
Substituting (80) and (81): (q1)v ÷ qx  z
F
or
1 1
F
z q
v x
q q
 
= +

÷ ÷
\ .
which is the equation oI our qline. This equation represents a linear combination oI the two
equations which are satisIied at the intersection oI the two operating lines. Thus this equation
must also be satisIied at that point. It turns out that that QL represents the locus oI intersections
oI the ROL and SOL Ior diIIerent reIlux ratios.
PLATE EFFICIENCY
So Iar we have always assumed that the vapor and liquid
streams leaving a given stage are at equilibrium. In
stepping oII the stages. we have always gone all the way
Irom the operating line to the equilibrium curve. II the
contacting oI the two phases on the tray is good (that is. iI
the area oI contact is large and the time oI contact is long)
we can approach this ideal state. but we will never quite
reach it. Eor a nonequilibrium stage. our horizontal step
will be a little shorter than Ior an ideal stage. OI course. we
still end up at a point on the operating line. because this
represents a mole balance which must still be satisIied.
Because the real steps are shorter. it will take more oI them to achieve the same separation. The
ratio oI the number oI ideal to real stages required will be less than one and is called the:
overall (column) efficiencv  N
ideal
/N
real
÷ E
oc
· 1
06361 page 96 Spring. 2001
While this eIIiciency is easy to use. the value oI the eIIiciency is hard to
determine. A more Iundamental quantity is the
Murphree (trav) efficiencv 
v v
v v
E
n n
n n
Mv
÷
÷
÷
+
+
1
1
*
(84)
where v
n
÷ actual v leaving stage n
v
n
*
÷ v in equil with x
n
On an xv diagram. this represents the height oI a real step
divided by the height oI an ideal step Ior the same x
n
.
Alternatively. one could also deIine eIIiciency based on the
change in liquid composition (rather than vapor composition):
E
x x
x x
Mx
n n
n n
÷
÷
÷
÷
÷
1
1
*
(85)
This deIinition is based on the width oI a step (involves
changes in x) rather than based on the height oI a step
(changes in v) as in (84).
Some typical values oI plate eIIiciencies are given in Table 184 (taken Irom Perry`s 6
th
edition).
x
n
v
n
*
v
n
v
n1
x*
n
x
n1
EC
OL
06361 page 97 Spring. 2001
06361 page 98 Spring. 2001
DETERMINING NUMBER OF REAL STAGES
Suppose we have a value Ior E
Mx
or E
Mv
. how do we use it to determine the number oI real
stages required? The procedure is similar to that Ior ideal stages:
Steps 1ô) same as Ior ideal stages
We locate the two operating lines and the q
line. iust as beIore. But beIore we step oII
the stages we use the eIIiciency to determine
a new curve between the operating lines and
the equilibrium curve.
Step 7) Plot psuedoequilibrium curve using
either (84) or (85).
The blue curve in the xydiagram at right
was drawn using (84). At several xvalues
between x
B
and x
D
. we draw a vertical line
between the lowest operating line and the
equilibrium curve. On each oI these line
segments. we locate a point which is a
Iraction oI the distance up the line segment
Irom the bottom. where that Iraction equals the plate eIIicients. The locus oI these points is the
psuedoequilibrium curve.
Einally. we step oII the stages as beIore. but using the psuedoequilibrium curve in place oI the
true equilibrium curve.
Step 8) Step oII stages between operating lines and pseudoequilibrium curve.
Since we used deIinition (84) based on the vapor mole Iractions. we should start our stepping
process at the bottom oI the column. rather than the top. In other words. we start at (x
B
. x
B
) and
step upwards until either the vapor or the liquid mole Iraction exceeds x
D
. By stepping Irom the
bottom up. the step Irom the operating line toward the equilibrium curve involves changes in v.
whereas when we step Irom the top down. the step Irom the operating line toward the
equilibrium curve involves changes in x instead oI v. The latter is appropriate when the
eIIiciency is deIined in terms oI x instead oI v.
v
n
*
v
n
v
n+1
06361 page 99 Spring. 2001
Chapter 12. MultiComponent
Distillation
The obiective oI distillation is the separation oI the Ieed into
streams oI nearly pure products. In binary distillation. we have two
components and two product streams. With more than two
components in the Ieed. there is no way to achieve this with a single
column (a single column might have a third product stream. but it`s
composition would never be nearly pure).
To separate a mixture oI three components into
three nearly pure streams. we will need at least two
separate distillation columns to get three streams. In
general. iI there are N
c
components. we will need N
c
1
columns.
N
c
components
N
c
1 columns
This assumes that each column can achieve a sharp
separation between two components oI adiacent
volatility.
Alternatively. the designer might try to Iirst split oII
component C in the Iirst column rather then A. The
choice between these two alternatives is a matter oI
experience. One 'rule oI thumb¨ is to perIorm the
easiest separations Iirst. In this course. we will Iocus
instead on the design oI the individual columns aIter
this decision has been made.
The Iirst step in the design oI a single column is to
speciIy the product distribution. Let A.B.C.... denote
components ranked in order oI decreasing volatility.
sharp split  distillate contains only components AM. while
bottoms contains only components NZ
In any real distillation. all components will be Iound in all
product streams in at least trace amounts. When we say 'only¨
components AM are Iound in the distillate. we usually mean
that the mole Iractions oI the remaining components (i.e. NZ)
can be neglected when summing the mole Iractions to unity.
Sharp separations are not always possible. but we will Iocus on
06361 page 100 Spring. 2001
them in this introduction. Ior the sake oI simplicity. In the description above. components M and
N play a special role and are called
kev components  M.N (Ior sharp split)
The more volatile oI the two is called the light key. while the other is the heavy key:
light kev  M
heavv kev N
PRODUCT DISTRIBUTION FOR A SHARP SPLIT
EXAMPLE #1: A mixture with 33° hexane. 37° heptane and 30° octane is to be distilled to
give a distillate product oI 1° heptane and a bottoms product oI 1° hexane. Eind D/F. B/F. and
x
Di
. x
Bi
Ior the other components.
Solution: Eirst we arrange the list oI components in order oI relative volatility. In this case. that
is easy since we have a homologous series* oI alkanes. Since vapor pressure general drops with
molecular weight in any homologous series. we don't need to consult tables oI boiling points or
vapor pressures to order the components.
Component Formula
hexane
C
6
H
14
most volatile
heptane
C
7
H
16
octane
C
8
H
18
least volatile
Let's take a basis oI 100 moles oI Ieed (F÷100) and try to Iill out the Iollowing table:
Component Fz
Fi
z
Fi
Dx
Di
x
Di
Bx
Bi
x
Bi
hexane 33 0.33    ô.ô1 light kev
heptane 37 0.37  ô.ô1   heavv kev
octane 30 0.30    
totals ÷ 100 1 D 1 B 1
Comment: Generally the more volatile components end up in the distillate stream and the less
volatile components in the bottoms. Being the most volatile. most oI the hexane is expected to
end up in the distillate; we are told that the bottoms actually contains a little hexane (x
B6
÷ 0.01).
Heptane is oI intermediate volatility and so might end up in either or both streams. Erom the
*
A 'homologous series¨ is a set of very similar items. which differ in some property. In this case. the series is a set
of components of similar molecular structure (the alkanes) which differ only in the number of CH
2
groups in the
chain.
06361 page 101 Spring. 2001
problem statement. we also know that the distillate contains a little heptane (x
B7
÷ 0.01) and so
presumably most oI the heptane ends up in the bottoms. Being less volatile than heptane. we can
reasonably assume that all oI the octane ends up in the bottoms.
In essence. we are then making a sharp split between hexane
and heptane with the '1°¨ values speciIying the sharpness oI
the split desired. In other words. hexane has been choosen as
the light key and heptane as the heavy key. II we assume that
there is virtually no octane in the distillate (octane is heavier
than the heavy key). then we can Iinish speciIying the
composition oI the distillate stream.
Component Fz
Fi
z
Fi
Dx
Di
x
Di
Bx
Bi
x
Bi
hexane 33 0.33  ô.99  0.01
heptane 37 0.37  0.01  
octane 30 0.30 ô ô 3ô 
totals ÷ 100 1 D 1 B 1
Knowing the concentration oI hexane in both oI the product streams allows us to determine the
Ilowrates Irom mole balances:
component C
6
: 0.99D ¹ 0.01B ÷ 33
total: D ¹ B ÷ 100
Solving simultaneously: D ÷ 32.65. B ÷ 67.35
Component Fz
Fi
z
Fi
Dx
Di
x
Di
Bx
Bi
x
Bi
hexane 33 0.33 32.32 0.99 ô.ô7 0.01
heptane 37 0.37 0.01 
octane 30 0.30 0 0 30 
totals ÷ 100 1 32.ô5 1 ô7.35 1
Now using the Iact that the balance oI the distillate and bottoms streams must be heptane. we can
Iill out the table:
C . C . C
C . C
C
06361 page 102 Spring. 2001
Component Fz
Fi
z
Fi
Dx
Di
x
Di
Bx
Bi
x
Bi
hexane 33 0.33 32.32 0.99 0.67 0.01
heptane 37 0.37 ô.33 0.01 3ô.ô7 ô.5445
octane 30 0.30 0 0 30 ô.4454
totals ÷ 100 1 32.65 1 67.35 1
Comment #1: In this example we have completed the speciIications oI the two product streams
Ior a 3component mixture in which the sharpness of split was speciIied by giving the mole
Iraction oI the heavy key in the distillate stream and the mole Iraction oI the light key in the
bottoms. Alternatively. we might have been given the recovery
+
oI the two key components in
either product stream.
Comment #2: The only additional inIormation that is needed iI the number oI components is
larger than 3 is the mole Iraction oI those components in the Ieed. The initial guess Ior the
distribution oI additional components in the product streams is determined by the Iollowing
rules:
Rule 1) Components heavier than the heavy key
are assumed to end up in entirely in the bottoms
Rule 2) Components lighter than the light key are assumed to end up in entirely in the
distillate
MINIMUM NUMBER OF TRAYS
Now let's see iI we can get some idea oI how many trays we will need. This is a diIIicult
problem to do precisely. What can be done relatively easily is to estimate the number oI trays
needed at total reflux  this is the minimum number oI trays. Some gross assumptions:
total reIlux: D~0. L~J
equal molal overIlow: L÷J÷const Ior all trays
constant relative volatilities: o
ii
÷const Ior all trays
Recall o
ii
i
i
K
K
÷ (86)
is the relative volatilitv oI component i compared to i. where
+
Eor example. '5° of the heavy key is recovered in the distillate¨ means Dx
D,HK
÷ 0.05×Fz
F,HK
.
06361 page 103 Spring. 2001
K
v
x
i
i
i
÷ (87)
is the distribution coefficient Ior component i (or i). With
these assumptions. we can start at the top oI the column and
work out the compositions oI streams leaving every stage.
Eor a total condenser:
v
1i
÷ x
0i
÷ x
Di
(88)
Ior i÷1.....N
c
. The Iirst subscript is the stage number (as in
binary mixtures) and the second subscript is the component.
With all the compositions oI the vapor stream leaving stage 1
known. we can determine the compositions oI the exit liquid
stream Irom the known values oI the relative volatility:
o
ii
i
i
i
i
i
i
K
K
v
x
v
x
÷ =
1
1
1
1
or
x
x
v
v
v
v
i
i ii
i
i
ii
i
i
1
1
1
1
1
1
1
= =
o
o (89)
Substituting (88):
x
x
x
x
i
i
ii
Di
Di
1
1
= o (90)
Ior each component i. Notice that iI i÷i. (1) yields
Ior i÷i:
x
x
x
x
i
i
ii
Di
Di
1
1
1
1
1
= o or 1 ÷ 1
which doesn`t tell us anything new; thus we have only N
c
1 independent relations oI this type
instead oI N
c
. Choosing one element as the reIerence (say i÷N
c
). we can write N
c
1 relations Ior
the N
c
1 independent mole Iractions. The missing equation is x
1i
÷ 1. Thus the composition oI
the liquid leaving tray 1 has been completely determined.
Next we determine v
2i
by mole balances.
component i: Jv
2i
÷ Dx
Di
¹ Lx
1i
but Ior total reIlux D~0 so that L~J. leaving:
06361 page 104 Spring. 2001
v
2i
÷ x
1i
(91)
Ior i÷1.....N
c
. Knowing the composition oI the vapor leaving stage 2. we can calculate the
composition oI the liquid Irom the known volatilities.
Rewriting (89). replacing the stage number 1 by 2:
x
x
v
v
i
i
ii
i
i
2
2
2
2
= o
Irom (91):
x
x
x
x
i
i
ii
i
i
2
2
1
1
= o
Using (90):
x
x
x
x
i
i
ii
Di
Di
2
2
2
= o (92)
Erom (90) and (92). we begin to see a trend. The generalization oI this trend yields:
x
x
x
x
ni
ni
ii
n Di
Di
= o
In particular. we are interested in the number oI steps required to get Irom the distillate to the
bottoms:
x
x
x
x
Bi
Bi
ii
N
Di
Di
= o
min
The exponent represents the minimum number oI steps on the xv diagram. One oI these steps is
the partial reboiler. Solving Ior N
min
:
N
x x
x x
Di Bi
Di Bi
ii
min
ln
ln
=
o
which is called Fenske's equation. Now in any real system. the relative volatility will not be
constant. One way to patch things up is to use some kind oI average volatility:
o o o
ii Dii Bii
=
where o
Dii
and o
Bii
are evaluated at the bubblepoints oI the distillate or bottoms. respectively.
In this case. an appropriate mean is the geometric mean oI the volatilities evaluated at the
conditions oI the distillate and bottoms compositions. We use the bubblepoint temperature
06361 page 105 Spring. 2001
rather than the dewpoint temperature because the distillate and bottoms streams are usually
saturated liquids. II they were saturated vapors. then we would use the dewpoint instead.
Example #2. Calculate the N
min
Ior the separation in Example #1 iI the column is operated at
1.2 atm.
Solution:
Evaluating the relative volatilities
We start by evaluating the relative volatilities in the Ieed. distillate and bottoms streams knowing
their composition and thermal state.
Time out: Vapor pressure data Ior pure components is available in the CRC handbook. C6. C7
and C8 Iorm a nearly ideal mixture and Raoult`s law applies:
p
i
÷ x
i
P
i
o
where p
i
is the partial pressure and P
i
o
is the vapor pressure. Then the distribution coeIIicient can
be calculated Irom
K
v
x
p
P
x
x P
x P
P
P
i
i
i
i
i
i i
o
i
i
o
= = = = (93)
and the relative volatility Irom o
ii
i
i
i
o
i
o
i
o
i
o
K
K
P
P
P
P
P
P
= = = (94)
Vapor pressure depends very strongly on temperature: recall the ClausiusClapevron equation
(S&VN. p182):
d P
dT
RT
i
o
i
ln
=
ì
2
or
d P
d T R
i
o
i
ln
1
=
ì
where ì
i
is the molar heat oI vaporization oI the pure component. Integrating this with respect to
T (ignoring the weak temperature dependence oI ì
i
) yields
ln P A
RT
i i
i 0
= ÷
ì
(95)
or P T A
RT
i
o
i
i
( )
= ' ÷
exp
ì
(96)
06361 page 106 Spring. 2001
where A
i
is iust some integration constant. Note the exponential sensitivity oI vapor pressure to
temperature. Vapor pressure data is oIten summarized in handbooks (e.g. Langes Handbook of
Chemistrv. 13
th
edition. pages 1029 to 1054) using Antoine`s equation:
ln P A
B
T C
i i
i
i
0
= ÷
+
(97)
which is a semiempirical generalization oI (95) that accounts Ior the variation oI ì
i
with T.
Other handbooks (e.g. CRC Handbook of Chemistrv & Phvsics. 57
th
edition. pages D183 to D
215) give vapor pressures at several temperatures and leave you to develop your own
interpolation scheme.
Since vapor pressure depends strongly on temperature. so does the partition coeIIicient K
i
given
by (93). However. the relative volatility o is much less dependent on temperature. The reason
becomes clear when we substitute (96) into (94):
o
ì ì
ii
i
o
i
o
i
i
i i P
P
A
A RT
÷ =
'
'
÷
÷
exp
Note that when the two molar heats oI vaporization are equal. the temperaturedependence
vanishes. Even iI they are only approximately equal. the temperaturedependence oI the relative
volatility will be much less than oI the vapor pressures. Eor this reason.
the assumption oI constant relative volatilitv is Irequently used.
Time in: We took the values oI the vapor pressure oI each component
given in CRC handbook and Iit them to (97) to Iind the constants A
i
. B
i
and C
i
Ior each component.
Now the distillate is a saturated liquid containing nearly pure hexane.
so its temperature is near the boiling point oI hexane at 1.2 atm (the
pressure throughout the column) or 75°C.
Component x
D
P
i
o
(atm)
K
P
P
i
i
o
=
i HK
i
HK
.
C6 0.990 1.200 1.000 2.574
C7 0.010 0.466 0.388 1.000
C8 0.000 0.187 0.156 0.401
The bubble point oI the bottoms is 115°C (see Geankoplis p6812 Ior how to determine bubble
points Ior multicomponent mixtures):
0.33
0.37
0.30
0.990
0.010
0.000
0.010
0.545
0.445
06361 page 107 Spring. 2001
Calculate Minimum Stages
To calculate N
min
. Eenske`s equation is usually applied to the heavy key and the light keys. So
we are interested in o
LK.HK
o
67
2 574 2 236 2 399 = × = . . .
Eenske`s equation is
N
x x
x x
Di Bi
Di Bi
ii
min
ln
ln
ln
. .
. .
ln .
. =
=
=
o
099 0 01
0 01 0544
2399
982
So at an absolute minimum. we need 10 ideal steps. or 9 ideal stages plus the reboiler. Knowing
the number oI trays. we can also use Eenske`s equation to check iI indeed the octane Iraction in
the distillate is negligible as we assumed in Example #1.
o
87
0 401 0 469 0 434 = × = . . .
N
x
D
min
ln
.
. .
ln .
= =
10
0 446
0 01 0544
0 434
8
Solving Ior x
D8
. we obtain x
D8
÷ 1.93×10
6
which indeed is negligible compared to the other mole Iractions in the distillate.
MINIMUM REFLUX RATIO
Method 1) PsuedoBinarv Method
Assuming a saturated liquid Ieed (q÷1) and constant relative volatility. the minimum reIlux
ratio turns out to be
Component x
B
P
i
o
(atm)
K
P
P
i
i
o
=
i HK
i
HK
.
C6 0.010 3.448 2.873 2.236
C7 0.544 1.542 1.285 1.000
C8 0.446 0.723 0.603 0.469
06361 page 108 Spring. 2001
R
x
z
x
z
D
F
AB
D
F
AB
min
=
÷
÷
÷
÷
o
o
1
1
1
(98)
where x
D
and z
F
are the moleIraction oI the light key in the psuedobinary mixture and 1x
D
and
1z
F
are the moleIraction oI the heavy key in the psuedobinary mixture:
z
z
z z
F
F LK
F LK F HK
=
+
.
. .
and 1÷ =
+
z
z
z z
F
F HK
F LK F HK
.
. .
where z
F.LK
and z
F.HK
are the mole Iractions in the multi
component mixture.
*
Proof: We can obtain the minimum reIlux ratio Irom the point oI
intersection oI the qline and the equilibrium curve. Recall (76)
Irom page 89:
R
x v
v x
D
min
=
÷ '
' ÷ '
(99)
which was derived using two points on the ROL to determine the
slope and knowing that the slope is R/(R¹1). Eor a saturated
liquid Ieed. the qline is vertical so that
' = x z
F
(100)
The vcoordinate oI this point is determined knowing that ( ' ' x v . ) lies on the equilibrium curve.
Eor constant relative volatility. we can express the equilibrium curve as a simple equation using
the deIinition oI relative volatility:
o
AB
A
B
A A
B B
K
K
v x
v x
v v
x x
÷ = =
÷
÷
1
1
Solving Ior v: v
x
x
=
+ ÷
o
o 1 1
Substituting x x z
F
= ' = . we can calculate
' =
+ ÷
v
z
z
AB F
AB F
o
o 1 1
(101)
*
To derive the relations above. take a basis of 1 mole of feed. then z
F.LK
and z
F.HK
represent the number of moles
of LK and HK in the feed.
06361 page 109 Spring. 2001
Substituting (101) and (100) into (99) leads to (98).
Method 2) Underwood's Method
This method makes similar assumptions to the psuedobinary method except that all
components are considered. not iust the two key components. In particular. the assumptions
made by Underwood`s method are:
1) equimolal overIlow
2) constant relative volatility
3) a sharp split with only one 'pinch¨
Eirst. we will iust state the method and then we will take a quick look at its prooI.
Recipe:
Step 1) Eind the root (denoted o) in the interval o o o
HK LK
< < which satisIies the
polynomial (order oI polynomial ÷ number oI components)
o
o o
i Fi
i
i
z
q
÷
= ÷
1 (102)
Step 2) Once we have o. we can compute the minimum reIlux ratio Irom
R
x
i Di
i
i
min
+ =
÷
1
o
o o
(103)
where the sum is iust over those components present in the distillate (i.e. we ignore components
heavier than the heavy key).
06361 page 110 Spring. 2001
ProoI: A mole balance on component i about the top n stages oI
the rectiIication section yields:
J
n¹1
v
n¹1.i
÷ L
n
x
n.i
¹ Dx
D.i
(104)
Recall that the distribution coeIIicient is deIined as:
K
i
÷ v
i
/x
i
or K
v
x
n i
n i
n i
.
.
.
=
We put the tray subscript on K because its value depends on the
temperature. which varies Irom tray to tray. Thus (104) can be
rewritten as:
J v L
v
K
Dx
n n i n
n i
n i
D i + +
= +
1 1.
.
.
.
Eor constant molal overflow. the Ilowrates will be the same Ior
each tray in the rectiIying cascade. iust as with binary mixtures.
Thus we can drop the subscripts on Ilowrate.
Jv L
v
K
Dx
n i
n i
n i
D i +
= +
1.
.
.
.
(105)
When we approach the minimum reIlux ratio. we will encounter a "pinch" somewhere in the
column. At the pinch. we take an inIinite number oI steps without changing the mole Iractions:
at a pinch: v
n¹1.i
÷ v
n.i
(106)
(106) into (105) and solving Ior v
i
:
v
D
J
x
L
J K
i
Di
i
=
÷
·
·
· ·
1
.
(107)
We have put a subscript '·¨ on each Ilow rate to emphasize that this corresponds to the
minimum reIlux. which requires an inIinite number oI trays. II we require (107) to be satisIied
Ior each component and sum over all components:
v
D
J
x
L
J K
i
i
Di
i
i
= =
÷
·
·
· ·
1
1
.
(108)
Now we can write K
i
in terms oI the relative volatility:
06361 page 111 Spring. 2001
o
i
i
ref
K
K
=
While the Ilowrate ratios can be related to the reIlux ratio:
L
J
R
R
·
·
=
+
min
min
1
and
D
J R
·
=
+
1
1
min
(108) becomes:
o
o o
i Di
i
i
x
R
÷
= +
min
1 (103)
where o ÷
+
R
K R
ref
min
min
1
II K
ref
were known. then R
min
could be determined as the root oI this equation. UnIortunately. to
calculate K
ref
we need to know the temperature at the pinch. which is not known.
Generally there is also a pinch in the stripping section oI the tower. Eor sharp splits. the
temperature at this second pinch will be the same. We can then derive a second equation like
(103) by perIorming our balances about the bottom n stages oI the column to obtain a second
equation.
v
B
J
x
L
J K
i
i
Bi
i
i
= =
÷
· ·
· ·
1
1
.
where the overbars denotes Ilowrates in the stripping section. Then we will have two equations
and two unknowns: K
ref
and R
min
. Their solution is the value oI o which satisIies the Iollowing
equation:
o
o o
i F i
i
i
z
q
.
÷
= ÷
1
where z
F.i
is the composition oI the Ieed and q is its thermal condition. There are several o's
which satisIy this equation. It turns out that we want:
o
HK
· o · o
LK
Once o is determined. we can calculate R
min
Irom (103). This is called Underwood's method.
Example #3. Calculate the R
min
Ior the separation in Examples #1 and #2 iI the Ieed is 60°
vapor (q ÷ 0.4).
06361 page 112 Spring. 2001
Solution: Recall the Ieed and product compositions (see sketch at
right). Using Underwood`s method. we Iirst determine the root oI
(102).
o
o o
i Fi
i
i
z
q
÷
= ÷
1
Substituting into known values:
2 399 0 33
2 399
1 0 37
1
0 434 0 30
0 434
1 0 4
. .
.
. . .
.
.
×
÷
+
×
÷
+
×
÷
= ÷
o o o
o f
.
which is a cubic equation. The leIthand side
f(o) is plotted at right. This equation has
three singular points at
o ÷ o
1
. o
2
and o
3
These are shown as the 3 vertical lines in the
plot. Notice that there are also 3 diIIerent o`s
Ior which
f(o) ÷ 1q ÷ 0.6
We are interested in the root in the interval:
o o o
HK LK
< < or 1 · o · 2.399
which turns to be o ÷ 1.739. Once we have the value oI o. we calculate the reIlux ratio Irom
(103):
R
x
i Di
i
i
min
+ =
÷
1
o
o o
where the sum only includes those components present in signiIicant quantities in the distillate.
In this case. octane (which is heavier than the heavy key) was neglected in the distillate Ior
Example #1. It should also be neglected in this sum. although in this case. it`s inclusion does not
change the result.
R
min
. .
. .
.
.
. + =
×
÷
+
×
÷
= 1
2 399 0 99
2 399 1739
1 0 09
1 1739
359
ANSWER: R
min
÷ 2.59
0.33
0.37
0.30
0.990
0.010
0.000
0.010
0.545
0.445
1 q
2 0 2 4
2
0
2
3
2
1
f (
06361 page 113 Spring. 2001
NUMBER OF IDEAL PLATES AT OPERATING REFLUX
ReI: MSH p588609
Method 1) Underwood's method
Underwood's method can be extended to calculate the number oI plates analytically when the
equal molal overIlow assumption and constant relativity are appropriate. But even then. the
calculations are suIIiciently involved that a
computer would be helpIul. II we are going to
use a computer. we might as well do the rigorous
traybytray calculations (see Method 3); thus we
will not extend Underwood`s method Iurther in
these Notes.
Method 2) Gilliland correlation
An empirical but much easier to use method is
the Gilliland correlation. This is an empirical
relation between the number oI ideal stages and
the operating reIlux ratio. You also need to
know the minimum number oI ideal stages (at
total reIlux) and the minimum reIlux ratio.
Because oI its simplicity. this correlation is
widely used Ior preliminary estimates.
A second type oI empirical correlation is Erbar
& Maddox (see Eig. 11.73 in Geankoplis):
N
N
f
R
R
R
R
min min
min
. =
+ +
1 1
Method 3) Rigorous Solution of MESH Equations
ReIerence: Henley & Seader. EquilibriumStage Separation Operations in Chemical
Engineering. Chpt. 15.
The Iinal design oI multistage equipment to multicomponent distillation usually requires
rigorous determination oI temperatures. Ilow rates. and compositions at each stage. This must be
done numerically by computer. We will use a computer program called CHEMSEP to look at a
couple oI typical columns. Although the program is designed to be used like a "blackbox". I'd
like to give you a little peek at what goes on inside.
06361 page 114 Spring. 2001
A rigorous mathematical description oI a multistage cascade involves material and energy
balances and some representation oI the vaporliquid equilibrium. The resulting set oI algebraic
equations is called the MESH Equations. Ior reasons which will soon become apparent.
Consider a general stage in the cascade. which we
will label stage n. It has the usual liquid and vapor
streams entering and leaving. It might also be a Ieed
stage. in which case F
n
= 0. II it is not a Ieed stage.
we iust set F
n
÷ 0. There might also be liquid or
vapor product streams U
n
or W
n
as well as a heat
removal Q
n
. The MESH equations result Irom
balances done about this arbitrary stage.
M Equations are Mole balances Ior each component i
(N
c
equations Ior each stage):
L x J v F z L U x J W v
n i n n i n n i n n n i n n n i n
+ + = + + +
1 1 1 1 , , , , ,
Note that the Iirst subscript is the component i and the second subscript Ior the stage n.
E Equations describe the liquidvapor Equilibrium relations among the two outlet streams. which
are assumed to be at equilibrium (N
c
equations Ior each stage):
v K x
i n i n i n . . .
=
where K
i.n
is the distribution coeIIicients.
S Equations are the mole Iraction Summations (2 equations Ior each stage):
x
i n
i
.
= 1 and v
i n
i
.
= 1
H Equations is the energy balance Ior each stage (1 equation Ior each stage):
L H J H F H L U H J W H Q
n L n n J n n F n n n L n n n J n n
+ + = + + + +
1 1 1 1 , , , , ,
II there are a total oI N
s
stages in the column and N
c
components. then the number oI equations is
number oI equations ÷ N
s
(2N
c
¹3)
Now we consider the Iollowing to be unknowns:
x
i.n
. v
i.n
. L
n
. J
n
. T
n
Ior i ÷ 1.....N
c
and n ÷ 1....N
s
where T
n
is the temperature oI the liquid and vapor streams leaving stage n.
number oI unknowns ÷ N
s
(2N
c
¹3)
L
L
U
J
W
J
F
Q
stage n
06361 page 115 Spring. 2001
OI course. there are more variables involved in the equations. We assume that the Ieeds and any
side drawoII Ilows are speciIied:
given: F
n
. z
i.n
. H
F.n
. U
n
. W
n
. Q
n
Also. we assume that the thermodynamic relations exists so that we can compute the enthalpy oI
saturated liquid and saturated vapor. given the composition. pressure and temperature:
known Iunctions: H H T P x x
L n L n n n n N n
. . . .
. . =
1
H H T P v v
J n J n n n n N n
. . . .
. . =
1
K K T P x x
i n n n n N n
. . .
. ; =
1
06361 page 116 Spring. 2001
Chapter 13. Computer Simulation of Distillation
We will be using a computer program called 'ChemSep¨ to simulate distillation. Today I'd like
to introduce this program. Compared with industrial soItware. it is userIriendly and written Ior
student use. Below is the welcoming screen.
Arno Haket and Harry Kooiiman are Irom the University oI Technology in DelIt (The
Netherlands). while Ross Taylor is a ProIessor oI Chemical Engineering at Clarkson University
(New York state).
AIter a copyright screen. we reach the main menu:
06361 page 117 Spring. 2001
SOME PRELIMINARY STEPS
Although a mouse can be used with the program. the deIault is to use the cursor keys to move
around the screen. When the desired menu item is highlighted. press ENTER to select it. You
can also select menu items by typing the Iirst letter oI the desired item. Below is the result oI
choosing the File menu.
File Input Results Options Help
e ep
F Help F st elp F o F e F nits F Options F In o F in enu
File Input Results Options uit
e ep
o
e
e
i e to
ie
it
op
Ren e
se
O s ell
it
F1:Help F2:Last help F3:Load F4:Save F5:Units F6:Options F9:Info F10:Main menu
06361 page 118 Spring. 2001
Notice that a submenu has appeared. You can probably guess what most oI these commands do.
BeIore going any Iurther. you should make sure that any Iiles we create will be placed on the
Eloppy Disk drive A:\. This can be accomplished by changing the deIault directory to A:\.
Select the Directory command. You will then be presented with the current directory name
which can be edited to read:
You should also save your conIiguration Iile on your Iloppy disk. This can be accomplished by
going to the Options menu and selecting the Save options command. You should edit the
Iile name to read 'A:\ChemSep.cnf¨:
I1]e lnpuf kesu]fs Opf1ons ue]p
Chem5ep v3.50
++
¦ Load ¦
¦ NeW ¦
¦ 5ave ¦
¦ D1¡ecfo¡y ¦
++
¦ Enfe¡ neW d1¡ecfo¡y A:\" ¦
++
¦ kename ¦
¦ E¡ase ¦
¦ DO5 she]] ¦
¦¦
¦ Ex1f ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
I1]e lnpuf kesu]fs Opf1ons ue]p
Chem5ep v3.50
++
¦ 5o]ve opf1ons ¦
¦ un1fs ¦
¦ Mac¡os ¦
¦ lnfe¡face ¦
¦ D1¡ecfo¡1es ¦
¦ v1deo dev1ce ¦
¦ Oufpuf dev1ce ¦
¦ 5ave opf1ons ¦
++
¦ Opf1ons f1]ename A:\Chem5ep.cnf ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 119 Spring. 2001
Now any changes you make in the conIiguration can be saved in this Iile and reloaded when you
return to ChemSep at some later time.
LOADING A FILE (PROBLEM)
We are going to create a new Iile which simulates the solution to Prob. 3 on Hwk. #6. We start
by selecting the New command Irom the File menu. You will then prompted Ior a Iile name:
type 'A:\HWK6P3.SEP¨. The 'A:\¨ will Iorce this Iile to be stored in the root directory oI the
Iloppy drive. which is the recommended location Ior your personal Iiles.
The Iirst step in inputing the problem description is to select the components. This particular
homework problem is based on MS&H5 Prob. 183 in which we are to separate a mixture oI
acetone and methanol. Under the Input menu. select Components. Iollowed by several
'Enter`s¨ until you are prompted Ior a name (see below):
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
¦ 5o]ve ¦
¦ ChemP¡op ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 120 Spring. 2001
Enter the Iirst component name (acetone) and hit 'enter¨. This will bring up another short menu
containing 'acetone¨ at the bottom: Select 'acetone¨ and hit 'enter¨.
This will add acetone to the list oI components. Next select >Restart search and type the
next component name (methanol). AIter selecting methanol and hitting 'enter¨. we have two
components in our list:
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++ +< Componenfs >
+
¦ Componenfs ¦ ¦ None
¦
¦++ ¦ +
+
¦¦ 5e]ecf ¦ ¦
¦¦++¦ ¦
¦¦¦ 5ea¡ch by ¦¦ ¦
¦¦¦¦¦ ¦
+¦¦ Name ¦¦+
++
¦ 15ubsf¡1ng of} name = ¦
++
¦¦ C]ass ¦¦
+¦ Iam1]y ¦+
¦ P¡ope¡fy ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++ +< Componenfs >
+
¦ Componenfs ¦ ¦ None
¦
¦++ ¦ +
+
¦¦ 5e]ecf ¦ ¦
++
¦ Name ¦
¦¦
¦ > kesfa¡f sea¡ch ¦
¦ > kef1ne sea¡ch ¦
¦ Acefone ¦
++
¦ kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 121 Spring. 2001
Hit 'Esc¨ twice brings us back to the Input menu. This time. select the Operation command.
then the Column subcommand. The cursor is now on the '*¨ on the line with Operation.
Hitting the 'enter¨ key leads to the Iollowing screen:
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++ +< Componenfs >
+
¦ Componenfs ¦ ¦ Acefone
¦
¦++ ¦ ¦ Mefhano]
¦
¦¦ 5e]ecf ¦ ¦ +
+
++
¦ Name ¦
¦¦
¦ > kesfa¡f sea¡ch ¦
¦ > kef1ne sea¡ch ¦
¦ Mefhano] ¦
++
¦ kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 122 Spring. 2001
Move the cursor to simple distillation and hit 'enter¨. This moves the cursor to the '*¨ on
the line with Condenser. Hitting 'enter¨ brings up a menu oI options Ior the operation oI the
condenser:
OI course. in the homework problem we want to subcool the condensate. so we choose Total
(Subcooled product). AIter making a Iew other choices in the remaining items. then selecting
Show flowsheet. we have:
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++
¦ Componenfs ¦
¦ Ope¡af1on ¦
++
¦ I]ash ¦
¦ Co]umn ¦
++
¦ Ope¡af1on " ¦
¦++
¦ Condense¡ ¦ 51mp]e D1sf1]]af1on ¦
¦ kebo1]e¡ ¦ Exf¡acf1ve D1sf1]]af1on ¦
¦ 5fages ¦ Azeof¡op1c D1sf1]]af1on ¦
¦ Ieed sfages ¦ 51mp]e Abso¡be¡/5f¡1ppe¡ ¦
¦ 51desf¡eam sfages¦ kebo1]ed Abso¡be¡/5f¡1ppe¡ ¦
¦ Pumpa¡ound sfages¦ kef]uxed Abso¡be¡/5f¡1ppe¡ ¦
¦ ¦ 51ng]e Co]umn 5fage ¦
¦¦ 51mp]e Exf¡acfo¡ ¦
¦ ¦ 51ng]e Exf¡acf1on 5fage ¦
+¦ Comp]ex Co]umn ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++
¦ Componenfs ¦
¦ Ope¡af1on ¦
++
¦ I]ash ¦
¦ Co]umn ¦
++
¦ Ope¡af1on 51mp]e D1sf1]]af1on ¦
¦¦
¦ Condense¡ " ¦
¦ kebo1]e¡ ++¦
¦ 5fages ¦ 1ofa] 1L1qu1d p¡oducf} ¦¦
¦ Ieed sfages ¦ 1ofa] 15ubcoo]ed p¡oducf} ¦¦
¦ 51desf¡eam sfages¦ Pa¡f1a] 1vapou¡ p¡oducf} ¦¦
¦ Pumpa¡ound sfages¦ None ¦¦
¦ ++¦
¦¦
¦ kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 123 Spring. 2001
We next select Return and the cursor moves to the Properties submenu oI Input. Hit 'enter¨
twice to enter the Thermodynamic models dialog box. Since this is not a course in
thermodynamics. I will always tell you which thermo models to us. AIter making a Iew choices.
the dialog box appears as Iollows:
I1]e lnpuf kesu]fs Opf1ons ue]p
A:\uWk6P3.5EP 1NeW p¡ob]em} Chem5ep v3.50
++ +I]oWsheef
+
¦ Componenfs ¦ ¦ ++
¦
¦ Ope¡af1on ¦ ¦ +>+ ¦
¦
++ ¦ ¦ ¦1 ¦ ¦
¦
¦ I]ash ¦ ¦ +¦+ +¦+
¦
¦ Co]umn ¦ ¦ ¦ ¦ +<>
¦
+¦ ¦¦¦¦
¦
¦ Ope¡af1on 51mp]e D1sf1]]af1on¦ ¦¦¦¦
¦
¦¦ ¦¦¦¦
¦
¦ Condense¡ 1ofa] 15ubcoo]ed p¡¦ ¦¦¦¦
¦
¦ kebo1]e¡ Pa¡f1a] 1L1qu1d p¡o¦ ¦¦¦¦
¦
¦ 5fages 23 ¦ >17¦¦¦¦
¦
¦ Ieed sfages 17 ¦ ¦¦¦¦
¦
¦ 51desf¡eam sfages ¦ ¦¦¦¦
¦
¦ Pumpa¡ound sfages ¦ ¦ +¦<+
¦
¦ 5hoW f]oWsheef ¦ +¦+ +¦+
¦
¦¦ +>>
¦
¦ kefu¡n ¦ 23++
¦
+¦
¦
¦
¦
¦
¦
+P¡ess any key fo conf1nue
+
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 124 Spring. 2001
Selecting Return takes us to the Load data submenu. Some thermo models do not require any
Iurther input Irom the user. but the cubic EOS does require a value Ior the interaction parameter.
AIter selecting Load data. then Cubic EOS leads us to the Iollowing dialog:
Move the cursor to Correlation and hit 'enter¨. A value Ior kii has been entered Irom the
library. then select Return. Hitting 'enter¨ three more times brings us back to the
Input/Specifications submenu. Hit 'enter¨ and choose Pressures. Make the selections
shown as Iollows:
I1]e lnpuf kesu]fs Opf1ons ue]p
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++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
++
¦ 1he¡modynam1c mode]s ¦
++
¦ 1he¡modynam1c mode]s: ¦
¦¦
¦ kmode] EO5 ¦
¦ Acf1v1fy coeff1c1enf ¦
¦ Equaf1on of 5fafe Pengkob1nson ¦
¦ vapou¡ p¡essu¡e ¦
¦ Enfha]py Excess ¦
¦¦
¦ kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
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++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
++
¦ 1he¡modynam1c mode]s ¦
¦ Load dafa ¦
¦++¦
¦ k¦ Load dafa fo¡: ¦ ¦
+¦¦+
¦ Cub1c EO5 ¦
++
¦ Cub1c EO5: Pengkob1nson 1} ¦
¦¦
¦ Componenf 1 Componenf ¸ k1¸ ¦
¦ Acefone Mefhano] " ¦
¦¦
¦ kesef L1b¡a¡y Co¡¡e]af1on kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
06361 page 125 Spring. 2001
The units Ior pressure might not show up as atm. II not. you can change the units Ior entering
any quantities hitting the Iunction key F5. AIter setting the pressure. choose Return which moves
the cursor to Heaters/Coolers. No heat is to be added or removed except Ior the condenser
and reboiler. so we move the cursor on down to Efficiencies. Here we enter the Murphree
tray eIIiciency. We enter '1¨ as the default to obtain ideal trays throughout the column.
Using the Insert command. we could speciIy diIIerent eIIiciencies Ior each tray. Choosing
Return moves the cursor to the Input/Specifications/Feeds command. This is where we
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¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ana]ys1s ¦
¦ P¡essu¡es ¦
++
¦ P¡essu¡es 1afm} ¦
¦¦
¦ Condense¡ p¡essu¡e 1.000 ¦
¦ Co]umn p¡essu¡e Consfanf p¡essu¡e ¦
¦ 1op p¡essu¡e 1.000 ¦
¦ P¡essu¡e D¡op 1afm/sfage} ¦
¦ 8offom p¡essu¡e ¦
¦¦
¦ kefu¡n ¦
++
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
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¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ana]ys1s ¦
¦ P¡essu¡es ¦
¦ ueafe¡s/Coo]e¡s ¦
¦ Eff1c1enc1es ¦
++
¦ Mu¡ph¡ee Eff1c1enc1es ¦
¦¦
¦ 5fage Eff1c1ency 1} ¦
¦ Defau]f 1.000 ¦
¦¦
¦ lnse¡f De]efe kefu¡n ¦
++
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06361 page 126 Spring. 2001
speciIy the thermal condition. composition and Ilowrate oI the Ieed. The thermal condition can
be speciIied either as temperature and pressure or as vapor Iraction and pressure. Since our Ieed
is 70° vapor. we use the latter option. AIter entering the values appropriate to our problem. we
have:
A second Ieed could be added using the Insert command. Selecting Return. brings us to the
Input/Specifications/Operation command. This is where we enter speciIications regarding
the two remaining degrees oI Ireedom in the column design. Hitting 'enter¨ twice brings up a
range oI choices Ior speciIying the Iirst degree oI Ireedom.
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++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ieed 1 ¦
¦¦
¦ Ieed sfage 17 ¦
¦ 5fafe: P & v ¦
¦ P¡essu¡e 1afm} 1.000 ¦
¦ vapou¡ f¡acf1on 1} 0.7000 ¦
¦ 1empe¡afu¡e 1´C} ¦
¦¦
¦ I]oW¡afes 1mo]/s} ¦
¦ Acefone 25.00 ¦
¦ Mefhano] 75.00 ¦
¦¦
¦ 1ofa] f]oW¡afe 100.0 ¦
¦¦
¦ lnse¡f De]efe kefu¡n ¦
++
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06361 page 127 Spring. 2001
We can choose only one oI these. II we speciIy the mole Iraction oI acetone to be 78° (as in our
problem statement). then the program adiusts the reIlux ratio in an eIIort to obtain this
composition. II we speciIy the reIlux ratio. then the program determines the composition oI the
distillate product. Here we will choose the reIlux ratio (to be 8.62) and see what happens. Since
we speciIied a subcooled reIlux. we next get to choose its temperature or the number oI degrees
oI subcooling. We speciIy the temperature as 25°C. Hitting 'enter¨ when the cursor is over the
only remaining '*¨ brings up the Iollowing list:
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¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ana]ys1s ¦
¦ P¡essu¡es ¦
¦ ueafe¡s/Coo]e¡s ¦
¦ Eff1c1enc1es ¦
++
¦ kef]ux ¡af1o ¦
+¦ ueaf dufy of condense¡ ¦
+
¦ "¦ D1sf1]]afe f]oW ¡afe ¦
¦
¦ D¦ kef]ux f]oW ¡afe ¦ "
¦
¦ "¦ Componenf f]oW ¦
¦
¦¦ Mo]e f¡acf1on of a componenf ¦
¦
¦ ¦ Componenf ¡ecove¡y ¦ kefu¡n
¦
+¦ I¡acf1on of comb1ned feeds ¡ecove¡ed ¦
+
¦ 5p]1f befWeen fWo componenfs ¦
¦ I]ex1b]e ¦
++
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06361 page 128 Spring. 2001
Now we get to speciIy one property oI the bottom stream. We choose to speciIy the mole
Iraction oI the bottoms product. Now the Operation speciIication is complete.
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++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ana]ys1s ¦
¦ P¡essu¡es ¦
¦ ueafe¡s/Coo]e¡s ¦
++
¦ 8o1]up ¡af1o ¦
¦ ueaf dufy of ¡ebo1]e¡ ¦
+¦ 1empe¡afu¡e of ¡ebo1]e¡ ¦
+
¦ k¦ 8offom p¡oducf f]oW ¡afe ¦ 8.620
¦
¦ 1¦ kebo1]ed vapou¡ f]oW ¦ 25.00
¦
¦ "¦ Componenf f]oW ¦
¦
¦¦ Mo]e f¡acf1on of a componenf ¦
¦
¦ ¦ Componenf ¡ecove¡y ¦ kefu¡n
¦
+¦ I¡acf1on of comb1ned feeds ¡ecove¡ed ¦
+
¦ 5p]1f befWeen fWo componenfs ¦
¦ I]ex1b]e ¦
++
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06361 page 129 Spring. 2001
Choosing Return twice places the cursor on the Input/Solve command. Hitting 'enter¨. the
program saves the description and attempts to solve the MESH equations. II all the data has been
entered correctly. the next screen appears:
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¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
¦ 5pec1f1caf1ons ¦
++
¦ Ana]ys1s ¦
¦ P¡essu¡es ¦
¦ ueafe¡s/Coo]e¡s ¦
¦ Eff1c1enc1es ¦
¦ Ieeds ¦
¦ Ope¡af1on ¦
+
+
¦ kef]ux ¡af1o 1} 8.620
¦
¦ 1empe¡afu¡e of ¡ef]ux 1´C} 25.00
¦
¦ Mo]e f¡acf1on of a componenf 1} Acefone 0.010000
¦
¦
¦
¦ kefu¡n
¦
+
+
I1:ue]p I2:Lasf he]p I3:Load I4:5ave I5:un1fs I6:Opf1ons I9:lnfo I10:Ma1n menu
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++
¦ G¡aphs ¦
¦ 1ab]es ¦
¦ 5p¡eadsheef ¦
++
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06361 page 130 Spring. 2001
Now we are ready to display the results. Choosing Results/Graphs gives us a menu oI choices:
PLOTTING THE MCCABETHIELE DIAGRAM
Let`s Iirst check out the McCabeThiele
diagram:
The diagram at right seems to resemble that
obtained in Hwkkey #6. except that the
azeotrope occurs at a mole Iraction oI about 0.76
instead oI 0.80. This diIIerence might occur
because the thermodynamic model we chose is
not the best one. In any case. it means that the
distillate composition will never reach the 0.78
required in Prob. 3.
Let`s take a closer look at the proIile. To get a
better look at what's happening at the top oI the
column. we might want to expand that section oI
the McCabeThiele diagram. The scale as well
as the Iormat oI any graph in ChemSep can be
customized by hitting the SPACE key when the
graph is displayed. The Iollowing dialog box
appears:
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¦ G¡aphs ¦
++
¦ L1qu1d phase compos1f1on p¡of1]es ¦
¦ vapou¡ phase compos1f1on p¡of1]es ¦
¦ kva]ue p¡of1]es ¦
¦ 1empe¡afu¡e p¡of1]e ¦
¦ P¡essu¡e p¡of1]e ¦
¦ I]oW p¡of1]es ¦
¦ Mass f¡ansfe¡ ¡afes ¦
¦ 5f¡1pp1ng facfo¡s ¦
¦ key ¡af1o p¡of1]es ¦
¦ ke]af1ve vo]af1]1f1es ¦
¦ McCabe1h1e]e d1ag¡am ¦
¦ Ponchon 5ava¡1f ¦
¦¦
¦ kefu¡n ¦
++
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06361 page 131 Spring. 2001
I have shaded the two lines which can be edited to expand the scale. Changing the range on both
x and v Irom the interval (0. 1) to the interval (0.6. 0.8) and then hitting the ESC key yields the
second McCabeThiele diagram below at the leIt. A second diagram appears below at right in
which we have expanded the lower end oI the diagram.
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++
¦ McCabe1h1e]e d1ag¡am ¦
¦¦
¦ 11f]e McCabe1h1e]e d1ag¡am ¦
¦ 1sf key componenf Acefone ¦
¦ 2nd key componenf Mefhano] ¦
¦ I]1p No ¦
¦ M1n1mum/Max1mum X 0 1 ¦
¦ X 11c 1nfe¡va] 0.2 0 ¦
¦ X Labe] X Acefone/1Acefone+Me ¦
¦ M1n1mum/Max1mum Y 0 1 ¦
¦ Y 11c 1nfe¡va] 0.2 0 ¦
¦ Y Labe] Y Acefone/1Acefone+Me ¦
¦ G¡1d Off ¦
¦ Ax1s co]o¡ ]G¡ay ¦
¦ 5fages ]1nes ]8]ue :Doffed ¦
¦ Equ1]1b¡1um L1ne ]ked :5o]1d ¦
¦ Ope¡af1ng ]1nes Ye]]oW :5o]1d ¦
¦ O ]1nes Wh1fe :5o]1d ¦
¦ P¡1nfe¡ 5efup P¡1nf ¦
++
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06361 page 132 Spring. 2001
PRINTING THE GRAPHS
Once you get the desired graph on the screen. you probably want to make a hard copy. To
print. hit the SPACE key to bring up the graph customization dialog box shown above. Notice
the "Print" and "Printer Setup" items on the bottom line oI the dialog. To print. you move the
cursor over the "Print" item and hit the ENTER key. ChemSep will send the graph to the printer
identiIied by the "Printer Setup" menu.
To get the graphs into this document. I instructed ChemSep to write a Windows bitmap into a
Iile which I later imported into MS Word. I edited the "Printer Setup" (by moving the cursor
over this item and hitting ENTER) to read as Iollows:
AIter you have Output Device Setup reading like that shown above. hit ESC to return to the
graph customization dialog. select Print and hit ENTER. You will be asked to supply a
Iilename. Use a diIIerent name Ior each graph.
When you "Quit" the ChemSep program. you can run Word. Bitmap Iiles can be imported
into Word using the Insert/Picture command. The picture can be cropped (eliminate unwanted
portions oI the picture around edges) and resized using the Eormat/Picture command. You can
also use the mouse to do this.
 In Word6 (OIIice 95). "Cropping" is done with the mouse by dragging one oI the six
"handles" while holding down the SHIET key. "Scaling" is done with the mouse by dragging
one oI the handles without using any keys. II you use one oI the Iour corner handles Ior
scaling. the ratio oI height to width will be preserved.
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++
++
¦ McCabe1h1e]e d1ag¡am ¦
¦¦
¦ 11f]e McCabe1h1e]e d1ag¡am ¦
¦ 1sf key componenf Acefone ¦
¦ 2nd key componenf Mefhano] ¦
¦ I]1p No ¦
¦ M1n1mum/Max1mum X 0 0.1 ¦
¦ X 11c 1nfe¡va] 2.0E02 0 ¦
¦ X Labe] X Acefone/1Acefone+Me ¦
¦ M1n1mum/Max1mum Y 0 0.2 ¦
¦ Y 11c 1nfe¡va] 5.0E02 0 ¦
¦ Y Labe] Y Acefone/1Acefone+Me ¦
++ ¦
¦ Oufpuf Dev1ce 5efup ¦ ¦
¦¦ :Doffed ¦
¦ Dev1ce 8MP ¦ :5o]1d ¦
¦ Po¡f A:\1E51.8MP ¦ :5o]1d ¦
¦ Mode ua]f ¦ :5o]1d ¦
¦ Wo¡k pafh ¦ ¦
+++
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06361 page 133 Spring. 2001
 In Word7 (OIIice 97). "Cropping" is done with the mouse using the 'Crop Tool¨ which is
shown by the icon at right. The Crop Tool can usually be Iound on the Picture toolbar. which
can be displayed with the View/Toolbar command.
Einally. you can position the graph anywhere on the page:
 In Word6. you can enclose the picture in a Irame and the move the Irame. Make sure the
picture is selected (a single click oI the mouse) and the six handles appear around it. Use the
"Insert Erame" command Irom the "Insert" menu. The program might ask iI you want to
switch to "Page View". Answer "yes". Once in pageview. you can drag the picture to the
desired position with the mouse. You can also use the "Eormat Erame" command to position
the picture and to control "text wrapping" etc.
 Word7 uses Textboxes instead oI Irames. When inserting the picture Irom Iile. check the
'Eloat over text¨ option oI the Insert Picture dialog box. This puts the picture inside a
Textbox which can be dragged anywhere on the page and text will wrap around it. II you
have already imported the picture and did not check this box. you can still do so by selecting
the picture with a single click. then use the Eormat/Obiect command. In the Eormat Obiect
dialog. click on the Position tab and check the 'Eloat over text¨ option.
You can add text. equations. drawings. and more bitmaps. Once you have the document looking
the way you want. print it using the "Eile/Print" command.
TESTING THE MCCABETHIELE METHOD
Now that we have some idea how to run ChemSep. let's use it to test the validity oI the
assumptions oI the McCabeThiele method. The main assumption is "equimolal overIlow." We
showed that iI 1) you neglect sensible heat changes compared to latent heat and 2) you assume
that the latent heat oI vaporization is independent oI composition. then the molar Ilowrates oI
liquid and vapor streams do not vary Irom stage to stage.
ProIiles oI liquid and vapor Ilowrates can be plotted using the Results/Graphs/Flow
Profiles command. Eor the description above. we obtain the graph below on the leIt:
06361 page 134 Spring. 2001
The discontinuity oI Ilowrates on the 17
th
stage occurs because this is the Ieed tray. Because the
Ieed is 30° liquid in the bottom cascade is higher than in the top; because the Ieed is 70° vapor
Ilowrate in the top cascade is higher than in the bottom. There is also a drop in both liquid and
vapor Ilows at the top oI the column. This drop occurs because oI the subcooled reIlux.
Beyond the expected changes in Ilowrates at the Ieed tray and at the top. there is a continuous
drop in Ilowrate oI both streams as we move down either the rectiIying cascade or the stripping
cascade. These changes in Ilowrates within a cascade are not consistent with the equimolal
overflow assumption.
The second graph on the right above is what would be predicted by making the equimolal
overIlow assumption. We Iorced Chemsep to make the equimolal overIlow assumption by
altering slightly the thermodynamic model. Navigating back to the
Input/Properties/Thermodynamic models menu. we change the Enthalpy setting to None:
06361 page 135 Spring. 2001
Selecting Return and reSolveing the model leads to the Ilowrate proIiles shown on the right
side.
These variations in Ilowrate within a cascade
stem Irom the Iact that the enthalpy oI
saturated liquid is not independent oI
temperature or acetone content as is required
Ior "equimolal overIlow." The plot at right
shows the liquid and vapor enthalpies. and the
mole Iraction oI acetone in the liquid. versus
stage number.
+
Eor equimolal overIlow. the enthalpy proIiles
should be two vertical lines. Clearly. they are
not vertical lines. The departure arises because
the heat oI vaporization oI acetone and
methanol are not quite equal. The Iollowing
values were read Irom the ChemSep library:
ì
acetone
÷ 29.5 kJ/mol
ì
methanol
÷ 35.3 kJ/mol
+
To obtain these plots. I customized the "liquid phase composition profile" graph  deleting the methanol
composition. and adding the enthalpies using the 'top axis¨ for enthalpy.
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++
¦ Componenfs ¦
¦ Ope¡af1on ¦
¦ P¡ope¡f1es ¦
++
¦ 1he¡modynam1c mode]s ¦
++
¦ 1he¡modynam1c mode]s: ¦
¦¦
¦ kmode] EO5 ¦
¦ Acf1v1fy coeff1c1enf ¦
¦ Equaf1on of 5fafe Pengkob1nson ¦
¦ vapou¡ p¡essu¡e ¦
¦ Enfha]py None ¦
¦¦
¦ kefu¡n ¦
++
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06361 page 136 Spring. 2001
How important are these enthalpy diIIerences? On the McCabeThiele diagram. these
diIIerences show up as curvature in the operating lines.
The plot at right shows points taken Irom
the operating lines in the rigorous
ChemSep separation and compares them
with the ROL and SOL calculated using
the McCabeThiele method.
+
These
calculated operating lines are the straight.
solid lines on the plot.
There is very little diIIerence. A closer
examination reveals that the maximum
diIIerence in mole Iraction is 0.00473.
which occurs on stage 19. Put another
way. the main prediction Ior this problem
is what the distillate composition and
Ilowrate will be
Enthalpy Model x
D
D/F
Excess 0.7161 0.3399
None 0.7142 0.3408
The diIIerence between the two is
insigniIicant. This insigniIicant diIIerence is typically the case when the molar heats oI
vaporization diIIer by less than 20°.
+
This graph was produced by EXCEL after importing the WK1 file produced by "Results Spreadsheet" menu of
ChemSep.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Acetone in Liquid
A
c
e
t
o
n
e
i
n
V
a
p
o
r
Excess
None
45deg
Equilib
06361 page 137 Spring. 2001
THE TEMPERATURE PROFILE
Another interesting proIile which can be
plotted by ChemSep is temperature. The plot
at right is obtained Ior the current problem.
Notice that the hotter temperature occur at the
bottom oI the column. This is because the
bottoms contain the less volatile component
which has the higher boiling point.
DEGREES OF FREEDOM
ChemSep lets you speciIy a number oI
attributes oI the distillate and bottoms streams. We saw this list when we speciIied the condenser
and the reboiler. In particular. there were 10 diIIerent kinds oI speciIications which can be made
regarding the condenser. product stream or reIlux (see page 127):
1. ReIlux ratio
2. Heat duty oI condenser
3. Temperature oI condensate
4. Distillate Ilow rate
5. ReIlux Ilow rate
6. Component Ilow
7. Mole Iraction oI a component
8. Component recovery ()
9. Eraction oI combined Ieeds recovered ()
10.Split between two components
There are also 10 diIIerent speciIications which can also be made about the reboiler (see page
128).
1. Boilup ratio
2. Heat duty oI reboiler
3. Temperature oI reboiler
4. Bottom product Ilow rate
5. Reboiled vapour Ilow
6. Component Ilow
7. Mole Iraction oI a component
06361 page 138 Spring. 2001
8. Component recovery
9. Eraction oI combined Ieeds recovered
10.Split between two components
How many oI these are independent? In ChemSep. you must speciIy the number oI stages in
each section. the pressures everywhere. and a complete description oI all Ieeds. Then it turns out
that there are really only two degrees oI Ireedom leIt: there are only two additional aspects oI the
solution which you can speciIy.
We conclude by comparing the list oI inputs and outputs Ior the two techniques we have
examined. The comparison assumes we have ideal stages. constant pressure. a total consender
producing a saturated liquid product. and a partial reboiler.
Solution by McCabeThiele Graphical Method
Given:
1. x
D
2. desired x
B
3. R ~ R
min
4. N
E
or use oI optimum Ieed
Eind:
1. N
S
2. (actual x
B
)
Solution by Chemsep
Given:
1. x
D
2. x
B
3. N
E
4. N
S
Eind:
1. R
06361 page 139 Spring. 2001
Chapter 14. Gas Absorption/Stripping
gas absorption  2 components oI a gas are separated by contact with
a liquid (in which one component is preIerentially soluble)
stripping  2 components oI a liquid are separated by contact with a
gas
An example oI gas absorption is the removal oI
ammonia Irom air by contact with liquid water.
Ammonia is very soluble in water whereas air is only
slightly soluble.
Both gas absorption and stripping involve at least
three components. Usually only one oI these
components crosses the phase boundary. In the
example oI ammonia and air. ammonia is the
component whose molar Ilowrate changes by the
largest percentage oI the inlet value. Although some
air will also dissolve in water. and some water will
evaporate into the air. the molar Ilowrates oI air and
water change by negligible Iractions: their Ilows can
usually be considered constant.
These are the two main diIIerences between them and
distillation: 1) at least 3 components. and 2) oIten
only "one transIerrable component". By constrast. in
distillation. all oI the components are present in both
phases.
EQUIPMENT FOR ABSORPTION/STRIPPING
Although liquid and gas streams Ior absorption or
stripping could be contacted using a tray column (like
that used in distillation). tray columns are seldom
used. The reason is that tray eIIiciencies are generally
much lower Ior absorption and stripping than Ior
distillation (perhaps only 5° instead oI 50°).
Because oI this very low eIIiciency. very large
numbers oI trays are required  perhaps 100's or
1000's. Eabrication costs iust become prohibitively
expensive. Eortunately. a viable alternative exists:
the packed tower.
06361 page 140 Spring. 2001
A packed tower is simply a tube or pipe. which is Iilled with some sort oI "packing." The
packing typically consists oI particles around an inch in diameter. In commercial packed towers.
the usual choice are particles with one oI three diIIerent shapes:
 raschig ring (which is iust a piece oI pipe which has been cut into segments. whose length
and diameter are about the same)
L D ~ ~
1
2
to 1 inches
1
2
 Berl saddle
 Pall ring
Although. in a pinch. almost anything you have laying around would do  pingpong balls. golI
balls. etc. The purpose oI the packing is to promote good contact between the liquid and vapor
streams which are being brought together to permit interIacial mass transIer.
The liquid stream is usually Ied into the top oI the tower while the vapor is Ied into the bottom.
Thus we have countercurrent Ilow oI the two streams. which has the same advantages Ior mass
transIer as it did Ior heat transIer.
The packing promotes good contact between the phases by dividing the two Ieed streams into
many parallel interconnected paths. Ideally. you would like the liquid to Ilow downward as a
thin Iilm over the surIace oI the packing. This would give the maximum surIace area oI contact
between the gas and liquid.
II you iust pour the liquid Irom the end oI the pipe onto the top oI the packing in tower having
much larger diameter than the pipe. most oI the packing will not even be wet. Only some oI the
channels will be carrying Ilow. This is called:
06361 page 141 Spring. 2001
channeling  maldistribution oI liquid Ilow
So some sort oI device to distribute the Ilow over the entire cross section oI the tower is needed.
This device is called a distributor.
Even iI the Ilow is evenly distributed at the top oI tower. channeling might still develop as the
Iluid trickles down. When two thin Iilms converge they tend Ior Iorm a thick Iilm and a dry
patch. which results in a reduction in contact area. So redistributors are placed every 1015 Ieet
along the length oI the tower.
A TYPICAL ABSORBER DESIGN PROBLEM
To motivate the next Iew lectures. let`s pose a typical design problem. Eor this example. I'm
going to take Prob. 221 Irom McCabe.
Smith & Harriott.
Problem: treat 500 SCEM oI air containing
14 mol° acetone to remove 95° oI the
acetone by absorption in liquid water in a
packed bed operating at 80°E and 1 atm.
with 1inch raschig rings. The Ieed water
contains 0.02° acetone and the Ilowrate is
1.1 times the minimum.
The partial pressure oI acetone over an
aqueous solution at 80°E can be calculated
Irom
p P x x
A A
o
A A A
= = ÷
( )
¸ ¸ where ln . 195 1
2
where P
A
o
÷ 0.33 atm is the vapor pressure oI acetone at 80°E. As the designer. you must select
the Iollowing:
500 SCEM
air containing
14 mol° acetone
water with
0.02° acetone
÷ 1.1 L L
min
80° E
1 atm
recover 95°
oI acetone
06361 page 142 Spring. 2001
 Ilowrate oI water
 diameter oI tower
 height oI packing
Solution Overview:
Choice of liquid flowrate: L L = 1.1 to 1.5 times
min
Just as with distillation. there is a minimum L/J required to achieve the desired separation. In
typical operation oI an absorber. the liquid rate is chosen to be iust above the minimum.
Tower diameter:
Ap
Z
T
= 0.25 to 0.5
inch H 0
It oI packing
2
The diameter oI the tower is usually chosen on the basis oI pressure drop. Generally. Ior a
particular L and J. the smaller the column diameter. the larger the mass velocities will be. and
the larger the pressure drop. Generally. large mass velocities are desirable because they give high
mass transIer coeIIicients. but too large mass velocities cause 'Ilooding¨ which severely
decreases mass tranIer rates. The pressure drop above is about optimum.
Tower height: Z
J S
K a
dv
v v
T
v
H
v
v
N
Ov
a
b
Ov
=
÷
*
.
The height oI the tower is determined by mass transIer rates. Basically. the gas and liquid phases
need to be in contact Ior a certain time Ior the acetone to diIIuse Irom the gas phase into the
liquid. The equation above is called the "design equation".
H
J S
K a
Ov
v
÷
is called the height of one transfer unit. where K
y
a is the overall mass transIer coeIIicient times
the interIacial area per unit volumn oI packing. and
N
dv
v v
Ov
v
v
a
b
÷
÷
*
is called the number of transfer units.
*
where v is the mole Iraction oI the transIerable
component and vv* is the local driving Iorce Ior mass transIer.
*
This particular formula is for dilute solutions. which is probably not really applicable to the current example. but it
is applicable in the homework problems.
06361 page 143 Spring. 2001
Detailed Solution:
Eirst oI all. what is 'SCEM¨? This stands Ior 'standard cubic Ieet per minute¨
SCEM ÷ standard (0°C. 1 atm) cubic Ieet per minute
where 'standard¨ means that the volume is evaluated at standard conditons. We can convert
SCEM into moles. Starting with the ideal gas law.
PJ nRT =
or
J
n
RT
P
R K
atm
= =
°
= =
273
1
22 4 359
.
liters
gmol
It
lbmol
3
depending oI which set oI units are used to express R. Recall that a gmol is the quantity oI
material whose mass equals the molecular weight in grams. Similarly. a lbmol is the quantity oI
material whose mass equals the molecular weight in pounds. Eor example. air has a molecular
weight oI 29:
MW oI air
g
gmol
lb
lbmol
= = 29 29
Thus we can convert 500 SCEM into a molar Ilowrate:
500
359
139
It min
It lbmol
lbmol
min
3
3
= = . J
Now let`s move on to determine the liquid Ilowrate required. Recall that in distillation the slope
oI the ROL is given by
slope oI ROL = =
+
L
J
R
R 1
You should also recall that there exists a minimum value oI the reIlux ratio Ior any given
combination oI product and Ieed speciIications. This minimum value oI R translates into a
minimum allowable L/J. There is a similar minimum L/J Ior gas absorption. To Iind the
minimum reIlux ratio in distillation. we needed to plot an operating line and an equilibrium
curve.
EQUILIBRIUM CURVE
In Prob. 221. McCabe gives us equilibrium data in the Iorm oI partial pressure oI acetone in
the gas phase. p
A
. as a Iunction oI the mole Iraction oI acetone in the liquid. x:
06361 page 144 Spring. 2001
p P x
A A
o
A
= ¸ (109)
P
A
o
÷ vapor pressure oI acetone at 80°E ÷ 0.33 atm
¸
A
÷ activity coeIIicient Ior liquid mixture
Activity coeIIicient is a measure oI nonideality oI the liquid phase. Eor ideal solutions the
activity coeIIicient is unity:
¸
A
÷ 1 (ideal solution)
Eor ideal solutions. (109) reduces to Raoult`s law. Our solution oI acetone in water is not ideal.
but McCabe kindly gives us a model
ln . ¸
A
x = ÷ 195 1
2
Note that ¸
A
÷ 1 (i.e. ln¸
A
÷ 0) as x ÷ 1. This is a
general rule: pure components also behave ideally
since nonideal behavior results Irom interactions
between diIIerent molecules; there are no diIIerent
molecules when the Iluid is pure. We can obtain an
expression Ior the mole Iraction oI acetone in the
gas iust by dividing the partial pressure by the total
pressure:
v
p
P
A
=
where we use P ÷ 1 atm. Repeating this Ior
diIIerent x`s to obtain v`s up to 0.14 (the Ieed
concentration). we obtain the curve at right. where
x ÷ mole Iraction oI acetone in the liquid (2
nd
component is water)
v ÷ mole Iraction oI acetone in the gas (2
nd
component is air)
OPERATING LINE
Suppose we are trying to absorb acetone Irom a mixture oI air and acetone by contacting the
air mixture with water. Let
x
v
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0 0.02 0.04 0.06 0.08 0.1 0.12
06361 page 145 Spring. 2001
L.J ÷ total molar Ilowrates
x.v ÷ mol.Irac. oI transI. comp.
where the transIerrable component is acetone in this
example. PerIorming a component balance on the
transIerrable component about the top section oI the
tower yields:
L
a
x
a
¹ Jv ÷ Lx ¹ J
a
v
a
(110)
Solving Ior v:
v
L
J
x
J v L x
J
a a a a
= +
÷
This relationship v(x) between the mole Iractions in the liquid
and gas streams is again known as the operating line. since the
relationship is imposed by a component mole balance. However
as acetone is transIerred Irom the gas to liquid. L and J change.
In particular. their ratio changes. Thus the operating line is not
straight. This makes it diIIicult to determine the minimum
water Ilowrate
There are two limiting cases where we can easily predict the
change in L and J.
Approx. #1: Onlv One 1ransferable Component
It is oIten possible to assume that only one component is undergoing tranIer between the
liquid and gas streams. Eor example. in our problem acetone is being transIerred Irom the air to
the water:
transIerable: acetone
nontransIerable: air. water
Although some oI the water will evaporate when it contacts the air and some oI the air will
dissolve in the water. the molar rates oI transIer oI these components can oIten (but not always)
be neglected compared to rate oI acetone transIer. When you can neglect the molar transIer rate
oI all but one component. then signiIicant simpliIication can be made. II we can neglect
evaporation oI water and dissolution oI air. then the moles oI water (the nontransIerable
component) in the liquid stream must be the same at all elevations:
(1x)L ÷ L´ ÷ const so L
L
x
=
'
÷ 1
(111)
E
C
OL Ior
L
min
x
a
v
a
v
b
OL`s Ior
inc L
06361 page 146 Spring. 2001
Similarly. the moles oI air in the gas stream must be the same at all elevations:
(1v)J ÷ J´ ÷ const so J
J
v
=
'
÷ 1
(112)
(111) and (112) into (110):
'
÷
+
'
÷
=
'
÷
+
'
÷
L x
x
J v
v
L x
x
J v
v
a
a
a
a
1 1 1 1
where L´.J´ are constants. II we now express concentrations in terms oI mole ratios instead oI
mole Iraction:
X
x
x
÷
÷
=
1
moles oI A in liquid
moles oI non  A in liquid
Y
v
v
÷
÷
=
1
moles oI A in gas
moles oI non  A in gas
then this equation becomes very simple:
L´X
a
¹ J´Y ÷ L´X ¹ J´Y
a
or Y
L
J
X Y
L
J
X
a a
=
'
'
+ ÷
'
'
(113)
Since L´/J´ ÷ const. this is the equation oI a straight line.
Thus Ior the special case oI onetransIerable component.
the operating line is straight on mole ratio coordinates.
Note that mole ratios need not be smaller than unity:
0 s x s 1
but 0 s X s ·
although they are in this example.
Let`s apply this 'one transIerable
component¨ approximation to Prob. 221.
One point on the operating line is (X
a
.Y
a
).
We are told that the inlet water contains a
small amount oI acetone:
x
a
÷ 0.0002 ÷ X
x
x
a
a
a
=
÷
=
1
0 0002 .
06361 page 147 Spring. 2001
The concentration oI acetone in the gas phase is determined Irom the speciIication that we want
to remove 95° oI the acetone Irom the Ieed:
v J v J
a a b b
= 0 05 .
v
J
v
v
J
v
a
a
b
b
'
÷
=
'
÷ 1
0 05
1
.
Since J´ (the molar air Ilowrate) is the same at either end oI the column. we can cancel it out.
leaving
Y Y
a b
= =
÷
=
0 05 0 00814
014
1 014
01628
. .
.
.
.
The second point on the operating line must lie somewhere along the line
Y ÷ Y
b
÷ 0.1628
When you plot this up. you Iind that the
equilibrium curve is below the operating
line. This is generally true Ior gas
absorption and makes sense when you
realize that the gas must be richer in the
ammonia than at equilibrium otherwise
the acetone would not spontaneously
absorb into the liquid.
Note that there is a minimum slope which
the operating line can have beIore a
'pinch¨ developes with the equilibrium
curve. This minimum slope represents the
minimum value oI
'
'
=
÷
÷
=
L
J
min
. .
. .
.
01628 0 00814
0 081 0 0002
191
' = ' = × = L J
min
. . . . 191 191 139 2 66
lbmol
min
lbmol
min
Multiplying this by the molecular weight oI water (18 lb/lbmol) and dividing by the density oI
water (8.33 lb/gal) yields a minimum water Ilowrate oI 5.75 gal/min.
X
Y
0
0.04
0.08
0.12
0.16
0 0.02 0.04 0.06 0.08 0.1
06361 page 148 Spring. 2001
Approx. #2: Dilute Solution
In other problems. the solutions might be very dilute. II the solutions are suIIiciently dilute. then
mole ratios are virtually equal to mole Iraction:
iI x ·· 1
then 1x ~ 1
and X
x
x
x ÷
÷
~
1
When this is also true Ior the gas stream. then (113) can be approximated as
v
L
J
x v
L
J
x
a a
=
'
'
+ ÷
'
'
In Iact. we can also drop the prime. since L´ ~ L:
v
L
J
x v
L
J
x
a a
= + ÷
Thus the operating line will also be linear on mole Iraction coordinates iI the solutions are
suIIiciently dilute. This linear operating line on mole Iraction coordinates will also apply even iI
we have more than one transIerrable component. provided both phases are sufficientlv dilute in
all the transferrable components.
INTERFACIAL MASS TRANSFER: REVIEW
An important design parameter is the depth oI packing required. In distillation. the tower
height was determined by the number oI plates required times the plate separation (which is
usually 12 Ieet). The number oI plates required Ior a given separation is determined by the
operating and equilibrium lines. Eor packed towers. the height also depends on the operating and
equilibrium lines. but in addition it is inversely proportional to the mass transfer coefficient.
which in distillation plays only a minor role in determining plate eIIiciency.
Now that we have established the importance oI interIacial mass transIer in packed towers. let's
talk about modelling mass transIer across a phase boundary.
06361 page 149 Spring. 2001
Let's start by recalling the driving Iorce Ior heat transIer
across an interIace. Suppose I contact a hot gas with a
cold liquid. The temperature proIile near the interIace
will look something like that show at right. There are
two characteristics oI this sketch which are important:
1. heat Ilows Irom high to low temperature
2. temperature is continuous across the interIace
InterIacial mass transIer is similar to interIacial heat
transIer. but it is also diIIerent.
1. mass transIer occurs in the direction Irom
high to low chemical potential (not
necessarily Irom high to low
concentration
*
)
2. chemical potential is continuous across
interIace (concentration is generally not
continuous)
The main diIIerence is evident in the sketch oI the
concentration proIile near the interIace. Note the discontinuitv in the mole fraction at the
interface.
+
v
i
= x
i
T
vi
÷ T
xi
÷ T
i
The reason Ior this discontinuity in concentration across the interIace has to do with
thermodynamic criteria Ior phase equilibrium. Recall:
phase equilibrium: u
i
J
÷ u
i
L
Ior i÷1.....N
c
thermal equilibrium: T
J
÷ T
L
where u
i
is called the chemical potential which plays
the role oI temperature in mass transIer. UnIortunately.
there exists no 'thermometer¨ Ior measuring chemical
potential. Instead. we are Iorced to measure chemical
concentration. While chemical potential usually
*
Within a single phase. transport is usually from high to low concentration.
+
Instead of component i. the subscript 'i ¨ will be used to denote quantities evaluated at the interface between two
phases. In place of i. we will use i to denote components.
06361 page 150 Spring. 2001
increases with concentration within any given phase (this is why diIIusion oI a solute occurs
Irom high to low concentration). when comparing chemical potentials between two phases. there
is no general correlation between chemical potential and concentration.
To illustrate this. recall the simplest case oI VLE: an ideal gas mixture in equilibrium with an
ideal solution. This leads to Raoult's law:
v P x P
i i i
o
=
Note that:
v
x
P
P
i
i
i
o
= = 1
Thus v
i
= x
i
Ior VLE
even in the simplest case oI vaporliquid equilibrium. the mole Iractions are not equal. except in
the trivial case when you have only one component and the total pressure is the vapor pressure.
Definitions of 1ransfer Coefficients
Recall Irom the Iirst part oI this course. the local heat Ilux through the interIace can be
related to the local temperatures using any one oI three types oI local heat transIer coeIIicients:
rate oI heat transIer
interIacial area
= ÷ = ÷ = ÷ h T T h T T U T T
x h i v i c h c
(114)
where h
x
.h
v
÷ onephase local heat transIer coeIIicients
U ÷ overall local coeIIicient.
Basically these equations say that the rate oI heat transIer is proportional to the driving Iorce
(which is the departure Irom equilibrium) and the proportionality constant is the heat transIer
coeIIicient.
Similar deIinitions oI transport coeIIicients can be made Ior mass transIer:
molar rate oI transIer
interIacial area
= ÷ = ÷ = ÷ = ÷ k x x k v v K x x K v v
x i v i x v
( ) ( ) ( * ) ( *) (115)
where k
x
.k
v
÷ onephase local mass transIer coeIIicients
K
x
.K
v
÷ overall local mass transIer coeIIicients
Comparing the mass transport expressions in (115) with their heattransIer analogues in (114).
there is a good deal oI similarity especially in the onephase relations. Eor a single phase. the
06361 page 151 Spring. 2001
driving Iorce is the diIIerence between the concentration or temperature in the bulk and in the
concentration or temperature at the interIace.
But the driving Iorce Ior the overall coeIIicients look a little diIIerent. The overall driving Iorce
Ior heat transIer is iust the diIIerence between the temperature oI the hot and cold Iluid
T
h
 T
c
By simple analogy. you might expect the overall driving Iorce Ior mass transIer to be the
diIIerence in concentration oI the two phases:
v  x = overall driving Iorce
Instead v  v* and x*  x
appear in (115) as the overall driving Iorce. The *'s are
deIined as shown on the Iigure at right. Basically v  v* and
x*  x are two diIIerent measures oI the distance between the
operating line and the equilibrium curve at that elevation in
the packed bed where the liquid and gas concentrations are
(x.v).
xv does not represent the overall driving Iorce Ior mass transIer. because the transport rate does
not go to zero when xv ÷ 0. The tranport rate is zero only at equilibrium. and xv = 0 at
equilibrium.
Determining the Interfacial Concentrations: (x
,v
)
Although overall masstransIer coeIIicients are the most easy to use in design. correlations
are sometimes more available in the Iorm oI singlephase coeIIicients. We may have a need to
calculate overall coeIIicients Irom the singlephase coeIIicients. Eor example. in Prob. 221 we
are given the values oI H
x
and H
v
. II we had instead the value oI H
Ov
we could use the value oI
N
Ov
we computed last time to calculate the height oI packing. In what Iollows. we derive a
relationship among H
Ov
. H
x
and H
v
.
Consider once again. the rate oI interIacial transport at some arbitrary
elevation in the absorber. denoted by the dotted line in the Iigure at right.
The proIile oI concentration oI the
tranIerable component near the
interIace at this location in the
absorbed looks like the sketch below
at leIt.
At steady state. the Ilux oI ammonia
through the gas Iilm must equal the
Ilux oI ammonia through the liquid
06361 page 152 Spring. 2001
Iilm:
N
A
÷ k
x
(x
i
x) ÷ k
v
(vv
i
) (116)
II the Iluxes were not equal. we would have ammonia building up at the interIace. We will
denote this interIacial Ilux by N
A
.
Suppose the bulk compositions x.v are known. together with the two singlephase mass
transIer coeIIicients. To determine the Ilux. we must also determine the interIacial compositions
x
i
.v
i
. Think oI these two interIacial concentrations as two unknowns. We need two
equations. One equation is provided by the requirement that (x
i
.v
i
) must lie on the equilibrium
curve. The second relation is (116). which can be rewritten as a linear relationship between v
i
and x
i
:
v
k
k
x v
k
k
x
i
x
v
i
x
v
= ÷ + +
slope
intercept
.
(117)
The intersection oI (117) and the equilibrium
curve gives the interIacial concentrations.
Example: In Prob. 221. we are given values oI
the heights oI both singlephase coeIIicients (H
x
and H
v
) and need to evaluate the height oI the overall gasphase coeIIicient (H
Ov
).
Solution: Consider the Iollowing problem:
Given: k
x
and k
v
Eind: K
v
Using the deIinitions oI the k´s and oI K
v
.
N
A
÷ k
x
(x
i
x) ÷ k
v
(vv
i
) ÷ K
v
(vv*) (118)
The relationship among the concentrations is
shown in the Iigure at right. Adding and
subtracting v
i
Irom
the overall driving Iorce v
v*:
* *
A A
v v
i i
N N
K k
v v v v v v ÷ = ÷ + ÷
. .
(119)
Using (118) we can assign meaning to two oI
the three diIIerences appear above. leaving:
slope = ÷
k
k
x
v
slope = ÷
k
k
x
v
06361 page 153 Spring. 2001
*
i
A A
i
v v
x x m
N N
v v
K k
÷
= + ÷
.
(120)
The remaining diIIerence v
i
v* can be related to x
i
x and the local slope oI the equilibrium curve
m:
*
A
i i
x
N
v v x x m m
k
÷ = ÷ = (121)
In the second equality above. x
i
x is expressed in term oI the remaining singlephase mass
transIer coeIIicient using (116). Substituting (121) into (120) and dividing by N
A
:
1 1
K k
m
k
v v x
= + (122)
where
*
i
i
v v
m
x x
÷
=
÷
÷ avg. slope oI E.C.
OI course. iI the equilibrium curve is straight (as it will be in dilute solutions). then m is its slope.
This is similar to the expression Ior overall heat transIer coeIIicients Ior a doublepipe heat
exchanger:
1 1 1
U h h
x v
= + (123)
We said that 1/U represented the total resistance to heat transIer through the two phases. which is
iust the sum oI the resistances oI each phase. The main diIIerence between (122) and (123) is the
appearance oI m in (122). Eor heat transIer. the slope oI the equilibrium line is unity (m ÷ 1)
because at thermal equilibrium T
v
÷ m T
x
÷ T
x
.
In short. (122) states that the total resistance to mass transIer equals the sum oI the resistances oI
the gas and liquid phases. We could also have showed. in a similar Iashion. that
1 1 1
K mk k
x v x
= + (124)
where now:
*
i
i
v v
m
x x
÷
=
÷
II the operating line is straight. these two slopes would be the same and we could relate the two
overall mass transIer coeIIicient:
06361 page 154 Spring. 2001
straight E.C.:
1
v x
m
K K
=
Equimolar CounterDiffusion vs. Diffusion through Stagnant Fluid
In the Iorm most analogous to Eourier's law oI heat conduction. Fick's law oI diIIusion oI a
binary mixture oI components A and B. the Ilux (moles/area/time) oI component A in the ¹z
direction is given by
* A
Az AB
dc
J D
dz
= ÷
where c
A
is the molar concentration oI component A and D
AB
is the diIIusion coeIIicient. This
gives the Ilux oI A relative to a reIerence Irame which moves with the moleaverage velocity (i.e.
the average oI the species velocity oI each component) oI the mixture (A¹B). More useIul in
calculations is the molar Ilux oI A relative to a stationary reIerence Irame is
*
mol average velocity
Az
A Az Bz
Az AB A
v
J
dc N N
N D c
dz c
=
+
= ÷ +
. .
(125)
where c ÷ c
A
¹c
B
is the total molar concentration.
Case I: II we use a capillary tube to connect two gas reservoirs having the same total pressure
but diIIerent amounts oI gases A and B (see Eig. 6.21). we will obtain equimolar counter
diffusion oI A and B (i.e. N
Az
÷ N
Bz
). In this way. the moleaverage velocity v ÷ 0 and the total
pressure in both reservoirs remains constant. Eor N
Az
÷ N
Bz
. (125) gives
* A
Az AB Az
dc
N D J
dz
= ÷ = (126)
Case II: II instead. we have diIIusion oI benzene vapor above its liquid through air (which is
virtually insoluble in the liquid). the air must remain stagnant (i.e. N
Bz
÷ 0) since it cannot enter
the liquid (see Eig. 6.22a). This is diIIusion oI A through stagnant B. Eor N
Bz
÷ 0. (125) gives
A
A A
Az AB Az
v
dc c
N D N
dz c
= ÷ + or
*
1
Az
A
A Az AB
J
dc
v N D
dz
÷ = ÷
.
Einally we have
*
1
Az
Az
A
J
N
v
=
÷
(127)
06361 page 155 Spring. 2001
Eor the same driving Iorce (concentration gradient).
*
Az
J is the same Ior both cases. but N
Az
are
diIIerent. Since 1v
A
is always less than one. we see that equimolar counterdiIIusion (126) is
slower than diIIusion through a stagnant Iluid (127). This can be qualitatively understood as
Iollows. Suppose that to get to class. you need to walk down a corridor that's crowded with other
students. II everyone else was standing almost still (stagnant Iluid). it would be easier to walk
around them than iI everyone is walking toward you (counter diIIusion).
All oI the Ilux expressions above apply locally at every point in the Iluid. Eor 1D steady
equimolar counterdiIIusion (Irom a reservoir having c
A1
to a second reservoir having c
A2
). (126)
integrates to
*
1 2 1 2 1 2
2 1 2 1
AB AB
Az Az A A A A v A A
D cD
N J c c v v k v v
z z z z
' = = ÷ = ÷ = ÷
÷ ÷
(128)
where z
2
z
1
is the length oI the capillary through which diIIusion is occuring and k´
v
is the
singlephase (gas) mass transIer coeIIicient to be used with mole Iractions and equimolarcounter
diIIusion. The analogous expression Ior diIIusion through stagnant Iilm oI B is (see Section
6.2C):
1 2 1 2
2 1
1
AB
Az A A v A A
A
M
cD
N v v k v v
z z v
= ÷ = ÷
÷ ÷
(129)
where
1 2
1
2
1 1
1
1
ln
1
A A
A
M
A
A
v v
v
v
v
÷ ÷ ÷
÷ =
÷
÷
is the logmean oI v
B
evaluated at either end oI the diIIusion path. Comparing (128) and (129).
we see that
1
v
v
A
M
k
k
v
'
=
÷
Similar relations exist Ior diIIusion in the liquid phase:
1
x
x
A
M
k
k
x
'
=
÷
and between the overall masstransIer coeIIicients Ior equimolar counterdiIIusion and diIIusion
through a stagnant Iilm:
*
1
v
v
A
M
K
K
v
'
=
÷
and
*
1
x
x
A
M
K
K
x
'
=
÷
06361 page 156 Spring. 2001
where
*
*
*
1 1
1
1
ln
1
A AG
A
M
A
AG
v v
v
v
v
÷ ÷ ÷
÷ =
÷
÷
and
*
*
*
1 1
1
1
ln
1
A AL
A
M
A
AL
x x
x
x
x
÷ ÷ ÷
÷ =
÷
÷
and where v
AG
is the mole Iraction in the bulk oI the gas.
*
A
v is the mole Iraction which would
be in equilibrium with the bulk liquid having a mole Iraction oI x
AL
. and
*
A
x is mole Iraction in
the bulk oI the liquid which would be in equilibrium with the bulk gas having a mole Iraction oI
v
AG
.
HEIGHT OF A PACKED TOWER
The analysis which Iollows has as its goal the determination oI the height oI packing
required. The approach is similar to that used in the design oI doublepipe heat exchangers in
which the goal is the determination oI the area oI heatexchange surIace required. The main
complication arises Irom the Iact that the mass Ilux is not proportional to vx; instead. the mass
Ilux is proportional to vv*.
We have to chop up the tower into pieces which are small
enough so that the driving Iorce is virtually uniIorm throughout
each piece. Since the compositions change only with z. we chop
up the tower in such a way that we produce pieces which have
z~const. which is a thin horizontal slice.
Now let's take a closer look at what happens inside this slice oI
the tower. The slice contains solid packing as well as liquid and
gas streams. In what Iollows. we will ignore the solid and treat
the liquid and gas phases as iI they were completely separated.
rather than interspersed in each other.
doublepipe hxer analogy:
Let's do a mass balance on the acetone in the gas phase only
contained within our slice oI column. Besides the liquid streams
entering and leaving the slice. we have acetone crossing the
06361 page 157 Spring. 2001
interIace between the gas and liquid phases. The rate oI
absorption per unit area can be expressed in terms oI the local
overall mass transIer coeIIicient:
molar rate oI transIer
interIacial area
= ÷ K v v
v
( *) (130) U T T
o h c
( ) ÷
We could also have used one oI the other expressions in (115);
this one proves later to be more convenient than some oI the
others.
Just like the overall heat transIer coeIIicient U
o
depends on the
Ilowrates oI both Iluids being contacted in the heat exchanger.
the overall mass transIer coeIIicient K
v
depends on both
Ilowrates
K K L J
v v
= .
To obtain the rate oI transIer across the interIace in our slice oI
column. we need to multiply (130) by the interfacial area in that
slice.
In a heat exchanger. the heat transIer surIace is Iixed by the
geometry oI the equipment selected: it is iust the area oI the pipe
wall or the tubes. In particular. the heat transIer area does not
depend on the Ilowrates oI the hot and cold streams. On the
other hand. the boundary between liquid and gas in a packed bed
is very complex and very hard to measure directly. Most
importantly. the area also depends on the Ilowrates oI the gas
and liquid streams (L.J).
The interIacial area is usually expressed as a. the interIacial area
per unit volume oI packing:
interIacial area
volume oI packing
÷ = a a L J ( . ) (131)
t
t
D dz
D dz
D
o
o
o 2
4
2
=
One empirical correlation relating area to Ilowrates is the
Schulman Correlation (Table 6.3 oI Treybal):
a mG G
x v
=
o 
where G
x
and G
v
are the mass Ilowrates oI the liquid or gas
stream divided by the crosssectional area oI the tower
06361 page 158 Spring. 2001
G
D
÷ =
mass time
mass velocity
t
2
4
and where m. o.  are constants which depend on the type and
size oI packing used. Multiplying (130) by (131):
rate oI transIer
interI area
interI area
vol. oI packing
× = ÷ × K v v a
v
( *)
r K a v v
v
÷ = ÷
molar rate oI transIer
volume oI packing
( *) (132)
4U
D
T T
o
o
h c
÷
II we now multiply by the volume oI this slice oI the packed
column. we will obtain the rate at which acetone crosses the
interIace in this slice:
rate oI transIer ÷ r S Az ÷ dN
A
dq U dA T T
o o
D dz
h c
o
= ÷
t
where S ÷ empty tower crosssection ÷
tD
T
2
4
S Az ÷ volume oI slice
At steady state. the rate oI transport oI acetone into the vapor
must equal the rate out:
in ÷ out
(Jv)
z
÷ (Jv)
z¹z
¹ rSAz (133)
`
`
m c T z
m c T z z dq
p
p
p
p
( )
=
+
( )
+ A
Dividing by Az and letting Az ÷ 0. (133) becomes:
d Jv
dz
rS
= ÷ (134)
` m c
dT
dz
dq
dz
U D T T
p
o o h c
p
t
= ÷
= ÷
06361 page 159 Spring. 2001
Now the total molar Ilowrate (J) will change as the gas phase loses acetone. but the Ilowrate oI
acetoneIree air (J´ ) does not change with Z:
J
J
v
=
'
÷ 1
÷ Jv
J v
v
=
'
÷ 1
d Jv d
J v
v
J d
v
v
J
dv
v
J
dv
v
=
'
÷
= '
÷
= = '
÷
=
÷ 1 1
1
1
2
(134) becomes:
J
v
dv
dz
rS K a v v S
v
1÷
= ÷ = ÷ ÷ * (135)
The second equation is obtained by substituting our expression Ior the rate oI absorption r Irom
(132). We can now solve this equation Ior the height dZ oI the slice:
dz
Jdv
v v v K a S
v
=
÷
÷ ÷ 1
*
So iI we know the local mole Iractions v and v* and the change in the mole Iraction dv oI the gas
phase which occurred between the top and bottom oI this slice. we can calculate the height oI the
slice. The total height oI packing is the sum oI the height oI each slice:
Z dz
Jdv
v v v K a S
T
Z
v v
v
T
b
a
= =
÷
÷ ÷
0
1
*
Eactoring out the S. which is constant along the entire height oI the packing. and changing the
order oI integration (since v
b
~v
a
):
Z
S
Jdv
v v v K a
T
v v
v
a
b
=
÷ ÷
1
1
*
Now K
v
depends on G
x
and G
v
. which in turn depend on gas composition. Eor the case oI a
dilute gas stream. we know that
v v J J K a
v
<< ÷ ~ ~ ' = ~ 1 1 1 const const
AIter making these approximations. we have
Z
J
K aS
dv
v v
T
v
H
v
v
N Ov
a
b
Ov
=
÷
.
.
*
(136)
06361 page 160 Spring. 2001
which serves as the basic design equation Ior packed bed absorbers.
Eor very dilute solutions. this integral can be evaluated analytically (i.e. numerical integration
is not required). II both x··1 and v··1 hold. then the molar Ilowrates oI the two streams won't
change much as the solute is transIerred across the phase boundary. In particular. the ratio oI the
Ilowrates will be constant:
then L/J L´/J´ ÷ const
This means that the operating line will be straight. even on mole Iraction coordinates:
v ÷ (L/J)x ¹ v
a
 (L/J)x
a

Also. Ior suIIiciently dilute solutions. Henry's law always applies so that
v* ÷ mx
will also be a straight line. When both operating and equilibrium curves are straight. then the
integration can be done analytically instead oI numerically. The result is:
straight OL & EC: N
v v
v v
Ov
b a
L
=
÷
÷ *
(137)
where v v
L
÷ * is the logmean oI v
b
v
b
* and v
a
v
a
* which represent the driving Iorce at the
bottom and top oI the tower. respectively.
TRANSFER UNIT
Meaning can be given to the integral. Even iI the integrand varies signiIicantly over the
domain oI integration. we can still pull it outside the integral. provided we replace it with some
appropriate value. which can be thought oI as the mean value Ior this range. Recall the Mean
Jalue 1heorem oI Calculus:
dv
v v v v
dv
v v
v v
v
v
v
v
b a
a
b
a
b
÷
=
÷
=
÷
÷
* * *
1
avg avg
(138)
OI course. it is not usually known what type oI average to use. but Ior the present purpose. the
precise value is not important. The integral can be thought oI as the total change in gas mole
Iraction divided by the average driving Iorce.
(Gas Phase) 1ransfer Unit  a slice (not necessarily thin) oI an absorber in which the gas
undergoes a change in v equal to v v ÷ *
avg
which represents the average driving Iorce
over the entire absorber.
06361 page 161 Spring. 2001
Ao. of 1U's  the number oI these it takes to make the entire absorber (not necessarily an
integer)
Height of 1U  height oI a slice oI an absorber corresponding to one TU
Erom (138). we see that the integral clearly represents the number oI transIer units:
N
dv
v v
Ov
v
v
a
b
=
÷
*
(139)
This is called the number oI overall gas phase transfer units since it is based on the overall
driving Iorce expressed as the gasphase mole Iraction. Since the product in (136) represents the
total height oI packing. the coeIIicient oI this integral must represent the height of a transfer
unit:
H
J S
K a
Ov
v
=
avg
So that our design equation can be rewritten as:
Z
T
÷ H
Ov
N
Ov
which is called the H1U method Ior sizing an absorber. Throughout the derivation above we
made use oI one type oI mass transIer coeIIicient:
r ÷ K
v
a(vv*)
OI course. other types oI mass transIer coeIIicient are commonly encountered and can also be
used to compute the height oI packing required:
r ÷ K
x
a(x*x) ÷ k
x
(x
i
x) ÷ k
v
(vv
i
)
to mention a Iew. OI course. there are still more deIinitions based on driving Iorces expressed as
diIIerences in molar concentration or partial pressure. Any one oI these mass transIer
coeIIicients can be used in the HTU method:
Z
T
÷ H
Ov
N
Ov
÷ H
Ox
N
Ox
÷ H
x
N
x
÷ H
v
N
v
where
06361 page 162 Spring. 2001
N
dx
x x
H
L S
K a
N
dx
x x
H
L S
k a
N
dv
v v
H
J S
k a
Ox
x
x
Ox
x
x
i
x
x
x
x
v
i
v
v
v
v
b
a
b
a
a
b
=
÷
=
=
÷
=
=
÷
=
*
avg
avg
avg
Note that the N's are not equal to each other; thus the number oI transIer units depends on which
driving Iorce you use.
N
v
= N
Ov
EVALUATION OF NTU'S
Let's see how this works by
continuing the example we started a
couple oI lectures back (see page
141). The problem is summarized in
the Iigure at right. We want to
evaluate N
Ov
Irom (139). The v in
this expression is the mole Iraction oI
acetone in the absorber at some
particular elevation. II the
corresponding mole Iraction oI
acetone in the water is x. then two are related by the operating line:
v(x): '
÷
÷
÷
= '
÷
÷
÷
L
x
x
x
x
J
v
v
v
v
a
a
a
a
1 1 1 1
(140)
To obtain x
b
÷ 0.07 (speciIied in problem statement) with x
a
÷ 0.0002. v
a
÷ 0.00807 (5° oI
acetone remains with gas) and v
b
÷ 0.14. we Iind that
'
'
=
L
J
2 06 .
With this ratio known. given a value oI v in the interval v
a
s v s v
b
. we can use the operating line
to solve Ior x(v). On the other hand. v*(x) is the mole Iraction oI acetone in the gas. which would
be in equilibrium with a liquid having mole Iraction x.
v x
p
P
P
P
x x x
ace ace
* . exp . = =
'
= ÷ ¸ 0 33 195 1
2
(141)
06361 page 163 Spring. 2001
A plot oI v(x) and v*(x) is shown below at leIt. Neither curve is a straight line on these
coordinates. although the operating line is close.
To evaluate the integral. we need to compute the integrand at various points in the domain:
v x Irom (140) v* Irom (141)
1
v v ÷ *
v
a
÷ 8.07E03 2.00E04 4.64E04 131.401
0.022 7.18E03 0.016 168.635
0.036 0.014 0.031 204.747
0.05 0.021 0.045 225.474
0.063 0.028 0.059 219.902
0.076 0.035 0.071 192.77
0.089 0.042 0.083 158.147
0.102 0.049 0.094 126.193
0.115 0.056 0.105 100.38
0.128 0.063 0.115 80.583
v
b
÷ 0.14 0.07 0.125 65.615
A plot oI the integrand might look something like that shown above at right. The area under this
curve represents N
Ov
.
N
dv
v v
Ov
v
v
a
b
=
÷
=
*
. 210
To evaluate this integral in Mathcad. it convenient to pose v and v* as Iunctions oI x: v(x) is the
operating line given by (140) and v*(x) is the equilibrium curve given by (141). Then
0 0.02 0.04 0.06 0.08
0
0.05
0.1
0.15
0
y
b
y
i
ye
i
x
a
x
b
x
i
0 0.05 0.1 0.15
0
100
200
1
y
i
ye
i
y
b
y
a
y
i
06361 page 164 Spring. 2001
N
dv
v v
v x
v x v x
dx
Ov
v
v
dv
dv
dx
dx v x dx
x
x
a
b
a
b
=
÷
=
'
( )
( )
÷
( )
=
= = '
( )
* *
. 210
The maximum value oI the integrand occurred at the point in the column where the operating line
comes closest to the equilibrium curve. The denominator vv* is a measure oI this distance.
Because the equilibrium curve turns downward in this case. the "pinch" point occurs in the
middle oI the range. In other cases (e.g. NH
3
in water). the equilibrium curve turns upward
instead.
Special Case: y
<<1 with concave downward EC.
The Iigure at right shows a similar plot you
will obtain Ior Prob. 22.2 on the Homework.
In this case. the denominator oI the integrand
becomes very small near the lower limit; thus
the integral has much oI its area under a
'spike¨ located at the lower limit.
To integrate such a Iunction accurately. you
will need a very small grid spacing which
means a lot oI points or at least very small
spacing under the spike which means a
nonuniIorm grid. One solution is to transIorm
the integral by multiplying and dividing the
integrand by v:
N
dv
v v
v
v v
dv
v
v
v v
d v
Ov
v
v
v
v
v
v
a
b
a
b
a
b
=
÷
=
÷
× =
÷
* * *
ln
Thus we plot v/(vv*) versus lnv. Since both
the numerator and the denominator become
small at the lower limit. the quotient tends to
be more near constant with v. allowing the
integration to be done with Iewer points and a
uniIormly spaced grid.
ANALOGY WITH DOUBLEPIPE HXER
Comparing (137) with (138). we see that
Ior very dilute solutions. the average driving
Iorce is the logmean. This result is quite
analogous to our design equation Ior double
0 0.05 0.1 0.15 0.2
0
200
400
y
a
y
b
1
y yeq
y
6 5 4 3 2 1
0
1
2
3
0
lny
0
lny
N
y
y yeq
ln( ) y
06361 page 165 Spring. 2001
pipe heat exchangers. To see this analogy. let's compute the total rate oI ammonia transIer over
the entire packed tower:
q
T
÷ J(v
b
v
a
) (142)
Recall the design equation: Z H N
J S
K a
v v
v v
T Ov Ov
v
b a
L
= =
÷
÷ *
(143)
This contains the product that appears in (142). Solving (143) Ior J(v
b
v
a
)
J v v K a SZ v v
b a v T
L
÷ = ÷
total volume
of packing
*
where SZ
T
is the total volume oI packing in the absorber and a is the interIacial area per unit
volume oI packing. Thus
aSZ
T
÷ total interIacial area in entire absorber ÷ A
T
and substituting in (142) yields:
q
T
÷ K
v
A
T
v v
L
÷ *
which is analogous to: q
T
÷ UA
T
T
L
Thus. Ior dilute solutions. the design equation Ior an absorber is identical in Iorm to that Ior heat
exchangers: with the overall mass transIer coeIIicient K
v
analogous to the overall heat transIer
coeIIicient U and the logmean oI vv* at the two ends oI the absorber analogous to the logmean
AT.
RELATIONSHIPS AMONG H
. H
. H
AND H
In (122) on page 153. we obtained a relationship between the overall masstransIer
coeIIicient and the singlephase masstransIer coeIIicients. This relationship can be easily
modiIied to relate the corresponding heights oI transIer units.
Dividing both sides oI (122) by a (the interIacial area per volume oI packing). we obtain:
1 1
K a k a
m
k a
v v x
= + (144)
where m ÷ (v
i
v*)/(x
i
x) ÷ avg. slope oI E.C.
06361 page 166 Spring. 2001
OI course. iI the equilibrium curve is straight (as it will be in dilute solutions). then m is its slope.
This is similar to the expression Ior overall heat transIer coeIIicients Ior a doublepipe heat
exchanger:
1 1 1
U h h
x v
= + (145)
We said that 1/U represented the total resistance to heat transIer through the two phases. which is
iust the sum oI the resistances oI each phase. The main diIIerence between (144) and (145) is the
appearance oI m in (144). Eor heat transIer. the slope oI the equilibrium line is unity (m ÷ 1)
because at thermal equilibrium T
v
÷ m T
x
÷ T
x
.
In short. (144) states that the total resistance to mass transIer equals the sum oI the resistances oI
the gas and liquid phases. Using (124). we could also have showed. in a similar Iashion. that
1 1 1
K a mk a k a
x v x
= +
where now: m ÷ (vv
i
)/(x*x
i
)
II the operating line is straight. these two slopes would be the same and we could relate the two
overall mass transIer coeIIicient:
straight E.C.: 1/K
v
÷ m/K
x
II we now multiply (144) by J/S we have the height on an overall gas transIer unit on the leIt
hand side:
J S
K a
J S
k a
mJ S
k a
J S
k a
m
J
L
L S
k a
v
H
v x v
H
x
H
Ov v
x
= + = +
Recalling the deIinitions Ior various heights oI a transIer unit we end up with
H H m
J
L
H
Ov v x
= +
06361 page 167 Spring. 2001
Fig. 8. Pressure drop across a packed bed of 1inch ceramic Intalox saddles as a function of
air and water flowrates. Taken from Fig. 224 of MS&H5.
PRESSURE DROP IN PACK BEDS
Usually. Ilow in a packedbed absorber is countercurrent.
Gravity causes the liquid to Ilow down through the packing.
whereas a small pressure drop drives the gas Ilow upward. This
pressure drop plays an important role in packed beds. Without
liquid present. the pressuredrop across dry packing increases
approximately with the square oI the gas Ilowrate (see Eig. 8).
G
v
÷ mass velocity oI gas ÷
lb / hr oI gas
cross  section oI tower
=
M J
S
v
06361 page 168 Spring. 2001
where M
v
is the average molecular weight oI the
gas. Once liquid is Ilowing down the column as
gas is Ilowing up. some oI the space between the
packing particles is taken up by liquid. leaving less
space Ior the gas to Ilow. Eorcing the same gas
Ilow through a smaller opening will increase the
Irictional contribution to the pressure drop. Thus
the curves Ior increasing liquid Ilow are above that
Ior dry packing although the curves tend to be
parallel.
Note that the curves with liquid Ilow curl up at
high gas Ilow rates. This can
be explained as Iollows:
The upward Ilow oI the gas
exerts a shear Iorce on the
liquid. retarding its downward
motion. As the gas Ilowrate
increases so does this shear
Iorce. When the shear Iorce
becomes comparable to gravity.
the liquid Ilow might slow
down and liquid begins to
accumulate in the tower.
The amount oI liquid residing or accumulating in the tower is called:
(liquid) holdup  Iraction oI interstitial volume occupied by liquid
intersticial volume  "empty" space between and inside packing particles; that volume
occupied by liquid or gas.
loading  an increase in liquid holdup caused by an increase in gas Ilowrate
Eor a given liquid Ilowrate. there is a maximum Ilowrate oI gas which can be Iorced through the
column. II you exceed this maximum the shear Iorces on the liquid are so high that they exceed
the weight oI the liquid. Then the net Iorce on the liquid is upward and you blow the liquid back
out the top oI the column. This is called:
flooding  liquid downIlow is essentially stopped by high gas upIlow
Since you can't get the liquid through the column. Ilooding is clearly a condition to be avoided.
Generally. to get a high area oI contact between liquid and gas. you want to operate well below
the Ilooding velocity:
at Ilooding: Ap
f
/L ~ 2 to 3 inch H
2
O/It oI packing
~ 1.8 to 2.0
(turbulent)
06361 page 169 Spring. 2001
loading: Ap
f
/L ~ 0.5 inch H
2
O/It
normal oper.: Ap
f
/L ~ 0.25 to 0.5 inch H
2
O/It
Normal operating pressure drops are iust below those Ior which loading begins.
Notice (Irom Eig. 8) that when we increase
the liquid Ilowrate. Ilooding occurs at
lower gas Ilows. II we increase the size oI
the packing particle. we can tolerate higher
gas Ilows. While higher gas Ilows can be
obtained with larger packing particles. the
amount oI interIacial area is generally less
(i.e. a is decreased). These eIIects are
summarized by Fig. 9 at right.
Eig. 8 and Fig. 9 are Ior a particular
packing (1¨ Intalox saddles) and Ior a
particular temperature and pressure (20 °C
and 1 atm). A more general correlation oI
pressure drop is provided by Fig. 10. The
size and type oI packing is accounted Ior
in this correlation through the parameter
F
p
÷ packing factor
Values oI the packing Iactor Ior various
types oI packing are given in Eig. 11. The vcoordinate oI this
graph in Fig. 10 is not dimensionless. so you need to use the units
summarized in the table at right.
TOWER DIAMETER
Once the total molar liquid and gas Ilowrates (L and J) are known. we can choose the
diameter oI tower we need. The diameter oI the tower is usually chosen such that the pressure
drop is some prescribed value below Ilooding:
choose D
T
such that:
T
dp p
dz Z
A
÷ = ~ 0.25 to 0.5 inch H
2
O/It oI packing
The pressure drop depends on the mass velocities:
Ap
Z
T
÷ f(G
v
.G
x
)
Eig. 9. Air flowrate at which flooding
occurs for ceramic Intalox saddles at
different water flowrates. Taken from Eig.
22.5 in MS&H5.
Symbol Units
G
x
. G
v
lb/It
2
s
u
x
cP
p
x
. p
v
lb/It
3
g
c
32.2 lb
f
It/lbs
2
06361 page 170 Spring. 2001
where G
M L
S
M L
x
x x
D
÷
= =
mass Ilowrate oI liquid
cross  sectional area oI column t
4
and where M
x
is the average molecular weight oI the liquid.
Similarly. G
M J
S
v
v
=
Eig. 10. General correlation of pressure drop across packed beds. Taken from Eig. 22.6 of
MS&H5.
06361 page 171 Spring. 2001
Eig. 11. Characteristics of common packings. Taken from Table 221 of MS&H5.
So to get a certain pressure drop Ior a certain set oI Ilowrates. we must choose a particular value
Ior the tower diameter. Although it looks like you have to guess the diameter D
T
in order to
calculate G
x
and G
v
to get Ap. a trialanderror can be avoided by noting that the abscissa
(xcoordinate) does not depend on the diameter:
G
G
M L
S
M J
S
M L
M J
x
v
x
v
x
v
= =
06361 page 172 Spring. 2001
Note that the unknown crosssectional area S conveniently cancels out. What remains is known.
So the procedure is as Iollows:
Given: L. J
Eind: D
T
Solution:
1. calculate the abscissa
2. locate the point on the curve oI Eig. 226 which has the desired Ap and this value
oI the abscissa
3. read the corresponding ordinate oI this point Irom Eig. 226
4. calculate G
v
which gives this value Ior the ordinate
5. calculate the desired tower diameter Irom
tD
S
M J
G
T
v
v
2
4
= =
06361 page 173 Spring. 2001
Chapter 15. Membrane Separation
In distillation. gas absorption. and extraction we have
two immiscible phases which we bring into intimate
contact.
Operation Phases contacted
distillation liquid and its vapor
gas absorption liquid and another gas
solid extraction solid and a liquid
liquid extraction two immiscible liquids
Another unit operation Ior masstransIer is the membrane
separator. Here the two phases are not immiscible usually they are both gases or both are
aqueous solutions. They are not intimately contacted; rather. a membrane is placed between
them.
This membrane serves two Iunctions:
1. keeps phases from mixing
This is also the primary Iunction oI the pipe wall in HXer;
however. the membrane has a second. even more important.
Iunction. Whereas the pipe wall plays a passive role in heat
transIer. the membrane plays an active role:
2. controls selectivity
Because oI diIIerences in molecular size or solubility oI the gas in the membrane material.
diIIerent species diIIuse through the membrane at diIIerent rates. This diIIerence is the basis oI
separation.
EXAMPLES
With the proper choice oI membrane material. a membrane separator can achieve signiIicant
separations in a single stage. Indeed. as we shall see. it usually turns out that multistage
operations with membranes are not economical (compared to cryogenic distillation). Thus most
industrial applications oI membranes do not require very high purity products.
Gases
separation of
238
UF
6
from
235
UF
6
. This was a very important part oI the atom bomb
proiect in World War II.
06361 page 174 Spring. 2001
separation of O
2
from N
2
in air. A number oI industrial processes require a chemically
inert gas (like nitrogen). Membranes can produce 9599° nitrogen Irom air (79°
nitrogen. 21° oxygen) in a single stage. Sometimes its the oxygenrich stream that useIul:
4050° oxygen can be obtained Irom air. which is useIul Ior medical patients having
respiratory conditions.
recover H
2
from purge streams in ammonia. methanol. and hydrogenation plants.
separation of He from CH
4
(natural gas). Because oI its very small molecular size. halI
oI the helium in a Ieed stream containing ·1° He can be recovered in a single stage.
resulting in a permeate stream contain 30 times greater concentration oI He.
Liquids
dialysis (or liquid permeation). Separation oI urea and other small molecules Irom protein
and cells in whole blood is accomplished in artiIical kidneys. Recovery oI caustic (NaOH)
Irom hemicellulose produced in the manuIacture oI rayon.
electrodialysis. Brackish water (containing less salt than sea water) can be made potable
by applying electric Iield across membrane.
reverse osmosis. Brackish water can also be made potable by applying pressure to Iorce
water through a membrane which is impermeable to ions.
In the 1950`s. President Eisenhower was convinced that drinking water was the key to world
peace in many parts oI the world. Eisenhower`s successor as President was John Kennedy. In a
Iamous speech. President Kennedy expressed his intention to 'land a man on the moon and make
the deserts bloom.¨ The second part oI this quote has been obscured by the Iirst part.
Nonetheless. Kennedy did Iollow through by creating the OIIice oI Saline Water. which provided
Iinancial support Ior much oI the early research on membranes.
EQUIPMENT
06361 page 175 Spring. 2001
Fig. 12. A spiralwound membrane
Fig. 13. Magnification of a hollowfiber
member. Outer diameter between 50
200 microns.
Fig. 14. A bundle of hollow fibers
resembles a shellandtube heat
exchanger.
06361 page 176 Spring. 2001
Fig. 15. A commercial cartridge containing hollow fiber membranes. This is a Permasep¹
cartridge made by DuPont.
Fig. 16. Flow patterns inside bundle
(side views). (a) shows hollow fibers
with left ends sealed and right ends
open to exit manifold. (b) shows hollow
fibers with both ends open to exit
manifolds.
Fig. 17. Flow patterns inside bundle (end view).
06361 page 177 Spring. 2001
SEPARATION OF GASES
Porous Membranes
Perhaps the simplest basis Ior separation oI two gases is molecular size. Gases oI diIIerent
molecular weights have diIIerent diIIusion coeIIicients and will diIIuse at diIIerent rates through
the membrane. Eor membranes having pores whose diameter is comparable or smaller than the
meanIree path oI gas molecules. the diIIusion coeIIicient is inversely proportional to the square
root oI molecular weight:
Ior Knudsen diIIusion: D r
T
M
A
A
= 9700 (146)
where r ÷ pore radius (cm)
T ÷ absolute temperature (K)
M
A
÷ molecular weight oI diIIusing gas A
D
A
÷ diIIusion coeIIicient (cm
2
/s)
Notice that larger molecules (i.e. larger M
A
) have smaller
diIIusion coeIIicients.
Eor membranes having Iine pores through which the gas
can diIIuse. the Iluxes oI two gases. A and B. through a porous
membrane are given by
(0) ( )
A A
Az Ae
C C
J D
÷
=
t
/
/
(147)
(0) ( )
B B
Bz Be
C C
J D
÷
=
t
/
/
where l is the thickness oI the membrane and t (which is greater than unity) is a dimensionless
Iactor called the tortuositv which accounts Ior the Iact that the pore length is generally larger than
the thickness oI the membrane.
Even iI there are equal driving Iorces Ior the two components to diIIuse across the membrane.
they will have unequal concentrations one the downstream side because oI their diIIerent
diIIusion coeIIicient. This is the basis Ior separation in a porous membrane.
06361 page 178 Spring. 2001
The best known example oI gas separation by a porous membrane is separation oI
238
UE
6
Irom
235
UE
6
. Most gases have much smaller molecules than these and polymer membranes are used
instead oI porous membranes
Aonporous Polvmer Membranes
Many polymer membranes do not have pores. Instead.
the gas must Iirst dissolve in the polymer. Then the
dissolved gas diIIuses through the membrane. which can be
thought oI as a liquidlike Iilm. As a result. the
concentration proIile oI the diIIusing component A is not
continuous (see Iigure at right).
Generally the mole Iraction oI the dissolved species is very
small so that the equilibrium solubility oI the gas in the
solid can be described by Henrv's law:
A A A
and
B B B
(148)
where C
A
÷ molar concentration oI A in membrane
P
A
÷ partial pressure oI A in gas
S
A
÷ solubility constant*
Again. at steady state the concentration proIile inside the membrane will be linear and Eick`s law
yields:
J D
dC
dz
D
C C
D S
P P
Az A
A
A
A A
A A
A A
= ÷ =
÷
=
÷ ( ) ( ) ( ) ( ) 0 0 /
/
/
/
(149)
Eor the purpose oI comparison. the Ilux through a porous membrane given by (147) can also be
written in terms oI the partial pressures. Eor an ideal gas. the molar concentration C
A
can be
related to the partial pressure oI the gas P
A
by
P J n RT
C
n
J
P
RT
A A
A
A A
=
= =
(147) becomes: J
D
RT
P P
Az
A A A
=
÷ ( ) ( ) 0 /
/
porous membrane
(149): J D S
P P
Az A A
A A
=
÷ ( ) ( ) 0 /
/
polymer membrane
* reciprocal of Henry`s law constant
06361 page 179 Spring. 2001
Although these two expressions have the same Iorm. the coeIIicients are diIIerent. In particular.
the solubility constant S
A
varies much more between various gas solutes than does the diIIusion
coeIIicient D
A
. This implies that polymer membranes tend to be much more selective in
separation various gas species than porous membranes. UnIortunately. diIIusion coeIIicients in
solids and liquids are much smaller than Ior gases so this increase in selectivity is oIten traded oII
with lower permeation rates.
The product D
A
S
A
is known as the
permeabilitv coefficient:
A A A
÷ Barrer
which has units oI Ilux per unit pressure gradient. Since these complex units occur Irequently in
such problems. a new unit is deIined. which is known as the Barrer:
1 10
1
10
10
3
10
3
Barrer
cm (STP)
s
cm
cm
cmHg
cm (STP)
s  cm cmHg
rate
2
1/ area
flux
÷ × × =
÷ ÷
.
.
.
dz
dP
OIten the thickness oI the commercial membranes is not known. Then it is easier to measure the
Ilux per unit pressure. rather than per unit pressure gradient. The Ilux per unit pressure drop is
known as the
permeabilitv: Q
D S
A
A A
÷
/
EXAMPLE: PRODUCTION OF ENRICHED AIR
It turns out that most polymers are more
permeable to O
2
than to N
2
. Let's see how this
Iact can be exploited to enrich the oxygen
content oI air. Consider the apparatus at right.
which has one Ieed and two product streams.
One oI the product streams has been pulled
through a polymer membrane with a vacuum
pump.
The Ieed is normal atmospheric air which
contains 21° oxygen and 79° nitrogen. We
will denote these as components A and B. Erom our analysis oI steady diIIusion through the
membrane. we know the Iluxes oI the two species must satisIy:
J Q P P Q xP v P xQ P
A A A A A
P
A
= ÷ = ÷
~
<<
1 2 1 2 1
1
(150)
concentrate
06361 page 180 Spring. 2001
J x Q P
B B
~ ÷ 1
1
Because we are using a vacuum pump to pull the gas through the membrane. the pressure on the
permeate side oI the membrane will be much below atmospheric. thus:
Ior vacuum (on side '2¨): P
2
·· P
1
This leads to the approximate expressions Ior the Iluxes (above). Since the entire permeate
stream must come through the membrane. the mole Iraction oI A in the permeate stream is
determined by the relative amounts oI the two species which come through. In time t the number
oI moles oI species A which comes through a membrane oI area A is J
A
At. Similarly. the number
oI moles oI species B which comes through is J
B
At. The mole Iraction oI A is the number oI
moles oI A divided by the total number oI moles. The area and time cancel leaving
v
J At
J At J At
J
J J
A
A B
A
A B
=
+
=
+
(151)
Substituting (150) into (151):
v
xQ P
xQ P x Q P
xQ
xQ x Q
A
A B
A
A B
=
+ ÷
=
+ ÷
1
1 1
1 1
Notice that the total pressure cancels out. Einally. we divide the numerator and denominator by
the permeability oI gas B:
v
x
x x
x
x
=
+ ÷
=
÷ +
o
o
o
o 1 1 1
(152)
where o ÷
Q
Q
A
B
is called the separation factor. It's role is similar to relative volatility in distillation so we give it
the same symbol. II we did not make the assumption oI a vacuum on the downstream side. the
analysis becomes a little more complicated. but still tractable. More generally. (150) becomes
J Q P x Rv
J Q P x R v
A A
B B
= ÷
= ÷ ÷ ÷
1
1
1 1
where R
P
P
÷
2
1
and (152) becomes the root oI the Iollowing quadratic equation:
R v x R v x o o o ÷ ÷ ÷ +
( )
+ + = 1 1 1 0
2
. :
(153)
06361 page 181 Spring. 2001
Note that iI R ÷ 0. (153) reduces to (152). At right is a plot oI v versus o Ior several diIIerent
R`s. A couple oI trends are apparent. Eirst.
v ÷ x as o ÷ 1
o÷1 means there is no diIIerence in
permeability oI the membrane to oxygen
or nitrogen: then the permeate has the
same concentration as the Ieed.
Second. note that the permeate tends to
pure oxygen iI the permeability ratio is
high enough:
Ior R·x: v ÷ 1 as o ÷ ·
A closer look reveals that pure oxygen is
only obtained iI the pressure ratio is
small enough. In particular. the ratio
must be smaller than the Ieed
moleIraction.
The plot at leIt shows how lim
o÷·
v depends on the
pressure ratio R. when R·x. then v÷1. When R÷1 (i.e.
no driving Iorce Ior Ilow through membrane). the
permeate has the same concentration as the Ieed.
R÷1 and o÷·: v ÷ x
This behavior can be rationalized as Iollows: the partial
pressure oI oxygen in the permeate can never exceed
that oI the Ieed:
vP xP
P P
O O
2 1
2 2
in permeate in feed
s (154)
but P
2
÷ RP
1
(155)
(155) into (154): v
x
R
s
Permeability Ratio. o
P
e
r
m
e
a
t
e
M
o
l
e
E
r
a
c
t
i
o
n
÷ 0
0.2
0.1
0.3
0.4
0.5
0 0.2 0.4 0.6 0.8 1
0
0.2
0.4
0.6
0.8
1
R
i
x÷0.6
x÷0.4
x÷0.2
Permeate concentration v in the limit
as ÷ · as a Iunction oI pressure
ratio R.
06361 page 182 Spring. 2001
II this inequality is not met. we would have diIIusion uphill. The upper bound in oxygen partial
pressure is reached when o ÷ ·:
lim min .
o÷·
=
v
x
R
1
Stage Cut
Now let`s look at a couple oI complications. The Iraction oI the Ieed which permeates
through the membrane is known as the stage cut:
u ÷ =
total molar permeate rate
total molar Ieed rate
J
L
out
in
When the stage cut is very small. then very little oI
the Ieed passes through the membrane
L
out
~ L
in
This also means the composition oI the Ieed doesn`t change much as a result oI passing though
the separator. so that
stage cut ·· 1: x
out
~ x
in
Then every point on the membrane surIace sees
the same Ieed concentration x. This is what we
have implicitly assumed in all oI the above
analysis. Under these conditions. it doesn`t
matter whether we operate the separator
cocurrently or countercurrently; we get the same v Ior both Ilow patterns. But this is not a very
economical way to operate: very little oI the Ieed is converted into product.
II the stage cut is not small. we will partially deplete the Ieed in the more permeable component:
oxygen and x varies locally along the surIace oI the membrane.
Ior signiIicant stage cut: x
out
· x
in
This complicates the analysis. because now there will be a continuous decrease in x and L as the
Ieed gas moves along the surIace oI the membrane toward the residue.
Cocurrent Ilow through separator
Countercurrent Ilow through separator
06361 page 183 Spring. 2001
Eig. 13.82 shows the eIIect oI stage cut on the permeate concentration Ior each oI the 4 Ilow
conIigurations illustrated in Eig. 13.34. These are calculated by carving the membrane into a
large number oI diIIerential slices and then integrating the resulting equations.
Note that in general permeate concentration decreases with stage cut. This occurs because the
local concentration on the Ieed side oI the membrane is lower than at the inlet oI the Ieed.
06361 page 184 Spring. 2001
Chapter 16. LiquidLiquid Extraction
liquidliquid extraction separation oI two components oI a liquid (the 'Ieed¨) by contact with
a second immiscible liquid (the 'solvent¨)
Extraction is used primarily when direct distillation is not economical (since the solvent usually
has to be recovered by distillation). This might be the case with mixtures have very similiar
boiling points. or substances that cannot withstand the temperatures oI distillation. even under
vacuum. Examples include:
extraction oI penicillin Irom Iermentation broth by contact with amyl or butyl acetate
recovery oI acetic acid Irom dilute aqueous solutions by contact with ethyl acetate
(Iingernail polish solvent) or ethyl ether
separation oI aromatics (rings) Irom aliphatics (straight chains) by contact with
triethylene glycol
separation oI highMW Iatty acids Irom vegetable oil by contact with liquid propane
06361 page 185 Spring. 2001
EQUIPMENT
Contacting oI the two liquids might be perIormed
in a countercurrent cascade oI stages. Sometimes this
can be accomplished in a sievetray tower like that
used in distillation (see Iigure at right). where the
diIIerence in density drives the heavy Iluid down while
the lighter one Iloats upward.
More oIten a mechanical agitator is required to Iorm
the emulsion oI the two immiscible liquids at each
stage. One common design is the mixersettler
(shown above). The two liquid phases are Ied to the
tank where the mixer imparts mechanical energy and
thus disperses one oI the phases as Iine droplets in the
second phases (usually continuous). This state oI
mixtures is called an emulsion.
This emulsion is then transIerred into a settler tank
where the droplets begin to coalesces aIter the solute
has redistributed across the liquidliquid interIace.
Once the two phases have separated. the lighter one is
drawn oII the top (shown as 'extract¨ in Iigure above)
oI the settler while the heavier one is drawn oII the
bottom ('raIIinate¨).
06361 page 186 Spring. 2001
Mixerssettlers can also be arranged as a countercurrent cascade oI stages. as shown in the Iigure
above.
TRIANGLE DIAGRAMS
Many extraction systems involve three components which Iorm two immiscible phases. Eor
example. acetone and water are miscible in all proportions. When an organic solvent. methyl
isobutyl ketone (MIK) is added to a waterrich acetone solution. two phases are Iormed: a water
rich phase and an MIKrich phase. both phases containing all three components. The
composition oI the two phases can be graphically represented by means oI tie lines on a 'triangle
diagram.¨
An equilateral triangle has the property that the sum oI the
lengths oI the three normals drawn Irom any interior point
to each side equals the height oI the triangle. regardless oI
which interior point is chosen.
II we normalize the lengths oI these three normals by the
height. the normalized length can represent a mass Iraction
or a mole Iraction oI one oI the three components. The
geometry oI the equilateral triangle assures that
A B C
Thus each point inside the triangle represents the
composition oI a possible threecomponent mixture. A point at one oI the three corners
represents a pure component. while the normal distance between an interior point and the side
opposite the corner Ior pure A represents the mole Iraction or mass Iraction oI component A in
the mixture.
06361 page 187 Spring. 2001
The phase diagram Ior a mixture oI acetone.
methyl isobutyl ketone (MIK) and water at 25°C
is shown at right. The shaded region (below the
curve) represents compositions Ior which two
immiscible liquid phases Iorm. while the
unshaded region (above the curve) are
compositions Ior which only one phase Iorms.
The nearly horizontal lines with the shaded region
represent tie lies connecting the compositions oI
two liquid phases that coexist at equilibrium.
In this system. acetone is completely miscible in
both water and MIK. but MIK is only slightly
soluble in water and water is only slightly soluble
in MIK. This is an example oI a 1vpe I triangle
diagram.
A very diIIerent looking triangle diagram results
when one oI the liquids is not completely miscible
with either oI other two. The diagram at right is
Ior the system anilineheptane
methylcyclohexane. This is an example oI a 1vpe
II triangle diagram.
NOMENCLATURE
Notice in the Type I triangle diagram that as
the Iraction oI acetone gets higher. the tie lines get
shorter. Eventually. the tie line becomes
inIinitesimally short. such that the composition oI
the two immiscible phases become equal at the
plait point point on the triangle
diagram at which the composition oI the two immiscible phases are
equal.
Under normal operation we contact the 'Ieed¨ stream
with a 'solvent¨ stream. producing two immiscible liquid
phases which are separated to Iorm two streams. which
are called the 'extract¨ and the 'raIIinate.¨
extract  product stream which is richer in the solvent
(the remains oI the solvent stream aIter the
solute has ioined it)
06361 page 188 Spring. 2001
raffinate product stream which is leaner in the solvent (what remains oI the Ieed aIter the
solute has been extracted)
RECTANGULAR DIAGRAMS
While triangle diagrams are commonly used to
present the phase diagram Ior threecomponent
mixtures. the geometry oI an equilateral triangle
complicates construction. Threecomponent
phase behavior can also be presented using a
rectangular diagram. an example oI which is
shown at right Ior a ternary system oI Type I.
As with an (equilateral) triangle. the point at each
apex oI this (right) triangle represents one oI the
three components in the pure state. Each oI the
three sides oI the triangle represents mixtures in
which one oI the three components is completely
absent. Eor example. the base oI the right triangle
at right represents mixtures oI acetic acid and
water which do not contain any ether.
The hypotenuse oI the right triangle corresponds to
x
A
¹ x
C
÷ 1 or x
B
÷ 0
where the subscripts denote components. Lines parallel to the hypotenus correspond to
x
A
¹ x
C
÷ const · 1 or x
B
~ 0
iI the line lies below the hypotenus and
x
A
¹ x
C
÷ const ~ 1 or x
B
· 0
iI the line lies above the hypotenus. Clearly. the latter situation is impossible so that points
outside the right triangle are extraneous.
FLASH MIXING OF TWO LIQUIDS
Suppose we take two immiscible liquids (Iormed oI
the same three components: A. B and C) and mix them.
What will be the composition oI the mixture? Let
06361 page 189 Spring. 2001
L. J ÷ total mass Ilowrate oI the two liquid input streams
M ÷ total mass Ilowrate oI the output stream (ignoring the phase distribution)
x
A
. x
C
÷ mass Iraction oI components A.C in the stream having Ilowrate L
v
A
. v
C
÷ mass Iraction oI components A.C in the stream having Ilowrate J
x
AM
. x
CM
÷ mass Iraction oI components A.C in the stream having Ilowrate M
E #1: Given: L. J. x
A
. x
C
. v
A
and v
C
Eind: M. x
AM
and x
CM
Solution: Here is a receipe Ior a graphical solution using a
rectangular diagram (see Iigure at right).
Step 1:Locate points L and V on the rectangular diagram
coordinates are (x
A
. x
C
) and (v
A
. v
C
)
Step 2:Locate point M on a straight line connecting L and V
using the inverse leverarm rule:
JM
LM
L
J
= (156)
where LM or JM denote the length oI the lines connecting points L and M or V and M.
respectively.
Step 3:Read coordinates oI point M as (x
AM
. x
CM
).
ProoI: A total mass balance is
L ¹ J ÷ M (157)
and mass balances on components A and C yield:
Lx
A
¹ Jv
A
÷ Mx
AM
(158)
Lx
C
¹ Jv
C
÷ Mx
CM
(159)
Substituting (157) into (158): Lx
A
¹ Jv
A
÷ (L¹J)x
AM
Collecting terms. we obtain L(x
A
x
AM
) ÷ J(x
AM
v
A
)
or
L
J
v x
x x
A AM
AM A
=
÷
÷
(160)
06361 page 190 Spring. 2001
Similarly combining (157) and (159). we obtain
L
J
v x
x x
C CM
CM C
=
÷
÷
(161)
Equating (160) and (161):
v x
x x
v x
x x
A AM
AM A
C CM
CM C
÷
÷
=
÷
÷
or
x v
x v
x x
x x
CM C
AM A
JM
C CM
A AM
LM
÷
÷
=
÷
÷
÷
slope of line slope of line
. .
tan u
This shows that line segments LM or JM have the same slope and thereIore point M must lie
on line LJ . Moreover. (160) can be rewritten as
L
J
x v
x x
JM
LM
AM A
A AM
=
÷
÷
=
sin
sin
u
u
which proves (156).
SINGLESTAGE EXTRACTOR
II point M in the previous example lies in the 1phase region oI the phase diagram. then we
are done because we know the composition (x
AM
. x
CM
) oI the single phase leaving the mixer. II
the point M lies in the twophase region and the two phases are allowed to reach equilibrium and
separate in the settler. we will have (not one. but) two product streams.
Let`s relabel the two input and two output streams as in the Iigure
at right. In a typical extraction problem. stream L
0
is an aqueous
solution containing a solute (component A) we are trying to extract by
contact with an organic solvent (component C). So let`s assume that the
second Ieed stream (labelled J
2
) is pure solvent. Let`s try to determine
the composition oI the two product streams.
E #2: Given: L
0
. J
2
. x
A0
. x
C0
÷ 0. v
A2
÷ 0 and v
C2
÷ 1
Eind: L
1
. J
1
. x
A1
. x
C1
. v
A1
and v
C1
06361 page 191 Spring. 2001
Solution: Here is a receipe Ior a graphical solution using a
rectangular diagram (see Iigure at right).
Step 1:Locate points L
0
and V
2
on the rectangular diagram
coordinates are (x
A0
. x
C0
÷0) and (v
A2
÷0. v
C2
÷1)
Step 2:Locate the mixing point M as in Example #1
Step 3:Eind the tie line which passes through M
Step 4:The endpoints oI this tie line represent L
1
and V
1
coordinates are (x
A1
. x
C1
) and (v
A1
. v
C1
)
Step 5:The Ilowrates L
1
and J
1
can be determined using the reverse oI the procedure Ior
determining the mixing point M in Example #1
Essentially the mixing point gives the composition oI a hypothetical singlephase mixture Iormed
Irom the two Ieed streams. According to a mass balance. this is the same mixture which would
be Iormed by mixing the two product streams. In other words. M is the mixing point Ior either
L
0
and V
2
or L
1
and V
1
.
MULTISTAGE EXTRACTOR
II we are satisIied with the amount oI solute we have been able to extract Irom the solution in
the singlestage extractor. then we are done. II we desire to extract more oI the solute (i.e. we
wish to achieve a smaller value oI x
A1
) then multiple stages might be used. Let`s speciIy an
arbitrarily small value Ior x
AN
. the concentration oI solute remaining aIter N stages.
E #3: Given: L
0
. J
N¹1
. x
A0
. x
C0
÷ 0. v
AN¹1
÷ 0. v
CN¹1
÷ 1 and x
AN
Eind: L
N
. J
1
. x
CN
. v
A1
and v
C1
06361 page 192 Spring. 2001
Solution:
Step 1:Locate points L
0
and V
N¹1
Step 2:Locate their mixing point M. Read coordinates (x
AM
.
x
CM
) and calculate M ÷ L
0
¹ J
N¹1
.
This will also be the mixing point Ior the two product streams L
N
and V
1
. although these streams are not coming Irom the same
stage (i.e. they contain the same material as in the two Ieed
streams). Assuming all the stages in the cascade are equilibrium
stages. we also know that the points L
N
and V
1
lie somewhere on
the equilibrium curve. but not necessarily on opposite ends oI the
same tie line (since these streams are not coming Irom the same stage. they don`t have to be in
equilibrium with each other).
Step 3:Using the known value oI x
AN
. locate the point L
N
on the lower portion oI the
equilibrium curve (i.e. on the raIIinate portion oI the curve). Read x
CN
.
Step 4:Draw a straight line connecting L
N
and M; then extend this line until it crosses the
equilibrium curve again.
Step 5:The intersection oI this line with the equilibrium curve is point V
1
. Read the coordinates:
(v
A1
. v
C1
).
Step 6:Calculate the Ilowrates L
N
and J
1
as the simultaneous solution oI the Iollowing two
equations:
total mass balance: L
N
¹ J
1
÷ M
component C balance: L
N
x
CN
¹ J
1
v
C1
÷ Mx
CM
Everything in these equations is known except Ior the two unknowns: L
N
and J
1
.
E #4: How many equilibrium stages are required to perIorm the separation described
in Example #3? In other words. what is the value oI
N?
Solution:
Step 1:PerIorm steps 16 in example #3 to locate point V
1
.
Step 2:Locate point L
1
at the other end oI the tie line passing through
V
1
.
AIter we remove extraneous lines and markings (Ior clarity). the
rectangular diagram looks as shown at right.
tie line
V
L
06361 page 193 Spring. 2001
Step 3:Knowing the Ilowrates and compositions oI the two output streams Ior stage #1. we can
calculate the mixing point M
1
using the method oI Example #1. This is also the mixing point
Ior the two Ieed streams: L
0
and V
2
.
Step 4:Locate the point V
2
by connecting L
0
and M
1
with a straight line
and extending it until it crosses the equilibrium curve.
Step 5:Locate L
2
at the other end oI the tie line passing through V
2
.
Step 6:Repeat steps 35 (aIter incrementing all the subscripts by ¹1)
until point L
N
has an xcoordinate x
AN
which equals or is smaller
than that speciIied as x
AN
Ior the entire cascade.
DIFFERENCEPOINT METHOD
Although the procedure in Example #4 works well (provided solvent Ilowrate J
N¹1
is above
the minimum required). the coordinates oI the mixing points M
1
. M
2
etc. have to be calculated
manually. This tedious step can be avoided by observing that all the 'operating lines¨ (i.e. L
0
V
2
.
L
1
V
3
etc.) have a common point called the difference point.
Consider a total mass balance around some arbitrary stage in the
cascade:
L
n1
¹ J
n¹1
÷ L
n
¹ J
n
which can be rearranged to obtain
L
n1
 J
n
÷ L
n
 J
n¹1
÷ A (162)
This diIIerence between the Ilowrates oI two 'adiacent¨ streams in the cascade has exactly the
same value Ior every stage in the cascade (i.e. n ÷ 1.2 ... N). We denote this diIIerence in
Ilowrates by A. II instead oI a total mass balance. we perIorm a mass balance on component A:
L
n1
x
An1
¹ J
n¹1
v
An¹1
÷ L
n
x
An
¹ J
n
v
An
which can be rearranged to obtain
L
n1
x
An1
 J
n
v
An
÷ L
n
x
An
 J
n¹1
v
An¹1
÷ Ax
A
(163)
Once again the diIIerence the mass Ilowrates oI component A in any two adiacent streams is
exactly the same. regardless oI which stage we pick. We denote this diIIerence as Ax
A
: the
product oI A and a Iicticious mass Iraction which we call x
A
. The value oI this Iicticious mass
Iraction can be calculated by dividing (163) by (162) Ior n÷1 (choosen because we know the
Ilowrates and compositions oI the two adiacent streams at the end oI the cascade Irom Example
#2):
tie line
V
L
L
L
M
V
06361 page 194 Spring. 2001
x
L x J v
L J
A
A A
A
=
÷
÷
0 0 1 1
0 1
and x
L x J v
L J
C
C C
A
=
÷
÷
0 0 1 1
0 1
(164)
An equation similar to this can be obtained Ior component C. which leads to the second equation
above. The point (x
A
. x
C
) is called the difference point and is denoted by A. All the operating
lines pass through this common point.
E #5: Repeat Example #4 using the diIIerence
point method
Solution:
Step 1:Locate points L
0
and A. The coordinates oI the
latter are calculated Irom (164).
Step 2:Connect L
0
and A with a straight line.
Step 3:Locate V
1
as the point where this line crosses the
(upper part oI) the equilibrium curve
Step 4:Determine the tie line passing through V
1
. Locate
L
1
as the other end oI this tie line.
Step 5:Connect L
1
and A with a straight line.
Step 6:Locate V
2
as the point where this line crosses the
(upper part oI) the equilibrium curve
Step 7:Determine the tie line passing through V
2
. Locate L
2
as the other end oI this tie line.
Step 8:Repeat steps 57 until the desired composition is obtained Ior L
N
.
ProoI (oI diIIerence point method):
06361 page 195 Spring. 2001
Lecture #
Class Notes
Unit Operations
of Chemical Engineering
bv
Dennis C. Prieve
Department of Chemical Engineering
Carnegie Mellon Universitv
Pittsburgh. PA 15213
An electronic version oI this book in Adobe PDE® Iormat was made available
to students oI 06202. Department oI Chemical Engineering.
Carnegie Mellon University. Spring. 2000.
Copyright © 2000 by Dennis C. Prieve
06202 page ii Spring. 2001
Table of Contents
COURSE INTRODUCTION..................................................................................................................................... 1
WHAT ARE "UNIT OPERATIONS"?............................................................................................................................. 1
CHAPTECOURSE INTRODUCTION..................................................................................................................... 1
WHAT ARE "UNIT OPERATIONS"?............................................................................................................................. 1
CHAPTER 2. HEAT EXCHANGE EQUIPMENT.................................................................................................. 3
DOUBLEPIPE HXER................................................................................................................................................... 3
SHELLANDTUBE HXER........................................................................................................................................... 3
CHAPTER 3. FUNDAMENTALS OF HEAT TRANSFER 2. ...................... HEAT EXCHANGE EQUIPMENT
3
DOUBLEPIPE HXER................................................................................................................................................... 3
SHELLANDTUBE HXER........................................................................................................................................... 3
CHAPTER 3. FUNDAMENTALS OF HEAT TRANSFER: REVIEW ................................................................. 5
LOGMEAN DRIVING EORCE ..................................................................................................................................... 5
RESISTANCES IN SERIES .......................................................................................................................................... 10
EOULING EACTORS.................................................................................................................................................. 13
CORRELATIONS TO ESTIMATE h`S ........................................................................................................................... 13
h
i
for Turbulent Flow In Long Pipes................................................................................................................. 15
CHAPTER 4. SHELLANDTUBE HEAT EXCHANGERS ................................................................................ 16
TUBE PITCH ............................................................................................................................................................ 16
BAFFLES.................................................................................................................................................................. 16
h
O
FOR SHELLANDTUBE EXCHANGER .................................................................................................................. 17
Appendix. Derivation for S
b
and S
c
.................................................................................................................. 19
MULTIPASS CONSTRUCTION.................................................................................................................................... 21
"TRUE" MEAN TEMPERATURE DIFFERENCE ........................................................................................................... 22
CHAPTER 5. EVAPORATION............................................................................................................................... 26
EQUIPMENT FOR EVAPORATION .............................................................................................................................. 26
LongTube Jertical Evaporator ........................................................................................................................ 27
ForcedCirculation Evaporator ........................................................................................................................ 28
EVAPORATOR PERFORMANCE................................................................................................................................. 28
EXAMPLE: SIMPLE EVAPORATOR PROBLEM............................................................................................................ 28
Steam Economv ................................................................................................................................................. 32
OVERVIEW OF EVAPORATOR DESIGN...................................................................................................................... 33
COMPLICATIONS...................................................................................................................................................... 34
BoilingPoint Elevation..................................................................................................................................... 34
Heat of Dilution................................................................................................................................................. 36
MULTIPLE EFFECTS................................................................................................................................................. 37
Performance ...................................................................................................................................................... 40
VAPOR RECOMPRESSION......................................................................................................................................... 41
CHAPTER 6. VAPORLIQUID EQUILIBRIUM.................................................................................................. 45
NO. OF PHASES PRESENT ........................................................................................................................................ 45
One Component ................................................................................................................................................. 45
Two Components ............................................................................................................................................... 45
IDEAL SOLUTIONS OBEY RAOULT`S LAW................................................................................................................ 47
06202 page iii Spring. 2001
IDEAL BINARY MIXTURES....................................................................................................................................... 47
XY AND TXY DIAGRAMS ......................................................................................................................................... 50
NONIDEAL BEHAVIOR ............................................................................................................................................. 51
CHAPTER 7. FLASH DISTILLATION................................................................................................................ 52
APPROXIMATE SOLUTION........................................................................................................................................ 52
Inverse LeverArm Rule on Txv Diagram.......................................................................................................... 54
RIGOROUS SOLUTION.............................................................................................................................................. 55
Inverse LeverArm Rule on Hxv Diagram......................................................................................................... 58
BATCH (DIFFERENTIAL) DISTILLATION.................................................................................................................... 58
CHAPTER 8. MULTISTAGE OPERATIONS....................................................................................................... 62
COUNTERCURRENT CASCADE ............................................................................................................................... 63
CHAPTER 9. EQUIPMENT FOR TRAY TOWERS ............................................................................................ 65
CHAPTER 10. PERFORMANCE OF A CC CASCADE.................................................................................. 68
ANALYSIS OF A CC CASCADE ................................................................................................................................ 68
CONSTANT MOLAL OVERFLOW............................................................................................................................... 69
A RECTIFYING CASCADE......................................................................................................................................... 71
A STRIPPING CASCADE............................................................................................................................................ 74
STEAM DISTILLATION.............................................................................................................................................. 77
CHAPTER 11. MCCABETHIELE METHOD................................................................................................... 78
LOCATION OF EEED PLATE...................................................................................................................................... 80
CONVERGENCE OF OPERATING LINE AND EQUILIBRIUM CURVE ............................................................................. 81
CHOOSING THE REFLUX RATIO................................................................................................................................ 86
1) Existence of R
min
.......................................................................................................................................... 86
2) Total Reflux. R÷· gives Minimum Stages................................................................................................... 88
CALCULATING ELOWRATES AND CONDENSER/REBOILER HEAT DUTIES.................................................................. 89
ROLE OF QLINE...................................................................................................................................................... 92
PLATE EFFICIENCY.................................................................................................................................................. 93
DETERMINING NUMBER OF REAL STAGES............................................................................................................... 95
CHAPTER 12. MULTICOMPONENT DISTILLATION................................................................................. 96
PRODUCT DISTRIBUTION FOR A SHARP SPLIT.......................................................................................................... 97
MINIMUM NUMBER OF TRAYS ................................................................................................................................ 99
MINIMUM REFLUX RATIO...................................................................................................................................... 104
Method 1) PsuedoBinarv Method .................................................................................................................. 104
Method 2) Underwood´s Method ..................................................................................................................... 106
NUMBER OF IDEAL PLATES AT OPERATING REFLUX.............................................................................................. 110
Method 1) Underwood´s method...................................................................................................................... 110
Method 2) Gilliland correlation ...................................................................................................................... 110
Method 3) Rigorous Solution of MESH Equations.......................................................................................... 110
CHAPTER 13. COMPUTER SIMULATION OF DISTILLATION............................................................... 113
SOME PRELIMINARY STEPS ................................................................................................................................... 114
LOADING A EILE (PROBLEM) ................................................................................................................................. 116
PLOTTING THE MCCABETHIELE DIAGRAM .......................................................................................................... 124
PRINTING THE GRAPHS.......................................................................................................................................... 126
TESTING THE MCCABETHIELE METHOD.............................................................................................................. 128
THE TEMPERATURE PROFILE ................................................................................................................................ 132
DEGREES OF EREEDOM ......................................................................................................................................... 132
06202 page iv Spring. 2001
CHAPTER 14. GAS ABSORPTION/STRIPPING............................................................................................ 134
EQUIPMENT FOR ABSORPTION/STRIPPING ............................................................................................................. 134
A TYPICAL ABSORBER DESIGN PROBLEM............................................................................................................. 136
Solution Overview. .......................................................................................................................................... 137
Detailed Solution............................................................................................................................................. 138
EQUILIBRIUM CURVE ............................................................................................................................................ 139
OPERATING LINE................................................................................................................................................... 139
Approx. =1. Onlv One Transferable Component............................................................................................. 140
Approx. =2. Dilute Solution............................................................................................................................. 143
INTERFACIAL MASS TRANSFER: REVIEW .............................................................................................................. 143
Definitions of Transfer Coefficients................................................................................................................. 145
Determining the Interfacial Concentrations. (x
i
.v
i
) ........................................................................................ 146
Equimolar CounterDiffusion vs. Diffusion through Stagnant Fluid .............................................................. 149
HEIGHT OF A PACKED TOWER............................................................................................................................... 151
TRANSFER UNIT.................................................................................................................................................... 155
EVALUATION OF NTU'S......................................................................................................................................... 157
Special Case. y
a
··1 with concave downward EC. ....................................................................................... 159
ANALOGY WITH DOUBLEPIPE HXER.................................................................................................................... 159
RELATIONSHIPS AMONG H
OX
. H
OY
. H
X
AND H
Y
................................................................................................. 160
PRESSURE DROP IN PACK BEDS ............................................................................................................................ 162
TOWER DIAMETER................................................................................................................................................ 164
CHAPTER 15. MEMBRANE SEPARATION................................................................................................... 168
EXAMPLES ............................................................................................................................................................ 168
Gases ............................................................................................................................................................... 168
Liquids............................................................................................................................................................. 169
EQUIPMENT........................................................................................................................................................... 169
SEPARATION OF GASES ......................................................................................................................................... 172
Porous Membranes.......................................................................................................................................... 172
Nonporous Polvmer Membranes ..................................................................................................................... 173
EXAMPLE: PRODUCTION OF ENRICHED AIR .......................................................................................................... 174
Stage Cut ......................................................................................................................................................... 177
CHAPTER 16. LIQUIDLIQUID EXTRACTION............................................................................................ 184
EQUIPMENT........................................................................................................................................................... 185
TRIANGLE DIAGRAMS ........................................................................................................................................... 186
NOMENCLATURE................................................................................................................................................... 187
RECTANGULAR DIAGRAMS.................................................................................................................................... 188
ELASH MIXING OF TWO LIQUIDS ........................................................................................................................... 188
SINGLESTAGE EXTRACTOR.................................................................................................................................. 190
MULTISTAGE EXTRACTOR................................................................................................................................... 191
DIFFERENCEPOINT METHOD................................................................................................................................ 193
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