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 1.21. 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. 1.31 Ammonia scrubbing easier to use k since the diffusion length is not well
defined unless detailed flows are well known.
Ex. 1.33 Corrosion of marble by acid rain D allows one to predict conc. vs.
position in marble. k only flux at interface
3
Ex. 1.34 Protein size in solution diameter is proportional to diffusion
coefficient.
Ex. 1.35 Antibiotic production oxygen uptake for aerobic fermentation. k
changes in bubble size, nonNewtonian flow, foam caused by biological
surfactants
Ex. 1.36 Facilitated transport across membranes
Diff. and reversible chem. Rxn. couple in nonlinear fashion. Need D to
understand system.
4
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
Fick¶s 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. 2.21 Fig. 2.22
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 Fick¶s 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 Oneway 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 counterdiffusion (e.g. binary distillation)
N
A
ĺ ĸ 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 (Fick¶s 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. Oneway 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 [(1y
A
)/( 1y
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 Semiinfinite 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 OneWay 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 (17.21)
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
1x 1x x x
= or =
1x 1x x x
+ +
© ¹ © ¹
ª º ª º
+
= =
© ¹
ª º
¦ ¦
2 A2
1 A1
z x
A A A2
A A1 z x
(N ) dx 1 x
From 17.21 const dz ln
cD 1 x 1 x
{
14
B2
A
2 1 B1
x cD
N n (17.2 14)
z z x
+
=
© ¹
ª º
"
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) ĺ 17.214 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 =
"
Oneway denoted by µ
= =
" 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 Semiinfinite 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 2.32 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 (2.311) 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) (2.315)
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: Don¶t 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) Semiinfinite 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
= ì
p = ì
ì ì 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
LennardJones 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 µ
Y
÷
=
x µ ÷
o
thermal activation energy for hops
kT
D
6 r friction
0 0 2
Electrolytes D 2 RT/(1/ 1/ )F 17.33
Y +
= ì + ì
A
Turbulent Diffusion J (D )dc / db
eddy diff
= f(u, roughness, position)
Y Y
Y
= + s
s
0
limitingconduc tance for anion
+
ì
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
+
© ¹
= p
© ¹
ª º
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,µ,D
v
, D) All variables that affect mass transfer.
= (const.) (u
E
, p
¡
, µ
¸
, 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
µ
1  E o
D
v
o
D
E  1
= (const) p
1
µD
1
(puD/µ)
E
(pD
v
/µ)
o
k
c
pD/µ = (const) N
Re
E
N
Sc
o
Multiply both sides by N
Sc
= µ/pD
v
k
c
D/D
v
= N
Sh
= (const) N
Re
E
N
Sc
(1o)
Fit const, Eo to data.
27
Dynamic light scattering (1 nm to 1 µm, polymers, proteins,
colloids
Incident light particle diffuses
Laser (HeNe 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 ĺ 0 initial positions correlated As (t ĺ no correlation between pairs
Auto correlation fxn < A(0) A(t) > E exp  (q
2
Dt) Higher D, faster decay
Measure q
2
D ĺ Know q, Get D
<A(0) A(t) >
x ¿ +
÷ ¿ =
© ¹
ì
ª º
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
= µ p = µ
Sc Pr p
viscous viscous
N / D N c / k
diffusion diffusivity energy
= µ µ
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 µ µ
= =
© ¹
© ¹
p µ p
ª º
ª º
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 =
© ¹
x
ª º
¦ ¦
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 +
µ
= =
© ¹
µ p
x
ª º
=
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. 18.11 (thin film) ± dissolution of solute
Accum Flux .A
Matrix system Diffusion thru
Eq. 18.12 (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
=
¦ ¦
÷
+
= = =
© ¹
ª º
s
s
1 1 1
c 1 1 c s s s
1 1
c c c M
ln Ak t / V 1c / 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 crosslinks
diffusion through swollen polymer leads to release that has t ½
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 ĺoperating 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 Ĺ x Ļ y Ļ x Ĺ y Ĺ x Ļ(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
µ = µ
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 (yy*) 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
twofilm 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
  
+
= +
© ¹
ª º
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
ĺy
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
Ĺ, convection Ĺ, N
Re
Ĺ, therefore, K
L
a Ĺ. However numer. dominates and H
ox
Ĺ
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 ĺ 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 )
+
= µ p
© ¹
E µ
ª º
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 (10.14) = 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(10.0002) x 18.02 = 3820 lb / h L¶ (const)
(b) Acetone balance Lx + V
a
y
a
= L
a
x
a
+ Vy
µ
Solute free basis: (V¶, L¶ constant)
V¶ = V (1y) L¶ = L(1x)
a a
a a
y x y x
V' L'
1 y 1 y 1 x 1 x
+ +
=
© ¹ © ¹
ª º ª º
Solutefree basis:
E.g. V
a
= V¶ / (1y
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
+
= = +
© ¹
ª º
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 1inch 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 ( )
µ
=
p p p
c y x y
y 0.1
0.115 g (
G
F
p
p p p
=
µ
For water at 80°F, 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
½ flooding: Gas: G
y
= 1225/2 = 613 lb / ft
2
± h
Liquid: G
x
= 613 x 4465 / 2764 = 990 lb / ft
2
± h
Calculate HTU¶s, using Eq. (18.44) for H
x
. Find D
vx
from Eq. (17.31).
At 80°F (26.7°C), µ
x
= 0.862 cP or 2.086 lb/ft ± h (App 9)
(assuming µ is the same as for water). Also
T = 299.7 K M
B
= 58.1
p
A
at 20°C: 0.792 g / cm
3
or 0.792 / 58.1= 0.0136 g mol / cm
3
Estimated p
x
at normal boiling point (56.1°C),
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.3230).
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
¸
=
µ
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 = µ / pD
For O
2
, Sc = 381 (see p. 582)
µ for water at 25°C: 0.90 cP (Appendix 6)
From Eq. (18.44), using n = 0.3
2
x,O
H 0.68 ft =
+ + µ
=
© ¹ © ¹
E µ p
ª º ª º
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 / hft
2
, by
interpolation:
3
y,NH
H 2.0 ft =
49
Use Sc for acetoneair for 0°C (Appendix 18). In view of the uncertainties
in the correlations, correction to 80°F 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
+
=
© ¹
ª º
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
µ = µ
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 (1V)
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 sat¶d liq.
For sat¶d vapor
q > 1 subcooled liq T
F
< T
bub pt
q = 1 sat¶d liq T
F
= T
bub pt
q = 0 sat¶d 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
ĺcalculate 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. (q1)(H
vap
= C
PL
(T
b
± T
f
)
Ĺ Ĺ Ĺ
fixed changes must be changed
64
Plate Efficiency
Murphree
Ș
M
= (x
n
± x
n1
) / (x
n
*± x
n1
)
Ș
Local effic. (µ means local
location on tray)
Ș ࣚ
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 gࣛ
2
E L E
uZ Z
D t D
p µ
=  =
µ 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
+
© ¹
ª º
M
y
s
s
K aZ
1 Ș' =exp where V isthesuperficial velocity
V ȡ
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 ĺStripping 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
ĺx
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
ĺx
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 Ĺ
V = L + D Ĺ
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
ĺ 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
Ö Ö
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
ĺ 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, PEGdextran protein extraction,
metals from ore
Leaching (optional)
Substrate entrains liquid. If p,µ of solution Ĺ with solute concentration, amount
entrained increases. L
n
= f(x
n
)
If p,µ 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 solidsfree basis
L
n1
L
n
73
Extraction  Bioseparations
Biomolecules often nondistillable thermally sensitive or nonvolatile
Belter, Cussler et al. Bioseparations
K = C
L
/ C
H
L = light (organic phase)
Antibiotics, etc. AH ļ 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 5.11
Fig 1.24
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 2n 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 Ĺ x
1
(less in raffinate) Ļ, y
1
Ĺ, fractional recovery Ĺ
÷ = =
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
n1
extract
x
n
75
Multistage extraction
Left stage (n): x
n1
= (1 + E) x
n
(1)
Next stage (n1): y
n
V + x
n2
L = x
n1
(L + KV) (2)
Subst y
n
= Kx
n
and (1) into (2) to yield x
n2
= (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
n1
extract
x
n
76
Belter, Cussler, H u Bioseparations
Example 5.31 Actinomycin D
At pH 3.5, protonated nonionic, 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
= (1R) x
F
(nonrecovered 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
ĺ
Square wave ± vertical profile (Precalc)
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
(1s) s ĺ 0 p
b
ĺ p
p
s ĺ 1 p
b
ĺ 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
+
=
© ¹
ª º
¦
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 ¹
=
`
÷
)
¦
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 8cm 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 (expt¶l 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
(tt
1
) =
cross sect¶l 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
© ¹
ª º
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 Ĺ, HTU Ļ, 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 ¹
`
t
)
92
Adsorption Chapter 15 p.783
Cylindrical pores (d
p
= pore diameter)
S
g
Ȅ 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
195.8°C (156)
Measure P, Y ĺ 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 (2D 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
ĺ 2H
+
Cl

ĺ 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 nonporous 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
Gasliq 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
[(1x) ± P
2
[1y]) = Q
B
P
1
[1x ± R(1y)]
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
[1x ± R(1y)] }
= 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
µ
w
o
(P) = µ
w
(P+H)
= µ
w
o
(P+H) + RT ln x
w
Superscript o means pure water.
In limit x
w
approaches 1, H approaches 0.
µ
w
o
(P+H)  µ
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 18.21
p. 473 Cussler, Diffusion
w s
P
J A A c
+
= (
© ¹
ª º
"
(µ
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 18.11 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 (1100°C)
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 Ĺ 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 µ due to surface tension ĺPĹ
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 SolidLiquid (SL) or Liquidvapor (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 ³flat´ particles
r , y > y
s
(shown later) r ĺ , y
s
(P = 2¸/r (P ĺ 0
Higher µ
s
since P Ĺ
State function change in µ around the thermo. square is zero:
S
M
S
M
s s
s
d V dP
V P
(pure) (pure)
(
µ =
µ ÷÷÷÷÷÷µ
L L
L
s
d
y(curved)
RTln
y (bulk)
RTdlny
(in solution) (in solution)
µ =
µ ÷÷÷÷÷÷÷÷ µ
=
=
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 Ļ y Ĺ small crystals are more soluble since large fraction of atoms at
surface raises ȝ
s
(Laplace P)
E = f(r): A higher supersaturation E = y/y
s
is needed to keep smaller crystals
from dissolving
ȝ
s
(small crystals) > ȝ
s
(large crystals)
Ostwald ripening ± mass transfer from small crystals to large crystals to lower ȝ.
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. 328332
Cluster of n
molecules: size r
Nucleation: V ĺ L or L ĺ S
If (µ = G
V
± G
L
(+); transfer from V ĺ L
per molecular favorable ()
(or L ĺ 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 (µ 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
Ö Ö 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
+
( = (µ = >
,
2
( )
n 4 r (1)
+
= (µ + 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 ¸Ļ, or E that is (µĹ
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
Ö d G/ dr 4 r 8 r 0 (4)
From(4)
( = x p(µ + x ¸ =
c
2
r (5) Subst(5) (3)
Ö
¸
= ÷
p(µ
3
c
2 3
32
n
Ö 3
x¸
=
p (µ
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 Ļ as ¸Ļ, E Ĺ
faster nucleation
1/ 2
0
max max
c
G G Z
B exp Becker 1935
n 3 KT KT
( ( + +
=
© ¹ © ¹
x
ª º ª º
2
max c c
G n 4 r (classical theory) ( = (µ + x ¸
2
3
2 3
32 2
4
Ö Ö 3
+ x ¸ ¸
= (µ + x ¸
© ¹
p (µ p(µ
ª º
3
2 2
32
16
Ö 3
x¸
+
= +
© ¹
p (µ
ª º
A A M
Ö 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¸
=
¬ ¼
E
¸ 
3 2
M A
3 2
16 V N
Cexp 27.9
3 (RT) (ln )
« » x¸
=
¬ ¼
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 (yy
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
= =
+
m
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 µ
0
number dist x
n
=N/V dµ
0
/dz
l µ
1
size dist x
L
2 µ
2
areadist x
a
1 µ
3
mass or volume dist x
m
dµ
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
· ·
µ ÷ =
¦ ¦
¦ ¦
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
© ¹ © ¹
·
ª º
ª º
¦ ¦
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
÷ ÷ =
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 1.21. flux = mol/cm2/s (amount/area/time) Model 1 flux = k (concentration difference) More applied. Easier to use. Less rigorous. flux = D (concentration difference/length) More fundamental, sometimes more difficult to apply
Model 2
Look at interesting examples in 1.3 to make this physically meaningful to you. Ex. 1.31 Ammonia scrubbing easier to use k since the diffusion length is not well defined unless detailed flows are well known. Ex. 1.33 Corrosion of marble by acid rain D allows one to predict conc. vs. position in marble. k only flux at interface
2
Ex. 1.34 Protein size in solution diameter is proportional to diffusion coefficient. Ex. 1.35 Antibiotic production oxygen uptake for aerobic fermentation. kchanges in bubble size, nonNewtonian flow, foam caused by biological surfactants Ex. 1.36 Facilitated transport across membranesDiff. and reversible chem. Rxn. couple in nonlinear fashion. Need D to understand system.
3
Diffusion and Mass Transfer Flux relative to stationary plane: VM  total molar density N ! VMuo y For species A. VM cm2 g mol g mol y ! s cm3 cm cm2 s = P/RT dcA + dcB = 0 VM is const. 4 .g. canoe relative to river Fick¶s Law JA ! DAB dc A / db Ideal gas cA + cB = At const T. P. g mol cm g mol = cm3 s cm2 s Flux relative to solvent flow at uo: JA = cA uA ± cA uo = cA (uA ± uo) NA ! c A uA e.
5 .DAB dcA/db ± DBA dcB / db = 0 DAB = DBA Total flux species A = Convective flux A + Diffusive flux A NA = = cA uo + cA (uA ± uo) JA (VM const) yA (NA + NB) + Suppose JA is 0. where N is the total flux. Then the convective flux of A is yAN.JA + JB = 0 (to maintain const and uniform VM) .
2 Steady state diffusion across a thin film Fig. 2.21 Fig. 2.22 6 .Cussler Chapter 2 2.
j1©z)/ [(z + (z) ± z] = dj1/dz From Fick¶s law. j1 = D dc1/dz. thus 0 = D d2c1/dz2 Boundary conditions: z=0 c1 = c10. into the layer at z ± diff.Accumulation= diff. 0 = A (j1©z . At steady state. z = l c1 = c1l Integrate twice: c1 = a + bz Flux expression: c1 = c10 + (c1l ± c10) z/l j1 = (D/l) (c10 ± c1l). 7 . the flux is constant.j1©z+(z) Divide by A(z and rearrange 0 = (j1©z+(z . out of layer at z + (z.
Diffusive flux const. flux + Conv. dominant dyA/dz small yA small dyA/d z Large bulk fluid Thin film diffusion or equimolar counter diffusion No convection dyA/dz = const. Oneway diffusion NA = const = Diff.yA large conv. flux 8 .
p.g.Equimolar counterdiffusion (e.1 (6th. @ Same as thin film w/ no convection 9 . Thus NA = JA 517) See Fig 17. binary distillation) NA NB NA = NB NA + NB = N = 0 NA = yA N + JA where N = 0.
flux is constant. yAN = yANA = f(z) 10 . Oneway diffusion of A only with convection (NB = 0) JA. linear b.cA) = (DvVm/l)(yAi ± yA) cAint = cAi + (cA ± cAi) z/l (int = intermediate) const.ChE 363 Summary of Mass Transfer Total flux NA = cAuA = Convective flux + Diffusive flux = cAuo + cA(uAuo) = yA(NA + NB) + JA if VM is constant where JA = cDv dyA/dz (Fick¶s Law) Steady state a. NA = JA Or Equimolar diffusion which eliminates convection JA = (Dv/l ) (cAi . Thin film with no convection.
profile is most curved.cAi) = erf ^. Here vmax is a constant. with no convection (cAint ± cAi)/(cA . flux JA is largest at z where yA is smallest. X = x/vmax. Here the conc. Steady diffusion into falling film with short contact time Identical to penetration theory below where time becomes a residence time. Unsteady Diffusion in a Semiinfinite slab (Penetration theory) xcA/xt = . As JA decreases yAN increases.xjA/xz = Dv x2cA/ xz2 Diffusion eqn. erf ^ = (2/T) ´0^ exp (s2) ds ^ = z /(4Dt)1/2 11 JA = Dv xcA/ xz = (Dv/Tt)1/2 exp(z2/4Dt) (cAi ± cA) JA©z=0 = (Dv/Tt)1/2 (cAi ± cA) JA©z=0time avg = 2(Dv/TtT)1/2 (cAi ± cA) .KPJ44 = (DvVM/l) ln [(1yA)/( 1yAi)] = (DvVM/l) (yAi ± yA)/(yB)lm where (yB)lm = (yB ± yBi)/ln (yB/yBi) yBint/yBi = (yB/yBi)z/l [= f(z)] NA constant Diff. c. The sum NA is constant.
Slide 11 KPJ44 need to think about notation on this sheet? Keith Johnston. 1/17/2005 .
KPJ39 BSL OneWay Diffusion/Convection Thru Gas Film (const T.21) Steady State Mass balance: S NA z ± S NA z + ( z = 0 12 . P) Transport Eqn (not mass balance) diffusion convection cDdxA/dz + xA (NA + NB) (a) NA = Assume B insoluble in A. NB ~ O NB << NA From eq (a) NA ! cD dx A / dz 1 x A (17.
Slide 12 KPJ39 fix subscripts in picture Keith Johnston. 1/9/2005 .
const T. xA = xA1 = PAsat / P z = z2 Solve for c1.21 const cD z2 ¨ 1 xA2 ¸ dx A ´ dz ! x´ 1 x A ! ln © 1 x A1 ¹ ª º z1 A1 13 .z1 z2 .z1 or ¨ xB2 ¸ xB = © ¹ xB1 xB1 º ª xA2 z .z1 z2 .Divide by (z dNA/dz = 0 NA { f(z) and is constant For ideal gas. c is const dx A 1 ! c1 1 x A dz ln(1 x A ) ! c1 z c 2 xA = xA2 BC1. P.z1 (NA ) From 17. 2 z = z1. c2 (fair amount algebra) { ¨ 1x A2 ¸ 1x A = © ¹ 1x A1 1x A1 º ª z .
Avg xB2 xB1 !  (xB )lm ln(xB2 / xB1 ) x A1 x A 2 (x B )lm (2) Subst (2) 17.2 14) Let E ! (z z1 ) /(z2 z1 ) Mean value xBAvg z2 (xB / xB1 ) dz ! ´ theorem xB1 z1 ´ dz xB Avg xB1 dE ! dz E (xB2 / xB1 ) dE ´ 1 0 ´ dE 0 1 1 (xB2 / xB1 )E 1 x / x 1 ! ! B2 B1 ln(xB2 / xB1 ) 0 ln(xB2 / xB1 ) audu ! au / ln a ´ xB.214 for ln (xB2/xB1) cD NA ! z 2 z1 n BSL Note : xB2 xB1 ! x A1 x A 2 14 .NA ! ¨x ¸ cD "n © B2 ¹ z 2 z1 ª xB1 º (17.
KPJ42 Our notation NA ! cD (x Ai x A" ) " (xB )lm z1 ! 0 z2 ! " x A1 ! x Ai x A 2 ! x A" NA (one way) N (y Ai y A" ) /(yB )"m ! A ! NA (equimolal) JA y Ai y A" ! (1/ yB )"m p.661 Oneway denoted by µ k c '/ k c ! k y '/ k y ! 1/(yB )"m 15 .
1/17/2005 . Dont have resistance from back flow of other species.Slide 15 KPJ42 one way in train station in tokyo is faster progress than two way. Keith Johnston.
= diff. A perpendicular to plane of paper x/xt (A(zc1) = A(j1¬z ± j1¬z+(z) Divide by A(z and use definition of derivative xc1/xt = . out no convection.xj1/xz = D x2c1/ xz2 Diffusion eqn. in ± diff. Linear concentration profile.32 Cussler t=0 t >0 all z z=0 z=g c1 = c1g (bulk) c1 = c10 c1 = c1g For small z or large t (small ^). Fig 2.2. erf ^ linear in ^.3 Unsteady Diffusion in a Semiinfinite Reservoir (Penetration theory) Solute accum. 16 .
3 11 17 .KPJ43 Define a new variable to generate ordinary differential equation (Boltzman. 1894): Method of combination of variables ^ = z (4Dt)1/2 Thus: x^/xt = (1/2) ^/t x^/xz = ^/z Use the chain rule for introduction of new variable: xc1/x^ x^/xt = D x2c1/ x^2 (x^/xz)2 Appendix 1: (Subst for two partial derivatives from above) xc1 / x^( 1/ 2)^ / t ! Dx 2c1 / x^ 2 (^ 2 / z2 ) 1 z2 xc1 / x^ ! x 2c1 / x^ 2 2 ^Dt Subst z 2 ! ^ 2 (4Dt) 2^ xc1 / x^ ! x 2c1 / x^ 2 2.
Slide 17 KPJ43 zeta?? Keith Johnston. 1/17/2005 .
to see it is correct. value slope decr. (see Appendix 2) ^ (c1 ± c10)/(c1g . of limit. abs.. x^/xz.One integration of the eqn x2c1/ x^ 2 +2^ xc1/ x^ = 0 xc1/ x^ = a exp(^2) (2. z = 0 erf ( ) = 1.311) gives Subst into above eqn.315) where erf ^ = (2/T) ´0 exp (s2) ds erf (0) = 0.. a useful result! 18 . j1 decr.c10) = erf ^ (2. z = c1 = c10 c1 = c1 The flux may be obtained by taking the derivative of this integral (Appendix 2) j1 = D xc1/ xz = (D/Tt)1/2 exp(z2/4Dt) (c10 ± c1g) Note: Don¶t forget to multiply integrand by deriv. At interface where z = 0 j1©z=0 = (D/Tt)1/2 (c10 ± c1g) t incr.
Appendix 2 c1 c10 ´ dc1 ! a proportional to erf ^ exp( ^ 2 )d^ ´ 0 .
.
.
.
to obtain j1 = . yields : a ! (c1g c10 ) /( T / 2) Second Fundamental Theorem of Calc. 19 .integral ! T / 2 Insertion of bound. cond. ^ For ^ p g.D dc1/dz j1 ! D(c1g c10 ) derf^ / dz derf^ ! 2T1/ 2 exp( ^ )2 d^ / dz dz upper limit of integration Re call d^ / dz ! ^ / z ! (4Dt)1/ 2 Subst : j1 ! D(c1g c10 ) 2 T1/ 2 exp( ^ )( 4 Dt)1/ 2 Insert this result into previous page.
convect.(j1W(x)z+(z + (c1vxW(z)x . Pure gas.(c1vxW(z)x+(x W = width perpendicular to plane of paper Divide by volume W(x(z 0 = xj1/xz .forced convection mass transfer (BSL p. 2. Cussler p. 4. Accum.x(c1vx)/xx 20 .5. 0 = (j1W(x)z . Contact between gas and liquid is short Constant solvent velocity. = diffusion in z direction + convection in x dir.2. Dilute soln. vx . 45) Semiinfinite film: limited penetration into film Assumptions: 1. 537.2 Steady Diffusion into a falling film. in x direction. result of assumptions 1 and 4.5 Convection and Dilute Diffusion 2. Diffusion in z direction. 3.
xc1/x(x/vmax) = D x2c1/ xz2 (Analogous to diffusion eqn) X = x/vmax B.C. Approximation for USS diffusion l = (Dt)1/2 2. j1 = (D/l) (c (thin film) (steady state) j1©z=0 = (D/Tt)1/2 (c (thick slab) 21 . all z. x > 0. x = 0.Let vx be a constant the maximum velocity at the gas surface. z = 0 c1 = 0 c1 = c1sat z=l c1 = 0 (short contact) c1/c1sat = 1 ± erf [z/(4Dx/vmax)1/2] j1©z=0 = (Dvmax/Tx)1/2 c1sat Final perspective: 1.
2 @ DY ~ T1.5 /P for ideal gas 22 . k is Boltzmann const. k=R/NAv .Diffusivities Gases DY ! 1/ 3 u P 1/VM ! RT / P P~1/P u ~ T1/2 .P~T u P avg molec vol mean free path (V goes down in both cases) 2 1 mu related to kT..
For real gas See eq 17. position) 23 . 522 Turbulent Diffusion JA ! (DY I Y )dc / db eddy diff I Y = f(u. 519 u ! 4I «( W / r)12 (W / r)6 » ½ LennardJones potential Liquids: Stokes Einstein Friction ! 6 Tr0Q DY ! n thermal activation energy for hops kT n friction 6 TroQ See empirical Wilke ± Chang (17.31) Electrolytes DY ! 2 RT /(1/ P 0 1/ P 0 )F2 17.1 cations less hydrated as size incr. P 0 limiting conduc tance for anion Table 17.33 F = Faraday constant. roughness. p.28 p.
Resistance in stagnant film. k x ! k c V / Ma v g Diffusion to wall in laminar layer (membrane or electrode) ¨ ¸ JA ! © DYVM / BT ¹ .KPJ40 Mass Transfer Coefficients k c  JA /(c Ai c A ) cm s g mol cm2s cm3 g mol k y  JA /(y Ai y A ) g mol cm2s since c A ! y A VM y A =c A /c k y ! k c VM g mol cm g mol cm2s s cm3 Fast mixing in core turbulent zone. For an ideal gas P ! (n / V)RT or VM ! P / RT k y ! k c (P / RT) For a liq.
y Ai y A .
© .
¹ ky ª º 24 .
1/9/2005 .Slide 24 KPJ40 make better dwg Keith Johnston.
Q. = (const.V. DvH . Diffusion. H = H K = 1 E H from eq. DI) L/t = (Lt1) E (ML3) F (ML1t1) K (L2t1) H LI Exponents must match on both sides: For L For M For t 1 = E . p.K + 2H + I 0 = F + K 1 = E . 3 F!K!EH (4) (5) 25 . QK .) (uE .Dimensional Analysis.Route to Correlations (Cussler.Dv. VF . 235) Show NSh = f(NRe NSc) kc = f(u.3F .H (1) (2) (3) Solve in terms of E and H (arbitrary choice) E = E.K. D) All variables that affect mass transfer.
5 substituted into 1)(6) kc1 = (const) uE VE H .I!E 1 (from 4.1 Q1 .1 = (const) V1QD1 (VuD/Q) E (VDv/Q)H kc VD/Q = (const) NReE NScH Multiply both sides by NSc = QVDv kcD/Dv = NSh = (const) NReENSc(1H) Fit const. EH to data. 26 .E H DvH DE .
proteins. colloids Incident light particle diffuses Laser (HeNe visible) by Brownian motion in and out of scattering volume Scattered light q 4T ¨U¸ sin © ¹ P ª2º U ! 90o usually 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 .(q2Dt) Higher D.Dynamic light scattering (1 nm to 1 Qm. faster decay Measure q2 D Know q. Get D <A(0) A(t) > 27 . polymers.
viscous diffusion NNu ! hD / k convection conduction viscous diffusivity energy NSc ! Q / VDY NPr ! cpQ / k Mass transfer to pipe walls (turbulent) 0.8 Nsh ! 0.t.023 NRe N1/ 3 (Q / Q w )0.Mass Transfer Heat Transfer NSh ! k cD / DY m.velocity diffus.14 Sc As Convenience: j  m NRe o k c o NSh NReN1/ 3 Sc k cD Q ¨ VDY ¸ © ¹ DY VuD ª Q º 1/ 3 ! kc ¨ Q ¸ ! © ¹ u ª VDY º 2/3 28 .vel.
For pipes 0.023 NRe As DY o . 537 k cD DY kc incr. NRe 0 Sh ! 2 analytical effective film thickness ! Dp / 2 NRe 2 ! NSh DY Dp ~ B T DY 1000 NSh ! f(N1/ 2 ) boundary layer theory Re greater flow rate effect NRe turbulent exponent " 1/2 29 . N1/ 3 q (a little). NSh (a little) q ! Sc Flow past single solid spheres p.2 jm ! 0.
8 behave like rigid sphere drops 30 Circulation currents raise exponents depending upon viscosities of the phases. .13 (NRe NSc)0.13 N1/ 2 N1/ 2 Re Sc 1/ 2 NRe y NSc ! Dpu0 / DY ! NPe (Peclet) ! in ertial forces / diffusion Cussler: Small liquid drops NSh = 1.Mass transfer to drops + bubbles: Penetration theory for time avg kc k c ! (DY / Tt)1/ 2 ¨D ¸ kc ! © Y ¹ ª T º 1/ 2 tT t 1/ 2 dt / ´ dt ´ 0 ! 2(DY / Tt T )1/ 2 For XT = Dp /u0 (flow past entire drop) kc ! 2(DYu0 / T Dp )1/ 2 NSh 2 ¨ Dpu0V Q ¸ ! kcDp / DY ! © ¹ T ª Q VDY º ! 1.
18. lim t p0 J1time avg ! 2(Dv /Tt T )1/ 2 (c1i c1 ).Controlled Release Cussler. released : M ! Ms (1 ekc At / V ) Matrix system Eq. 2nd Ed (Review of mass transfer) Diffusion Eq.A d s Vc1 ! AN1 ! Ak c (c1 c1 ) dt t c1 dc1 ´0 c1s c1 ! ´ (Ak c / V)dt 0 s ¨ c1 c1 ¸ ln © s ¹ ! Ak c t / V ª c1 0 º s ! sat 1 ! drug s 1c1 / c1 ! exp( k c At / V) c1 M ! s s c1 M amt. 18. c1 is external to slab KPJ41 M ! J1time avg At T ! 2(Dv t T /T)1/2 A(c1i c1 ) t1/2 kinetics Mg =c1i AL 31 M / M g ! 2( Dv tT / L2T )1/ 2 Saltzman : dual slab is twice this value .11 (thin film) ± dissolution of solute Accum Flux .12 first order release kinetics Diffusion thru (thick slab) at small times.
Slide 31 KPJ41 fix style of last line Keith Johnston. 1/9/2005 .
21.1 Drug dispersed in polymer (Matrix release ±hydrogels) Control crosslinks diffusion through swollen polymer leads to release that has t ½ Glassy polymers ± zero order (tortuous unfolding of chains) 32 .Controlled Release by Solvent Diffusion 18.
KJ4 Chapter 20 Equil Stage Operations Total mat bal (mb) on top to tray n La + Vn+1 = Ln + Va Component mat bal on more vol. (20.2 operating line VN+1 yb ! yN1 Va y a La x a Ln x n yn1 ! Vn1 Vn1 20. comp.2) La xa + Vn+1 yn+1 = Lnxn + Va ya Total mb (entire column) La + Vb = Lb + Va y n 1 ! Ln xn Va y a L a x a Vn1 Vn1 20.7 L b ! LN x b ! xN 33 .7 Solve 20.
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 .
bottom Lean gas at top after absorption Rich liquid at top Lean liquid at bottom after desorption 34 . column Absorption of gas into liq.) Operating to equilibrium line: y x y Enriched at top x Rich gas.KJ9 Rectification at top distil. Desorption or stripping from liq. to gas y x (opposite of absorpt.
Slide 34 KJ9 Keith Johnston. 9/11/2004 .
Gas Absorption (Chpt. (a = interfacial area/vol) g mol g mol cm2 r = k ya (y yi ) 3 cm s cm2s cm3 ! k xa(xi x) ! K y a(y y*) ! K y a[(y yi ) (yi y*)] ! K x a(x * x) 1 y yi yi y * ! K ya r r ! y yi yi y * kya(y y i ) k xa(xi x) 1 m k ya k xa m = slope eq curve ! Likewise 1 1 1 ! K xa k xa mk ya 35 .interface) Rate of Adsorption / vol. 18) (No accum.
Note: xi > yi even though mass transfer is to the right due to phase equilibria (solubility of gas in liquid) At interface Q v ! QL A A For low solubility gases (O2 in water). Major resistance is likely to be in the gas phase where concentrations are low 36 . y = mx. Major resistance is in liq phase where concentrations are low For high solubility gases (NH3 in water). m is large and x is small. m is small and x is large.
to liquid .KJ10 Transfer unit concept: Material balance on gas bubbles in shell (define upwards for in): In Out ! Absorp.
.
.
.
.
.
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.
. dilute systems). area of column Noy ! (yb y a ) / (y "m Note : lm for yb yb * and ya y a * driving forces 37 As driving forces incr. smaller Noy needed to achieve overall change in y from b to a . analytical integration S = cross sect. (V dV)(y dy) Vy ! rSdZ Both sides are positive quantities dV << V (dilute systems) dy is + in Z direction downwards + Vdy = Kya (yy*) SdZ Ky aS V ZT dy V /S dz ! ´ or ZT ! ´ yy* K ya 0 a b dy ´ yy* a b = Hoy .g. Noy For straight operating + equil curves (e.
9/11/2004 .Slide 37 KJ10 dz is upper case Keith Johnston.
18.Ny . Hoy . Eq.Noy .Nox Hy ! V /S k ya p. Hx .See Hy .Nx . 564 GM ! VMu ! V / S 1 K ya ! 1 k ya molal mass velocity = molar flux m k xa twofilm theory ¨ LM ¸ 1 1 m y GM ! y GM y GM © ¹ K ya k ya k xa LM º ª mGM Hoy ! Hy Hx LM Note: LM = L/S : molar flux Note: mGM/LM =ratio of slope of eq. Hox . line. line to op.28 Notice the H values take ratio of convection to kya 38 .
13 (b) p. 563 NTP = 1 for a column w/plates yb yb * yb y a NTU ! "1 (ylm for y a y a * (ylm Since lm avg driving force is < yb ± ya More transfer units are required to achieve yb ± ya since driving forces are smaller.Absorption: Comparison of plates (discrete) versus packed bed (differential) (optional minor point) Fig 18. The discrete plate system achieves a huge driving force from op line to equil line at state yb yb*.not general. 39 . This distinction is simply a result of the two slopes shown.
Mass transfer correlations To focus on liquid resistance control: Desorption of O2 from H2O yiP ! xi K iHi yi / xi ! Ki Hi / P m (slope eq curve) > > L/V Hi large. since xi small very low xi so most resistance is in liquid 40 Hox ! Hx Lm Hy ! Hx mGM .
xb gives little accuracy (loss of significant figs) In contrast. Measure concentrations and flow rates.Choice of determination of Hox from absorption versus desorption Why is desorption preferable to absorption here? Hox ! ZT / ´ dx x * x For H0x.xb Goal of engineering: Run absorption pilot unit (e. and to design large columns 41 . Develop correlation for Hox. for desorption xb* = 0 More significant figures are obtained in xb ± 0 vs. focus is on liquid phase For absorption xb* . 2 inch diameter). Use mass transfer model to predict other conditions and systems.g. xb* .
715 Correlation for Hx in terms of Gx = Vu = mass flow rate/S = GMM Gx / M G /V ! Hox  x x K xa K La . NRe . m is small most resistance is in vapor phase where concent. therefore.Fig 18. dominates and Hox To convert from O2 in water to other systems: 1¨G ¸ Hx ! © x ¹ (Q / V Dv )0.22 ± focus is on vapor phase. convection .5 Eª Q º n E is an empirical constant Gas film resistance (highly soluble gases) Absorption of NH3 in water yiP ! Hi xi K i xi is large. is small Fig 18. However numer. KLa . Absorption from rich gases not covered 42 .21 p. K x a  K L a Vm Vm M ! V x KL is a Kc [cm/s] As Gx .
70 Acetone out: 0.05 x 11.03 mol / h Lb = 223.14 x 83.0002 Lx Lb xb = 0.585 _ 5% loss 95% Acetone absorbed = 11.57 lb mol / h 349 vapor Acetone in: 0.115 0.0002 La = 11.57 = 11.145 Total Liquid Gain Acetone Gain 43 .57 (10.70 = 0.1 y a Va La Xa = 0.18.14) = 71.87 + 0.585) = 0.05 Vb yb = 0.115 Moles air in: 83.14 500 ft3/m (STP) 359 ft3 / lb mol (STP) Basis: 1 hour 500 Vb ! x 60 ! 83.87 V¶ (const) ya = 0.115 La = 212.585/(71.008074 Lb = La + 11.05 Lb ± 0.0002 Vy xa = 0.
02 = 3820 lb / h L¶ (const) (b) Acetone balance Lx + Va ya = La xa + Vy µ Solutefree basis: Solute free basis: (V¶.g.008074 xa =0.0002) x 18.02 = 211.87 44 . Va = V¶ / (1ya) From this: where y = F(x) / (1+F(x)) const L¶/ V¶ ya xa ¸ y L' ¨ x ! F(x) ! © ¹ 1 y 1 ya V ' ª 1 x 1 xa º ya = 0.0002 L¶ = 3820 / 18.03(10.98 V¶ = 71. L¶ constant) V¶ = V (1y) L¶ = L(1x) ¨ y ¨ x ya ¸ xa ¸ V '© ¹ ! L '© ¹ 1 y 1 ya º 1 x 1 xa º ª ª E.(a) Water to tower: 212.
21) by numerical integration over dy. The computer solution is Noy = 9. calculate y and y* and solve Eq.6. The mass flow rates. 554 lb/h MW acetone in 45 . p.08.1) ! 2764 lb / h air Use Fig 18. (18.95(1 x ) x Noy ! ya ´ dy yy* (18.87x29) (11.33e1.7x58.21) For values of x between 0.0002 and 0.115x58.1) ! 4465 lb / h Gas : my ! (71.Equilibrium relationship: P = 1 atm Acetone yb 2 y* ! P' A K A x ! 0. mx and my are MW water + acetone Liquid : m x ! 3820 (11.34 (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).
Since this is greater than 60. the pressure drop at flooding. By extrapolation of the data in Fig. Assume Vx = 60.1 y gc Vy (V x V y ) Gy ! FVQ0.1 ! 0.17x108 x0.h 8 Actual rates: ! 32.115 gc V y (V x V y For water at 80°F.0791) Gy ! 155x0.1.6 to this (P. Vy = 0. for 1inch Raschig rings.0791x(60. 553.115x4.0584 (ideal mixing) lbm 60.5 Gx Gy Vy Vx ! 4465 2764 0. as recommended on p.0791 ! 0. is 2. 18.17x10 gc 2 lbm ft s2 lb f s2 h2 46 . Fp = 155.42 ft 3 p. ux = 0.8620.862 cP (Appendix 6) 0.0 in. 549 From Table 18.0791.For 7% acetone in air.1 = 1225 lb / ft 2 . H2O / ft.5 0.174(3600) ! 4.115 0. G2Fp (Q x )0.
31).1 VA at 20°C: 0.792 / 58.p. since ]B = 2.29x105 cm2 / s Dvx ! 0. Qx = 0.4x10 8 x(2.086 lb/ft ± h (App 9) (assuming Q is the same as for water).0 x 105 ft2 / h (Appendix 1) (NBMB )1/ 2 T Dv ! 7.1= 0.0128 g mol/cm3. (18.44) for Hx.½ flooding: Gas: Gy = 1225/2 = 613 lb / ft2 ± h Liquid: Gx = 613 x 4465 / 2764 = 990 lb / ft2 ± h flux ratio Calculate HTU¶s.1 cm3 / g mol (see Perry. Also T = 299. p..7 K MB = 58. At 80°F (26.862x78.1°C).6 assoc parameter or 5.0128 = 78. using Eq. (17.31) gives. Find Dvx from Eq.7 ! 1. is 0. 5th ed. Substitution in Eq.6x18)1/ 2 x299.10.6.3230).862 cP or 2. (17.792 g / cm3 or 0. Hence VA = 1/0.7°C).4x10 QVA 0.0136 g mol / cm3 Estimated Vx at normal boiling point (56. 8 47 . Wilke ± Chang 7.6 Solute normal b.
5x5.44).68 (0.90 cP (Appendix 6) From Eq. 18. Gx = 990 (above) . 582) Q for water at 25°C: 0.9/0.O2 ! 0. using n = 0.5= 0.086 / (60. 581 From Fig. 1´ rings Hx. For Gy = 613 and Gx = 990 lb / hft2.68 ft For acetone in water. by interpolation: Hy. 18.NH3 ! 2.p.44 Hx = 0.0x105) = 689 For O2.862)0.0 ft 48 . Sc = 381 (see p.21.93 ft To find Hy. (18.3 (689/381)0. use Fig.3 Penetration theory = Q / VD 1¨G ¸ ¨ Q ¸ Hx ! © x ¹ © ¹ E ª Q º ª VDv º n 1/ 2 18.22. Sc = 2.
y* = 0.Use Sc for acetoneair for 0°C (Appendix 18). y* = 0.11 ft Find the average slop of the equilibrium curve for use in Eq (18.NH3 © ¹ ª 0.02 ! 52.02 GM ! 613 / 31. from Eq.66)0.15 ! 19.05 Hoy ! Hy m Gm Hx Lm (18.6 / 0.1 0.0002.28).0002 My ! [(0.09589 x = 0. In view of the uncertainties in the correlations.14) / 2]x58.000464 0.926x29 ! 31.47) ¨ Sc ¸ Hy ! Hy. correction to 80°F is not worthwhile.008074 0. Then Sc = 1. at x = 0.0251x58.1) (0.09589 0.68 lb mol / h ft 2 LM ! 990 /19.9749x18. (18.0 x 1.5 = 3.05.916 0.000464 ! 1.6 º 1/ 2 Hy = 2.05 0.28) 49 .02) ! 19. From the equation given in part (b).6.15 m! Mx ! (0.
(18.4 ft T 2 m D ! 4 Gy NOTES: Since the equilibrium and operating lines are nearly parallel the number of transfer units about equals the number of theoretical stages.68 / 52.78 x 9.From Eq. The column height is 3.11 + 1.3 ft.916 (19.28) Hoy = 3.93 = 3.05) x 0.78 ft Column diameter D = (4my / TGy)1/2 = ((4 x 2764) / (Vx 613))1/2 = 2. 50 .34 = 35.
Phase Equilibria Review QiL ! Qi V fiL ! fi V xi K i Pisat ! yiJiP K i  yi / xi ! Ki Pisat / P E ij  K i / K j ! K iPisat / K jPjsat At azeotrope yi ! xi Ki ! 1 Eij ! K i / K j ! 1/1 In K i / K j ! ln Pjsat / Pisat 51 .
§ yi ! 1 ! § K i xi P.x i 52 .x i p T.y i p T.yi § xi ! 1 ! § yi / K i P.
Flash calculation (after thermo done to determine yD. xB) Thermo notation z1 = y1 V + x1 (1V) MSH notation xF = fyD + (1 .f) xB (1 .f) xF yD = xB f f 53 .
". s.v. f=0 f=1 xB = xF yD = xF f! AB AC xB x.s. y 54 .
55 .
Binary Distillation Va Total F = D + B Component: FxF = DxD + BxB Elimin. B D/F = (xF ± xB)/(xD  xB) Elimin. D B/F = (xD ± xF)/(xD  xB) Condenser D = Va ± La
La F
D
B
56
Va
Rectification (Enriching) Section (Above feed line): D = Vn+1 ± Ln DxD = Vn+1 yn+1 ± Ln xn = Va ya ± La xa Figure: Seader and Henley,
Sep. Proc. Principles
Va y a L a x a Ln Ln xn DxD yn1 ! xn = + Vn1 Vn1 Ln + D Ln + D
(20.12,14)
57
Constant molar overlow: simplifying assumption to obtain linear operating line leads to simple graphs (pedagogical and conceptual value)
Ln x n DxD yn+1= + Ln + D Ln + D
Recyle ratio
(20.14)
(Hvap per mol ~ const @ L, V const
RD  L / D
yn1 ! RD xD xn RD 1 RD 1
qo 1L, 1H 1L, 1H qo
Likewise in stripping section L BxB ym+1= m xm Lm B Lm B
58
59 .
60 .
27) @ L ! L qF (21. liq added to L by F q>1 q=1 q=0 q<0 subcooled liq TF < Tbub pt sat¶d liq TF = Tbub pt sat¶d vap TF = Tdew pt superheated vapor TF > Tdew pt Energy balance on feed tray for sub cooled liq. L ! L F For sat¶d vapor V!V L !L V ! V F V ! V (1 q) F (21.Feed tray energy balance to determine changes in L and V For sat¶d liq.26) Let q  mol. (q 1)(Hvap ! CPL (Tb TF ) bubble T ( " TF ) As TF q qo L o 61 .
27) f ! 1 q (same as 1 stage distillation) (1 q) Fy ! qF x FxF y! x q x F 1 q 1 q vap ms (Hs ! V (Hvap o V o L Reboiler energy balance At 20 psia.BxB Let m = n at feed tray where the two sections meet: (V V) y ! (L L) x DxD BxB Subst (21.Determination of feed line from material balances and feed tray energy balance Enriching section Stripping section Vyn+1=Lxn + DxD Vym+1=Lxm . (21.26) . 939 Btu / lb mw Cp (T2 T1 ) ! V(Hvap Rise in cooling water T 62 . Condenser vap (HS ! 522 cal / g.
g. xF. driving forces go to zero. yet operating + feed lines are fixed Pinch pt limits: a and b. e.l. and s.15 p. xD. 21. in feed must be changed. Here concentrat. B Both operating lines and feed line are fixed Fig. (q1)(Hvap fixed = CPL (Tb ± Tf) changes must be changed 63 . q.v. F. If feed tray changed at const q Tf or ratio of s.Feed tray location (optimization) Given RD. 660 Switch may be delayed past optimum. xB calculate D.
yn 1 LM "" L ' can be " 1 64 .Plate Efficiency Murphree M = (xn ± xn1) / (xn*± xn1) yn yn1 M! yn * yn1 Local effic. (µ means local location on tray) yn ' y 'n1 ! y *n y 'n1 mV large L mV/L small xn .
same concepts / L ' ! f(L '.' = exp © ¹ where Vs is the superficial velocity ª Vs M º 65 . NPe = NRe NSc VuZ Q Z2 ! y ! Q VDE t LDE convec visc visc diff LM L' Low NPe fast diffus. Z: flow path.32 As UsingNPe o. L ' q LM as in absorption an d definition of L Z o. LM p L ' High NPe slow diffus.LM / L ' vs NPe tL : res time DE : effective D. p L ' p 1. NPe ) ¨ KyaZ ¸ 1. L ' small Fig 18.
xB. B. RD xD. xB RD. 1 op line. xf. xD. D. Existing column (fixed feed tray) F. Nenrich Vary feed tray until Nenrich + Nstrip = Ntotal 3. xB. D. Ntotal or Nstripping RD. xD xB. D. xF. Nstrip F. B 66 . 1 equil curve (Enrich + q + xB + L Stripping Line) 1. q. q 2. RD. xF. B. Nenrich. Nstrip.Analysis of McCabe .Thiele Variables (10) F. xF. Existing column (variable feed tray) F. q. Design column Variables Calculate D. Nenrich. column. q Equations (4) 2 total mat. xD. Ntotal. Nenrich. B. Bal.
25 yn+1 = f (Ln) Ln = f (Hy. Around enriching section Vn+1 Hy.a ± RHD op line curved Ln x n DxD yn 1 ! + Ln + D Ln + D see fig 18.Energy Balances DHD + B HB ± F HF = qr + qc As RD = L/D V=L+D V ! V (1 q) F o qr o E.B. n+1) where Hy. n+1 = Ln Hx.n+1 = f (yn+1) Simultaneous eqns Skip books tedious method ± use professional software 67 .n + VaHy.
D only 68 . B only Ki > KLK by ~10%.Multicomponent Distillation VLE y i P = x i K i Pi sat yi K i Pisat Ki = = xi P K iPisat yi /xi Pisat Eij ! } = sat Pjsat K jPj y j /x j Dew §x i !1 Bubble §y i !1 Flash p.717 or thermo book Fenske Min plates 21.42 E ij ! 3 ED ij EF ij EB ij Keys ± choose more concentrated components Sharp separation ± only keys distribute Ki < KHK by ~10%.
5 (empirical) Do problem 22. 732 Fig 22.Underwood (min reflux) ± not covered Gilliland p.4 (Fenske part only) towards Nmin N Nmin log N1 RD p g RD RDmin log RD 1 69 .
N trays On each tray. xF Solve D.T unknowns (2C+3) Material balance for each C C Ö Ö fiL ! fiV 1 energy balance C 1 1 1 Per tray Binary: Given xD. B Greater number of degrees of freedom Invariant zones may be found at other locations than feed tray 70 .V.Tray by Tray Calculation C components. xBL cannot solve for D. { xi } { yi } L. B 2C + 3 §x §y i i !1 !1 Multicomp: Given xDH. xB.
{xBi } ± PREFERRED M. Nstrip Conceptual Design of Dist. 2001 71 . Given Nenrich. Doherty Determine Nenrich. McGraw Hill. Desired { xDi } {xBi } and RD 2.Methods 1. Nstrip Calc {xDi }.
Constant molar under flow. natural substances (caffeine from coffee. taxol from yew bark. soybean oils from seeds aromatics from aliphatics.Leaching and Extraction 1. amount If V. Ln = f(xn) with solute concentration. No adsorption on surface. antibiotics from fermentation broth. metals from ore Leaching (optional) Ln Ln1 Substrate entrains liquid. The solution fills pores. PEGdextran protein extraction.Q constant amount entrained relatively constant.Q of solution entrained increases. If V. Ln constant Equilibrium y* = x (solids ± free basis) entrained solution has the same composition as overflow. Methylene chloride from poly (glycolic ± co ± lactic acid) biodegradable microcapsules. Often concentration for solidsfree basis 72 .
+ H+ high pH higher water solubility 73 . etc.Bioseparations Biomolecules often nondistillable thermally sensitive or nonvolatile Belter. Ka = [ A] [H+] / AH pH < pKa favors protonation (nonionic) pH > pKa favors dissociation and greater water soln For COOH pKa ~ 4. Cussler et al. Bioseparations K = CL / CH L = light (organic phase) Antibiotics.24 AH low pH A.5 See Table 5.Extraction .11 Fig 1.
extract
Pure solvent
yn+1
Raffinate
V n
yn 2 xn1
y2
1
x1
y1,V xF,L
xn
One stage dilute extraction (mat bal stage 1) (L,V constant) Assume y2 = 0 (Pure solvent) (Stages 2n are not present) xF L + y2 V = x1 L + y1 V Subst. y1= Kx1
x1 !
xFL x ! F L KV 1 E
where E  KV/L Recall absorption factor A  mV/L
x1/xF = 1/(1 + E) Fractional recovery As E  y1V / xFL ! x1KV E ! xFL 1+E , fractional recovery
74
x1 (less in raffinate) , y1
Multistage extraction Left stage (n): xn1 = (1 + E) xn Next stage (n1): ynV + xn2L = xn1(L + KV)
(1) (2)
Subst yn = Kxn and (1) into (2) to yield xn2 = (1 + E + E2) xn After n sequential material balances, we can show xF = (1 + E + E2 +«En) xn Geom series
extract
yn+1 xn
V n
yn 2 xn1
y2
1
x1
y1,V xF,L
En1 1 xF ! xn E 1
E
n 1
xF ! (E 1) 1 xn
(like 20.17)
n 1 ! ln[RHS] / ln E
This result is simpler than A method since the solvent was not pure in absorption. 75
Belter, Cussler, H u Bioseparations Example 5.31 Actinomycin D L ! 450" / h V ! 37" / h At pH 3.5, protonated nonionic, K = 57 99% recovery. Calculate n E = KV/L R = Recovery  y1 V / xFL By total mat bal xFL = xnL + y1V xF ! 260 mg / " feed
or 1 = xn/xF + R (definition of R)
xn = (1R) xF (nonrecovered material is in raffinate)
76
5 10/450* 1.7 99 1. 77 .69 90* 1. factor (input) Base case Lower recovery Greater Solvent Less Solvent 37/450 4.8 12 37/450 4. L/V decr..Problem type V/L (input) E=KV/L % R (input) n y1/xF= RL/V concentrat.3 11 100/450* 12.8 4.26 99 n decr. 13.3 45 As V/L incr..69 99 2.
capacity inlet flux Co C 78 .Adsorption/Fixed Bed Separation W kc ! Wmax 1 kc Langmuir isotherm For a given time interval from 0 to t* deal breakthrough Kca/u0 Square wave ± vertical profile (Precalc) IN ± OUT Accum / Area cm gs g LVb (Wsat W0 ) ! u0c 0 t * 0 cm3 gs W g ads gs c t* ! LVb (Wsat W0 ) / u0c 0 Non ideal breakthrough adsorp.
LVb (Wb W0 ) ! u0 ´ (c 0 c)dt 0 tb breakthrough IN OUT ! u0c 0 ´ (1 c / c 0 )dt Vb vs. Vp density q = Vb W (g/cm3) Vb = Vp (1I) (Area above curve) I: external voids Vp: interval voids only I 0 Vb Vp I 1 Vb 0 Vb gives mass of solid in a given volume for adsorption 79 .
Ideal (fast mass transfer) 2. Irrev Adsorption W = W sat for C > 0 ¨ c ¸ t u ! ´ © 1 ¹ dt co º 0ª amt adsorbed tb 80 .KJ23 Summary of Adsorption 1.
10/17/2004 .Slide 80 KJ23 only sq wave. tb curvature on one on far reight middle row Keith Johnston.
Choose c/c0. Linear adsorption Large N. ideal ! ! 1 Wsat L 3. N X X ! Vz t t u L b ! ! L t* L Wb LUB As N p g. X p 1. Small HTU sharp Small N pink blue Large HTU diffuse 81 .
Ex 25.2 t*: time equiv of total capacity KPJ24 t* ! LVb (Wsat Wo ) ¾ ± uoc o ± ¿ in notes g  ´ (1 c / co )dt ± ± 0 À tb t u  ´ (1 0 c )dt co usable capacity time equivalent Definition of Lb: used bed length (fully saturated) Lb tu  LT t* where LUB = LT ± Lb 82 LT : actual physical length .
10/10/2004 .Slide 82 KPJ24 fix curve shapes on figure Keith Johnston.
Xb  t u / t* ~ tb / t * (small c / c o ) if sliver on rt. negligible ! Lb / L T ! Wb / Wsat compared to area of rec tan gle t L T LUB ! u L T .
.
79 ! 1 LUB ! 4.5 p.4 / 4.04 cm . t* Lb LUB tu / t* ! 1 LT 25.37h co LUB 8 tb ! 2.4 As tu p t* LUB p 0 Lb p L T (HTU p 0) 8. 825 For 8cm bed t*= ´ (10 tu ! ´ (1 0 tb c )dt = 4.4h 83 Xb ! 2.79h co c )dt ! 2.
For 16 cm bed tu 7.74 ! 1 t* 9.87 ~const '))))))& ) 84 .2 cm Notice LUB did not change much (expt¶l uncert).1 32 16.74 0.7 Wb Wsat 2. All we did was added a larger saturated zone. Summary LT tb tu/t* = LUB 8 16 7.5 0.59 16 LUB = 4.4 0.07 LUB ! ! 0.
int ! 1 k c.6) Mass Transfer model: dq / dt ! Vp (1 I)dW / dt ! K c a(c c*) gs g cm3 gs s cm cm2 g g ! s cm3 cm3 cm3 s c*: eq conc.ext 1 k c. tortuosity.ext DV 10 De 85 Dp = particle diameter De = effective diffusivity in pores (De: porosity. at surface a: external area/volume 1/ K c ! 1 k c.Material Balance Including Mass Transfer Model xc IdL (1 I )dLVpxW / dt ! uoc uo (c dc) xt voids cm g cm3 s particles I xc xW (1 I )Vp ! u0 xc / xL xt xt (25. pore diameter) .
int limiting Surface area 100 ± 1000 m2/g 86 .Water vapor. HC vapors ± both resistances are important Solutes in aq soln ± slow diff in pores. often kc.
18) (L L sat ) u0 No time dependence since wave has constant exponential shape as it moves thru. since isotherm is so strong (irrev) u0 xc / xL ! K c a(c c * ) Ka dc / c ! c ´ dL ´ u0 Lsat c0 c L c* = 0 for any W for irrev adsorption L is end of profile and not Ltotal K ca (25.Irrev Adsorption W = W sat for all c Accum. Fluid << Accum in solid. ln c / c 0 ! 87 .
time is only variable ln(c / c 0 ) ! N = N N ¨ XL ¸ (LX) © ¹ t1 L L t º ª . = u0c0 (tt1) = WsatVp (1 I )Lsat cross sect¶l area Velocity of mass transfer profile (wave) v z  Lsat /(t t1 ) ! From prev page. u0c 0 Vp (1 I )Wsat = inlet flow/ads capacity ln(c / c o ) ! K ca (L L sat ) ! ( N / L)[L v z (t t1 )] u0 N  K c aL / u0 ! L / HTU HTU  u / K a Define MHS chooses 0 c X  v zt / L X  t/t* L = L(relative to Lsat).From t1 to t: Amount adsorb.
.
!1(see below ) N (X1) ± 1 see Figure 25.11 88 .
Ways to think of t1 (time to establish sat. zone in first part of bed For ideal adsorption (vertical wave): t*
t* ! L / v z ! t / X
t1  t * / N ! t / XN
or
X  t/t*
v zt L !  HTU XN N
Optional: v z t1 !
Approach of MSH to describe t1
WsatVp (1 I )L u equil capacity t L ! ! ! ! y o t1  XN v zN K c a(c 0 0) initial rate uoc o K c aL
t1 o as capacity o, K c a q
89
WsatVp (1 I)
Linear isotherm
W = k 1C
Solve 25.6 (material balance) p. 827 25.7 (mass transfer rate) Bessel fxns (p 833) N = L/HTU = KcaL/u0 Kc = f (Kc,cxt, Kc,int) as before As N , HTU , steeper breakthrough curve
Xb 
v z t b Lb tu W t ! ! ! b ~ b L L t * Wsat t *
X!
t t*
90
For c/c0 =0.05 at tb:
¾ ± 10 0.35 ± Linear isotherm ± 20 0.5 ± ¿ As N incr, better mass tran.  sharper profile 100 0.8 ± Note: N(X1) = 1.6 ± IRREV : ± 10 0.84 ± Greater fraction of bed is used due to stronger isotherm. À N
Xb
91
Emmett.5 Vp ~ 1 g/cm3 dp = 2 nm Sg = 1000 m2/g BET eqn.Adsorption Cylindrical pores (dp = pore diameter) Chapter 15 p. Y Regress Ym Ym = volume of monomolecular layer of adsorbed gas 92 .8°C (156) Measure P. Teller) Liq N2 195. (Brunauer.783 Tdp L S/V ! ! 2 Tdp L / 4 Sg specific surface area = 4 / dp area mass S particle volume pore volume 4 Ip Sg ! y ! V mass particle volume dp Vp 1 Vp Ip dp Ip ~ 0.
Sg = E Ym NA/V V = 22.091 (MW(N2) / NA VL)2/3 93 . 400 cm3/mol m2 cm3 (STP) molec mol m2 ! 3 molec g mol cm (STP) g Molecular model for E (2D closest packed) E = 1.
15. Ca+2 2H+ ClOH94 .g.less hydrated. greater charge/volume. stronger ion pairing Regeneration ± Add salt or change pH Ultrapure water (low conductivity) anion + cation exchange resins E.6 neglecting K 'i s if dilute Let C ! NH4 Li+ Na+ K+ K' ! K 'NH4 K 'Li ! 2.98 2.5.55 1 K¶ 1 1.+ Li+ K' ! (CCR )(CLi ) (CC )(CLiR ) Fig 15.Ion Exchange Henley & Seader McCabe C+ + Li+ R.90 .= C+ R.
JA = DeA((cA/(z) = DeA(([pA/RT]/(z) Dense nonporous uniform membrane layers where gases do not interact with each other.5 [cm2/s] where r is pore radius in cm.Membranes McCabe. DeA = DAIXwhere X is the tortuosity.700r(T/MA)0. Harriott Porous membranes: Knudson diffusion through small pores DA = 9. Smith. JA = DA(dcA/dz) = DA (cA1 ± cA2)/z Equilibrium (ideal solution) SA = solubility coefficient HAcA = pA or cA = pASA KPJ27 Gasliq equilibria Slope = SA = 1/HA cA pA 95 .
10/31/2004 .Slide 95 KPJ27 all membrane slides have been edited except drug delivery Keith Johnston.
1. 96 .JA = DASA (pA1 ± pA2)/z.4.2.) qA units: 1 Barrer = 1010 cm3 (STP) cm2s1 / (cmHg cm1) Flux / ((pressure/ length) JA = qA (pA1 ± pA2)/z = QA (pA1 ± pA2) where QA is permeability. 26. Let qA = DASA (permeability coeff. QA is used when z is unknown and qa cannot be determined. If S values are similar as in case of O2. N2 then DA/DB can play a large role as shown in Table 26. See Fig. For a given pA1 ± pA2 (QA/QB) = (DASA/DBSB) See Fig. 26.
6) y = y¶ at the closed end of the tube with only new permeate R = P2/P1 E = QA/QB y¶ = JA/(JA + JB) JA = QA (P1x ± P2y) = QAP1 (x ± Ry) JB = QB (P1[(1x) ± P2[1y]) = QB P1[1x ± R(1y)] 97 .Product purity and yield Countercurrent Flow Membrane Assume asymmetric membrane and uniform distribution of feed with negligible boundary layer resistance. 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. x. y refer to component A. Assume no axial (P in shell side and tube side. 26.
As x increases. JA incr.y. thus y¶ incr. y¶ = f(E. y¶= JA/(JA + JB) y¶ = QAP1 (x ± Ry) /{ QAP1 (x ± Ry) + QBP1 [1x ± R(1y)] } = f (x.Subst.. E = QA/QB. and JB decr. x.7) At R = 1. therefore. Upper limit on y¶ so that driving force in partial pressure is positive : P1x > P2y¶ = P1Ry¶ or y¶max = x/R (see Fig 26. above eqns to get local permeate comp.17) 98 . y = y¶. R) since P1 cancels out. Membrane area may be obtained from flux for more permeable gas A = Voutyout/QA(P1x ± P2y)average At closed end. R) (26. y¶ = x and there is no permeation and no separation since there is no driving force in expression for JA.
municipal water (salts. etc. Removal of heavy metal ions. recovery of sugars.035 dense polymer films c(right) > c(left) Desalinization. in wastewater. bacteria) amino acid concentration 99 .Reverse Osmosis Jw ! Pw ( (P ( ) z ( ! 1(c1 ) 2 (c 2 ) If (P ! ( Jw ! 0 equilibrium Pw ! c wD w v w RT c w ! sol' y in membrane Sw ! c w (membrane) c w (soln) cw = 1/vw Js ! DsS s (c s / z c s (membrane) cs (soln) Ss ! ~ 0. sulfites in pulp effluent.
In limit xw approaches 1. cs Hydration of salt s pulls in water ns ns 4! RT ! RT ! c sRT nVw V 100 .xs)= RT xs Pure water Water and salt. Qwo(P+4) . 4approaches 0.Osmotic pressure at equilibrium at constant T Qwo(P) = Qw(P+4) = Qwo(P+4) + RT ln xw Superscript o means pure water.Qwo(P) = RT ln xw Vw4 = RT ln (1 .
2 Osmotic Pump Fig 18.21 p.5 solubility coeff V " ª º w KJ46 Since Jw f(t) drug release rate is zero order.2.18. Diffusion 101 . P = permeability (Q w ¨P¸ Note 4 ! ! c sRT Jw A ! © ¹ A(c s 0.2.1 ± 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. See Ex 18. 473 Cussler.
11/13/2004 .Slide 101 KJ46 the arrow is the bag containing drug pinhole too large see p 472 Cussler Keith Johnston.
11 p. 471 Cussler c1 s c1 102 .Reservoir system Permeation through membrane polymer or liposome P M ! N At ! c1(sat)At 1 l M / t ! const zero order releaselinear in time! P!D S solubility coeff membrane S! Avoid burst + rupture Do Ex 18.
(free energy K (A Move barrier by (x dG  KdA TOP VIEW dW = Fdx dG = K Ldx (rev work) Fdx = K Ldx or K = F/L K units: mN/m = dyn/cm = erg/cm2 Surface tension or line tension Surface free energy L Langmuir trough (top view) KPJ28 dx d x F 103 . Nanotechnology Surface Tension A liquid draws into a drop to minimize surface area (surface is in tension) Therefore.Crystallization. Interfacial Phenomena. Molecules are drawn inwards for approximately three molecular diameters. surface has higher energy than bulk.
Slide 103 KPJ28 fix drawing to show x and delta x and L isheight Keith Johnston. 10/31/2004 .
Surface tension values at 20 oC Water 72.94 Hg Ethanol 22.5 878 (1100°C) 1800 (mp) Pendant drop tensiometer (shown here) Spinning drop tensiometer (centrifugal forces) (UT.89 486.62 Pt Perfluoropentane 9.39 Ag Octane 21.Wade and Schechter) surface tension favors a sphere p Gravity produces Elongation q 104 .
PwdVw + Kow dA = 0 at mechanical equilibrium Since dVo = dVw (Po ± Pw) dVo= Kow dA (P = Po ± Pw = 2 Kow/r (P ! 2K r Laplace P Since K > 0 dG = K dA surface tension raises G. raises Q due to surface tension P 105 .Laplace Pressure Consider A = 4T r2 V = 4/3 T r3 (P = Po ± Pw > 0 Po 2K (P ! r Pw r dr in r of a sphere at const T: dA = 8T r dr dV = 4Tr2 dr dA/dV = 2/r dW = .PodVo . Molecules pull towards the inside. (P > 0: curving interface raises P on inside.
Laplace P becomes important for micron sized drops r(nm) 1.1 (P(bar) 1 10 100 1 2K mN = r m nm 109nm m 106N = ! MPa 2 m 106 .5 (P (MPa) 0.000 100 10 10 K (mN/m) 50 50 50 0.1 1 10 0.
square is zero: Q (pure) s S dQs ! VM dP s n Q (pure) S VM (P Q (in L = = dQL !RTdlny solution) n y(curved) RTln y s (bulk ) QL (in solution) 107 .change in Q around the thermo.: y = f (r) because of Laplace P curved droplets Bulk or ³flat´ particles @ r . Liquid cluster formed in case 2.Kelvin eqn SolidLiquid (SL) or Liquidvapor (LV) equilibria Solid cluster formed in case 1. Equilibrium ± Objective: solubility in soln. y > ys (shown later) r . ys (P = 2K/r (P 0 Higher Qs since P State function.
5) (Tc = Ts ± Tc = k (y ± ys) where k is slope of T vs y line 108 s . Nanocrystals will grow to reduce surface area unless stabilized with ligands. 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/ys is needed to keep smaller crystals from dissolving (small crystals) > s(large crystals) Ostwald ripening ± mass transfer from small crystals to large crystals to lower .E = fractional supersaturation y ys y E ! 1 ! 1 S ys ys RT ln E ! (P ! 2 K / r s VM Kelvin eqn s ln E ! 4VM K / YRTL (McCabe) L ! 2r In that case Y ! 1 ion / molecule Implications of Kelvin eqn. Supersaturation in temperature or concentration on phase diagram (Fig 27.
Classical Nucleation Theory Adamson. Gast. transfer from V per molecular favorable () (or L S for solid cluster) Nucleation of cluster of radius n: Favorable bulk driving force r or n1/3 (G(nucleation) = (G(bulk transfer) + (G (surface) 109 . energy penalty 4Tr 2 K S L (G 0 n(Q Er3 If (Q = GV ± GL (+). 328332 V L Cluster of n molecules: size r Nucleation: V L or L Surf. P Chem Surfaces pp.
! n. (Q () 4T r 2 K penalty to create interface (L ) (S) (1) favorable bulk change (Gcondensation ! n(Q ! n(G V .
L ) .
G P " P sat (2) ! nkT ln P / Psat "1 For a spherical nucleus or cluster. or nkT ln y / y s "1 4 3 Ö Ö Tr V (3) V ! VNAV / M number density 3 n = number molecules in a cluster n! g molec. ! vol mol g volume 110 . mol molec.
tiny amt of catalyst can lower barrier(cloud seeding)± heterogeneous nucleation orders of magnitude faster than homogeneous nucleation 111 .Max (G Ö d(G / dr ! 4 Tr 2 V(Q 8 TrK ! 0 (4) From(4) 2K rc ! (5) Subst(5) p (3) Ö V(Q Bulk term eventually wins due to r3 or small surface area/volume barrier 32TK 3 nc ! 2 3 Ö 3V (Q As K . (G rc r or n 1/3 large surface area/volume : interfacial penalty dominant for small nucleii Barrier to form critical radius = (Gmax Once r is greater than rc. and it is easier to pass rc in 4Tr2K term. it is easy for the nucleus to grow(downhill). or E that is (Q rc decr.
factor 2 2 2 3 R T (ln E ) kT ½ 0 « 16 TK 3 VM2 NA » ! C exp ¬ ¼ 3 (RT)3 (ln E )2 ½ E o.9 112 . E ¨ 32 ¸ TK ! © 16 ¹ 2 2 faster nucleation Ö 3 V (Q ª º ! NA ! R / k Ö V ! NA / VM 16 TK 3 Vm 2 ! 3 NA 2 k 2T 2 (ln E )2 « 16TK 3 VM2 » B ! C exp ¬ ¼ where C is freq. K q: B o 0 27.Rate of nucleation (Adamson & Gast) text (optional) 1/ 2 Z ¨ (Gmax ¸ ¨ (Gmax ¸ B0 ! © exp © Bec ker 1935 ¹ ¹ nc ª 3TKT º ª KT º Frequency factor from kinetic theory of gases (Gmax ! nc (Q 4Trc 2 K 3 (classical theory) 2 ¨ 2K ¸ 32 T K (Q 4T © ¹ K 2 3 Ö Ö 3 V (Q ª V(Q º 3 Barrier as K .
dislocations NA = ks (y¶ ± ys) Sum of resistances m 1 @ K! ! sp (y y s ) 1/ k y 1/ k s diff rxn ys y' y bulk For invariant crystals (same growth in all directions) vp = aL3 moles: m = aL3 VM sp TDp 2 6 ! ! sp = 6vp/L = 6aL3/L 3 vp TDp / 6 m Dp = dm/dt = 3 a L2 VM dL/dt where G = dL/dt G = 2K (yys) / VM 113 @ K! 3aL VMG 6aL2 (y y s ) 2 . m NA ! ! k y (y y ') sp Surface rxn (definition of ks) layer by layer incl. area cryst.Crystal Growth ± releases heat at surface Diffusion to surface sp: surf.
uniform supersat.2 See Fig.14 L N/V = xn cumulative N/V N / V ! ´ ndL d(N / V) n population density dL 0 (N / V ! ndL.Continuous Stirred Tank Crystallizer (ChE 372 Reactor) Mixed Susp Mixed Prod Removal Cont Stirred Tank Crystallizer Steady State. G f (L) Start: p934 Table 27.. 27. (L = G(t. between sieves L and L dL n N/V Sum of each bar in n yields N/V. 114 .
For crystals from L to L+dL d(N/V) = ndL = differential number/volume in this size interval (N (between sieves) ~ V Withdraw a fraction of the crystals in dL size interval: dndL (Here dL is const) Q is volumetric flow rate leaving crystallizer dndL Qdt ! ndL Vc Volume removed total volume The crystals grow during dt: dL = Gdt dn Gdt Qdt ! or ndL Vc n dn Qn ! dL GVc L Let X  Vc / Q dn 1 ´ ! ´ dL n GX 0 n0 no L ln ! z n GX n ! n0e z 115 .
14 dxm/dz = 0 where distribution changes the fastest Kinetic coefficients (const volume basis) Thus B0 = Gn0 lim d(N/ V) dL d(N/ V) ! Lpo dt dt dL B0 G n0 Nucleation rate size where nucleii are formed Thus. dist to determine number. Larger no for large Bo and small G. 116 . size. mass or volume cumulative values j 0 Cumulative number dist size dist areadist xa mass or volume dist Name xn=N/V xL xm Qj  0 g nz jdz ´ nz jdz ´ 0 z ! 0 g z je zdz ´ z je zdz ´ 0 z Q0 Q1 Q2 Q3 Differential dQ0/dz dQ3/dz Fig 27. High nucleation rate and slow growth.Normalized jth moment (cumulative 0 to z) Integrate slope of cumul. no=Bo/G where both Bo and G are known.
ª g ºº 1 ª 0 0 3 mc ! ´ mndL ! aVc (GX)4 n0 ´ z.Total number of crystals/mass GXdz g g Recall: z = L/GXdL = n ! n0e z ¨ ¨1 ¸¸ nc ! N / V ! ´ ndL ! n0 XG´ e z dz ! n0 XG © ?1A© 1¹ ¹ .
zdz e .
44) 117 B0 Given G. mc / VL p B .cyrstals ncmc mc (9) ! Bo ! mc Vc 2aVcL3pr Vc Here we assume one nucleus produces one final crystal ratio is fxn of GX above (27. (ex. size distrib. g g where m =aL3Vc nc 1 ! mc 6aVc (GX)3 Lpredom ! 3GX nc 9 ! mc 2aVcLpr 3 0 0 6 greatest change in cumulative dist for mass Fig 27. Lpr .27. mother liq. from no pred.6) G 0 0 . nc vol time no. Q. p n ! .14 mc production rate m # nucleii mass ! ! B0 c Vc vol.