Prof. Dr. Sotiris E.

Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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Mass Transfer

Examination (Winter) HS 2018

Name:______________________________________________

Legi-Nr.:_____________________________________________

Which edition of “Diffusion” by E. L. Cussler is used?  2nd  3rd  none

Exam Duration: 120 minutes

The following materials are not permitted on your table and have to be deposited in
the front or the back of the examination room:

 bags and jackets

 exercise solutions of the mass transfer lecture (also no such handwritten notes
on the summary sheet, the lecture script or in the textbook “Diffusion”)
 notebooks, mobile phones, devices with wireless communication ability

The following materials are permitted at your table:

 1 calculator
 1 copy of the book “Diffusion” (2nd or 3rd edition) by E. L. Cussler
 1 printout of the lecture script
 1 sheet (2 pages) summary in format DIN A4 or equivalent

Please read these points:

 write your name and Legi-Nr. on each sheet of your solution

 begin each problem on a new sheet
 write only on the front side of each sheet
 if any information is missing, make an assumption and justify it
1
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
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Problem 1 (25 Points)

Zeolite membranes are used for separation of gas molecules. Here a 5 𝜇𝑚 thick
membrane is employed to separate CO2 from CH4. On the feed side of the membrane
CO2 and CH4 are supplied at constant concentration of 1 ppm* in nitrogen. They diffuse
from the feed side through the membrane to the permeate side where they are
constantly removed by pure nitrogen. The diffusion coefficient of CO2 in the membrane
𝑐𝑚2
is 1.28 ∙ 10−8 with a partition coefficient of 40, while the partition coefficient of CH4
𝑠
is 6.

a) Draw a sketch of the expected concentration profiles of both CO2 and CH4 when
steady state is reached including all boundary condition.
(4 Points)
b) How long does it take for CO2 concentration to reach steady-state at the given
conditions?
(3 Points)
c) Assuming steady state, what is the molar flux of CO2 through the membrane?
d) You measure that the flux of CO2 is 100 times larger than the flux of CH4, what is
the diffusion coefficient of CH4 in the membrane?
(8 Points)
e) If the permeate side is a well-mixed closed chamber and the gases are not
removed by nitrogen, the CO2 and CH4 concentration steadily increase over time.
Derive this concentration profile for CO2 as a function of time for a membrane
area of 1 𝑐𝑚2 and a volume of the closed chamber of 1 𝑚𝑙. What is the CO2
concentration in the chamber after 10 min?
(10 Points)

Additional information:
*: ppm = parts per million, i.e. 1 ppm of one component means that the partial pressure or
concentration of the component is 1·10-6 of the total pressure or concentration.

2
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
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SOLUTION
a) (5 Points)

b) (3 Points)
For steady-state the Fourier number must be much larger than 1:
𝐷1 𝑡
𝐹𝑜 = ≫1
𝑙2
𝑙2 5 ∙ 10−4 𝑐𝑚
𝑡≫ = = 19.53 𝑠
𝐷1 −8 𝑐𝑚2
1.28 ∙ 10 𝑠

c) (8 Points)
At steady-state this problem is described as diffusion across a thin film:
𝐷1 𝐻1 𝐷1 𝐻1
𝑗1 = (𝐶10 − 𝐶1𝑙 ) = 𝐶10
𝑙 𝑙
The concentration at the feed side is calculated as:
𝑝 101′ 325 𝑃𝑎 𝑚𝑜𝑙
𝐶10 = 1 𝑝𝑝𝑚 ∙ = 10−6 ∙ = 4.16 ∙ 10−5 3
𝑅𝑇 𝐽 𝑚
8.314 ∙ 293.15 𝐾
𝑚𝑜𝑙 ∙ 𝐾
𝑚𝑜𝑙
= 4.16 ∙ 10−11
𝑐𝑚3
With this:
𝑐𝑚2
1.28 ∙ 10−8 𝑠 ∙ 40 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑗1 = −4
∙ 4.16 ∙ 10−11 3
= 4.26 ∙ 10−14
5 ∙ 10 𝑐𝑚 𝑐𝑚 𝑐𝑚2 ∙ 𝑠

3
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With the given information the flux of CH4 is:

1 𝐷2 𝐻2
𝑗2 = 𝑗1 = 𝐶20
100 𝑙
𝑗1 𝑙
𝐷2 =
100 ∙ 𝐻2 𝐶20
𝑚𝑜𝑙
𝐶20 = 𝐶10 = 4.16 ∙ 10−11
𝑐𝑚3

𝑚𝑜𝑙
4.26 ∙ 10−14 ∙ 5 ∙ 10−4 𝑐𝑚 𝑐𝑚2
𝐷2 = 𝑐𝑚2 ∙ 𝑠 = 8.53 ∙ 10−10
𝑚𝑜𝑙 𝑠
100 ∙ 6 ∙ 4.16 ∙ 10−11
𝑐𝑚3

d) (10 Points)

The concentration profile is found from a mass balance:

𝑟𝑎𝑡𝑒 𝑜𝑓 𝐶𝑂2 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑛𝑔 𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡ℎ𝑒 𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 = 𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛 𝑖𝑛 𝑡ℎ𝑒 𝑐ℎ𝑎𝑚𝑏𝑒𝑟
𝑑𝐶1𝑙 (𝑡)
𝑗1 (𝑡) ∙ 𝐴𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 = ∙ 𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟
𝑑𝑡
The flux of CO2 is (as C1l changes much slower than it takes for the membrane to reach
steady-state, the diffusion within the membrane can always be modelled as being at
steady-state. “Pseudosteady-state”):
𝐷1 𝐻1
𝑗1 (𝑡) = ∙ (𝐶10 − 𝐶1𝑙 (𝑡))
𝑙
Plugging into above equation and rearranging:
𝐷1 𝐻1 𝑑𝐶1𝑙
∙ (𝐶10 − 𝐶1𝑙 ) ∙ 𝐴𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 = ∙ 𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟
𝑙 𝑑𝑡
𝐷1 𝐻1 𝐴𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝑑𝐶1𝑙
∙ ∙ 𝑑𝑡 =
𝑙 𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟 𝐶10 − 𝐶1𝑙
BC:
𝐶1𝑙 (0) = 0

Integrate on both sides:

𝐷1 𝐻1 𝐴𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒 𝐶10 − 𝐶1𝑙
− ∙ ∙ 𝑡 = ln ( )
𝑙 𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟 𝐶10

With BC:
4
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
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𝐷1 𝐻1 𝐴𝑚𝑒𝑚𝑏𝑟𝑎𝑛𝑒
𝐶1𝑙 (𝑡) = 𝐶10 ∙ [1 − exp (− ∙ ∙ 𝑡)]
𝑙 𝑉𝑐ℎ𝑎𝑚𝑏𝑒𝑟
Plugging in the values to receiver the concentration after 10 min:
𝑐𝑚2
1.28 ∙ 10−8 𝑠 ∙ 40 1 𝑐𝑚2
𝐶1𝑙 (600 𝑠) = 1 𝑝𝑝𝑚 ∙ [1 − exp (− ∙ ∙ 600 𝑠)] = 0.459 𝑝𝑝𝑚
5 ∙ 10−4 𝑐𝑚 1 𝑐𝑚3

= 459 𝑝𝑝𝑏

5
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Problem 2 (25 Points)

A tubular reactor coated on the inside with a catalytic material is used for CO oxidation
1
(CO + 2 O2 → CO2 ) with a rate constant (𝜅𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 ) given below. The tube is 7 cm long with
an internal diameter of 1 cm. A helium stream containing CO (1 vol.%) and O2 (5 vol.%)
flows inside the tube at 1 atm and 300 K. The flow inside the tube is laminar. The reaction
is instantaneous, irreversible and first order with respect to CO (the reaction rate does
not depend on the concentration of O2).

𝐸𝑎
𝜅𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝜅0 ∙ exp (− )
𝑅𝑇
𝑐𝑚 𝑘𝐽
with 𝜅0 = 1.2 ∙ 1014 and 𝐸𝑎 = 80
𝑠 𝑚𝑜𝑙

a) Calculate the overall mass transfer coefficient of CO.

(9 Points)

b) Calculate the percentage of CO removed at the end of the tube.

(9 Points)

c) For the chemical reaction to be the rate determining step of the whole process,
the chemical reaction must happen slower than the diffusion step. Determine
the temperature at which the rate constant for the reaction is 1% of the mass
transfer coefficient of the diffusion step. For this step, consider the diffusion
coefficient to be constant with temperature.
(7 Points)

Data:
Diffusion coefficient of CO in the mixture at 300 K: 0.6 cm2/s
Flow rate of the mixture: 2 L/min

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Particle Technology Laboratory
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SOLUTION
(a)
The overall mass transfer correlation is given by (Cussler, 3rd ed., Eq.16.3-7):
1
K
1 1 1
 
k1  reaction k3 K 2
Since we have an irreversible reaction, it is 2  0 and therefore:
 reaction
K2  
  reaction
Mass transfer coefficient of CO, k1, can be calculated using mass transfer correlation for
fluid-solid interfaces, which is the one for laminar flow through circular tube (Cussler,
3rd ed., Table 8.3-3):
1
 d 2v0  3 D
k1  1.62   
 LD  d
where L is the length of the tube, D is the diffusion coefficient of CO in the mixture and
v 0 is the velocity that can be calculated as:
Q Q
v0  
Across  d 2
4
cm3 1 min
2000 
 v0  min 60 s  42.44 cm
 s
 (1cm)2
4

The fact that we are in the presence of laminar flow can be assessed considering the
Reynolds number of the system, which is

0.002 m3
4 
Qd 4Q 60 s
Re     283
  Across    d m 2
 1.5 10 5
 0.01m
s

And therefore
1
 cm  3 cm2
 (1cm ) 2
 42.44  0.6
k1  1.62   s  s  2.101 cm
2
 7cm  0.6 cm  1cm s
 
 s 
The chemical reaction rate can be calculated with the given Arrhenius formula
 
 E  cm  80000 J mol  cm
 reaction   0  exp   a   1.2 10
14
 exp     1.41
 RT  s  8.314
J
 300 K  s
 mol  K 
Thus, from Eq. 1 & 2 we get:
7
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1 cm
K  0.844
1 1 s

cm cm
2.101 1.41
s s

(b)
The mass balance over a section of the reactor is:
Across  v0  c( z )  c( z  z )  K  Atube  c( z )  cwall ( z )
Considering the instantaneous reaction we have cwall ( z)  0

where Atube    d  dz and Across   d 2 thus
4


c( z  z)  c( z )  4K
 c( z )
z v0  d
dc 4K
   0  c(z)
dz v d

After integration with boundary conditions ( z  0: c  c0 ; z  7 cm : c  c(7 cm) ), we

obtain the concentration profile of CO as function of z:

 4K 
c( L)  c0  exp   0 L 
 v d 
 cm 
c(7 cm)  4  0.844 s 
  exp    7cm   0.573
c0 cm
 42.44 1 cm 
 s 

Therefore, 43% of CO is removed.

(c)
For this part we have to solve the equation
 Ea 
 reaction   0  exp     0.01 k1
 RT 
Ea
T
 0 
R  ln  
 0.01 k1 
80000 J mol
T  265 K
 14 cm 
 1.2  10
J
 ln  s 
cm 
8.314
mol  K  0.01  2.101 
 s 

8
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Particle Technology Laboratory
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Problem 3 (25 Points)

A heated tube 5 cm long with 0.6 cm inner diameter can be used to selectively remove
hydrogen over acetone by exploiting their different diffusivity. Both acetone and
hydrogen are oxidized instantly and irreversibly upon contact with the tube wall. Gases
at a concentration of 100 ppm* (25 °C, 1 atm) in air flow at a rate of 1 L/min through the
tube at 300 °C.

a) Calculate the acetone and hydrogen diffusion coefficients at the given

conditions.
(9 points)

b) What are the corresponding mass transfer coefficients for acetone and
hydrogen?
(5 points)

c) What is the concentration profile of the two gases along the tube? Clearly state
the boundary conditions and solve the differential equation.
(7 points)

d) The acetone selectivity is defined as the concentration of acetone at the tube

outlet divided by that of hydrogen. What is the selectivity for the given
configuration?
(4 points)

Additional information:
*: ppm = parts per million, i.e. 1 ppm of one component means that the partial pressure or
concentration of the component is 1·10-6 of the total pressure or concentration.

9
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Particle Technology Laboratory
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SOLUTION
a) (9 points)
Diffusion coefficient of Hydrogen is given at 9 ℃ in Cussler (Table 5.1-1):
𝑐𝑚2
𝐷1 (282.0 𝐾) = 0.710
𝑠
To calculate the diffusion coefficient at the desired temperature the following formula
is used:
3
𝑇1 2
𝐷(𝑇1 ) = 𝐷(𝑇2 ) ( )
𝑇2
3 3
573.15 𝐾 2 𝑐𝑚 573.15 𝐾 2 𝑐𝑚2
𝐷1 (573.15 𝐾) = 𝐷(282.0 𝐾) ∙ ( ) = 0.710 ∙( ) = 2.06
282.0 𝐾 𝑠 282.0 𝐾 𝑠

For acetone the diffusion coefficient can be calculated from the Chapman-Enskog
Theory:
1
3 1 1 2
1.86 ∙ 10−3 𝑇 2 (𝑀𝑎𝑐𝑒 + 𝑀𝑎𝑖𝑟 )
𝐷2 = 2
𝑝𝜎12 Ω
Where from Cussler Table 5.1-2:
1 1
𝜎12 = (𝜎𝑎𝑐𝑒 + 𝜎𝑎𝑖𝑟 ) = (4.600 Å + 3.711 Å) = 4.156 Å
2 2
and

𝜀12 𝜀𝑎𝑐𝑒 𝜀𝑎𝑖𝑟

=√ ∙ = √560.2 ∙ 78.6 = 209.84
𝑘𝐵 𝑘𝑏 𝑘𝑏

𝑇𝑘𝐵 573.15
= = 2.73
𝜀12 209.84
Giving from Table 5.1-3:
2.73 − 2.7
Ω = 0.9770 + ∙ (0.9576 − 0.9770) = 0.9741
2.9 − 2.7
1
13 1 2
−3
1.86 ∙ 10 (573.15)2 (+ 28.97) 𝑐𝑚2
𝐷2 = 58.08 = 0.345
1 𝑎𝑡𝑚 ∙ (4.156)2 ∙ 0.9741 𝑠

10
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b) (5 Points)

The correct mass transfer correlation is “Laminar flow through circular pipe”:
1
𝑘𝑑 𝑑2𝑣 0 3
= 1.62 ( )
𝐷 𝐿𝐷
The velocity in the tube can be calculated from the volumetric flow rate and the filter
cross section:
𝐿 𝑐𝑚3 1 𝑚𝑖𝑛
𝑄 𝑄 (1 ∙ 1000 ∙ ) 𝑐𝑚
𝑚𝑖𝑛 𝐿 60 𝑠
𝑣0 = = 2 = 2 = 58.95
𝐴 𝑑 (0.6 𝑐𝑚) 𝑠
𝜋 𝜋
4 4
For hydrogen this results in:
1
3
2 2
1 𝑐𝑚 𝑐𝑚
𝑣 0 𝐷12 3 58.95 𝑠 ∙ (2.06 𝑠 ) 𝑐𝑚
𝑘1 = 1.62 ( ) = 1.62 = 7.08
𝐿𝑑 5 𝑐𝑚 ∙ 0.6 𝑐𝑚 𝑠
( )

Similarly, for acetone:

1
3
2 2
1 𝑐𝑚 𝑐𝑚
𝑣 0 𝐷22 3 58.95 𝑠 ∙ (0.345 𝑠 ) 𝑐𝑚
𝑘2 = 1.62 ( ) = 1.62 = 2.15
𝐿𝑑 5 𝑐𝑚 ∙ 0.6 𝑐𝑚 𝑠
( )

c) (7 points)
The mass balance on a differential volume 𝐴Δ𝑧 at position z:

(𝑎𝑐𝑐𝑢𝑚𝑢𝑙𝑎𝑡𝑖𝑜𝑛) = (𝑓𝑙𝑜𝑤 𝑖𝑛 − 𝑓𝑙𝑜𝑤 𝑜𝑢𝑡) − (𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑜𝑛 𝑓𝑖𝑙𝑡𝑒𝑟 𝑤𝑎𝑙𝑙)

0 = (𝐴𝑐𝑟𝑜𝑠𝑠 𝑣 0 𝑐(𝑧) − 𝐴𝑐𝑟𝑜𝑠𝑠 𝑣 0 𝑐(𝑧 + Δ𝑧)) − 𝐴𝑚𝑎𝑛𝑡𝑙𝑒 N1
The two areas are:
𝜋
𝐴𝑐𝑟𝑜𝑠𝑠 = 𝑑 2
4
𝐴𝑚𝑎𝑛𝑡𝑙𝑒 = 𝜋𝑑Δ𝑧
And the flux is:
𝑁1 = 𝑘Δ𝑐 = 𝑘(𝑐(𝑧) − 0) = 𝑘𝑐
Combined:
𝜋
0 = − 𝑑2 𝑣 0 Δ𝑐 − 𝜋𝑑Δ𝑧𝑘𝑐
4
𝑑𝑐 4𝑘
= − 0 𝑑𝑧
𝑐 𝑣 𝑑
With boundary condition:
𝑐(𝑧 = 0) = 𝑐0
Solving the DGL gives:
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4𝑘
𝑐(𝑧) = 𝑐0 exp (− 𝑧)
𝑣 0𝑑

d) (4 points)
The selectivity is calculated from the concentrations at the filter exit:

For hydrogen at 𝑧 = 𝐿:
𝑐𝑚
7.08 𝑠
𝑐1 (𝐿) = 1 𝑝𝑝𝑚 ∙ exp (−4 ∙ 𝑐𝑚 ∙ 5 𝑐𝑚) = 0.018 𝑝𝑝𝑚 = 18 𝑝𝑝𝑏
58.95 𝑠 ∙ 0.6 𝑐𝑚
For acetone at 𝑧 = 𝐿:
𝑐𝑚
2.15 𝑠
𝑐2 (𝐿) = 1 𝑝𝑝𝑚 ∙ exp (−4 ∙ 𝑐𝑚 ∙ 5 𝑐𝑚) = 0.296 𝑝𝑝𝑚 = 296 𝑝𝑝𝑏
58.95 𝑠 ∙ 0.6 𝑐𝑚

The selectivity is thus:

𝑐2 (𝐿) 296 𝑝𝑝𝑏
𝑆= = = 16.44
𝑐1 (𝐿) 18 𝑝𝑝𝑏

12
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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Problem 4 (25 Points)

Acetic acid can be removed from polluted water with a circular tube made of a polymer
membrane. There, acetic acid diffuses from inside the tube through the wall into a tank
of fresh water surrounding the tube. The polluted stream enters the tube with a
volumetric flow rate of 𝑄̇ = 0.1 𝑐𝑚3 ⁄𝑠 and concentration of acetic acid of 𝑐1,𝑏𝑢𝑙𝑘 =
0.15 𝑀. The tube is 40 cm long, has an internal diameter of 0.5 cm and a membrane
wall thickness of 0.01 cm. The tank of fresh water is large by volume, perfectly and
continuously stirred and has a molar fraction of acetic acid equal to 𝑐1,𝑡𝑎𝑛𝑘 = 0.01 𝑀.

a) Give a sketch of the problem. Indicate all boundary conditions and draw the
expected concentration profile. (3 points)

b) Determine the overall mass transfer coefficient. (8 points)

c) Determine the percentage of acetic acid removed by the system. (8 points)

d) What is the required tube length to remove 90% of the acetic acid? (6 points)

13
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Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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SOLUTION
Point a)

Point b)
A generic problem of this type would include three types of resistances to MT:
 A resistance to the MT on the inside of the polymeric tube. In this case the MTC
can be determined using the laminar flow through circular tube equation in
Table 8.3-3, page 254.
 A resistance to the MT inside the walls of the polymeric tube. In this case the
MTC can be determined using the membrane equation in Table 8.3-3, page 254.
 A resistance to the MT inside the stirred tank. Due to the fact that the stirring is
ideal, we have constant acetic acid concentration in any point of the stirred tank
and, therefore, this resistance is zero in this problem.

For this reason, we have to calculate on two mass transfer coefficients.

For the resistance inside the tube we use the laminar flow through circular tube
equation in Table 8.3-3, page 254.
The velocity of the flow inside the tube is
𝑄̇ 𝑄̇ 0.1𝑐𝑚3 ⁄𝑠
𝑣0 = 𝐴 = 𝜋 =𝜋 = 0.51 𝑐𝑚⁄𝑠
𝑑2 (0.5 𝑐𝑚)2
4 4

and therefore

1 1
𝐷 𝑑2𝑣 0 3 1.21 ∙ 10−5 𝑐𝑚2 ⁄𝑠 (0.5𝑐𝑚)2 ∙ 0.51 𝑐𝑚⁄𝑠 3
𝑘𝑡𝑢𝑏𝑒 = 1.62 ∙ ( ) = 1.62 ∙( )
𝑑 𝐿𝐷 0.5 𝑐𝑚 40 𝑐𝑚 ∙ 1.21 ∙ 10−5 𝑐𝑚2 ⁄𝑠
= 2.51 ∙ 10−4 𝑐𝑚⁄𝑠
For the resistance inside the wall we use the membrane equation in Table 8.3-3, page
254.

14
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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𝐷 1.21 ∙ 10−5 𝑐𝑚2 ⁄𝑠

𝑘𝑤𝑎𝑙𝑙 = = = 1.21 ∙ 10−3 𝑐𝑚⁄𝑠
𝑙 0.01 𝑐𝑚

The two resistances to the MT go together with two MT flows in the system: a first one
from the bulk water in the tube towards the walls and a second one from the
membrane to the bulk water in the tank.
The molar flux of acetic acid from the bulk water in the tube (at a given position z
along the tube) towards the wall is given by:
𝑛1 = 𝑘𝑡𝑢𝑏𝑒 ∙ (𝑐1,𝑏𝑢𝑙𝑘 − 𝑐1,𝑤𝑎𝑙𝑙 )
The one from the membrane to the tank can be written as
𝑛1 = 𝑘𝑤𝑎𝑙𝑙 ∙ (𝑐1,𝑤𝑎𝑙𝑙 − 𝑐1,𝑡𝑎𝑛𝑘 )
Since the problem is at the steady state, the two flux must equalize each other,
otherwise we would have accumulation, and the flux can be rewritten as
𝑛1 = 𝐾 ∙ (𝑐1,𝑏𝑢𝑙𝑘 − 𝑐1,𝑡𝑎𝑛𝑘 )
Where
1 1
𝐾= = = 2.08 ∙ 10−4 𝑐𝑚⁄𝑠
1 1 1 1
+ +
𝑘𝑡𝑢𝑏𝑒 𝑘𝑤𝑎𝑙𝑙 2.51 ∙ 10−4 𝑐𝑚⁄𝑠 1.21 ∙ 10−3 𝑐𝑚⁄𝑠

Point c)

To determine the removal efficiency, a mass balance must be solved

𝑑 2 0
𝐾 ∙ (𝜋𝑑∆𝑧) ∙ (𝑐1,𝑏𝑢𝑙𝑘 (𝑧) − 𝑐1,𝑡𝑎𝑛𝑘 ) = −𝜋 ( ) 𝑣 (𝑐1,𝑏𝑢𝑙𝑘 (𝑧 + ∆𝑧) − 𝑐1,𝑡𝑎𝑛𝑘 (𝑧))
2
Which follows
𝑑𝑐1,𝑏𝑢𝑙𝑘 4𝐾
= − 0 (𝑐1,𝑏𝑢𝑙𝑘 − 𝑐1,𝑡𝑎𝑛𝑘 )
𝑑𝑧 𝑑𝑣

Subject to: 𝑐1,𝑏𝑢𝑙𝑘 (𝑧 = 0) = 0.15 𝑀 and 𝑐1,𝑏𝑎𝑡ℎ = 0.01 𝑀. So, integration yields:

15
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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4𝐾
𝑐1,𝑏𝑢𝑙𝑘 (𝑧) = 𝑐1,𝑡𝑎𝑛𝑘 + (𝑐1,𝑏𝑢𝑙𝑘 (0) − 𝑐1,𝑡𝑎𝑛𝑘 ) ∙ 𝑒𝑥𝑝 (− 𝑧)
𝑑𝑣 0

Therefor for z=40 cm

4 ∙ 2.08 ∙ 10−4 𝑐𝑚⁄𝑠
𝑐1,𝑏𝑢𝑙𝑘 (40 𝑐𝑚) = 0.01𝑀 + (0.15𝑀 − 0.01𝑀) ∙ 𝑒𝑥𝑝 (− 40𝑐𝑚)
0.5 𝑐𝑚 ∙ 0.51 𝑐𝑚⁄𝑠
= 0.133 𝑀
Therefore only 11.3 % of acetic acid is removed!

Point d)

In the case we want to reach 90% of acetic acid removal we need to consider a longer
tube, in particular the length can be calculated through the formula:

𝑐1,𝑏𝑢𝑙𝑘 (𝑧) − 𝑐1,𝑡𝑎𝑛𝑘 4𝐾

ln = − 0𝑧
𝑐1,𝑏𝑢𝑙𝑘 (0) − 𝑐1,𝑡𝑎𝑛𝑘 𝑑𝑣

𝑑𝑣 0 𝑐1,𝑏𝑢𝑙𝑘 (0) − 𝑐1,𝑡𝑎𝑛𝑘

𝑧= ln
4𝐾 𝑐1,𝑏𝑢𝑙𝑘 (𝑧) − 𝑐1,𝑡𝑎𝑛𝑘

0.5 𝑐𝑚 ∙ 0.51 𝑐𝑚⁄𝑠 0.15𝑀 − 0.01𝑀

𝑧= ∙ ln = 1021 𝑐𝑚
4 ∙ 2.08 ∙ 10−4 𝑐𝑚⁄𝑠 0.015𝑀 − 0.01𝑀

So the tube should be at least 10.21 m to remove 90% of the acetic acid

16
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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Backup Question (25 points)

After a hard day of work in the lab you want to take a relaxing bath. You dissolve spheres
(dgrain = 0.25 cm) of bath salt in the water. The water already has an initial salt
concentration of 1 g L-1. You are wondering how long it will take to dissolve the spheres
by diffusion through a thin film. Neglect convection.

a) Start with the generalized mass balance and simplify the equation by appropriate
assumptions.
(7 Points)

b) Derive an equation of the concentration profile outside of a salt grain and calculate
flow of salt from a single sphere as a function of its radius. State all your boundary
conditions clearly.
(8 Points)

c) Derive an equation for the sphere radius during dissolution. How large are the
spheres after 20 min? Assume that the bathtub is large, so that salt concentration
in the water stays constant.
(10 Points)

Additional information:
Saturation concentration at 37 °C: 𝑐𝑠𝑎𝑡 = 201 𝑔/𝐿
Diffusivity of salt in water: 𝐷𝑆𝑎𝑙𝑡 = 1.7 ∙ 10−4 𝑐𝑚2 𝑠 −1
Density of Salt: 𝜌𝑆𝑎𝑙𝑡 = 2.16 𝑔/𝑐𝑚3

17
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Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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SOLUTION
a)
𝜕𝑐1 𝑑𝑐1 𝑣𝜃0 𝑑𝑐1 𝑣0
𝜑 𝑑𝑐 1 𝑑𝑐1 𝑑𝑐1 1 𝑑𝑐1 𝑑𝑐1
+ 𝑣𝑟0 + + 𝑟∙sin 1
= 𝐷 [𝑟 2 (𝑟 2 ) + 𝑟 2 ∙sin 𝜃 (sin 𝜃 )+
𝜕𝑡 𝑑𝑟 𝑟 𝑑𝜃 𝜃 𝑑𝜑 𝑑𝑟 𝑑𝑟 𝑑𝜃 𝑑𝜃
1 𝑑2 𝑐1
] + 𝑟1
𝑟 2 ∙sin2 𝜃 𝑑𝜑 2

No convection
𝑣𝑟0 = 𝑣𝜃0 = 𝑣𝜑0 = 0
Symmetry
𝑑𝑐1 𝑑𝑐1
= =0
𝑑𝜃 𝑑𝜑
No reaction
𝑟1 = 0
Steady state
𝜕𝑐1
=0
𝜕𝑡
1 𝑑𝑐1 2 𝑑𝑐1
0 = 𝐷[ (𝑟 )]
𝑟 2 𝑑𝑟 𝑑𝑟

b)
1 𝑑𝑐1 2 𝑑𝑐1
𝐷[ (𝑟 )] = 0
𝑟 2 𝑑𝑟 𝑑𝑟
𝑑𝑐1
𝑟2 = 𝐾1
𝑑𝑟
𝐾1
∫ 𝑑𝑐1 = ∫ 2 𝑑𝑟
𝑟
𝐾1
𝑐1 = − + 𝐾2
𝑟
BC:
𝑐1 (𝑅) = 𝑐1,𝑠𝑎𝑡
𝑐1 (∞) = 𝑐1,𝑏𝑎𝑡ℎ

𝐾2 = 𝑐1,𝑏𝑎𝑡ℎ
𝐾1 = −𝑅(𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ )

𝑅
𝑐1 (𝑟) = 𝑐1,𝑏𝑎𝑡ℎ + (𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ )
𝑟
18
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
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𝑑𝑐1 𝑅
𝑗(𝑟) = −𝐷 = 𝐷 ∙ 2 (𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ )
𝑑𝑟 𝑟
At the grains surface
𝐷
𝑗𝑅 = (𝑐 − 𝑐1,𝑏𝑎𝑡ℎ )
𝑅 1,𝑠𝑎𝑡

c)
Mass balance:
𝑑𝑉
𝜌1 = −𝐴 ∙ 𝑗
𝑑𝑡
4
𝑑 (3 𝜋𝑅 3 ) 𝐷
𝜌1 = −(4𝜋 ∙ 𝑅 2 ) ∙ (𝑐 − 𝑐1,𝑏𝑎𝑡ℎ )
𝑑𝑡 𝑅 1,𝑠𝑎𝑡
Take the derivative
𝑑𝑅 𝐷
4𝜋 𝑅 2 𝜌1 = −(4𝜋 ∙ 𝑅 2 ) ∙ (𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ )
𝑑𝑡 𝑅
𝐷
∫ 𝑅 𝑑𝑅 = − ∫ (𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ ) 𝑑𝑡
𝜌1
1 2 𝐷
𝑅 = − (𝑐1,𝑠𝑎𝑡 − 𝑐1,𝑏𝑎𝑡ℎ ) ∙ 𝑡 + 𝐾1
2 𝜌1

𝐷
𝑅 = √𝐾1 − 2 (𝑐 − 𝑐1,𝑏𝑎𝑡ℎ ) ∙ 𝑡
𝜌1 1,𝑠𝑎𝑡

BC: at the start the concentration is

𝑡 = 0, 𝑅 = 𝑅0

𝐷
𝑅 = √𝑅02 − 2 (𝑐 − 𝑐1,𝑏𝑎𝑡ℎ ) ∙ 𝑡
𝜌1 1,𝑠𝑎𝑡

𝑐𝑚2
1.7 ∙ 10−4 𝑠 𝑔 𝑔
𝑅 = √(0.25 𝑐𝑚)2 − 2 ∙ 𝑔 (0.201 3
− 0.001 ) ∙ 20 𝑚𝑖𝑛
2.16 𝑐𝑚 𝑐𝑚3
𝑐𝑚3
𝑅 = 0.157 𝑐𝑚

19