Prof. Dr. Sotiris E.

Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Mass Transfer (Stoffaustausch) Fall 2013

Examination 21. August 2014

Name:______________________________________________

Legi-Nr.:_____________________________________________

Edition Diffusion by E. L. Cussler: none 2nd 3rd

Exam Duration: 120 minutes

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

bags and jackets

exercises of the mass transfer lecture (also handwritten on summary sheet or
textbook)
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

1
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Problem 1 (25 points)

A cylindrical container filled with liquid aniline (molar mass: 93.13 g/mol) is stored in a large
room. The diameter of the container is 45 cm. The ambient air (1 atm) is initially aniline-free
and the room temperature is constant at 20 oC. At t = 0, the lid of the container is removed
and the aniline evaporates slowly. Error Function
a) Calculate the diffusion coefficient of aniline in air. Use the empirical equation from Fuller,
Schettler, and Giddings (1966). x (8 points)
2

b) Estimate whether the aniline diffusion has reached steady tstate at 15 cm above the
erf x
2
e dt
surface after 4 min.
(3 points)
c) Calculate the concentration of aniline in the air at the 0position and time of question b.
(6 points)
d) 1.0
How much mass of aniline will have evaporated after 4 min? (8 points)
0.9
0.8
Additional Data:
0.7
Chemical
0.6 formula of aniline: C6H5NH2 or
erf x

0.5
Composition of air: 21 vol% O2, 79 vol% N2
0.4
Molar masses: O2=32 g/mol, N2=28 g/mol
0.3
Saturation vapor pressure of aniline at 20 oC: 0.5 kPa
0.2
R = 8.314 J/mol K
0.1
0.0
0.00 0.50 1.00 1.50 2.00 2.50 3.00

2 2 x
erf =
0

x erf(x) x erf(x) x erf(x) x erf(x) x erf(x) x erf(x)

0.00 0.00000 0.52 0.53790 1.04 0.85865 1.56 0.97263 2.08 0.99673 2.60 0.99976
0.02 0.02256 0.54 0.55494 1.06 0.86614 1.58 0.97455 2.10 0.99702 2.62 0.99979
0.04 0.04511 0.56 0.57162 1.08 0.87333 1.60 0.97635 2.12 0.99728 2.64 0.99981
0.06 0.06762 0.58 0.58792 1.10 0.88021 1.62 0.97804 2.14 0.99753 2.66 0.99983
0.08 0.09008 0.60 0.60386 1.12 0.88679 1.64 0.97962 2.16 0.99775 2.68 0.99985
0.10 0.11246 0.62 0.61941 1.14 0.89308 1.66 0.98110 2.18 0.99795 2.70 0.99987
0.12 0.13476 0.64 0.63459 1.16 0.89910 1.68 0.98249 2.20 0.99814 2.72 0.99988
0.14 0.15695 0.66 0.64938 1.18 0.90484 1.70 0.98379 2.22 0.99831 2.74 0.99989
0.16 0.17901 0.68 0.66378 1.20 0.91031 1.72 0.98500 2.24 0.99846 2.76 0.99991
0.18 0.20094 0.70 0.67780 1.22 0.91553 1.74 0.98613 2.26 0.99861 2.78 0.99992
0.20 0.22270 0.72 0.69143 1.24 0.92051 1.76 0.98719 2.28 0.99874 2.80 0.99992
0.22 0.24430 0.74 0.70468 1.26 0.92524 1.78 0.98817 2.30 0.99886 2.82 0.99993
0.24 0.26570 0.76 0.71754 1.28 0.92973 1.80 0.98909 2.32 0.99897 2.84 0.99994
0.26 0.28690 0.78 0.73001 1.30 0.93401 1.82 0.98994 2.34 0.99906 2.86 0.99995
0.28 0.30788 0.80 0.74210 1.32 0.93807 1.84 0.99074 2.36 0.99915 2.88 0.99995
0.30 0.32863 0.82 0.75381 1.34 0.94191 1.86 0.99147 2.38 0.99924 2.90 0.99996
0.32 0.34913 0.84 0.76514 1.36 0.94556 1.88 0.99216 2.40 0.99931 2.92 0.99996
0.34 0.36936 0.86 0.77610 1.38 0.94902 1.90 0.99279 2.42 0.99938 2.94 0.99997
0.36 0.38933 0.88 0.78669 1.40 0.95229 1.92 0.99338 2.44 0.99944 2.96 0.99997
0.38 0.40901 0.90 0.79691 1.42 0.95538 1.94 0.99392 2.46 0.99950 2.98 0.99997
0.40 0.42839 0.92 0.80677 1.44 0.95830 1.96 0.99443 2.48 0.99955 3.00 0.99998
0.42 0.44747 0.94 0.81627 1.46 0.96105 1.98 0.99489 2.50 0.99959 3.02 0.99998
0.44 0.46623 0.96 0.82542 1.48 0.96365 2.00 0.99532 2.52 0.99963 3.04 0.99998
0.46 0.48466 0.98 0.83423 1.50 0.96611 2.02 0.99572 2.54 0.99967 3.06 0.99998
0.48 0.50275 1.00 0.84270 1.52 0.96841 2.04 0.99609 2.56 0.99971 3.08 0.99999
0.50 0.52050 1.02 0.85084 1.54 0.97059 2.06 0.99642 2.58 0.99974 3.10 0.99999

2
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Problem 2 (25 points)

Acetone is stored in a vessel with a cylindrical capillary on top, as shown in Setup I (Figure
1). The capillary is 2 mm in diameter and 10 cm in length. The acetone evaporates from the
liquid surface at (1) and flows through the capillary towards (2). There is continuous flow of
fresh air above the capillary that quickly removes the evaporated acetone from (2). Assume
that there is no uptake of air by the acetone. The total pressure of the system is 1 atm.

a) If the temperature of the system is 20 oC, calculate the total molar flow rate (evaporation
rate) of acetone. (9 points)
b) How much faster compared to the question a) is the evaporation rate if the temperature
of the system is 40 oC. (8 points)
o
c) To minimize the evaporation of acetone at 40 C, the cylindrical capillary is replaced by a
conical one (see Setup II of Figure 1). The diameter at the top of the conical capillary (2)
is 1 mm. How much slower is the evaporation rate now compared to that of b)?
(8 points)

Additional data:
Temperature, oC 20 40
Saturation pressure of acetone, kPa 25.3 58.7
2
Diffusion coefficient of acetone in air, cm /s 0.107 0.120

R = 8.314 J/mol K

Figure 1. Schematic of the acetone vessel with cylindrical capillary (Setup I, questions a-b)
and conical one (Setup II, question c)

3
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Problem 3 (25 points)

A hailstone1 of 8 mm initial diameter is falling from high altitude. As it moves through the air,
its size reduces because of sublimation. The local gas-phase mass transfer coefficient for the
sublimation of ice changes as a result. Assume that the terminal free fall velocity depends on
the diameter of the hailstone as

0 m / s 0.9d m

Make the following assumptions:

I. The hailstone always has the terminal free fall velocity corresponding to its diameter
(pseudo-steady state).
II. The ambient air is at -2 C, 1 atm total pressure and 70% relative humidity.
III. The hailstone temperature is constant at -2 C.
IV. The hailstone remains spherical all the times.

a) Calculate the initial (for d = 8 mm) mass transfer coefficient. (9 points)

b) Calculate the time required for the initial size of the hailstone to be reduced to 7.99 mm.
(11 points)
c) What is the initial mass transfer coefficient (for d = 8 mm) if we neglect convection?
(5 points)

Additional Data:

Diffusivity of water vapor in air: 0.178 cm2/s

Density of air: 1.29 kg/m3
Density of ice: 917 kg/m3
Molar mass of air: 28.9 g/mol
Molar mass of ice: 18 g/mol
Viscosity of air: 1.710-5 kg/ms
Saturation vapor pressure of ice at -2 C: 0.00511 atm
Universal gas constant, R: 0.082 Latm/(molK)

dx bx a log a bx
Hint: ( a / x) b
b2

1
in german: Hagelkorn
4
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Problem 4 (25 points)

The catalytic converter of a car contains a monolith (like in Figure 2) that consists of 200
uniform circular channels, internally coated with catalysts. Each channel has inner diameter
of 0.02 cm and a length of 50 cm. The gas mixture reaches the inlet of the catalytic converter
at a flow rate of 5.2510-6 m3/s. The gas mixture has a methane (CH4) concentration of
0.001mol/m3 at the inlet of the converter. While the gas mixture passes through the channels,
the CH4 is catalytically oxidized to CO2 and H2O. The reaction is first order with respect to
CH4 and irreversible with rate constant of 4.210-4 m/s. The gas flow through each channel is
laminar. Assume excess of oxygen. Assume constant temperature and pressure throughout
the system.
CH4 + 2O2 CO2 + 2H2 O
a) Draw a detailed sketch of the concentration profile and the processes taking place in a
single channel and indicate all important parameters. (5 points)
b) Calculate the overall mass transfer coefficient in one channel. (8 points)
c) Starting with the mass balance over a section of the channel, derive an equation for the
CH4 concentration as a function of the channel length. (6 points)
d) Calculate the concentration of CH4 at the outlet of the channel. By what factor did the
initial concentration decrease? (6 points)

Additional Data:

Diffusion coefficient of CH4 in the gas mixture: 2.0110-5 m2/s

Figure 2. Typical monolith in the catalytic converter of a car.

5
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Solution 1
a)

The required gaseous diffusion coefficient can be calculated by the following empirical
equation (Fuller, Schettler, and Giddings, 1966/ Cusslers book, 3rd ed., Eq.5.1-9):

T1.75 (1/M1 1/M 2 )1/2

D 10-3 (1)
V V
1/3 2
p
1/3

i i1 i i2

where Vij are the diffusion volumes of parts i of the molecule j, p is in atm and T is in K.

For air (molecule 1):

M1 0.21 32 0.79 28 28.84 g / mol ( 29 g / mol )

and

V i i1 20.1 (Cusslers book, 3rd ed., Table 5.1-4)

For aniline (molecule 2):

M2 93.13g / / mol

V i i2 6 16.5 7 1.98 1 5.69 20.2 98.35

Also:
p = 1 atm
T = 20+273=293 K

So, from Eq.1 we get:

1
1 1 2
2931.75
D 10-3 28.84 93.13
1 2
1

1 20.1 98.35 3
3

D 8.22 10-2cm2 / s
6
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

b)

1 l
2
criterion
Fo D t
(1)
15 cm
2

criterion 11.4
2 cm2 s
8.22 10 4 min 60
s min

criterion 1 non steady state

c)

Since the diffusion takes place at non-steady state, the semi-infinite slab approach should be
used. So, the concentration profile of aniline (species 1) in the air is described by (Cusslers
book, 3rd ed., Chapter 2.3-Unsteady Diffusion in a Semi-infinite Slab, Eq.2.3-15):
c1 (z, t) c10
erf
c1 c10

where:
c1 0
z

4Dt

Thus:
z
c1 c10 1 erf
4Dt
where:

p1sat
c10 c1sat
RT

7
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

0.5 103 Pa mol

c10 0.205 3
J m
8.314 293K
mol K

and:
z 15cm
1.69
4Dt 2cm 2 s
4 8.22 10 4 min 60
s min

erf erf (1.69) 0.98307

So:
c1 c10 1 0.98307 0.0169c10 3.48 103 mol / m3

d)

Since the diffusion takes place at non-steady state, the flux across the interface (at z = 0) as
a function of time is given by (Cusslers book, 3rd ed., Eq.2.3-18):

D
j1 z 0 c10 c1
t

D
j1 z 0 c10
t

and the flow rate across the interface at z=0 as a function of time is given by:

J1 z0 A j1
z 0

D
J1 z 0 A c10
t

So, the amount of aniline that evaporates after time tf is calculated by integrating J1 z 0 from
t=0 to t=tf:
tf

n1 J A
0
z 0
dt

t
D f 1
0 t
n1 A c10 dt

8
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

D tf
n1 2A c10 t
0

D
n1 2A c10 t f

where:

d2
A
4

So:

cm 2 m2
2 8.22 102 104
(0.45m) s cm 2 0.205 mol 4 min 60 s 1.64 103 mol
n1 2
4 m3 min

And:

g
m1 1.64 103 mol 93.13
mol

m1 0.152g

9
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Solution 2

a)
The total flux of acetone in the capillary, which is independent of l, is given by (Cusslers
book, 3rd ed., Equation 3.3-11):

Dc 1 y1l
n1 ln
L 1 y10

where:
y1 ( z L) y1l 0

c1sat Ideal gas law p1sat 25.3KPa

y1 ( z 0) y10 y1sat 0.250
c ptot 101.3KPa

where:

ptot 1.013 105 Pa mol

c 41.6mol / m3 4.16 105 3
RT 8.314 J 293K cm
mol K

The total flow rate is therefore:

N1 n1 A

with:

d2
A
4
(2mm)2
A mm 2 102 cm 2
4

So:

cm2 mol
0.107 4.16 105 3
s cm ln 1 9 mol
10 cm 4.02 10
2
N1
2

10cm 1 0.250 s

(Intermediate result:

mol
n1 1.28 107
cm2 s )

10
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

b)
n1,new A n1,new
It is:
n1 A n1

At 40 oC, the acetone-air interface (l = 0), the mole fraction of acetone is:

c1sat Ideal gas law p1sat 58.7KPa

y1 ( z 0) y10 y1sat 0.58
c ptot 101.3KPa

where:

ptot 1.013 105 Pa mol

c 38.9mol / m3 3.89 105 3
RT 8.314 J 313K cm
mol K

Thus:

cm2 mol
0.120 3.89 105 3
s cm ln 1 4.04 107 mol
n1,new (7)
10cm 1 0.58 cm2 s

Therefore,
mol
n1,new A n1,new 4.04 107
cm2 s 3.16 times faster
n1 A n1 mol
1.28 107 2
cm s

c)
dy1
n1 (1 y1 ) Dc
dz
N1 dy
(1 y1 ) Dc 1
A dz
where:

d ( z )2 d d
2

A d L o L z
4 4 L

So:

zL 1L y
1 dy1
N1
z 0
A
dz Dc
y10
1 y1

11
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch
L

4 N1 L 1 1 y1L
Dc ln
(d 0 d L ) d (d 0 d L ) z 1 y10
0
L
L

4 N1L 1 1 1 y1L
Dc ln
(d 0 d L ) d L d 0 1 y10

4L 1 y1L
N1 Dc ln
d0 d L 1 y10

d0 d L Dc 1 y1L
N1,new2 ln
4 L 1 y10

Thus:

d0 d L
N1,new 2 4 d L 1mm 0.5

n1,new A (d0 )2 d0 2mm
4

which means 2 times slower.

12
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Solution 3

a)
Forced convection around a sphere
1/ 2

1/ 3
kd dv
2.0 0.6 rel
D D (1)

D dv
1/2 1/3

k 2.0 0.6 rel

d D
0.9
1/2 1/3
2D
k 0.6 D (2)
d v D

2D
k C (3)
d
0.9
1/2 1/3

C 0.6 D 0.25cm / s
v D
1.7 105 kg / (m s)
kinematic viscosity: 1.32 105 m2 / s
1.29kg / m3

1/3
2 0.178cm2 / s 0.178cm2 / s 0.8cm 0.72cm / s 0.132cm2 / s
1/2

k 0.6
0.132cm / s 0.178cm / s
2 2
0.8cm 0.8cm

k 0.697cm / s

b)
The mass transfer equation for the sublimation of the naphthalene sphere is:

N1 A k (c1i c1 ) A (4)

where c1i and c1 are the concentrations of water vapor at the interface and in the bulk phase
of air, with:

Psat 0.00511atm
c1i 0.23mol
RT 0.082L atm / mol / K 271K
(5)
c1 RH c1i 0.7 0.23mol 0.161mol

and A is the interfacial area, given by:

A d2 (6)
13
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

The dissolution rate of the hailstone is also given by:

d3
d
m d
M M 6 dd
N1 A d2 (7)
dt dt 2M dt

So:

dd
d2 k c1i d 2 (8)
2M dt

df

t
1

dt
0
2M (c1i c1 )
k dd
d0
(9)

applying eq. 3:
df

t
1

dt
2M (c1i c1 )
2D
dd (10)
0 d0 C
d

2D Cd f
t C d f d 0 2Dlog (11)
2M (c1i c1 ) 2D Cd 0

917kg / m3
t
2 18 103 kg / mol (0.23 0.161)mol(0.25cm / s) 2

2 0.178cm 2 / s 0.25cm / s 0.799cm

0.25cm / s 0.799 0.8 cm 2 0.178cm / s log
2

2 0.178cm / s 0.25cm / s 0.8cm
2

t 18min

c)
Mass transfer coefficient of pure diffusion:

2 D 2 0.178cm2 / s
k
d 0.8cm
k 0.445cm / s

14
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Solution 4

a)

Note: In the solution, concentration of CH4 = CA

b)

The overall mass transfer correlation is given by (Cussler, 3rd ed., Eq.16.3-7):

1
K (1)
1 1 1

k1 2 k3 K 2

Since we have an irreversible reaction, it is 2 0 and therefore:

2
K2 (2)
2

Now, we get following expression for overall mass transfer correlation:

1
K (3)
1 1

k1 2

Where k1 is the local mass transfer coefficient of CH4 (A) and 2 is the reaction rate constant.

For k1 we can find the appropriate mass transfer correlation for fluid-solid interfaces, which is
laminar flow through a circular tube (Cussler, 3rd ed., Table 8.3-3):

1/3
d 2u D
k1 1.62 (4)
LD d

15
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

where D is the given diffusion coefficient of CH4 in exhaust gas and u is the gas velocity,
which can be calculated from the exhaust gas feed rate in single channel, Q, and the tube
cross sectional area, Across, as:

Q
u (5)
Across

Exhaust gas flowrate in single channel is calculated using cross section area of the channel
and the gas flowrate per unit cross section area of the channel.

m3
Q Across flowrate per unit cross section area of a channel 3.14 108 m 2 0.833
s m2

m3
Q 2.62 108
s

Now the velocity of the gas through the channel using equation 5.

m3
2.62 108
u s 0.833m / s

0.0002 m2
2

So, from Eq.4 we get:

1/3
m 5 m
2

0.0002 m 0.83 2.0110

2 2

k1 1.62 s s 0.0243 m
2
0.50m 2.01105 m 0.0002m s

s

Consequently, the overall MTC from Eq.1 is:

1 1 m
K 4.13 104 (6)
1 1 1 1 s

k1 2 0.0243
m
4.2 104
m
s s

c)
/i)

The mass balance over a section of the pipe is:

16
 Prof. Dr. Sotiris E. Pratsinis
Particle Technology Laboratory
Sonneggstrasse 3, ML F13
http://www.ptl.ethz.ch

Across u cA ( z ) cA ( z z ) K Acirc cA ( z ) (7)

d 2 u cA ( z ) cA ( z z ) K d z cA ( z )
4

d u cA ( z ) cA ( z z ) 4K z cA ( z )

cA ( z z) cA ( z) 4K
cA ( z )
z d u

dcA 4K
cA (z) (8)
dz d u

Boundary conditions: z 0: cA cA0 ; z : cA cA ( z ) (9)

After integration equation 8 using boundary conditions from equation 9, we obtain the
concentration profile of CH4 (A) as function of z:

4K
cA ( z ) cA0 exp z (10)
d u

/ii)

For z L :

4 m
mol 4 4.13 10 s mol
cAL 0.001 3 exp 0.5m 7.05 106 3
m 0.0002m 0.833
m
m
s

/iii)

Thus, the conversion of CH4 (A) is given by:

mol
0.001
c A0 m3
142 times lower
cAL mol
7.05 106 3
m

17