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Hazardous Waste management, 2

nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 1 of 12
CHAPTER
9
PHYSICO:CHEMICAL PROCESSES

Supplemental Questions:

In the first line of the opening quote, what is "it"? i.e. what were they proposing to sweep for seven years?

The sands at the seashore.

9 -1. Derive Eq. 9-20 starting with Eq. 9-16.

Equation 9-16


But Equation 9-19




Let U =C(R-1); dU =(R-1) dc



Divide numerator and denominator by C
out


Equation 9-20




=
Cin
Cout eq
C C
dC
NTU
R
C C
C
t ou
eq

=
) (
1
) (
R
C C
C
dC
R
R
R
C C
C
dC
NTU
out out

=


+
=
+
=
t ou out
C R C
dC
R
C C RC
dC
R
) 1 (

= U
U
dU
ln
Cin C
Cout C
out
t ou
C R C
R
R
C R C
dC R
R
R
=
=
+

=
+

=

) ) 1 ( ln(
1 ) 1 (
) 1 (
1
} { ) ) 1 ( ln( ) ) 1 ( ln(
1
out out out in
C R C C R C
R
R
+ +

=
)
) 1 (
) 1 (
ln(
1
out out
out in
C R C
C R C
R
R
+
+

=
(
(
(
(

+
+

=
out
out
out
out
out
out
out
in
C
C
R
C
C
C
C
R
C
C
R
R
) 1 (
) 1 (
ln
1
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 2 of 12
9-2. Provide a preliminary design of an air stripping column to remove toluene
from ground water. Levels of toluene range from 0.1 to 2.1 mg/L and this
must be reduced to 50 g/L. A hydrogeologic study of the area indicates that
a flow rate of 110 gal/min is required to ensure that contamination not spread.
Laboratory investigations have determined the overall transfer constant, K
L
a =
0.020 sec
--1
. Use a column diameter of 2.0 feet and an air to water ratio of
15. Specifically determine: Liquid loading rate, stripping factor, height of
the tower and provide a sketch of the unit indicating all required
appurtenances.
Assumptions: Temp =20C =293K;
Influent: C
in
=2.1 mg/L
Effluent: C
out
=0.05 mg/L
Column diameter =2.0 ft =0.61 m;
1 mole of water =18 g.

Henry's constant: From App. B:


A =5.13 B =3.02 x 10
3
=3020








=0.235 (dimensionless)


1) Liquid Loading Rate:

Cross-sectional Area of column


Mass Rate
F =45 (Table 9-2)



2) Stripping Factor:


dimensionless


3) Height of Transfer Unit:



) (
exp
T
B
A
H

=
mol m atm e H / 10 64 . 5
3 3
)
293
3020
13 . 5 (
= =

K K mol m atm RT
H
H
293 / 10 205 . 8
10 64 . 5
3 5
3


= =

2
2
292 . 0
4
) 61 . 0 (
m =

2
sec
1806 . 0
(sec) 60
(min) 1
785 . 3
min
110 0 . 1
ft
lb
gal
L gal
L
Kg

=
2
3
2
sec
1320
)
18
1
)(
10
)(
sec
8 . 23
(
m
mol
g
mol
kg
g
m
kg
L

=
525 . 5 15 235 . 0 = =
|
|
.
|

\
|
=
W
A
Q
Q
H R
m
K M
L
HTU
a L w
187 . 1
020 . 0 55600
1320
=

= =
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 3 of 12


4) Number of Transfer Units:



transfer units



5) Height of packing in column:

9 - 3 . Using the data in problem 9-2, determine the pressure drop through the tower.

1) Select 2" Rasching Rings as packing.
2) Calculate Pressure Drop. The parameters for Figure 9-5:

A
=Air Density = (@20C)

W
=Water Density =62.3 lb/Ft
3
(@20C)





F =45 (Table 9-2)

Ordinate =



Abscissa =


This point intersects the curves of Fig 9.5 at dp =0.25 inches of water per foot of packing depth (2050 Pa/m) . This
pressure drop is the lower limit of the recommended range of 0.25 to 0.5 inches of water per foot of packing depth,
indicating that the air flow rate could be increased significantly without causing flooding.
Pressure Drop =(Ht. of packing in column Z) x (dp)
=(23) x 0.25 =5.75 in =0.021 psi =1430 Pascals

9-4. Using the data in problem 9-2, determine the impact on effluent quality by varying the air to
water ratio and the packing height.
Molecular weight: 92.2 g/mol
Boiling point : 111 C
Molal Volume at boiling point: 0.1182 L/mol
Henry's Constant: 0.19000
765 . 4
525 . 3
) 1 525 . 3 (
05 . 0
1 . 2
ln
1 525 . 3
525 . 3
1 ) 1 )( (
ln )
1
( =


|
.
|

\
|

=
R
R
Cout
Cin
R
R
NTU
ft HTU NTU Z 6 . 18 656 . 5 187 . 1 765 . 4 = = = =
2 2
sec
874 . 4
2048 . 0
sec
8 . 23
Ft
lb
m
Kg
L

=
sec
2129 . 0
sec
85 . 212
) 15 ( 19 . 14 ) (
3
m L
W
A
QW QA = = = =
3 3
075 . 0 205 . 1
Ft
lb
m
Kg
=
2 2 3
3
3
sec
1806 . 0
sec
881 . 0
291 . 0
)
205 . 1
)(
sec
2129 . 0
(
Ft
lb
m
Kg
m
m
Kg m
G

= =
00976 . 0
) 17 . 32 )( 3 . 62 )( 075 . 0 (
) 45 ( ) 1806 . 0 (
) (
2 2
=

=
g
F G
W A

936 . 0
3 . 62
075 . 0
1806 . 0
874 . 4
5 . 0
5 . 0
=
|
.
|

\
|
|
.
|

\
|
=
|
|
.
|

\
|
|
.
|

\
|
W
A
G
L

Hazardous Waste management, 2


nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 4 of 12
Temperature Constant: 3517 K

Solution:
(1) Choose a column packing =Ceramic 2.0 in Ranching Ring
(2) Choose Design temperature and pressure
T =20C =68F
P =101.3 kpa =1.0 ATM
(3) Choose a Liquid's loading rate
L =23.8 kg/M
2
s
(4) Choose a range of A/W ratios:



(5) Choose a range of packing depth

(6) Indicate contaminant
Toluene

The problem was solved by putting the above data into the program AIRSTRIP. This program may be
ordered from: AIRSTRIP, 3209 Garner Street, Ames, IA 50010.
The computer will then calculate the effluent concentration of toluene over the indicated range of A/W
ratios and depth. The next page shows the screen display for the above reference problem. An effluent
concentration of 30.3 g/L is chosen corresponding to A/W =20 and Z =7.1m. The F9 key produces
the second display.

Toluene Concentration In 2.1 mg/L
C-Raschig Rings 50.8 mm Atmospheric Pressure 101.3 k
Design Temperature 20.0 C Liquid Loading Rate 23.8 kg/m
2
s
Minimum Packing Depth 4.6 meter Minimum A/W Ratio 10.0
Maximum Packing Depth : 9.1 meter Maximum A/W Ratio 30.0

Concentration Remaining (mg/L)
Packing Depth A/W =10 A/W =15 A/W =20 A/W =25 A/W =30
(meter)
4.6 0.2 0.2 0.1 0.1 0.1
5.7 0.2 0.1 0.1 0.1 0.0
6.9 0.1 0.1 0.0 0.0 0.0
8.0 0.1 0.0 0.0 0.0 0.0
9.1 0.0 0.0 0.0 0.0 0.0
R 1.9 2.8 3.8 4.7 5.7
dP(Pa/m) 79 149 246 381 563

F10 Toggle to English units F 1 Help F7 Quit Program
F9 Continue with design procedure F3 Main menu Esc to go back


30 10
W
A
m Z m 0 . 9 6 . 4
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 5 of 12
AIRSTRIP Release 1.2 Summary of Selected Design Copyright 1988

Contaminant Toluene
Concentration In 2.1 mg/L
Concentration Out 30.3 g/L
Percentage Removed 98.6 %
Packing C-Rasching Rings 50.8 mm
Water Temperature 20.0 C.
Atmospheric Pressure 101.3 kPa
Packing Depth 7.1 meter
Liquid Loading Rate 23.8 kg/m
2
s
Air/Water Ratio 20
Stripping Factor 3.8
Air Pressure Gradient 246 Pa/m

F 10 Toggle to English units F1 Help F7 Quit Program
F6 Save design "P" print report F3 Main menu Esc to go back


9-5. Determine the overall mass transfer coefficient, K
La
, given the following data
from an air stripping column: contaminant = tetrachloroethene(C
2
CL
4
); liquid
mass loading rate = 10.2 kg/m
2
s; packing =1" polyethylene Tri-paks

; air
mass loading rate = 1.5 kg/m
2
s; temperature = 6C; diffusion coefficient in
water = 1.1 x 10
-6
cm
2
/s.

Given: Contaminant =tetrachloroethene (C
2
Cl
4
)
Liquid mass loading rate =10.2 kg/m
2
s
Air mass loading rate =1 kg/m
2
s
Packing =1 polyethylene Tri-packs


Temperature =6C
Diffusion coefficient in water =1.1 x 10
-6
cm
2
/s
Assume: Column Diameter =3m
Solution:
According to Onda Correlations (eqn. 9-5):




Let a
t
total packing area =279 m
2
/m
3
(table 9-2)
d
p
nominal packing diameter =

L liquid mass loading rate =10.2 kg/m
2
s

L
liquid density =997 kg/m
2
@ 6 C

L
viscosity of water =1.4728 x 10
-3
kg/m
2
s @ 6C
g acceleration due to gravity =9.81m/sec
2


( )
4 . 0
3
2
3
1
0051 . 0
p t
L L
L
L w L
L
L
d a
D a
L
g
K
|
|
.
|

\
|
|
|
.
|

\
|
=
|
|
.
|

\
|

m
in
m
in in 051 . 0
37 . 39
2 2 = =
3
1
3
3
2
81 . 9 10 4728 . 1
997
|
.
|

\
|

w L
a K
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 6 of 12


D
L
is obtained by The Wilke-Chang method (Sec. 3.2)
The Molar Volume: (See Table 3-4, p. 97) of C
2
Cl
4


C =2 x 14.8 =29.6 Cl =4 x 24.6 =
128.0
98.4

Total V =29.6 +98.4 =128.0 cm
3
/mo1

Using (eqn. 3-13)


From equation 9-6:

=89.18 m
2
/m
3


KL =19.86 x 10
-4
ms
-1

From equation 9-7:



K
La
=0.065 (sec
-1
) A =124 B =4.92 x 10
3


H =exp [12.4 (4.92 x 10
3
) / 279] =0.00533
( )
4 . 0
5 . 0
3 3
2
3
051 . 0 279
997
10 4728 . 1
10 4728 . 1
2 . 10
0051 . 0
|
|
.
|

\
|

|
|
.
|

\
|

=

L w
D a
sec
10 215 . 5
10 sec ) 128 ( 14728 . 1
) 6 273 ( 10 06 . 5
2
9
2 4
2 2
6 . 0
7
m
cm
m cm

+
=

(
(

|
|
.
|

\
|
|
|
.
|

\
|
|
|
.
|

\
|
|
.
|

\
|
=
2 . 0
2
05 . 0
2
2
1 . 0
75 . 0
45 . 1 1
t L L L t
c
t w
a
L
g
L
a
L
e a a

(
(

|
|
.
|

\
|

|
|
.
|

\
|

|
.
|

\
|

|
.
|

\
|
=

2 . 0
2
05 . 0
2
2
1 . 0
3
75 . 0
279 075 . 0 997
2 . 10
81 . 9 977
2 . 10
10 4728 . 1 279
2 . 10
075 . 0
033 . 0
45 . 1 1 279 e
( )
4 . 0
5 . 0
9
3
3
2
3
051 . 0 279
10 215 . 5 997
10 4728 . 1
10 4728 . 1 18 . 89
2 . 10
0051 . 0 07 . 41
|
|
.
|

\
|


|
.
|

\
|

=

L
K
( )
2
3
1
7 . 0
23 . 5

|
|
.
|

\
|
|
|
.
|

\
|
=
p t
a a
a
a t a t
a
d a
D C a
a
D a
K

2
3
1
6
5
7 . 0
5 6
) 051 . 0 279 (
10 1 . 1 247 . 1
10 81 . 1
10 81 . 1 279
5 . 1
23 . 5
10 1 . 1 279



|
|
.
|

\
|

|
.
|

\
|

=

a
K
1 3 6 4
10 94 . 4 10 427 . 1 36 . 2 82 . 53 23 . 5 10 069 . 3

= = ms K
a
233 . 0
279 10 205 . 8
00533 . 0
5
=

= =

RT
H
H
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 7 of 12

K
L
a =0.065 (sec
-1
)


9-6. Recalculate K
L
a from Example 9-1 incorporating the following changes: H is given as
0.0704 (dimensionless) at a temperature of 6C, at = 138 m
2
/m
3
.

This surface tension of water is a function of temperature. From "Tables of Physical and Chemical Constants
and Some Mathematical Functions", Kaye, G. W. C. and Labe., T. H., London, Longman Publishers, 1986:

At 0C, =0.076
At 10C, =0.0742

At 6C,


diameter =3 ft =0.91m =


Unit weight of water =8.34 lb/gal

A
t
=138 m
2
/m
3








39 . 15
18 . 89 10 84 . 19
1
18 . 89 10 94 . 4 233 . 0
1 1
4 3
=

+

=

a K
L
075 . 0 07492 . 0 6
0 10
0018 . 0
076 . 0 = =
|
.
|

\
|

+ =
44 . 0
075 . 0
033 . 0
= =

c
2
2
650 . 0
4
) 91 . 0 (
m =

sec
49 . 16
650 . 0
204 . 2
1
34 . 8
sec 60
min 1
min
170
2 2

=

=
m
Kg
m
lb
kg
gal
lb gal
L
sec
10 404 . 9 10
sec
09404 . 0
2
6
2
2 2
m
cm
m cm
D
G

= =
sec
379 . 0
sec 60
min 1
48 . 7 min
170
3 3
ft
gal
ft gal
Q
W
= =
sec
99 . 1
650 . 0
205 . 1 02832 . 0
sec
9 . 37
2 2
3 3
3 3

=

=
m
kg
m
m
kg
ft
m ft
G
sec
10 6
10 sec
10 6
2
10
2 4
2 2
6
m
cm
m cm
D
L

= =
m
in
m
in d
p
051 . 0
37 . 39
2 = =
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 8 of 12

Reynolds No.:

(dimensionless)


Froude No.:

(dimensionless)


Weber No.:


(dimensionless)



From equation 9-6:


From equation9-5:

K
L
=1.546 x 10
-4
m/sec
Viscosity of air@0C =1.71 x 10
-5
NS/m
2

Viscosity of air @ 10 C =1.76 x 10
-
5 NS/m
2

Viscosity of air @ 6 C =171 +(0.5) x 6 =174
@6C .
G
=1.74 x 10
-5
NS/m
2

From equation 9-7:
K
G
=1.717 x 10
-2
ms
-1

Approximately 1/3 smaller than the value @ 20C calculated in example 9-1.





13 . 81
sec
10 4728 . 1 138
sec
49 . 16
3
2
=

m
kg
m
kg
a
L
L t

3
2
2
2
2
10 848 . 3
81 . 9 ) 997 (
138 ) 49 . 16 (

=

=
g
at L
L

0264 . 0
138 075 . 0 ) 997 (
) 49 . 16 (
2
2 2
=

=
t L
a
L

( ) | | { }
3
2
2 . 0
05 . 0
3 1 . 0 75 . 0
5 . 74 49 . 74 ) 0264 . 0 ( 10 848 . 3 ) 13 . 81 ( ) 44 . 0 ( 45 . 1 1 138
m
m
e a
w
= = =

4 . 0
5 . 0
10
3
3
2
3
3
1
3
) 051 . 0 138 (
10 6 997
10 74 . 1
10 473 . 1 5 . 74
49 . 16
0051 . 0
81 . 9 10 473 . 1
997

|
|
.
|

\
|


|
.
|

\
|

=
|
.
|

\
|

L
K
) 10 404 . 9 )( 138 (
6

G
K
2
3
1
60
5
7 . 0
5
) 0051 . 0 )( 138 (
) 10 404 . 9 ( ) 265 . 1 (
10 74 . 1
10 74 . 1 138
99 . 1
23 . 5

|
|
.
|

\
|


|
.
|

\
|

=
) 5 . 74 )( 10 564 . 1 (
1
) 5 . 74 )( 10 717 . 1 )( 0704 . 0 (
1 1 1 1
4 4

= +

=
a K a K H a K
L G L
sec 93 . 96
1
=
a K
L
) (sec 0103 . 0
1
= a K
L
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 9 of 12
9-7. Design an air stripping column to remove TCE from water. The initial concentration of TCE
is 1.3 mg/L and this must be reduced to 75 g/L. Use the following criteria: water flow rate: 350
gal/min; water temperature: 16C; air temperature: 23C; packing: use 2" Intalox saddles.

Liquid Loading Rate:

Select column diameter =2 Ft
Area of column =0.292 m
2

Mass Rate =1.0 Kg/L x 350 gal/min
=1.0 Kg/L x (3503.785/60 L/sec) =22.08 Kg/sec
Mass Loading =22.08/0.292 =75.62 Kg/secm
2

L =(75.62 Kg/secm
2
)(10
3
g/Kg)(1/18 mol/g) =4201.11 mol/secm
2


Stripping Factor:

For TCE K
L
=20.4 cm/hr

H =exp(9. 7 - 4308/T) =exp(9.7 - 4308/289. 3) =5. 566 10 9
-3


H' =H/RT =5.566 9
-3
/(8. 206 9
-5
x 289. 3) =0.234 (dimensionless)
R =H'(Q
A
/Q
W
) =0. 234(70) =16. 38 (dimensionless)

Height of Transfer Unit:




For 2" Intolox
Saddles
a =118 m
2
/m
3

K
L
a =(20. 4cm/hr)(118 m
2
/m
3
) =20. 4 x 118 x 10
-2
/(3600) sec
-1
=0. 0067 sec
-1


Number of Transfer Units:

NTU =(R/ R-1) ln{ ( (C
in
/C
out
) (R-1)+1)/R}

=(1.07) ln {( (1300/75) (16.3-1) +1)/16.3} =2.99 Transfer Units

Height of Packing in Column:

Z =NTU x HTU =(2.99)(11.28) =33.72m

Note: In an actual design, a safety factor of 2% would be added the height of packing raised to the next whole
number!

Z =33.72 (1.2) =40.464 =41 m

But the tower height should be between l and 15 meters
Provide three towers of 14 m (45 feet).

m
a K M
L
HTU
L W
28 . 11
) 0067 . 0 )( 55600 (
4201
= = =
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 10 of 12
9 - 8 . Demonstrate that the stripping factor used in this book is numerically similar to that in
common use by chemical engineers:

R = H'G/L
H'= Henry's constant (dimensionless)
G = gas loading rate (kmol/hr)
L = liquid loading rate (kmol/hr)

First note that the chemical engineering equation defines the stripping factor in terms of molar flow rates,
while equation 9-20 defines R in terms of volumetric flow rates:

(i)



where Ha = Henry's constant in Atmosphere
G, L = Loading Rates (Kmol/sm
2
)

(ii)


(From eqn. 9-20)


where H' = Henry's Constant (Dimensionless)
Q
A
= Air Flow Rate (m
3
/sec)
Q
w
= Water Flow Rate (m
3
/sec)
Note: at 20C
M
w
=molar vol of water =55,600 mol/m
3

R=8.25x10
-5
atmm
3
/molk

From eqn (i):


From eqn (ii):


( From the Chemical engineering literature (reference 6):

L
G H
R
a
=
|
|
.
|

\
|
=
W
A
Q
Q
H R
1340
A
W
A
H
RT M
H
H = =
A
H
R
L
G
=
A N
A
H
R
Q
Q
H
R ) 1340 (
= =

) 10 5 . 7 (
4
=
W
A
A
Q
Q
H
R
) 10 5 . 7 (
4
=
W
A
Q
Q
L
G
m
m
L
G
m S =
Hazardous Waste management, 2
nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 11 of 12

where

G
m
= molar air flow rate (Kmol/sm
2
)
L
m
= molar liquid air flow rate (Kmol/s m
2
)
M = slope (i.e. dimensionless Henry's constant, H')

G
m
=Q
A

A
/ mol wt of air
L
m
=Q
w

w
/mol wt of water

A
=1. 205 Kg/m
3
air @ 20 C

w
=998.2 Kg/m
3
water @ 20 C
MW
air
=28.97 Kg/mol
MW
water
=18 Kg/mol


@20C, the value of the dimensionless stripping factor is the same for both equation.

( )
4
10 5 . 7
97 . 28
18
2 . 998
205 . 1

= = =
W
A
W
A
air
water
W
A
W
A
m
m
Q
Q
Q
Q
MW
MW
Q
Q
L
G

Hazardous Waste management, 2


nd
ed. Instructors Manual Chapter 9:Physicochemical Processes
2001McGraw-Hill, Inc.
Page 12 of 12
9-9. 100 mL of a solution with a TOC (total organic carbon) concentration of 0.5% is
placed
in each of flue containers with activated carbon and shaken for 48 hours. The samples
are filtered and the concentration of TOC measured, yielding the following analyses:
Container: 1 2 3 4 5
Carbon (grams): 10 8 6 4 2
TOC (mg/L): 42 53 85 129 267

Determine the Freundlich constants, K and n, and plot the isotherm.

Sample Volume, V = Liters 0.1
Initial Concentration, Ci= mg/L 5000

M Cf X =(Ci-Cf)V Cf X/M Log(X/M) Log Cf
grams mg/L mg mg/L
10 42 495.8 42 49.6 1.70 1.62
8 53 494.7 99 61.8 1.79 1.72
6 85 491.5 212 81.9 1.91 1.93
4 129 487.1 310 121.8 2.09 2.11
2 267 473.3 510 236.7 2.37 2.43

Slope =1/n =0.834442 0.3340686 Constant= Log K
Std Error 0.036627 0.0726537 Std Error of constant
R-Squared 0.994253 0.0234578 Std Error o y
F 519.0196 3 d. f.
SS reg 0.285601 0.0016508 SS residual


K = 2.16 mg/gram
1/n = 0.834

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