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Chapter 2 Diffusion in dilute solutions page 2-1

Chapter 2 Diffusion in dilute solutions

1. Water evaporation
To find the rate of evaporation, we need to find the flux of water across the air film:
DH
j1 = Δc1
l
Since the film is made up of air, H = 1. We are given D and ℓ, so we need to find Δc1. We first
calculate the difference in the partial pressure of water across the film. From a steam table we
find that at 20 °C, psat = 2.3388 kPa. Since the air immediately above the water is saturated we
have:
Δp1 = psat − 0.5 psat = 0.5 psat = 0.5(2.3388 kPa ) = 1.1694 kPa = 1169.4 Pa
Assuming an ideal gas, we can find the concentration difference:
Δp 1169.4 Pa mol mol
Δc1 = 1 = = 0.48 3 = 4.8 ⋅10 −7
RT ⎛ J ⎞ m cm3
⎜ 8.3145 ⎟(293 K )
⎝ K ⋅ mol ⎠
We can now calculate the flux:
cm 2
0.25
j1 = s ⎛⎜ 4.8 ⋅10 −7 mol ⎞⎟ = 8.0 ⋅10 −7 mol
0.15 cm ⎝ cm3 ⎠ cm 2 s
To find the height change, we divide by the molar density of water:
mol
8.0 ⋅10 −7
cm 2 s = 1.44 ⋅10 −5 cm = 1.25 cm
g 1 mol s day
1 3⋅
cm 18.015 g

2. Diffusion across a monolayer

Recalling that the resistance is the inverse of the permeance, we have:
1 s cm
=2 ⇒ P = 0.5
P cm s
We know that the permeance is given by:

DH Pl ⎝
⎛
⎜ 0.5
cm ⎞
( −7
⎟ 2.5 ⋅10 cm )
− 6 cm
2
s ⎠
P= ⇒D= = = 7 ⋅10
l H 0.018 s
3. Diffusion coefficient of NO2 in water
We treat the water as a semiinfinite slab. From Eq. (2.3-18) we know that the flux at the surface
is given by:
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Chapter 2 Diffusion in dilute solutions page 2-2

D
j1 z =0 = (c10 − c1∞ )
πt
The concentration at the surface is given by Henry’s Law:
p 0.93 atm mol
c10 = = = 2.5 ⋅10 −5 3
H cm atm
3
cm
37000
mol
Since we have a semiinfinite slab we assume c1∞ = 0. To find the flux over the total time t, we
integrate:

[ t]
t t t
D
(c10 − 0)dt = Ac10 D ∫ dt = 2 Ac10 D Dt
t
N1 = ∫ A j1 z =0 dt = A∫ = 2 Ac10
πt π 0 t π π
0
0 0

Assuming an ideal gas, the flux N1 is given by:

N1 =
PV
=
( )
(0.93 atm ) 0.82 cm3 = 3.2 ⋅10 −5 mol
RT ⎛ cm3atm ⎞
⎜⎜ 82.06 ⎟(289 K )
⎝ K ⋅ mol ⎟⎠
Solving for D, we have:
2
⎡ ⎤
⎛ N1 ⎞ π
2
⎢ −5
3.2 ⋅10 mol ⎥ π − 6 cm
2
⎜
D=⎜ ⎟
⎟ ⋅ = ⎢ ⎥ ⋅ = 5.4 ⋅10
⎢⎣
( )
⎝ 2 Ac10 ⎠ t ⎢ 36.3 cm 2 ⎛⎜ 2.5 ⋅10 −5 mol ⎞⎟ ⎥ 180 s
3 ⎥
cm ⎠ ⎦
s
⎝
4. Permeability of water across a polymer film
The rate of water loss can be found by linear regression or by simply using the first and last data
points:
14.0153 g − 13.5256 g g
N1 = = 0.031
16 days day
The molar flux is given by:
g 1 mol 1 day 1 hr
0.031 ⋅ ⋅ ⋅
N1 day 18.015 g 24 hr 3600 s mol
j1 = = = 2.3 ⋅10 −10
A 85.6 cm 2
cm 2 s
From Eq. (2-2.10) we have:
DH
j1 = Δc1
l
We need to find Δc1. We first calculate the difference in the partial pressure of water across the
film. From a steam table we find that at 35 °C, psat = 0.0555 atm. Since the air inside the bag is
saturated, we have:
Δp1 = psat − 0.75 psat = 0.25 psat = 0.25(0.0555 atm ) = 0.0139 atm
Assuming an ideal gas, the concentration difference is:
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Chapter 2 Diffusion in dilute solutions page 2-3

Δp1 0.0139 atm mol

Δc1 = = = 5.49 ⋅10 −7
RT ⎛ cm atm ⎞
3
cm3
⎜⎜ 82.06 ⎟⎟(308 K )
⎝ K ⋅ mol ⎠
The permeability DH is given by:
⎛ −10 mol ⎞
⎜ 2.3 ⋅10 ⎟(0.051 cm )
j1l ⎝ cm 2 s ⎠ cm 2
DH = = = 2.1 ⋅10 −5
Δc1 mol s
5.49 ⋅10 −7
cm 3

5. Diaphragm cell
From Ex. (2.2-4) we have:
1 ⎛ Δc ⎞ AH ⎛⎜ 1 1 ⎞
⎟
D = ln⎜⎜ 10 ⎟⎟ β= ⎜
+
⎟
βt ⎝ Δc1 ⎠ l ⎝ Vlower Vupper ⎠
(a) Using the first equation and solving for β we have:
1 ⎛ Δc10 ⎞ 1 ⎛ 1 ⎞
β= ln⎜⎜ ⎟⎟ = ln⎜ ⎟
Dt ⎝ Δc1 ⎠ ⎛ − 5 cm ⎞⎛
2
3600 s 60 s ⎞ ⎝ 0.492 ⎠
⎜⎜1.859 ⋅10 ⎟⎜ 36 hr ⋅ + 6 min ⋅ ⎟
⎝ s ⎟⎠⎝ hr min ⎠
= 0.294 cm −2
(b) Using the second equation and solving for ℓ we have:
⎡π
(2.51cm)2 ⎤⎥(0.34)
AH ⎛⎜ 1 1 ⎞⎟ ⎢⎣ 4 ⎦ ⎛ 1 1 ⎞
l= + = ⎜⎜ + ⎟⎟ = 0.276 cm
β ⎜⎝ Vlower Vupper ⎟⎠ 0.294 cm − 2
⎝ 42.3 cm 40.8 cm ⎠
3 3

(c) Since the porosity is the same, the result is the same.
6. Measuring diffusion coefficient of gases
The maximum concentration will be at the center of the pipe so r = 0 and the equation reduces
to:
Q
c1 =
4πDz
Dimensional analysis tells us that the concentration must be dimensionless, so we simply
convert it from a weight fraction w1 to a mole fraction y1:
4 y1 1 7 7 7
w1 = ⇒ = − 6 ⇒ y1 = = = 0.033 = c1
4 y1 + 28(1 − y1 ) w1 y1 1 1
+6 +6
w1 0.0048
Solving for D, we have:
cm 3
0.045
Q s cm 2
D= = = 0.11
4πc1 z 4π (0.033)(1.031 cm ) s
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Chapter 2 Diffusion in dilute solutions page 2-4

7. Carburizing of steel
Rearranging Eq. (2.3-15) we have:
⎛ z ⎞
c1 = c10 − (c1∞ − c10 ) erf ⎜ ⎟
⎝ 4 Dt ⎠
Since this is a semiinfinite slab, c1∞ = 0. Assuming the argument of the error function is small
(i.e. less than about 0.7), we can approximate it as the argument itself:
c z
c1 ≈ c10 − 10
4 Dt
Using the data for 10 hr we calculate the slope from its endpoints:
0.7 − 1.35
m= = 5.12 cm −1
2.54 cm
(0.05 − 0)in ⋅
in
The data show that the concentration c1 at 10 hr is given by:
c1 = 1.35 − 5.12 z
By comparison with our approximation we have:
c10 = 1.35
c10
= 5.12
4 Dt
Solving for D gives:
2
⎛ c10 ⎞
2
⎛ 1.35 ⎞
⎜ ⎟ ⎜⎜ ⎟
⎝ 5.12 ⎠ ⎝ 5.12 cm −1 ⎟⎠ cm 2
D= = = 4.8 ⋅ 10 −7
4t ⎛ 3600 s ⎞ s
4⎜10 hr ⋅ ⎟
⎝ hr ⎠
To check whether our approximation was valid, we calculate the argument of the error function:
2.54 cm
0.05 in ⋅
z in
= = 0.48
4 Dt ⎛ cm 2
⎞⎛ 3600 s ⎞
4⎜⎜ 4.8 ⋅ 10 −7 ⎟⎜10 hr ⋅ ⎟
⎝ s ⎟⎠⎝ hr ⎠
The assumption is valid.
8. Twin-bulb method
We define the direction of positive flux is from bulb A into bulb B. A balance on bulb A gives:
V 1 A = −(π r 2 ) j1
dc
dt
Similarly for bulb B we have:
V 1B = (π r 2 ) j1
dc
dt
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Chapter 2 Diffusion in dilute solutions page 2-5

Subtracting the second equation from the first, we get:

d
V (c1 A − c1B ) = −2π r 2 j1
dt
The flux is given by:
DH
j1 = (c1 A − c1B )
l
In this case H = 1 since there is no interface. Combining these equations and substituting Δc1 for
c1A – c1B we have:
dΔc1 2πDΔc1 r 2 dΔc1 2πDr 2
V =− ⇒ =− dt
dt l c1 lV
Integration gives:
Δc1 2πDr t
2
dΔc1 2πDr 2
t
⎛ Δc1 ⎞ 2πDr 2t −
∫Δc Δc1 = −
lV ∫0 dt ⇒ ln ⎜
⎜ Δc ⎟
⎝ 10 ⎠
⎟ = −
l V
⇒ Δc1 = Δc10 e lV

10

9. Steady-state flux out of a pipe with porous wall

From Eq. (2.4-29) we have:
∂c1 D ∂ ⎛ ∂c1 ⎞
= ⎜r ⎟
∂t r ∂r ⎝ ∂r ⎠
Since we are at steady state, the time derivative is zero and we are left with:
D d ⎛ dc1 ⎞ d ⎛ dc ⎞
0= ⎜r ⎟ ⇒ ⎜r 1 ⎟ = 0
r dr ⎝ dr ⎠ dr ⎝ dr ⎠
Integrating twice we have:
dc dr
r 1 = A ⇒ ∫ dc1 = A∫ ⇒ c1 = A ln r + B
dr r
This is subject to boundary conditions:
r = Ri c = c1i
r = R0 c = 0
Applying the second and then the first we have:
0 = A ln R0 + B ⇒ B = − A ln R0
Ri c
c1i = A ln Ri + B = A ln Ri − A ln R0 = A ln ⇒ A = 1i
R0 R
ln i
R0
c1i ln R0
B = − A ln R0 = −
R
ln i
R0
Substitution gives:
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Chapter 2 Diffusion in dilute solutions page 2-6

r
ln
c ln r c1i ln R0 R0
c1 = 1i − = c1i
R R R
ln i ln i ln i
Ro R0 R0
The flux at the outside of the pipe is given by Fick’s Law:

dc1 Dc1i Dc1i

j = −D =− =
dr R R
r = R0 r ln i R0 ln 0
R0 r = R0
Ri

10. Controlled release of pheromones

From a balance on the device we have:
dc
V 1 = r0 − Aj1
dt
Since we are interested in the steady state case, the time derivative is 0 and we find that the rate
of sublimation must equal the rate of transport through the membrane. Substituting for r0 and j1
we have:
⎡ ⎛ cm 3 ⎞ ⎤ mol ADH
r0 = Aj1 ⇒ 6 ⋅ 10 −17 ⎢1 − ⎜⎜1.1 ⋅ 10 7 ⎟c1 ⎥ = (c1 − 0)
⎣ ⎝ mol ⎟⎠ ⎦ s l
(a) Solving for c1 we have:
mol mol
6 ⋅ 10 −17 6 ⋅ 10 −17
c1 = s = s
ADH −10 cm
( )⎛⎜⎜1.92 ⋅10 cm 2 ⎞
3
+ 6.6 ⋅ 10 1.8 cm 2 −12
⎟
l s ⎝ s ⎟⎠ cm 3
+ 6.6 ⋅ 10 −10
0.06 cm s
mol
= 8.4 ⋅ 10 −8
cm 3
(b) Solving for r0 or Aj1 gives:
⎛ −12 cm ⎞
( )
2
⎜
1.8 cm ⎜1.92 ⋅ 10 2
⎟⎟
ADH ⎝ s ⎠ ⎛ 8.4 ⋅ 10 −8 mol ⎞ = 4.8 ⋅ 10 −18 mol
Aj1 = c1 = ⎜ ⎟
l 0.06 cm ⎝ cm 3 ⎠ s

11. Measuring age of antique glass

Based on Example 2.3-3, we have:
D(1 + K )
j1 z =0 = (c10 − c1∞ )
πt
Since the water is consumed as it enters the glass, we assume that c1∞ = 0. The total hydration is
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Chapter 2 Diffusion in dilute solutions page 2-7

then:
D(1 + K ) dt Dt (1 + K )
t t
N1 = A∫ j1 z =0 dt = Ac10 ∫ = 2 Ac10
0
π 0 t π
Solving for t we have:
π ⎛ N1 ⎞
t= ⎜ ⎟
D(1 + K ) ⎜⎝ 2 Ac10 ⎟⎠
12. Diffusion in a reactive barrier membrane
(a) Mass balances on mobile species 1 and immobile species 2 give:
∂c1 ∂ 2c
= D 21 − k R c1c2
∂t ∂z
∂c2
= − k R c1c2
∂t
(b) The boundary conditions for this situation are:
t<0 all z c1 = 0 c2 = c20
∂c2
t≥0 z=0 c1 = Hc10 =0
∂z
∂c2
z=l c1 = 0 =0
∂z
(c) The reaction term would exist only in a front, moving across the film with time. Everywhere
else in the film either c1 or c2 is zero and the reaction term drops out of the differential
equations.
13. Diffusion of dopant in arsenide
From Eq. (2.4-14) we have:
z2
M / A − 4 Dt
c1 = e
4πDt
Since the maximum concentration will be at z = 0 i.e. the site of the scratch we can write:
z2
M/A c −
c1max = ⇒ 1 = e 4 Dt
4πDt c1max
Solving for t, we have:

t=
z2
=
(
4 ⋅10 −4 cm )
2

= 1740 s = 29 min
⎛ c1max ⎞ ⎛ −11 cm 2 ⎞
4 D ln⎜⎜ ⎟⎟ 4⎜⎜10 ⎟ ln (10 )
⎝ c1 ⎠ ⎝ s ⎟⎠

14. Concentration profile in Fick's experiment

(a) For the cylinder, the cross sectional area A is constant. Since the experiment is at steady
state, j1 is also constant. Using Fick’s Law, we have:
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Chapter 2 Diffusion in dilute solutions page 2-8

dc1 B
j = −D = B ⇒ c1 = − z + C
dz D
The boundary conditions are:
z = 0 c1 = 0
z = l c1 = c1sat
The first boundary condition tells us that C = 0. Applying the second gives:
B c D z
c1sat = − l ⇒ B = − 1sat ⇒ c1 = c1sat
D l l
(b) For the funnel, the cross sectional area A is not constant. The area at height z is given by:
R − R0
2
⎛ ⎞ Rl − R0
A = π ⎜ R0 + l z ⎟ = π (R0 + kz ) k=
2

⎝ l ⎠ l
where k has been defined for convenience. Since the area is a function of z, the condition
of steady state requires that the product Aj1 be constant. As a result we have:
d ( Aj1 ) dA dj
0= = j1 +A 1
dz dz dz
Using Fick’s Law to substitute for j1 and the above expression for A we have:
⎡
⎣
dc ⎤
[ 2 ⎡
]
d 2c ⎤
0 = ⎢− D 1 ⎥[2πk (R0 + kz )] + π (R0 + kz ) ⎢− D 21 ⎥
dz ⎦ dz ⎦
⎣
dc1 d 2c
0 = 2k + (R0 + kz ) 21
dz dz
We now define a function u and redefine our differentials in terms of it:
u = R0 + kz
dc1 dc1 du dc
= =k 1
dz du dz du
2
d 2 c2 d 2 c1 ⎛ du ⎞ 2 d c1
2
= ⎜ ⎟ = k
dz 2 du 2 ⎝ dz ⎠ du 2
Our equation now becomes:
dc d 2c d 2 c1 dc
0 = 2k 2 1 + k 2u 21 ⇒ u 2 + 2u 1 = 0
du du du 2
du
This equation is of the Euler-Cauchy form, which means the solution is of the form
c1 = um:
[ ] ( )
u 2 m(m − 1)u m − 2 + 2u mu m −1 = 0 ⇒ m 2 + m = m(m + 1) = 0 ⇒ m = 0,−1
The solution is a linear combination of the two roots:
C C
c1 = B + = B +
u R0 + kz
Applying the same boundary conditions as above we find:
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Chapter 2 Diffusion in dilute solutions page 2-9

C C
0= B+ ⇒B=−
R0 R0
C C c1sat c1sat R0 (R0 + kl )
c1sat = − ⇒C = =
R0 + kl R0 1
−
1 kl
R0 + kl R0
The concentration profile is therefore:
c R (R + kl ) ⎡ 1 1⎤ R + kl z Rl z
c1 = 1sat 0 0 ⎢ − ⎥ = c1sat 0 = c1sat
kl ⎣ R0 + kz R0 ⎦ R0 + kz l R0 l + z (Rl − R0 )

15. Bacteria between membranes

(a) From Fick’s Law we have:
dc
jS = −D S
dz
At steady state we know that jS is independent of z:
dj S d 2 cS z = 0 cS = cS 0
= 0 = −D
dz dz 2
z = l cS = 0
By applying the boundary conditions and integrating twice we have:
D
jS = cS 0
l
By comparison with Fick’s Law we can write:
cS
dc S D cS 0 z ⎛ z⎞
−D = c S 0 ⇒ ∫ dc S = − ∫ dz ⇒ c S = c S 0 ⎜1 − ⎟
dz l cS 0
l 0 ⎝ l⎠
(b) Once again assuming steady state, we know that jB is independent of z. We also know
from the boundary conditions that jB = 0 at z = 0 and z = ℓ, so jB = 0 for all z. The given
equation then becomes:
dc dc dc ⎛ c ⎞
0 = − D0 B + χc B S ⇒ D0 B = χc B ⎜ − S 0 ⎟
dz dz dz ⎝ l ⎠
Integration gives:
cB χcS 0 z
dc B χc S 0 z cB χc S 0 z −

∫ =−
D0 l ∫0
⇒ = − ⇒ = D0 l
dz ln c B c B 0 e
cB 0
cB cB0 D0 l
where cB0 is the concentration of B at z = 0.
16. Extraction of sucrose
From Eq. (2-3.18) the flux through the surface of a slice is:
D
j1 = c
π t 10
The total flux is a weighted average of the individual fluxes:
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Chapter 2 Diffusion in dilute solutions page 2-10

Dc D
j1 = ε jc + (1 − ε ) jw = ε c10 + (1 − ε ) w c10
πt πt
Integrating over time to get the total sucrose extracted per unit area we have:

[ ]
t t
c Dc D t
M = ∫ j1dt = 10 ∫ ε + (1 − ε ) w dt = 2c10 ε Dc + (1 − ε ) Dw
0 π0 t t π
From the given expression we have:

[ ]
2
⎛ t ⎞
⎜ 2c10 ε Dc + (1 − ε ) Dw ⎟
[ ]
2
π ⎛M ⎞ π π
D = ⎜⎜ ⎟⎟ = ⎜ ⎟ = ε D + (1 − ε ) D 2

4t ⎜ ⎟ c w
4t ⎝ c10 ⎠ c10
⎜ ⎟
⎝ ⎠
Not sure this answers the question