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363 Class Notes


Keith P. Johnston
Chemical Engineering
2
ChE 363 Mass Transport
E.L. Cussler, Diffusion, Chpt. 1.
As shown in Cussler in section 1.1, there are two basic models for treating diffusion
as shown in Figure 1.2-1. flux = mol/cm
2
/s (amount/area/time)
Model 1 flux = k (concentration difference)
More applied. Easier to use. Less rigorous.
Model 2 flux = D (concentration difference/length)
More fundamental, sometimes more difficult to apply
Look at interesting examples in 1.3 to make this physically meaningful to you.
Ex. 1.3-1 Ammonia scrubbing- easier to use k since the diffusion length is not well
defined unless detailed flows are well known.
Ex. 1.3-3 Corrosion of marble by acid rain- D allows one to predict conc. vs.
position in marble. k- only flux at interface
3
Ex. 1.3-4 Protein size in solution- diameter is proportional to diffusion
coefficient.
Ex. 1.3-5 Antibiotic production- oxygen uptake for aerobic fermentation. k-
changes in bubble size, non-Newtonian flow, foam caused by biological
surfactants
Ex. 1.3-6 Facilitated transport across membranes-
Diff. and reversible chem. Rxn. couple in non-linear fashion. Need D to
understand system.
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Diffusion and Mass Transfer
Flux relative to stationary plane:
Flux relative to solvent flow at u
o
:
J
A
= c
A
u
A
c
A
u
o
= c
A
(u
A
u
o
)
e.g. canoe relative to river
Ficks Law
Ideal gas c
A
+ c
B
= = P/RT
At const T, P, is const. dc
A
+ dc
B
= 0
M
total molar density p
M o A A A
N u For species A, N c u - = p =
3 2
g mol cm g mol
=
cm s cm s
2
A AB A 3 2
cm g mol g mol
J D dc / db
s cm cm cm s
= - =
M
p
M
p
5
J
A
+ J
B
= 0 (to maintain const and uniform p
M
)
- D
AB
dc
A
/db D
BA
dc
B
/ db = 0
D
AB
= D
BA
Total flux species A = Convective flux A + Diffusive flux A
N
A
= c
A
u
o
+ c
A
(u
A
u
o
)
= y
A
(N
A
+ N
B
) + J
A
(p
M
const)
Suppose J
A
is 0. Then the convective flux of A is y
A
N, where N is the total flux.
6
Cussler Chapter 2
2.2 Steady state diffusion across a thin film
Fig. 2.2-1 Fig. 2.2-2
7
Accumulation= diff. into the layer at z diff. out of layer at z + (z.
0 = A (j
1

z
- j
1

z+(z
)
Divide by A(z and rearrange
0 = -(j
1

z+(z
- j
1

z
)/ [(z + (z) z] = -dj
1
/dz
From Ficks law, -j
1
= D dc
1
/dz, thus 0 = D d
2
c
1
/dz
2
Boundary conditions: z = 0 c
1
= c
10
, z = l c
1
= c
1l
Integrate twice: c
1
= a + bz
Flux expression:
c
1
= c
10
+ (c
1l
c
10
) z/l
j
1
= (D/l) (c
10
c
1l
). At steady state, the flux is constant.
8
Thin film diffusion or equimolar One-way diffusion
counter diffusion N
A
= const
= Diff. flux + Conv. flux
No convection
dy
A
/dz = const.
Diffusive flux const.
y
A
large conv. dominant
dy
A
/dz small
y
A
small
dy
A
/d
z
Large
bulk fluid
9
Equimolar counter-diffusion (e.g. binary distillation)
N
A
N
B
N
A
= -N
B
N
A
+ N
B
= N = 0
N
A
= y
A
N + J
A
where N = 0. Thus N
A
= J
A
See Fig 17.1 (6
th
, p.
517)
Same as thin film w/ no convection

10
ChE 363 Summary of Mass Transfer
Total flux = Convective flux + Diffusive flux
N
A
= c
A
u
A
= c
A
u
o
+ c
A
(u
A
-u
o
)
= y
A
(N
A
+ N
B
) + J
A
if p
M
is constant
where J
A
= -cD
v
dy
A
/dz (Ficks Law)
Steady state
a. Thin film with no convection- flux is constant. N
A
= J
A
Or Equimolar diffusion which eliminates convection
J
A
= (D
v
/l ) (c
Ai
- c
A
) = (D
v
p
m
/l)(y
Ai
y
A
) const.
c
A
int
= c
Ai
+ (c
A
c
Ai
) z/l (int = intermediate) linear
b. One-way diffusion of A only with convection (N
B
= 0)
J
A
, y
A
N = y
A
N
A
= f(z)
11
N
A
= (D
v
p
M
/l) ln [(1-y
A
)/( 1-y
Ai
)] constant
= (D
v
p
M
/l) (y
Ai
y
A
)/(y
B
)
lm
where (y
B
)
lm
= (y
B
y
Bi
)/ln (y
B
/y
Bi
)
y
B
int
/y
Bi
= (y
B
/y
Bi
)
z/l
[= f(z)]
Diff. flux J
A
is largest at z where y
A
is smallest. Here the conc. profile is most
curved. As J
A
decreases y
A
N increases. The sum N
A
is constant.
c. Steady diffusion into falling film with short contact time
Identical to penetration theory below where time becomes a residence time,
t = x/v
max
. Here v
max
is a constant.
Unsteady Diffusion in a Semi-infinite slab (Penetration theory)
c
A
/t = - j
A
/z = D
v

2
c
A
/ z
2
Diffusion eqn. with no convection
(c
A
int
c
Ai
)/(c
A
- c
Ai
) = erf , erf = (2/.x)
0

exp (-s
2
) ds = z /(4Dt)
1/2
J
A
= -D
v
c
A
/ z = (D
v
/xt)
1/2
exp(-z
2
/4Dt) (c
Ai
c
A
)
J
A

z=0
= (D
v
/xt)
1/2
(c
Ai
c
A
) J
A

z=0
time avg
= 2(D
v
/xt
T
)
1/2
(c
Ai
c
A
)
KPJ44
Slide 11
KPJ44 need to think about notation on this sheet?
Keith Johnston, 1/17/2005
12
BSL One-Way Diffusion/Convection Thru Gas Film (const T, P)
Transport Eqn (not mass balance)
diffusion convection
N
A
= -cDdx
A
/dz + x
A
(N
A
+ N
B
) (a)
Assume B insoluble in A.
N
B
<< N
A
N
B
~ O
From eq (a)
Steady State Mass balance:
S N
A
|
z
S N
A
|
z + ( z
= 0
A A
A
cD
N dx / dz (17.2-1)
1 x
=

KPJ39
Slide 12
KPJ39 fix subscripts in picture
Keith Johnston, 1/9/2005
13
Divide by (z -dN
A
/dz = 0 N
A
f(z) and is constant
For ideal gas, const T, P, c is const
BC1, 2 z = z
1
, x
A
= x
A1
= P
A
sat
/ P z = z
2
x
A
= x
A2
Solve for c
1
, c
2
(fair amount algebra)
{
A
1 A 1 2
A
dx 1
c ln(1 x ) c z c
1 x dz
= = +

1 1
2 1 2 1
z - z z - z
z - z z - z
A A2 B B2
A1 A1 B1 B1
1-x 1-x x x
= or =
1-x 1-x x x
+ +


+
= =




2 A2
1 A1
z x
A A A2
A A1 z x
(N ) dx 1 x
From 17.2-1 const dz ln
cD 1 x 1 x
{
14
B2
A
2 1 B1
x cD
N n (17.2 14)
z z x
+
=


"
E = E =
1 2 1
Let (z z ) /(z z ) d dz
2
1
1
z B2 B1
BAvg
0 B B1
1
B1 z
0
(x / x ) d
x Mean value
(x / x )
dz
theorem x
dz
d
E
E
=
E

u u
a du a / ln a =

B Avg
B2 B1 B2 B1
B1 B2 B1 B2 B1
x 1
(x / x ) x / x 1

x ln(x / x ) 0 ln(x / x )
E

= =
B2 B1
B,Avg B l m
B2 B1
x x
x (x ) (2)
ln(x / x )

=
1
Subst (2) 17.2-14 for ln (x
B2
/x
B1
)

= =

A1 A2
A B2 B1 A1 A2
2 1 B lm
x x cD
N BSL Note : x x x x
z z (x )
15
1 2
A1 Ai A2 A
z 0 z
Our notation
x x x x
= =
= =
"
"
Ai A
A
B lm
(x x ) cD
N
(x )

=
"
"
A A Ai A B m
A A Ai A
N (one way) N (y y ) /(y )

N (equimolal) J y y

= =

" "
"
B m
(1/ y ) p.661 =
"
One-way denoted by
= =
" c c y y B m
k '/ k k '/ k 1/(y )
KPJ42
Slide 15
KPJ42 one way in train station in tokyo is faster progress than two way. Dont have resistance from back flow of other species.
Keith Johnston, 1/17/2005
16
2.3 Unsteady Diffusion in a Semi-infinite Reservoir (Penetration theory)
Solute accum. = diff. in diff. out no convection, A perpendicular
to
plane of paper
/t (A(zc
1
) = A(j
1

z
j
1

z+(z
)
Divide by A(z and use definition of derivative
c
1
/t = - j
1
/z = D
2
c
1
/ z
2
Diffusion eqn. Fig 2.3-2 Cussler
t = 0 all z c
1
= c
1
(bulk)
t > 0 z = 0 c
1
= c
10
z = c
1
= c
1
For small z or large t (small ),
erf linear in .
Linear concentration profile.
17
Define a new variable to generate ordinary differential equation
(Boltzman, 1894):
Method of combination of variables
= z (4Dt)
-1/2
Thus: /t = -(1/2) /t /z = /z
Use the chain rule for introduction of new variable:
c
1
/ /t = D
2
c
1
/
2
(/z)
2
Appendix 1: (Subst for two partial derivatives from above)
2 2 2 2
1 1
c / ( 1/ 2) / t D c / ( / z ) =
2
2 2
1 1
1 z
c / c /
2 Dt
=

2 2
Subst z (4Dt) =
=
2 2
1 1
2 c / c / 2.3 11
KPJ43
Slide 17
KPJ43 zeta??
Keith Johnston, 1/17/2005
18
One integration of the eqn
2
c
1
/
2
+2 c
1
/ = 0 (2.3-11) gives
c
1
/ = a exp(-
2
) Subst into above eqn. to see it is correct.
(c
1
c
10
)/(c
1
- c
10
) = erf (see Appendix 2) (2.3-15)
where erf = (2/.x)
0

exp (-s
2
) ds
erf (0) = 0; z = 0 c
1
= c
10
erf ( ) = 1; z = c
1
= c
1
The flux may be obtained by taking the derivative of this integral (Appendix 2)
j
1
= -D c
1
/ z = (D/xt)
1/2
exp(-z
2
/4Dt) (c
10
c
1
)
Note: Dont forget to multiply integrand by deriv. of limit, /z.
At interface where z = 0 t incr., j
1
decr., abs. value slope decr.
j
1

z=0
= (D/xt)
1/2
(c
10
c
1
) a useful result!
19
Appendix 2
1 1 10
j D(c c ) derf / dz

=
1/ 2 2
derf
2 exp( ) d / dz
dz

= x
upper limit of integration

= =
1/ 2
Recall d / dz / z (4Dt)
1 1 10
Subst :
j D(c c ) 2

=
1/ 2
exp( )( 4
2
x
1/ 2
Dt)

Insert this result into previous page.

1
10
c
2
1
c 0
proportional to erf
dc a exp( )d
= x For ,integral / 2

= x
1 10
Insertion of bound. cond. yields : a (c c ) /( / 2)
Second Fundamental Theorem of Calc. to obtain j
1
= - D dc
1
/dz
20
2.5 Convection and Dilute Diffusion
2.5.2 Steady Diffusion into a falling film- forced convection mass transfer
(BSL p. 537; Cussler p. 45) Semi-infinite film: limited penetration into film
Assumptions: 1. Dilute soln. 2. Diffusion in z direction; convect. in x direction.
3. Pure gas. 4. Contact between gas and liquid is short
Constant solvent velocity, v
x
, result of assumptions 1 and 4.
Accum. = diffusion in z direction + convection in x dir.
0 = (j
1
W(x)
z
- (j
1
W(x)
z+(z
+ (c
1
v
x
W(z)
x
- (c
1
v
x
W(z)
x+(x
W = width perpendicular to plane of paper
Divide by volume W(x(z
0 = -j
1
/z - (c
1
v
x
)/x
21
Let v
x
be a constant the maximum velocity at the gas surface.
c
1
/(x/v
max
) = D
2
c
1
/ z
2
(Analogous to diffusion eqn) t = x/v
max
B.C. x = 0, all z, c
1
= 0
x > 0, z = 0 c
1
= c
1
sat
z = l c
1
= 0 (short contact)
c
1
/c
1
sat
= 1 erf [z/(4Dx/v
max
)
1/2
]
j
1

z=0
= (Dv
max
/xx)
1/2
c
1
sat
Final perspective:
1. Approximation for USS diffusion
l = (Dt)
1/2
2. j
1
= (D/l) (c (thin film) (steady state)
j
1

z=0
= (D/xt)
1/2
(c (thick slab)
22
Diffusivities
Gases
Y
=
p =
p

M
2
1/2
D 1/ 3 u u avg molec vol
1/ RT/ P mean free path
~1/P , ~T ( goes down in both cases)
1
u ~ T mu related to kT, k is Boltzmann const
2
Y

Av
1.5
., k=R/N .
D ~ T /P for ideal gas
23
For real gas
See eq 17.28 p. 519
Lennard-Jones potential
See empirical Wilke Chang (17.31)
F = Faraday constant,
Table 17.1 cations less hydrated as size incr.
p. 522
12 6
u 4 ( / r) ( / r) = s o o
|
0
Liquids: Stokes Einstein Friction 6 r = x
Y

=
x
o
thermal activation energy for hops
kT
D
6 r friction
0 0 2
Electrolytes D 2 RT/(1/ 1/ )F 17.33
Y +
= +
A
Turbulent Diffusion J (D )dc / db
eddy diff
= f(u, roughness, position)
Y Y
Y
= + s
s
0
limitingconduc tance for anion
+

24
Mass Transfer Coefficients

c A Ai A y A Ai A
k J /(c c ) k J /(y y )
3
2 2
cm g mol cm g mol

s cm s g mol cm s
= p = p
y c M A A M
A A 2 3
k k since c y
g mol cm g mol
y =c /c
cm s s cm
M
For an ideal gas P (n/ V)RT or P/ RT = p =
= = p
y c x c av g
k k (P/ RT) For a liq, k k / M
)
Y
+

= p

y
A M T Ai A
k
J D / B y y
Diffusion to wall in laminar layer
(membrane or electrode)
Fast mixing in core turbulent zone.
Resistance in stagnant film.
KPJ40
Slide 24
KPJ40 make better dwg
Keith Johnston, 1/9/2005
25
Dimensional Analysis- Route to Correlations (Cussler, Diffusion, p. 235)
Show N
Sh
= f(N
Re
N
Sc
)
k
c
= f(u,p,,D
v
, D) All variables that affect mass transfer.
= (const.) (u
E
, p

, D
v
o
, D
s
)
L/t = (Lt
-1
)
E
(ML
-3
)

(ML
-1
t
-1
)

(L
2
t
-1
)
o
L
s
Exponents must match on both sides:
For L 1 = E - 3 - + 2o + s (1)
For M 0 = + (2)
For t -1 = -E - - o (3)
Solve in terms of E and o (arbitrary choice) E = E, o = o
= 1 E o from eq. 3 (4)
= = E + o l (5)
26
s = E -1 (from 4, 5 substituted into 1)(6)
k
c
1
= (const) u
E
p
E + o - 1

1 - E o
D
v
o
D
E - 1
= (const) p
-1
D
-1
(puD/)
E
(pD
v
/)
o
k
c
pD/ = (const) N
Re
E
N
Sc
o
Multiply both sides by N
Sc
= /pD
v
k
c
D/D
v
= N
Sh
= (const) N
Re
E
N
Sc
(1-o)
Fit const, Eo to data.
27
Dynamic light scattering (1 nm to 1 m, polymers, proteins,
colloids
Incident light particle diffuses
Laser (He-Ne visible) by Brownian motion
in and out of
scattering volume
Scattered light
For two particles near each other constructive and destructive interference
t = 0 particles certain distance apart
t + (t relative distance changes
As (t 0 initial positions correlated As (t no correlation between pairs
Auto correlation fxn < A(0) A(t) > E exp - (q
2
Dt) Higher D, faster decay
Measure q
2
D Know q, Get D
<A(0) A(t) >
x +
=


o
4
q sin 90 usually
2
28
Mass Transfer Heat Transfer
Mass transfer to pipe walls (turbulent)
Convenience:
Y
= =
Sh c Nu
m.t.velocity convection
N k D/ D N hD/ k
diffus.vel. conduction
Y
= p =
Sc Pr p
viscous viscous
N / D N c / k
diffusion diffusivity energy
=
T T
0.8 1/ 3 0.14
sh Re Sc w
Re c
N 0.023 N N ( / )
As N k
Sh
m 1/ 3
Re Sc
N
j
N N

Y
Y Y
+
+ p
= =


p p


1/ 3 2/ 3
c c
k D D k

D uD u D
29
For pipes
Flow past single solid spheres p. 537

=
0.2
m Re
j 0.023 N
1/ 3
c
Sc Sh
k D
As D , N (a little), N (alittle)
D
Y
Y
T + + =
=
Re
N 0 Sh 2 analytical
Y
Y
= =
p
p/ 2 Sh
T
D
D
effective film thickness D 2 N ~
B D
=
1/ 2
Re Sh Re
N 1000 N f(N ) boundary layer theory
Re
N turbulent exponent 1/2 greater flow rate effect >
k
c
incr.
30
Mass transfer to drops + bubbles:
Penetration theory for time avg k
c
T
1/ 2 t
1/ 2 1/ 2
c c
0
D
k (D / t) k t dt / dt

Y
Y
+
= x =

x


1/ 2
T
2(D / t )
Y
= x
T p 0
For = D /u (flow past entire drop) t
1/ 2
c 0 p
k 2(D u / D )
Y
= x
1/ 2
p 0
Sh c p
1/ 2 1/ 2
Re Sc
D u
2
N k D / D
D
1.13 N N
Y
Y
p +

= =

p
x

=

Re Sc p 0 Pe
N N D u / D N (Peclet) inertial forces/ diffusion -
Y
= = =
Cussler: Small liquid drops
N
Sh
= 1.13 (N
Re
N
Sc
)
0.8
behave like rigid sphere drops
Circulation currents raise exponents depending upon viscosities of the
phases.
31
Controlled Release Cussler, 2
nd
Ed (Review of mass transfer) Diffusion
Eq. 18.1-1 (thin film) dissolution of solute
Accum Flux .A
Matrix system Diffusion thru
Eq. 18.1-2 (thick slab) at small times, lim t 0
s
1 1 c 1 1
s sat
d
Vc AN Ak (c c )
dt 1 drug
=
= =
=
1
t
1
c s
0
1 1 0
c dc
(Ak / V)dt
c c
=

+
= = =


s
s
1 1 1
c 1 1 c s s s
1 1
c c c M
ln Ak t / V 1-c / c exp( k At / V)
c 0 c M

=
c
k At / V s
amt. released: M M (1 e ) first order release kinetics

= x
= = x
time avg 1/ 2
1 v T 1i 1 1
time avg 1/2 1/2
1 T v T 1i 1 1i
J 2(D / t ) (c c ), c is external to slab
M J At 2(D t / ) A(c -c ) t kinetics M =c AL
2 1/ 2
/ 2( / ) :
v T
M M D t L Saltzman dual slabis twice this value x

=
KPJ41
Slide 31
KPJ41 fix style of last line
Keith Johnston, 1/9/2005
32
Controlled Release by Solvent Diffusion
18.21.1 Drug dispersed in polymer (Matrix release hydrogels)
Control cross-links
diffusion through swollen polymer leads to release that has t
Glassy polymers zero order (tortuous unfolding of chains)
33
Chapter 20 Equil Stage Operations
Total mat bal (mb) on top to tray n
L
a
+ V
n+1
= L
n
+ V
a
Component mat bal on more vol. comp.
L
a
x
a
+ V
n+1
y
n+1
= L
n
x
n
+ V
a
y
a
(20.2)
Total mb (entire column)
L
a
+ V
b
= L
b
+ V
a
Solve 20.2 operating line
a a a a n n
n 1
n 1 n 1
V y L x L x
y 20.7
V V
+
+ +

= +
b N 1
y y
+
=
b N
b N
L L
x x
=
=
a a a a n n
n 1
n 1 n 1
V y L x L x
y 20.7
V V
+
+ +

= +
V
N+1
KJ4
Slide 33
KJ4 the blue boxes should be lower
Notice I made the inset much larger.
Keep in mind they will get 4 per page
Keith Johnston, 8/16/2004
34
Rectification at Absorption of gas Desorption
top distil. column into liq. or stripping
from liq. to gas
Operating to equilibrium line:
y x y x y x (opposite of absorpt.)
Enriched at top Rich gas- bottom Rich liquid at top
Lean gas at top Lean liquid at
after absorption bottom after desorption
KJ9
Slide 34
KJ9
Keith Johnston, 9/11/2004
35
Gas Absorption (Chpt. 18) (No accum.-interface)
Rate of Adsorption / vol. (a = interfacial area/vol)
Likewise
2
y i 3 2 3
g mol g mol cm
r = k a (y y )
cm s cm s cm

x i
y y i i
x
k a(x x)
K a(y y*) K a[(y y ) (y y*)]
K a(x * x)
=
= = +
=
i i
y
y y y y * 1
K a r r

= +
i i
y
i x i
y y y y *
k a(y y ) k a(x x)

= +

y x
1 m
k a k a
= +
x x y
1 1 1
K a k a mk a
= +
m = slope eq
curve
36
Note: x
i
> y
i
even though mass transfer is to the right due to phase
equilibria (solubility of gas in liquid)
At interface
For low solubility gases (O
2
in water), y = mx, m is large and x is small.
Major resistance is in liq phase where concentrations are low
For high solubility gases (NH
3
in water), m is small and x is large. Major
resistance is likely to be in the gas phase where concentrations are low
v L
A A
=
37
Transfer unit concept:
Material balance on gas
bubbles in shell (define upwards for in):
Both sides are positive quantities
dV << V (dilute systems)
dy is + in Z direction downwards
+ Vdy = K
y
a (y-y*) SdZ
= H
oy
.
N
oy
For straight operating + equil curves (e.g. dilute systems), analytical integration
In Out Absorp. to liquid
(V dV)(y dy) Vy rSdZ
+
+
=
+ + =


T
Z
b b
y
T
y 0 a a
K aS dy V/ S dy
dz or Z
V y y * K a y y *
= =


oy b a m b b a a
N (y y ) / y Note : lmfor y y * and y y * driving forces = (
"
S = cross sect. area of
column
As driving forces incr., smaller N
oy
needed to achieve overall change in y from b to a
KJ10
Slide 37
KJ10 dz is upper case
Keith Johnston, 9/11/2004
38
See p. 564
molal mass velocity = molar flux
two-film theory
Note: L
M
= L/S : molar flux
Note: mG
M
/L
M
=ratio of slope of eq. line to op. line, Eq. 18.28
Notice the H values take ratio of convection to k
y
a
y y x x oy oy ox ox y
y
V/ S
H ,N ; H ,N ; H ,N ; H ,N H
k a
=
M M
G u V/ S = p =
M
M
M M
y y x M
L 1 1 m
G G G
K a k a k a L
- - -
+
= +


M
oy y x
M
mG
H H H
L
= +
y y x
1 1 m
K a k a k a
= +
39
Absorption: Comparison of plates (discrete) versus packed bed
(differential) (optional minor point)
Fig 18.13 (b) p. 563
NTP = 1 for a column w/plates
Since lm avg driving force is < y
b
y
a
More transfer units are required to achieve y
b
y
a
since driving forces are
smaller. This distinction is simply a result of the two slopes shown- not general.
The discrete plate system achieves a huge driving force from op line to equil line
at state y
b
y
b
*.
b b
b a
lm
a a lm
y -y *
y y
NTU 1 y for
y -y * y

= > (
(
40
Mass transfer correlations
To focus on liquid resistance control: Desorption of O
2
from H
2
O
m (slope eq curve) > > L/V
very low x
i
so most resistance is in liquid
i i i i
yP x H =
i i i i i i
y / x H / P H l arge, since x small =
m
x
ox x y
M
L
H H H H
mG
= + =
41
Choice of determination of H
ox
from absorption versus desorption
Why is desorption preferable to absorption here?
For H
0x
, focus is on liquid phase
For absorption x
b
* - x
b
gives little accuracy (loss of significant figs)
In contrast, for desorption x
b
* = 0
More significant figures are obtained in x
b
0 vs. x
b
* - x
b
Goal of engineering:
Run absorption pilot unit (e.g. 2 inch diameter). Measure concentrations
and flow rates. Develop correlation for H
ox
. Use mass transfer model to
predict other conditions and systems, and to design large columns
ox T
dx
H Z /
x * x
=

42
Fig 18.21 p. 715 Correlation for H
x
in terms of G
x
= pu = mass flow rate/S = G
M
M
K
L
is a K
c
[cm/s]
As G
x
, convection , N
Re
, therefore, K
L
a . However numer. dominates and H
ox

To convert from O
2
in water to other systems:
E is an empirical constant
Gas film resistance (highly soluble gases)
Absorption of NH
3
in water
x
i
is large, m is small most resistance is in vapor phase where concent. is small
Fig 18.22 focus is on vapor phase.
Absorption from rich gases not covered
v
n
0.5
x
x
G 1
H ( / D )
+
= p

E

x x x
ox x L m
x L
m x
G / M G /
H ; K a K a
K a K a
M
p
= p
p = p
i i i i
yP Hx =
43
L
a
V
a
y
a
L
x V
y
x
a
= 0.0002
X
a
= 0.0002
L
b
x
b
= 0.05
V
b
y
b
= 0.14
359 ft
3
/ lb mol (STP) 500 ft
3
/m (STP)
18.1
Basis: 1 hour
Acetone in: 0.14 x 83.57 = 11.70
Acetone out: 0.05 x 11.70 = 0.585 5% loss
Acetone absorbed = 11.115 95%
Moles air in: 83.57 (1-0.14) = 71.87 V (const)
y
a
= 0.585/(71.87 + 0.585) = 0.008074
L
b
= L
a
+ 11.115 Total Liquid Gain
0.05 L
b
0.0002 L
a
= 11.115 Acetone Gain
L
a
= 212.03 mol / h L
b
= 223.145
b
500
V x 60 83.57 lb mol / h
349
= =
vapor
,
44
(a) Water to tower:
212.03(1-0.0002) x 18.02 = 3820 lb / h L (const)
(b) Acetone balance Lx + V
a
y
a
= L
a
x
a
+ Vy

Solute free basis: (V, L constant)


V = V (1-y) L = L(1-x)
a a
a a
y x y x
V' L'
1 y 1 y 1 x 1 x
+ +
=



Solute-free basis:
E.g. V
a
= V / (1-y
a
)
From this: y = F(x) / (1+F(x))
where
const L/ V
a a
a a
y x y L' x
F(x)
1 y 1 y V' 1 x 1 x
+
= = +



y
a
= 0.008074 x
a
=0.0002
L = 3820 / 18.02 = 211.98 V = 71.87
45
Equilibrium relationship: Acetone
P = 1 atm
For values of x between 0.0002 and 0.08, calculate y and y* and solve
Eq. (18.21) by numerical integration over dy. The computer solution is N
oy
= 9.34
2
1.95(1 x)
A A
y* P' x 0.33e x

= =
=

b
a
y
oy
y
dy
N
y y *
(c) Calculate the operating mass velocities from the flooding velocities based
on flow rates at the bottom of the column (where both rates are greatest).
The mass flow rates,
x y
x
y
m and m are
lb/h MW water + acetone
Liquid: m 3820 (11.115x58.1) 4465 lb/ h
Gas : m (71.87x29) (11.7x58.1) 2764 lb/ h
air
= + =
= + =

MW
acetone in
Use Fig 18.6, p. 554
(18.21)
46
For 7% acetone in air, p
y
= 0.0791. Assume p
x
= 60.5
y
x
y x
G 4465 0.0791
0.0584
G 2764 60.42
p
= =
p
(ideal mixing) m
3
lb
ft
p. 549
From Table 18.1, for 1-inch Raschig rings, F
p
= 155. Since this is
greater than 60, the pressure drop at flooding, as recommended on p. 553,
is 2.0 in. H
2
O / ft. By extrapolation of the data in Fig. 18.6 to this (P,
2 0.1
y p x
c y x y
G F ( )
0.115
g ( )

=
p p p
c y x y
y 0.1
0.115 g (
G
F
p
p p p
=

For water at 80F, u


x
= 0.862 cP (Appendix 6)

=
8
y 0.1
2
0.115x4.17x10 x0.0791x(60.5 0.0791)
G
155x0.862
= 1225 lb / ft - h
Actual rates:
= =
8
2
c
2
m
2 2
f
g 32.174(3600) 4.17x10
lb ft s

lb s h
47
flooding: Gas: G
y
= 1225/2 = 613 lb / ft
2
h
Liquid: G
x
= 613 x 4465 / 2764 = 990 lb / ft
2
h
Calculate HTUs, using Eq. (18.44) for H
x
. Find D
vx
from Eq. (17.31).
At 80F (26.7C),
x
= 0.862 cP or 2.086 lb/ft h (App 9)
(assuming is the same as for water). Also
T = 299.7 K M
B
= 58.1
p
A
at 20C: 0.792 g / cm
3
or 0.792 / 58.1= 0.0136 g mol / cm
3
Estimated p
x
at normal boiling point (56.1C),
is 0.0128 g mol/cm
3
.
Hence V
A
= 1/0.0128 = 78.1 cm
3
/ g mol
(see Perry, 5
th
ed., p.3-230).
Substitution in Eq. (17.31) gives, since Wilke Chang

B
= 2.6,
8 1/ 2
5 2
vx 0.6
7.4x10 x(2.6x18) x299.7
D 1.29x10 cm / s
0.862x78.1

= =
or 5.0 x 10
-5
ft
2
/ h (Appendix 1)
1/ 2
8
B B
v 0.6
A
( M ) T
D 7.4x10
V

Solute normal b.p.


assoc parameter
flux ratio
48
p. 581
From Fig. 18.21, G
x
= 990 (above) , 1 rings
For acetone in water,
Sc = 2.086 / (60.5x5.0x10
-5
) = 689 = / pD
For O
2
, Sc = 381 (see p. 582)
for water at 25C: 0.90 cP (Appendix 6)
From Eq. (18.44), using n = 0.3
2
x,O
H 0.68 ft =
+ +
=

E p

1/ 2
n
x
x
v

G 1
H
D
Penetration theory
18.44
H
x
= 0.68 (0.9/0.862)
0.3
(689/381)
0.5
= 0.93 ft
To find H
y
, use Fig. 18.22. For G
y
= 613 and G
x
= 990 lb / h-ft
2
, by
interpolation:
3
y,NH
H 2.0 ft =
49
Use Sc for acetone-air for 0C (Appendix 18). In view of the uncertainties
in the correlations, correction to 80F is not worthwhile. Then Sc = 1.6.
from Eq. (18.47)
H
y
= 2.0 x 1.6 / 0.66)
0.5
= 3.11 ft
Find the average slop of the equilibrium curve for use in Eq (18.28). From the
equation given in part (b),
at x = 0.05, y* = 0.09589
x = 0.0002, y* = 0.000464
3
1/ 2
y y,NH
Sc
H H
0.6
+
=


0.09589 0.000464
m 1.916
0.05 0.0002

= =

y
M [(0.008074 0.14) / 2]x58.1 0.926x29 31.15 = + + =
x
M (0.0251x58.1) (0.9749x18.02) 19.02 = + =
2
M
G 613/ 31.15 19.68 lb mol / h ft = =
M
L 990/ 19.02 52.05 = =
m
oy y x
m
G
H H m H (18.28)
L
= +
50
From Eq. (18.28)
H
oy
= 3.11 + 1.916 (19.68 / 52.05) x 0.93 = 3.78 ft
Column diameter D = (4m
y
/ xG
y
)
1/2
= ((4 x 2764) / (p x 613))
1/2
= 2.4 ft
NOTES: Since the equilibrium and operating lines are nearly parallel
the number of transfer units about equals the number of theoretical
stages. The column height is 3.78 x 9.34 = 35.3 ft.
x
=

2
y
m
D
4 G
51
Phase Equilibria Review
L V
i i
=
L V sat
i i i i i i i
f f x P y P = = o
sat
i i i i i
K y / x P / P =
sat sat
ij i j i i j j
K / K P / P E =
At azeotrope
i i i
y x K 1 = =
ij i j
K / K 1/1 E = =
sat sat
i j j i
In / ln P / P =
52
i i i
i i
y 1 K x
P, x T, y
= =

i i i
i i
x 1 y / K
P, y T, x
= =

53
Flash calculation (after thermo done to determine y
D
, x
B
)
Thermo notation
1 1 1
z = y V + x (1-V)
MSH notation
F D B
x = fy + (1 - f) x
F
D B
x (1 - f)
y = x
f f
+
54
B F
D F
s. . f = 0 x = x
s.v. f = 1 y = x
"
AB
f
AC
=
x
B
x, y
55
56
Total F = D + B
Component:
Fx
F
= Dx
D
+ Bx
B
Elimin. B
D/F = (x
F
x
B
)/(x
D
- x
B
)
Elimin. D
B/F = (x
D
x
F
)/(x
D
- x
B
)
Condenser D = V
a
L
a
V
a
L
a
D
B
F
Binary Distillation
57
Rectification (Enriching) Section (Above feed line):
D = V
n+1
L
n
Dx
D
= V
n+1
y
n+1
L
n
x
n
= V
a
y
a
L
a
x
a
a a a a n n n D
n 1 n
n 1 n 1 n n
V y L x L L x Dx
y x = + (20.12,14)
V V L + D L + D
+
+ +

= +
Figure: Seader and Henley,
Sep. Proc. Principles
V
a
58
Constant molar overlow: simplifying assumption to obtain linear operating
line- leads to simple graphs (pedagogical and conceptual value)
Recyle ratio
n n D
n+1
n n
L x Dx
y = + (20.14)
L + D L + D
D
R L/ D
1L, 1H
1L, 1H
+T +
+ +T
vap
D D
n 1 n
D D
m B
m+1 m
m m
H per mol ~ const
L, V const
R x
y x
R 1 R 1
Likewise in stripping section
L Bx
y = x
L -B L B
+
(

= +
+ +

59
60
61
Feed tray energy balance to determine changes in L and V
For satd liq.
For satd vapor
q > 1 subcooled liq T
F
< T
bub pt
q = 1 satd liq T
F
= T
bub pt
q = 0 satd vap T
F
= T
dew pt
q < 0 superheated vapor T
F
> T
dew pt
Energy balance on feed tray for sub cooled liq.
L L F V V = + =
L L V V F = = +
L L qF (21.26) V V (1 q) F (21.27) = + = +
Let q mol. liq added to L by F
vap
PL b F
F
F
(q 1) H C (T T )
bubble T ( T )
As T q L
( =
>
+ T T
62
Determination of feed line from material balances and feed tray
energy balance
Let m = n at feed tray where the two sections meet:
Subst (21.26) , (21.27)
(same as 1 stage distillation)
n+1 n D
m+1 m B
Enriching section Vy =Lx + Dx
Stripping section Vy =Lx - Bx
D B
(V V) y (L L) x Dx Bx = + +
F
(1 q) Fy qF x Fx = +
F
x q
y x
1 q 1 q
= +

f 1 q

V L
=
T T
Reboiler energy balance
At 20 psia,
Condenser
Rise in cooling water T
vap vap
s s
m H V H ( = (

vap
S
H 522 cal / g, 939 Btu/ lb ( =
vap
w p 2 1
m C (T -T ) V H = (

63
Feed tray location (optimization)
Given R
D
, q, x
F
, F, x
D
, x
B
calculate D, B
Both operating lines and feed line are fixed
Fig. 21.15 p. 660
Switch may be delayed past optimum, yet operating + feed lines are fixed
Pinch pt limits: a and b. Here concentrat. driving forces go to zero.
If feed tray changed at const q
T
f
or ratio of s.l. and s.v. in feed must be changed.
e.g. (q-1)(H
vap
= C
PL
(T
b
T
f
)

fixed changes must be changed
64
Plate Efficiency
Murphree

M
= (x
n
x
n-1
) / (x
n
* x
n-1
)

Local effic. ( means local


location on tray)

n n 1
M
n n 1
y y
y * y
+
+

n n 1
n n 1
y ' y'
y * y'
+
+

mV
l arge
L
n n 1 M
x , y '
can be 1
+
g >> g
>
mV/L small
65
D
E
: effective D, Z: flow path, t
L
: res time
N
Pe
= N
Re
N
Sc
Using same concepts as in absorption an d definition of g
2
E L E
uZ Z

D t D
p
= - =
p
convec visc

visc diff
M
'
g
g
Pe M
Pe
Low N fast diffus. ' 1, '
High N slow diffus. ' small
g g g
g
Pe M Pe
Fig 18.32
As Z , N , ' / ' f( ', N ) T T g + g g = g
M Pe
/ ' vs N g g
+


M
y
s
s
-K aZ
1- ' =exp where V isthesuperficial velocity
V
66
Analysis of McCabe - Thiele
Variables F, x
F
, x
D
, x
B
, D, B,
(10)
N
enrich
, N
total
or N
stripping
R
D
, q
Equations (4) 2 total mat. Bal. column, 1 op line, 1 equil curve
(Enrich + q + x
B
+ L Stripping Line)
1. Design column
Variables Calculate
F, x
F
, x
D
, x
B
D, B, N
enrich
, N
strip
R
D
, q
2. Existing column (variable feed tray)
F, x
f
, q, N
total
, R
D
, x
D
x
B
, D, B, N
enrich
Vary feed tray until N
enrich
+ N
strip
= N
total
3. Existing column (fixed feed tray)
F, x
F
, q, N
enrich
, N
strip
, R
D
x
D
, x
B
, D, B
67
Energy Balances
DH
D
+ B H
B
F H
F
= q
r
+ q
c
As R
D
= L/D
V = L + D
E.B. Around enriching section
V
n+1
H
y, n+1
= L
n
H
x,n
+ V
a
H
y,a
RH
D
r
V V (1 q) F q = T T
n n D
n 1
n n
op line curved
L x Dx
y +
L + D L + D see fig 18.25
+
=
y
n+1
= f (L
n
)
L
n
= f (H
y, n+1
) where H
y,n+1
= f (y
n+1
)
Simultaneous eqns
Skip books tedious method use professional software
68
Multicomponent Distillation
Dew Bubble
Flash p.717 or thermo book
Keys choose more concentrated components
Sharp separation only keys distribute
K
i
< K
HK
by ~10%, B only
K
i
> K
LK
by ~10%, D only

sat
sat i i i
i i i i i
i
y P
VLE y P = x P K = =
x P

E = <

sat
sat
i i i i
i
sat
ij
sat
j
j j j j
y /x P
P
=
P
y /x P
=
i
x 1 =
i
y 1

E = E E E
ij ij ij
3
ij D F B
Fenske Min plates 21.42

69
Underwood (min reflux) not covered
Gilliland p. 732 Fig 22.5 (empirical)
Do problem 22.4 (Fenske part only)

+
min
N N
log
N 1
min
D
towards N
R

+
D Dmin
D
R R
log
R 1
70
Tray by Tray Calculation
C components, N trays
On each tray, { x
i
} { y
i
} L,V,T unknowns (2C+3)
Material balance for each C C
Binary: Given x
D
, x
B
, x
F
Solve D, B
Multicomp: Given x
DH
, x
BL
cannot solve for D, B
Greater number of degrees of freedom
Invariant zones may be found at other locations than feed tray
=
=
=

L V
i i
i
i

f f C
1 energy balance 1
x 1 1
y 1

1
Per tray 2C + 3
71
Methods
1. Desired { x
Di
} {x
Bi
} and R
D
Determine N
enrich,
N
strip
2. Given N
enrich
, N
strip
Calc {x
Di
}, {x
Bi
} PREFERRED
M. Doherty Conceptual Design of Dist. McGraw Hill, 2001
72
Leaching and Extraction
1. Methylene chloride from poly (glycolic co lactic acid) biodegradable
microcapsules, soybean oils from seeds
aromatics from aliphatics, natural substances (caffeine from coffee, taxol from
yew bark, antibiotics from fermentation broth, PEG-dextran protein extraction,
metals from ore
Leaching (optional)
Substrate entrains liquid. If p, of solution with solute concentration, amount
entrained increases. L
n
= f(x
n
)
If p, constant amount entrained relatively constant. Constant molar under flow.
L
n
constant
Equilibrium y* = x (solids free basis) entrained solution has the same
composition as overflow. The solution fills pores. No adsorption on surface.
Often concentration for solids-free basis
L
n-1
L
n
73
Extraction - Bioseparations
Biomolecules often non-distillable thermally sensitive or nonvolatile
Belter, Cussler et al. Bioseparations
K = C
L
/ C
H
L = light (organic phase)
Antibiotics, etc. AH A
-
+ H
+
low pH high pH
K
a
= [ A
-
] [H
+
] / AH
pH < pK
a
favors protonation (nonionic)
pH > pK
a
favors dissociation and
greater water soln
For COOH pK
a
~ 4.5
See Table 5.1-1
Fig 1.2-4
higher
water solubility
74
Pure solvent
Raffinate
One stage dilute extraction (mat bal stage 1) (L,V constant)
Assume y
2
= 0 (Pure solvent) (Stages 2-n are not present)
x
F
L + y
2
V = x
1
L + y
1
V Subst. y
1
= Kx
1
x
1
/x
F
= 1/(1 + E)
Fractional recovery
As E x
1
(less in raffinate) , y
1
, fractional recovery
= =
1
1 F
F
x KV E
y V/ x L
x L 1+E

= =
+ +

F F
1
where E KV/L
x L x
x Recall absorption
L KV 1 E
factor A mV/L
n 1
y
n+1
y
1
,V
x
F
,L
2
V y
n
y
2
x
1 x
n-1
extract
x
n
75
Multistage extraction
Left stage (n): x
n-1
= (1 + E) x
n
(1)
Next stage (n-1): y
n
V + x
n-2
L = x
n-1
(L + KV) (2)
Subst y
n
= Kx
n
and (1) into (2) to yield x
n-2
= (1 + E + E
2
) x
n
After n sequential material balances, we can show
x
F
= (1 + E + E
2
+E
n
) x
n
Geom series
(like 20.17)
This result is simpler than A method since the solvent was not pure in absorption.
n 1
F n
E 1
x x
E 1
+

n 1
F
n
x
E (E 1) 1
x
+
= +
n 1 ln[RHS] / ln E + =
n 1
y
n+1
y
1
,V
x
F
,L
2
V y
n
y
2
x
1 x
n-1
extract
x
n
76
Belter, Cussler, H u Bioseparations
Example 5.3-1 Actinomycin D
At pH 3.5, protonated non-ionic, K = 57
99% recovery. Calculate n
E = KV/L
R = Recovery
By total mat bal
x
F
L = x
n
L + y
1
V or 1 = x
n
/x
F
+ R (definition of R)
x
n
= (1-R) x
F
(non-recovered material is in raffinate)
F
L 450 / h x 260 mg/ feed
V 37 / h
= =
=
" "
"

1 F
y V/ x L
77
Problem V/L E=KV/L % R n y
1
/x
F
= RL/V
type (input) (input) (input) concentrat. factor
Base 37/450 4.69 99 2.8 12
case
Lower 37/450 4.69 90* 1.3 11
recovery
Greater 100/450* 12.7 99 1.8 4.5
Solvent
Less 10/450* 1.26 99 13.3 45
Solvent
As V/L incr., L/V decr., n decr.
78
Adsorption/Fixed Bed Separation
Langmuir isotherm
For a given time interval from 0 to t*
deal breakthrough K
c
a/u
0

Square wave vertical profile (Pre-calc)
Accum / Area IN OUT
Non ideal breakthrough
=
+
max
W kc
W 1 kc
s
W
g ads
g
b sat 0 0 0
adsorp. capacity
t* L (W W ) / u c
inlet flux
= p
b sat 0 0 0
L (W W ) u c t * 0 p =
s
3
s
g cm g
cm g
o
C C
c
79
(Area above curve)
p
b
vs. p
p
density s: external voids
q = p
b
W (g/cm
3
) p
p
: interval voids only
p
b
= p
p
(1-s) s 0 p
b
p
p
s 1 p
b
0
p
b
gives mass of solid in a given volume for adsorption
p =

b
t
b b 0 0 0
0
L (W W ) u (c c)dt breakthrough

0 0 0
IN OUT
u c (1 c / c )dt
80
Summary of Adsorption
1. Ideal (fast mass transfer)
2. Irrev Adsorption W = W
sat
for C > 0
+
=

b
t
u
o 0
c
t 1 dt
c
amt adsorbed
KJ23
Slide 80
KJ23 only sq wave, tb
curvature on one on far reight middle row
Keith Johnston, 10/17/2004
81
Choose c/c
0
,
b
sat
W LUB
As N , 1, ideal 1
W L
t = =
u b z
t L V t
N
L t * L
t t = = =
3. Linear adsorption
Large N, Small HTU sharp
Small N Large HTU diffuse
pink blue
82
Ex 25.2
t*: time equiv of total capacity
Definition of L
b
: used bed length (fully saturated)

p
=

b sat o
o o
o
0
L (W W )
t*
u c
in notes
(1 c / c )dt

b
t
u
o 0
c
t (1 )dt
c

u
b T
t
L L where
t *

usable capacity time equivalent


L
T
: actual physical length LUB = L
T
L
b
KPJ24
Slide 82
KPJ24 fix curve shapes on figure
Keith Johnston, 10/10/2004
83
u
T T
b
t
L LUB L
t *
L
=

=
u
T
LUB
t / t* 1 25.4
L
u b T
As t t* LUB 0 L L (HTU 0)

8.5
o 0
c
p. 825 For 8-cm bed t*= (1- )dt = 4.79h
c
= = =

b
t
u b
o 0
c
t (1 )dt 2.37h t 2.4h
c
b
LUB
2.4/ 4.79 1 LUB 4.04 cm
8
t = = =
b T b sat
L / L W / W = =
b u b
t / t* ~ t / t * t
o
(small c / c )
if sliver on rt. negligible
compared to area of rec tangle
84
For 16 cm bed
Notice LUB did not change much (exptl uncert). All we did was added a
larger saturated zone.
Summary
L
T
t
b
t
u
/t* =
LUB
= = =
u t 7.07 LUB
0.74 1
t * 9.59 16
LUB = 4.2 cm
b
sat
W
W
8 16 32
2.4 7.1 16.7
0.5 0.74 0.87
~const
')))))))&
85
Material Balance Including Mass Transfer Model
voids particles
Mass Transfer model:
c*: eq conc. at surface
a: external area/volume
D
p
= particle diameter D
e
= effective diffusivity in pores
(D
e
: porosity, tortuosity, pore diameter)

s + s p = +

p o o
c
dL (1 )dL W/ dt u c u (c dc)
t
3
cm g
cm s
= p s =
p c
dq/ dt (1 )dW/ dt K a(c c*)
s
3
s
g g
cm g s
=
2
3 3 3
cm cm g g
s cm cm cm s
p
= + = +
c
c,ext c,int c,ext e
D
1 1 1
1/ K
k k k 10 D
p 0
c W
(1 ) u c / L (25.6)
t t

s + s p =

86
Water vapor, HC vapors both resistances are important
Solutes in aq soln slow diff in pores; often k
c,int
limiting
Surface area 100 1000 m
2
/g
87
Irrev Adsorption W = W
sat
for all c
Accum. Fluid << Accum in solid, since isotherm is so strong (irrev)
c* = 0 for any W for irrev adsorption
L is end of profile and not L
total
(25.18)
No time dependence since wave has constant exponential shape as it
moves thru.
=
*
0 c
u c / L K a(c c )
0 sat
c L
c
0 c L
K a
dc / c dL
u
=

=
c
0 sat
0
K a
ln c / c (L L )
u
88
From t
1
to t:
Amount adsorb. = u
0
c
0
(t-t
1
) =
cross sectl area
Velocity of mass transfer profile (wave)
= inlet flow/ads capacity
From prev page,
Define MHS chooses
L = L(relative to L
sat
),
time is only variable
= N (t1) 1 see Figure 25.11
p s
sat
sat p
W (1 )L
=
p s
sat
0 0
z 1
p sat
u c
v L /(t t )
(1 )W
=
c 0 0 c
N K aL/ u L/ HTU HTU u / K a
c
o sat z 1
0
K a
ln(c / c ) (L L ) ( N/ L)[L v (t t )]
u
= =
z
v t / L t
t / t * t
0 1
1(see below)
N N L
ln(c / c ) N (L ) t
L L t
=
t
+
= + t

89
Ways to think of t
1
(time to establish sat. zone in first part of bed
For ideal adsorption (vertical wave): t*
Approach of MSH to describe t
1
z
t* L/ v t / or t / t * = = t t
= =
t
= t
z
1 z 1
v t L
t t * / N Optional: v t HTU
N N
t / N
p s p s
= = = = -
t
sat p sat p
o
1
c 0 z o o c
W (1 ) W (1 )L
u equil capacity t L
t
K a(c 0) initial rate N v N u c K aL
1 c
t as capacity , K a T T +
90
Linear isotherm W = k
1
C
Solve 25.6 (material balance)
p. 827 25.7 (mass transfer rate)
Bessel fxns (p 833)
N = L/HTU = K
c
aL/u
0
K
c
= f (K
c,cxt
, K
c,int
) as before
As N , HTU , steeper
breakthrough curve
z b b u b b
sat
b
v t L t W t t
~
L L t * W t * t *
= = = t = t
91
For c/c
0
=0.05 at t
b
:
Greater fraction of bed is used due to stronger isotherm.
b
N
10 0.35
Linear isotherm
20 0.5
As N incr, better mass tran. - sharper profile
100 0.8
Note: N( -1) = 1.6
IRREV :
10 0.84
t

)
92
Adsorption Chapter 15 p.783
Cylindrical pores (d
p
= pore diameter)
S
g
specific surface area =
s
p
~ 0.5 p
p
~ 1 g/cm
3
d
p
= 2 nm
S
g
= 1000 m
2
/g
BET eqn. (Brunauer, Emmett, Teller)
Liq N
2
-195.8C (15-6)
Measure P, Y Regress Y
m
Y
m
= volume of monomolecular layer of adsorbed gas
p
p
2
p
d L
S/ V 4/ d
d L/ 4
x
= =
x
area
mass
p
g
p p

1

p
p
S particlevolume pore volume 4
S
V mass particle volume d
s
p
s
= - =
p
p
d
93
S
g
= E Y
m
N
A
/V V = 22, 400 cm
3
/mol
Molecular model for E (2-D closest packed)
E = 1.091 (MW(N
2
) / N
A
p
L
)
2/3
=
2 3 2
3
m cm (STP) molec mol m
molec g mol cm (STP) g
94
Ion Exchange
Henley & Seader Fig 15.5, 15.6
McCabe C
+
+ Li
+
R
-
= C
+
R
-
+ Li
+
K
Li
+
1
Na
+
1.98
K
+
2.90 - less hydrated, greater charge/volume, stronger ion pairing
Regeneration Add salt or change pH
Ultrapure water (low conductivity) anion + cation exchange resins
E.g.
Ca
+2
2H
+
Cl
-
OH
-
+ +
+ +

=
i
C R Li
C Li R
(C )(C ) neglecting ' s
K'
(C )(C ) if dilute
4
NH
4
Li
K'
2.55
Let C NH K'
K' 1
+ +
= = =
95
Membranes
McCabe, Smith, Harriott
Porous membranes: Knudson diffusion through small
pores
D
A
= 9,700r(T/M
A
)0.5 [cm
2
/s]
where r is pore radius in cm.
D
eA
= D
A
s/t where t is the tortuosity.
J
A
= D
eA
((c
A
/(z) = D
eA
(([p
A
/RT]/(z)
Dense non-porous uniform membrane layers where
gases do not interact with each other,
J
A
= -D
A
(dc
A
/dz) = D
A
(c
A1
c
A2
)/z
Equilibrium (ideal solution) H
A
c
A
= p
A
or c
A
= p
A
S
A
S
A
= solubility coefficient
c
A
p
A
Gas-liq equilibria
Slope = S
A
= 1/H
A
KPJ27
Slide 95
KPJ27 all membrane slides have been edited except drug delivery
Keith Johnston, 10/31/2004
96
J
A
= D
A
S
A
(p
A1
p
A2
)/z. Let q
A
= D
A
S
A
(permeability coeff.)
q
A
units: 1 Barrer = 10
-10
cm
3
(STP) cm
-2
s
-1
/ (cmHg cm
-1
)
Flux / ((pressure/ length)
J
A
= q
A
(p
A1
p
A2
)/z = Q
A
(p
A1
p
A2
) where Q
A
is permeability.
Q
A
is used when z is unknown and q
a
cannot be determined.
For a given p
A1
p
A2
(Q
A
/Q
B
) = (D
A
S
A
/D
B
S
B
) See Fig. 26.2.
If S values are similar as in case of O
2
, N
2
then D
A
/D
B
can play a large role as
shown in Table 26.1. See Fig. 26.4.
97
Product purity and yield
Countercurrent Flow Membrane
Assume asymmetric membrane and uniform distribution of feed with negligible
boundary layer resistance. Assume no axial (P in shell side and tube side.
x, y refer to component A. At a particular axial position
y is average composition of gas (all permeate to this position)
y is the local composition of gas (see Fig. 26.6)
y = y at the closed end of the tube with only new permeate
R = P
2
/P
1
E = Q
A
/Q
B
y = J
A
/(J
A
+ J
B
)
J
A
= Q
A
(P
1
x P
2
y) = Q
A
P
1
(x Ry)
J
B
= Q
B
(P
1
[(1-x) P
2
[1-y]) = Q
B
P
1
[1-x R(1-y)]
98
Subst. above eqns to get local permeate comp. y= J
A
/(J
A
+ J
B
)
y = Q
A
P
1
(x Ry) /{ Q
A
P
1
(x Ry) + Q
B
P
1
[1-x R(1-y)] }
= f (x,y, E = Q
A
/Q
B
, R) since P
1
cancels out.
As x increases, J
A
incr. and J
B
decr., thus y incr.
Upper limit on y so that driving force in partial pressure is positive :
P
1
x > P
2
y = P
1
Ry or y
max
= x/R (see Fig 26.7)
At R = 1, y = x and there is no permeation and no separation since there is no
driving force in expression for J
A
.
Membrane area may be obtained from flux for more permeable gas
A = V
out
y
out
/Q
A
(P
1
x P
2
y)
average
At closed end, y = y; therefore, y = f(E, x, R) (26.17)
99
Reverse Osmosis
equilibrium
c
w
= 1/v
w
Desalinization, Removal of heavy metal ions, sulfites in pulp effluent,
recovery of sugars, etc. in wastewater, municipal water (salts, bacteria)
amino acid concentration
= ( (
w
w
P
J ( P )
z
( =
1 1 2 2
(c ) (c )
( = ( =
w
If P J 0
=
w w w
w
c D v
P
RT
= (
s s s s
J D S c / z
=
w
w
w
c (membrane)
S
c (soln)
=
w
c sol ' y in membrane
=
s
s
s
c (membrane)
S ~ 0.035
c (soln)
dense polymer films
c(right) > c(left)
100
Osmotic pressure at equilibrium at constant T

w
o
(P) =
w
(P+H)
=
w
o
(P+H) + RT ln x
w
Superscript o means pure water.
In limit x
w
approaches 1, H approaches 0.

w
o
(P+H) -
w
o
(P) = -RT ln x
w
V
w
H = -RT ln (1 - x
s
)= RT x
s
s s
s
w
n n
RT RT c RT
nV V
H = = =
Pure
water
Water and salt, c
s
Hydration of salt s pulls in
water
101
18.2.2 Osmotic Pump
Fig 18.2.1 constant flux for osmosis: incoming water pushes drug out hole
with zero order release
The brine solution remains saturated as water comes in due to excess salt.
P = permeability
0.5 solubility coeff
Since J
w
f(t)
drug release rate is zero order.
See Ex 18.2-1
p. 473 Cussler, Diffusion
w s
P
J A A c
+
= (


"
(
H = =
w
s
w
Note c RT
V
KJ46
Slide 101
KJ46 the arrow is the bag containing drug
pinhole too large
see p 472 Cussler
Keith Johnston, 11/13/2004
102
Reservoir system polymer or
liposome
Permeation through
membrane
Avoid burst + rupture
Do Ex 18.1-1 p. 471 Cussler
1
P
M N At c (sat)At zero order releaselinear intime!
1
l
= =
M/ t const P D S
solubility coeff membrane
= =
1
s
1
c
S
c
=
103
Crystallization, Interfacial Phenomena, Nanotechnology
Surface Tension A liquid draws into a drop to minimize surface area
(surface is in tension) Therefore, surface has higher energy than bulk. Molecules
are drawn inwards for approximately three molecular diameters.
Move barrier by (x
TOP VIEW
dW = Fdx
dG = Ldx (rev work)
Fdx = Ldx or = F/L Langmuir trough (top view)
units: mN/m = dyn/cm = erg/cm
2
Surface tension or line tension
Surface free energy
(

(
free energy
dG dA
A
L
F
d
x
dx
KPJ28
Slide 103
KPJ28 fix drawing to show x and delta x and L isheight
Keith Johnston, 10/31/2004
104
Surface tension values at 20
o
C
Water 72.94 Hg 486.5
Ethanol 22.39 Ag 878 (1100C)
Octane 21.62 Pt 1800 (mp)
Perfluoropentane 9.89
Pendant drop tensiometer (shown here)
Spinning drop tensiometer (centrifugal forces)
(UT- Wade and Schechter)
surface tension favors a sphere
+ Gravity produces Elongation
105
Laplace Pressure (P = P
o
P
w
> 0
Consider in r of a sphere at const T:
A = 4x r
2
dA = 8x r dr
V = 4/3 x r
3
dV = 4x r
2
dr dA/dV = 2/r
dW = - P
o
dV
o
- P
w
dV
w
+
ow
dA = 0 at mechanical equilibrium
Since dV
o
= -dV
w
(P
o
P
w
) dV
o
=
ow
dA
(P = P
o
P
w
= 2
ow
/r
Laplace P
Since > 0 dG = dA surface tension raises G. Molecules pull towards the inside.
(P > 0: curving interface raises P on inside; raises due to surface tension P
2
P
r

( =
w
P
r
o
P
dr
2
P
r

( =
106
Laplace P becomes important for micron sized drops
r(nm) (mN/m) (P (MPa) (P(bar)
1,000 50 0.1 1
100 50 1 10
10 50 10 100
10 0.5 0.1 1

=
9 6
2
2 mN 10 nm 10 N
= = MPa
r m nm m m
107
Kelvin eqn Solid-Liquid (SL) or Liquid-vapor (LV) equilibria
Solid cluster formed in case 1. Liquid cluster formed in case 2.
Equilibrium Objective: solubility in soln.: y = f (r) because of Laplace
P
curved droplets Bulk or flat particles
r , y > y
s
(shown later) r , y
s
(P = 2/r (P 0
Higher
s
since P
State function- change in around the thermo. square is zero:

S
M
S
M
s s
s
d V dP
V P
(pure) (pure)
(
=

L L
L
s
d
y(curved)
RTln
y (bulk)
RTdlny
(in solution) (in solution)

=

=
=
108
E
= ( =
s
M
RTln
P 2 / r
V
Kelvin eqn
s
M
ln 4V / RTL (McCabe) L 2r
In that case 1 ion/ molecule

E = Y =
Y =
s
s s
=fractional supersaturation
y y y
1 1 S
y y

E

E = + = +
Implications of Kelvin eqn.
y = f(r): As r y small crystals are more soluble since large fraction of atoms at
surface raises
s
(Laplace P)
E = f(r): A higher supersaturation E = y/y
s
is needed to keep smaller crystals
from dissolving

s
(small crystals) >
s
(large crystals)
Ostwald ripening mass transfer from small crystals to large crystals to lower .
Nanocrystals will grow to reduce surface area unless stabilized with ligands.
Supersaturation in temperature or concentration on phase diagram (Fig 27.5)
(T
c
= T
s
T
c
= k (y y
s
) where k is slope of T vs y line
109
Classical Nucleation Theory
Adamson, Gast. P Chem Surfaces pp. 328-332
Cluster of n
molecules: size r
Nucleation: V L or L S
If ( = G
V
G
L
(+); transfer from V L
per molecular favorable (-)
(or L S for solid cluster)
Nucleation of cluster of radius n:
(G(nucleation) = (G(bulk transfer) + (G (surface)
G
0
(
2
4 r x
3
n r ( E
V
L
Favorable bulk
driving force
Surf. energy
penalty
r or n
1/3
110
For a spherical nucleus or cluster,
3
AV
4
n r (3) N / M number density
3
n = number molecules in a cluster
= x p p = p
g molec. mol molec.

vol mol g volume
=
(L) (S)
sat V L
condensation
G n n(G G ) P P
+
( = ( = >

,
2
( )
n 4 r (1)
+
= ( + x
favorable bulk change penalty to create interface
sat
s
nkT ln P/ P or nkT ln y / y (2)
1 1
=
> >
111
Max (G
As , or E that is (
r
c
decr. and it is easier to pass r
c
in 4xr
2
term.
large surface area/volume : interfacial penalty dominant for small nucleii
Barrier to form critical radius = (G
max
Once r is greater than r
c
, it is easy for the nucleus to grow(downhill).
tiny amt of catalyst can lower barrier(cloud seeding) heterogeneous nucleation
orders of magnitude faster than homogeneous nucleation
2
d G/ dr 4 r 8 r 0 (4)
From(4)
( = x p( + x =
c
2
r (5) Subst(5) (3)

=
p(
3
c
2 3
32
n
3
x
=
p (
G (
barrier
c
r
1/3
r or n
Bulk term eventually
wins due to r
3
or small
surface area/volume
112
Rate of nucleation (Adamson & Gast) text (optional)
Frequency factor from kinetic theory of gases
Barrier as , E
faster nucleation
1/ 2
0
max max
c
G G Z
B exp Becker 1935
n 3 KT KT
( ( + +
=

x

2
max c c
G n 4 r (classical theory) ( = ( + x
2
3
2 3
32 2
4
3
+ x
= ( + x

p ( p(

3
2 2
32
16
3
x
+
= +

p (

A A M
N R/ k N / V = p =
2 3
m
2 2 2 2
A
V 16

3 N k T (ln )
x
=
E
3 2
0
M
2 2 2
16 V
B Cexp where C is freq. factor
3 R T (ln ) kT
x
=

E
|
3 2
M A
3 2
16 V N
Cexp 27.9
3 (RT) (ln )
x
=

E
|
0
, : B E T + T
113
Crystal Growth releases heat at surface
Diffusion to surface s
p
: surf. area cryst.
Surface rxn (definition of k
s
) layer by
layer incl. dislocations
N
A
= k
s
(y y
s
)
Sum of resistances
For invariant crystals (same growth in all directions)
v
p
= aL
3
moles: m = aL
3
p
M
s
p
= 6v
p
/L = 6aL
3
/L
= dm/dt = 3 a L
2
p
M
dL/dt where G = dL/dt
G = 2K (y-y
s
) / p
M
A y
p
m
N k (y y')
s
= =

p s y s
m 1
K
s (y y ) 1/ k 1/ k
diff rxn
= =
+

bulk
s
y y' y
2
M
2
s
3aL G
K
6aL (y y )
p
=

2
p p
3
p p p
s D
6
v D / 6 D
x
= =
x
114
Continuous Stirred Tank Crystallizer (ChE 372 Reactor)
M
ixed
S
usp
M
ixed
P
rod
R
emoval
C
ont
S
tirred
T
ank
C
rystallizer
Steady State, uniform supersat., (L = G(t, G f (L)
Start: p934 Table 27.2 See Fig. 27.14
N/V = x
n
cumulative N/V
d(N/ V)
n population density
dL

L
0
N/ V ndL =

N/ V ndL, between sieves Land L dL ( = +


n
N/V
Sum of each bar in n yields N/V.
115
For crystals from L to L+dL
d(N/V) = ndL = differential number/volume in this size interval
(between sieves)
Withdraw a fraction of the crystals in dL size interval: dndL
(Here dL is const) Q is volumetric flow rate leaving crystallizer
The crystals grow during dt: dL = Gdt
N
~
V
(
c
dndL Qdt Volume removed

ndL V total volume
=
c c
dn Gdt Qdt -dn Qn
or
ndL V dL GV
= =
0
n L
o
0
n
dn 1 n L
dL ln z
n G n G
= =
t t

c
Let V / Q t
0 z
n n e

=
116
lim
d(N/ V) dL d(N/ V)

L o dt dt dL
=

j Cumulative Name Differential


0
0
number dist x
n
=N/V d
0
/dz
l
1
size dist x
L
2
2
areadist x
a
1
3
mass or volume dist x
m
d
3
/dz
Fig 27.14 dx
m
/dz = 0 where distribution changes the fastest
Kinetic coefficients
(const volume basis)
Thus B
0
= Gn
0
B
0
G n
0
Nucleation rate size where nucleii are formed
Thus, n
o
=B
o
/G where both B
o
and G are known. Larger n
o
for large B
o
and
small G. High nucleation rate and slow growth.
z z
j j z
0 0
j
j j z
0 0
nz dz z e dz

nz dz z e dz

=


Normalized jth moment (cumulative 0 to z)
Integrate slope of cumul. dist to determine number,
size, mass or volume cumulative values
117
Total number of crystals/mass Recall: z = L/Gt dL =
Gtdz
greatest change in
cumulative dist for mass Fig 27.14
,
? A
0 z 0
c
1
0 0
1
n N/ V ndL n G e dz n G 1 1

+
+
= = = t = t




4 0 3 z 3
c c c
6 0 0
m mndL a (G ) n z e dz where m =aL

= = p t p

c
3
c c
n 1
m 6a (G )
=
p t
predom
L 3G = t
0
c c
c c
m m production rate #nucleii mass
B
V vol. mother liq. n vol time no.cyrstals
= =

c
3
c c pr
n 9
m 2a L
=
p
o
c c c
3
c c c pr c
ratio is fxn of G above (27.44)
n m m (9)
B
m V 2a L V
t
= =
p

Here we assume one nucleus
produces one final crystal
0 z
n n e

=
0
0 0 o
pr c L
B
Given G, L , Q, m / V B , n ; from n pred. size distrib. (ex.27.6)
G
=