RECUEIL 67 (1948)

541.183.26 : 541.124

STUDIES OF GAS ABSORPTION.

IV. SIMULTANEOUS GAS ABSORPTION AND

CHEMICAL REACTION.
BY

D. W. VAN KREVELEN, P. J. HOFTIJZER and

C. J. VAN HOOREN
(Central Institute for Technical Research of the Netherlands' Statc Mines.
Chemical Laboratory, GeIc.cn, T h e Netherlands).
G a s absorption with simultaneous chemical reaction can bc dividcd into
three characteristic groups.
F o r the very slow reactions the rate-determining step is the diffusion of
the solute g a s throuc;h the liquid film.
Chemical reaction velocity is determinative for modcrately rapid a n d sloiv
reactions.
For the very fast wactions gas film resistance to the solute gas and liquid
film resistance to the reactive liquid component a r e rate-detcrrnining.
Rate equations for the last group in terms of the individual mass transfer
cocfficients have been derived and have been chcckcd o n absorption
experiments.
T h e experimental i.esults prove t o be correlated satisfactorily.

1.

Introduction.

In many chemical processes gas absorption with simultaneous

chemical reaction between the solute gas and a reactive component of
the liquid ( t h e "second" component) is an important unit operation.
T h e knowledge of this "chemical absorption" is still relatively scarce
compared with that of physical absorption. Perhaps this is due to the
fact that obviously the mechanism of the chemical absorption varies
from one case to an3ther. T h e influence of the concentration of the
second component is quite different in the cases of absorption of
ammonia in sulphuric acid. carbon dioxide in alkaline lye-solutions and
hydrogen sulphide iri soda ash solutions.
In physical absorption the rate is determined by two separate factors:
mass transfer from the gas phase to the interface, and
mass transfer from the interface into the liquid phase.
In chemical absorptions the mechanism is more complicated. Here
LXVlI

RECUEIL 67 (1948)
134

D. W. van Krevelen. P. J. Hoftijzer

and

C. J. van Hooren,

we have 5 successive steps each of which may be rate-determining:

1. mass transfer of the solute gas A in the gas phase;
2. mass transfer of A in the liquid phase (to the reaction zone);
3. mass transfer of the component B in the liquid phase ( t o the
reaction zone) :
4 . chemical reaction between A and B during diffusion of both components;
5. mass transfer of the reaction product from the reaction zone into
the bulk of the liquid.

Sometimes only one of these steps is rate-determining; it is evident

that the rate-equation of the absorption process depends on the
character of the rate-determining step.

2. Three main-types of chemical absorption.

In physical absorption the two-film theory proved fm afford a useful
pattern for calculations. T h e same pattern will be used now for
chemical absorption.
In fig. l a the course of the concentration in the liquid film is
Fig, la.
concentration

Moderately rapid reaction.

I

gar

--a

positive direction
of diffusion

Significance of symbols:
f = film boundary
i = gas-liquid interface
r = reaction zone
x = film thickness

drawn for the general case. We shall use the simple notation A and B
for the concentrations of the reactants.
A t a distance x from the interface the diffusion velocity of A per
unit surface is:

RECUEIL 67 (1948)
135

Studies of gas absorption.

+ tix the rate of diffusion will be:

At a distance x

T h e difference in 'diffusion velocities between x and x 4-dx:

D Ad'A
- 7dx
dx
is due to chemical reaction, so that

An analogous reasoning can be applied to the concentrations of H:

'g2=

B - kA . B
DBd2
-dx2 -

~~~~~~~

At x = 0, viz. on the interface, a stationary equilibrium exists

between gas and liquid:

A. = H Pi
(where H = Henry coefficient of A in the boundary layer). A t x = x,:
A = A, (concentration in the bulk of the liquid) and B = B,.
A

==

Furtheron the following expressions will be valid at the interface:

i i",).
( (3
-DA

== N A= rate of absorption per unit surface

x 0

= 0 assuming that the component B

is not volatile

r0

A general solution of this differential equation cannot be given.

However, for each individual absorption process a graphical
integration (by step:;) is possible if values of the diffusion coefficients
and the reaction velocity coefficient are known.
Under special coriditions relatively simple solutions are possible.
T h e reaction is :io slow, that it takes place exclusively in the bulk
of the liquid, so that in the liquid film only diffusion takes place.
T h e only difference with physical absorption is that by reaction the
concentration A , in the bulk of the liquid is much lower now. T h e
concentration pattern is drawn in fig. lb.
T h e reaction is moderately rapid so that diffusion and absorption
occur simultaneously; however in thc rather broad reaction zone
the concentra:ion of the reactant b is nearly constant.

RECUEIL 67 (1948
D. W .van Krevelen, P. J. Hoftijrer and C . I. van Hooren.

136
.

_ _ .

c ) T h e reaction is immeasurably rapid. The situation is a s drawn in

fig. 2a; the reaction takes place in an extremely thin reaction zone;
as well A a s B must be transferred by diffusion to this reaction
zone; the reaction product must be removed from it by diffusion.
T h e reaction zone may coincide with the interface. In this case
Fig. lb.

Very slow reaction.

concentration

gas

liquid

I
I
-A

positive direction
of diffusion

only B diffuses to the reaction zone and the reaction product

diffuses away from it (fig. 2b).
Cases a ) and b ) have been treated already in the parts I and
this series 1 ) . Case c ) will be treated in this paper.

I1 of

3. Extremely rapid irreversible reactions.

At very large reaction velocities the concentration course will
approach to the pattern of fig. 2a. T h e rate of absorption is determined
Fig. 2a. Extremely rapid reaction (irreversible).
concentration
f

I
/
&

---A

X.

I
--

positive direction

of diffusion

in this case by the mass transfer of A and B into the extremely thin
reaction zone. This case has already been treated by Sherwood 2 ) .
D. W. van Krevelen and P. I. Hoftijzer. Rec. trav. chim. 66, 49 (1947).
Th. K . Sherwood, Absorption and Extraction (Monograph), N e w York (1937),
pag. 194.
1)

2)

RECUEIL 67 (1948)

137

Studies of gas absorption.

_ _ ~ - - _ _ _ ~ _ _ _

Starting with the basic equations:

NA kc(pc-P)

\ NA

zz

XI

DA
-(A,-O) = DB
-- (BL-0)
=DAB
- - (ABi-ABL)
X1

x2

x2

x2

= x-.

Sherioood derives the formula:

T h e limiting condition of this equation is that Ai must always be

0. i.e.:

s
.

If this condition is not fulfilled, the rate of absorption will be:

. .

(3)

First of all it was necessary to consider which class of reactions is

sufficiently fast in order to be described by the equations ( 2 ) and ( 3 ) .
T h e measurements by Saal : I ) allow one to draw the conclusion that the
following reactions are immeasurably rapid (k 109 kmol 1 m:I sec

Solute gas
acetic acid
hydrogen sulphidc
hydrogen cyanide
sulphur dioxide
ammonia

I1

Absorption liquid

Reaction

alkali hydroxide
,,

HAc f OH---+
AcH20
HS- +H2O
H2S +OH-H20
HCN f OH- ---t C N SO2 +OH-HSO3NH3 + H + + NH,+

acid

+
+

W e shall show that in these cases the rate of absorption a n

described indeed by the equations ( 2 ) and ( 3 ) .

')

R. N . 1. Saal.

Rec. trav. chim. 47, 73, 264 (1928).

RECUEIL 67 (1948)
D. W . van Krevelen, P . J. H o & j z e r and C. J. van Hooren,

138

Table
Absorption of ammonia in water
Height of column = 0.15 m : diameter of column = 0.034 m:

48
47
49
50
51

Temp.

VG

OC

mjsec

- ._

-~

1
mjsec

PGc
atm

PGo
atm
-

1.13.10-2
1.56
1.65
1.88
2.54

6.88. lo-
7.34
6.85
6.24
5.55

20
20
21
23
18

0.0467
0.0614
0.0793
0 0971
0 200

6.22.10
6.05
6.29
6.18
5.83

21
20
21
23
20
21

0 0760
0 0809
0 147
0.150
0 214
0 259

5.7 I
5.72
5 54
5.74
5.75
5.68

9.30
13*.4I
8.28
7.06
8.18
6 72

2.03
3.20
2.68
2.64
3.00
2.75

21
25
21
21
Ill
24
At bottom
25
kL
20
P G ~ B L k~
~
21
23
23
At top
23
kL
~ G ~ < B~L ~ 21
kG
22
22
22
22

0.05 I0
0 0539
0.0623
0 0748
0 0809
0 0793
0 0824
0 0824
0 193
0 158
0 0989
0 0606
0 0679
0 0778
0.128
0.113

5.77
5.83
5.81
5.75
5.75
5.72
5 61
5.77
5.68
5.83
5 77
5 73
5.83
5.62
5.78
5.83

7.04
7.29
6.75
6 92
6.98
7.20
7.71
7.18
6.52
6.13
7.12
6.94
7.42
8.24
5.99
6.41

0.96
1.32
1.16
1.45
1.63
1S O
1.37
1.70
1.x0
1.49
1,37
0.56
q.53
0.82
0.97
0.95

I
Absorption
in water

.-.

.
~~

45
32
46
44
34
35
41
42
52
53
54
55
56
57

>

4. Application of equations (2) and (3) to ammonia

absorption in sulphuric acid.
Data on ammonia absorption in water and sulphuric acid solutions
are compiled In table.1 (experiments by the authors). A convenient
method for evaluation of k,; and k,, from the absorption data has been
derived.
From the absorption data of ammonia in water the k,; and k,, values
can be evaluated in the well known way. Here we have:

,
I

RECUEIL 67 (1948)

1.
and in sulphuric acid.
packing material: glass rings 5
I

X 5 rnm.
-

B L ~

kgmol,rn3

NA.

1 kgmolisec mz

0 6 8 lo-'
0 895
1 04
1.07
1.53
~

1 39
2 08
2.08
166
2 79
2.60

0 38
0:52
0 20
0.25

HQm

knmol/
m3 atm

m/sec

3.16.1O6
2:98
2.43
2.13
2.00

75
75
72
65
83
..

I
I

3.20
3 02
2.13
2.29
1.65
1.52

72
75
72
65
75
72

1.03.10-8
1.01
I .03
1.03
0.98
0.965
0.965
0.95
0.965
0.965
0.965

3 '00

0.78
0.75
0.75
0 70
0 67
0 67
0.61
0 67
2 34
2.48
2.59

0 78

0.885
0 875,
1.03
1.14
1.14
131
104
2.26
185
143
0.975
I 18
I46
163
135

2 72

2 67
2.55
2 54
2 62

3.55
3 01
3.39
3.26
2.70
2.53
2.77
3.23
1.98
2.14
2.66
2.91
2.51
2.48
2.05
2.50

72
59
72
72
62
59
75
72
65
65
65
72
68
68 .
68
68

0.98
0.98
0 98
0.965
0 965
0 965
0.95
0.98
0.965
0.98
0 98
0.965
0.98
0.Y5
098
0.98

As k,; cu v(;O.H,k,;and k,, can be obtained by plotting

The intercept on the ordinate is .~--, whereas

Hk L

3 03 10-5
3.78
4 85
56
8.5
____3 34
3 78
6.75
5.2
12.4
I5 0

__

~~

1 .oo

kc
kgmol/
sec rnz atrn

kL
~

2.84
2.97
3.03
3 25
3 72
3 97
4 35
3 25
6 85
58
3.97
3.84
5.1
5.35

6.6
4.6

1
~

KG

versus

1
~

--

VO a

k,; can be calculated

from the slope of the line.

An analogous method can be applied when equation ( 2 ) is valid.
Now we plot

Then again

HkL

.
is equal to the intercept on the ordinate.

RECUEIL 67 (1948

D. W .v a n

140

Krevelen,

P. 1. Hoftijzer and

C. 1. v a n H o o r e n ,

However this method can only be applied when equation ( 2 ) i s

valid in the whole absorption column.
W h e n p,;

< B&r.
- --

kc

equation ( 3 ) must be used ( A , = 0).

T h e concentration course is sketched in fig. 2b.

q=;

Fig. 2b.

Extremely rapid reaction (irreversible).

concentration

Hp9

gar

,,,
L -!
-B

I
I

BI

liquid

positive direction
of diffusion

In order to represent in the same graph as used in the former cases

the absorption data of the experiments for which equation ( 3 ) is valid
in the whole column, we can apply the following method:
PlottingPG"'versus

NA

Plotting
to

,I: + Akr

1
V*

we get a line through the origin.

versus

we

vuy

obtain

an

intercept

equal

Hkr.

so that if we plot

N,versus

Q2

1 .
,,

,a j a i n

an intercept

Hkr,

is obtained.

I t is t r u e that k L itself is not known in advance, but the ratio

kc;
can always be estimated rather accuratelv.
kL

T h c iriiportancc o) this proccdurc is obrtious when in f h c column

both equations ( 2 ) and ( 3 ) arc dcfcrminatioc viz. equation ( 2 ) at
the bottom of the column and equation ( 3 ) at the top.

RECUEIL 67 (1948)
141

Studies of gas absorption.

In this case we can use as a first approximation for the driving force
the logarithmic mean value of

after which we get:

In fig. 3 all our experiments are represented.

3x10

HQm

1%

- -

rm-

VPOB

Fig. 3.

Indeed all the data give the same line: kl, can be calculated from
the intercept and k,; from the slope (see table I ) .
5. Application of the equations ( 2 ) and ( 3 ) to hydrogen
sulphide absorption in alkali hydroxide.

Also in this case the equations ( 2 I and ( 3 ) are valid. T h e important

difference with the former case is that the H e n r y coefficient is much
smaller (500 X as sinall as for NH,). T h e consequence is that HpG
can be neglected cotnpared with Bl, and that

can be neglected
kG

2
5

9 i

;8

15

0.125

8.46
8.78
7.90
8.68
8.68
1.5
3.0

8.68
7.16

0.127 18 68.10-'
0.128 3.68
0.128 t.35
5.42
0 128
0.127 1.92
3.68
0 128
3.68
0.127

111
0.128
At bottom
o,130
~ G kL
> ~ ~ B0.112
L

">kGBL

kL

j
6.25
7.60
6.07
6.33
6.32

7.53

7.12
6.46

1 7.45

i 6.22

0.767
0.646
0.850
l.( 35
, 1.745
1.96
2.24

0.462
0.368

1
'
~

,.

I,

o:io

0:iO

0.950
0.944

..
..

,,

i
I

1 1.32.10-'

*I

'

2.14
1.98

1.32

1.40

2.20
2.23
1.52
j 2.08
1.38

'

1.31
i 0.78
1 0 905
0'53
0 i34 10.83
,,
10.815

0.074

0 358
0 358
, 0.168
0.160
0.074

.. I

l:pO

5.97.10-' 11.863.10-3~ 0.10

12.16
,,
i 6.78
4.37
6 37
3.59
579
4.15
6.20
3.65
0'05
15.63
3.09

I
~

8.8.10-5
9.3

0.148
1 .t9
0.139
1.61
0.0925
1.64
0.098
2.12
1.67
0.083
0080
1 1.75
0.083
1.59

1.52.
1'51
0.895
1.04
0.61
1.98
1.94

____

mjsec

kL

T a b l e 11.
Absorption of hydrogen sulphide in sodium hydroxide solutions.
Height of column 0.15 m : diameter of column 0.029 m . packing material: glass rings 5 X 5 mm. temperature 20 OC.

RECUEIL 67 (1948)

143

Studies of gas absorption.

.

-.BLkL

- so that N,,= kLB,, as long as P,; >

If this
kL
kG
condition is no longer fulfilled equation ( 3 ) must be used.
O u r experimental data are collected in table 11. T h e experiments
can be divided into three series:

compared with

For the first series w t have: pG > BLkL in the whole absorption column.
kc
Here N A= kL(Br.),

For the second series:

PG

For the third series we have

LkL
< B kC

is valid in the whole column

so that w e have to use:

NA= kc(pG)m
T h e index m indicates the logarithmic
mean value.
BLkL

in the upper part of the

column:

p G < X *

in the lower part however:

For the upper part we use the general equation ( 3 ) :

kGPC = k L ( B L - BI).
From the first and the second series the kc-ratio can be calculated.
k I.
Then the driving force in the liquid phase at the top of the column
follows from:

(BL

BI)tCP
=

kc,
(pc) top.
kL

The
T h e driving force in the liquid phase at the bottom == (Br,),,ottom.
average driving force in the column is then nearly equal to the
logarithmic mean between ( B,, -- Bi)tc,p and ( B , ) botto,,,.
In this way the k,,-./alues in table I1 are calculated. It is obvious that
the agreement betwetzn the experimental k,,-values of the first and
third group is satisfactory (k,, is a function of I ) .

6 . V e r y rapid reversible reactions.

T h e conditions are shown in fig. 2c where also the symbols are
indicated. Generally the reaction is of the following type:

A+BfC+D
A t equilibrium

I)

A X--I3

K (the equilibrium constant).

RECUEIL 67 (1948
144

D. W . v a n Krevclen, P . J. Hoftijzer and C. J.

___-~

__~.___

v a n Hooren.

.-

In fig. 2c the concentrations of D are not drawn but the course is

quite analogous to C.
Fig. 2c. Extremely rapid reaction (revrrsihle).
concentration

ga,

~-

positive direction
of diffusion

T h e reaction takes place mainly in the extremely thin reaction zone.

However there must also be some reaction in the diffusion layers on
both sides of the reaction zone, as equilibrium is always established,
so that

ASA, > AR. C,D, must b e <

B1

BR

or

CRDR

B, < BR, C, > CR and D, >DR.

Diffusion takes place for B to the interface, for C and D from the
interface backwards.
As this effect (reaction in the diffusion layer outside of the reaction
zone) is only a small correction with regard to the reaction as a whole
we can approximate it by:

DB(BR-B,) = D-C (CR-C,) = DD- (DR-D,)

X1

XI

XI

( x l is thickness of the diffusion layer between interface and reaction

zone).
T h e rate of mass transfer of A will be:

correction due to reaction

outside the r u c t i o n zone

In the same way we have for the mass transfer of B, which must be
equal to that of A:

NA = XL- x, [(BL-BR)+(AR-AL)]
ecorrection due to reaction
outside the reaction zone

. . . .

(5)

RECUEIL 67 (1948)
Studies of gas absorption.

___

_____..

___

_____

145

From ( 4 ) and ( 5 ) xI, can be solved. Substituting k,,x,, = D gives

There are two methods for the application of this equation to the
experiments. In the first the

k-c ratio is estimated and equation (6)

kL

is solved by trial and error. This method is rather laborious. In the

second certain simplifications are applied to equation ( 6 ) after which

a mathematical solution is possible.
7.

Mathematical solution of equation 6 in some special cases.

For sparely soluble gases Ai .- A,, can often be neglected compared

with Bi, - B,. so that

= C,
B,,- B,
D, = D, -t B,, - B, gives
KA,B, = CLDL CLBL DLBL BL-B,(CL

Substituting C,

+ DLf 2 BL)+ BIZ

Now the following approximations can be made:

First approximatiort B,* zz 0.

- ~ _ _ _CLDL
____

_.

+ +

CL DL

DLBL
f BL
CLBLf - 2 BL K H ~ G KHNA
kc

After some rearrangements we find:

kL

where: P = N , ( C , , t D,, t 2 Bi,

Q = KHN,?
R - (BL
C:,,Di,
S = KHN,B,,

Pkc- Q
. .
Rkc-s

. . .

. .

(7)

+ KHp,,)

+ KHp,,BJ

Second approximation BIZ - B,2 2: 0.

In this case we find the same expressions for k,, P, Q and S, but R
becomes:

KHP,,B,, - C , D ,

2
5
6
7
8
9
10
11
19
20
22
23
24
25
26

Run

13 16.10-3, 3.36.10-3'
5.22
1.47
6 55
1.99
6.15
1.59
0.645
5.80
0.722
l 5.95
1.81
6 43
1.13
'
6.45
0 581
5.01
72.2
85 0
84.5
92.2
85.0
93.4
43 2
52.5
30.7
40.7
7.52
15.4

0.289
0.20 1
0 106
0.0735
0.0675
0.106
0 143
0.0675
0.248
0.205
0.248
0.203
0.143 , 0.100
0.182 I 0.137
0 165 ' 0.124
0.059
0.165
0.073
0. I 50
0.150
0.0685
0.150
0.062
0.052
0.150
0.0765
0 150

kgmol/
m3

I::

3.96.10-'~ 4 15 lo-'
1.51
0.635
1.79
085
1.77
0.795
1.98
1.37
2.05
1.44
2.19
2.12
0.895
1.79
26 4
4.83
20 4
3.36
3.56
3.86
4.17
3.20

sec m2

kgmoli

B = NH,
C = HSD = NH2

10 3.10-i'
1.48
i 2.10
2.06
2.57
2.76
3 14
2.95
2.11
15.3
7.4
9.1
9.8
11.4
67

'

16.3.10-2
2.52
0.88
2.82
1.oo
2.60
0.99
9.3
2.94
9.4
3.03
4.66
1.72
' 2.22
5.95
I 1.70
4.31
52.5
3.26
62.1
2.36
60.1
2.43
31.3
12.54
21.4
2 54
2 29
I 87
1

5.36
5.82
6.12
4.24
4.36
5.65
529 .
5.50
6.64
4.31
4.76
5.65
6.90
5.92

' kgmol/m'
s catm

T a b l e 111.
Absorption of hydrogen sulphide in ammonia liquor.
Superficial gas velocity = 0 30 m/sec
Height of column = 0 285 m
Superficial liquid velocity = 1 4 10-3 mjsec
Diameter of column = 0 027 m
Temperature = 2OoC
Packing material: glass rings 5 X 5 mm
KH = 65 kgmol m3 atm

4.44.10 4.09
4.44
4.67
3 24
3.33
4.31
4.01
4.20
5.07
3.29
3.63
4.31
5.27
4.52

kL
mjsec
____

..

,,

1 2.00

2 62

122 6.30

123 5.30
124 6.34

121 6.43

0.681

0.758

0.454
1.362
1516

0.908

0.758

0.606

0.303

0.379

0.254

0.152

~~-~

0.227

0 076

~~

0253

I 0258

0.248

0.247

,.

..

0247

0.242

0247

.,

..

175
2 08
2 14

0.288

120 6.19

166

118' 5.99.103

119 6.32

- - --

1113

m3

D L ~
kgmoli

kgmol

N HilzS01

1.550

0.948
1.392

0.799

0.295
0.647

1.689

00345 1.421

0.0402 1.658
0.0296 1.221

I 0.0410

.-

..

...

~~

~~

~~

R ,_ _

kG
kgmol/
m*atm sec

2 97
2.69

2.75

1.88
2.47

1 3.42

2.10
2.08

1 1.47

2.09

8.24

7.94
8.41

8.30

2.43

3.24

3.29

3 29
3.30

I280

'

6.4
6.65

6.95

5.65
6.65

kL
m/sec

iI

6.95
7.25

6-15
7.25

8.5.1W

~___

'
1
1
1 1
S

mjsec

1.919.10-7, 1.85.10--'I 2.69.10-1z, 6.52.10~ 3.71.10-6' 7.8.10-51

1.692
0.0411 '1.694

I 0.0410

kgmoli
sec m2

1 P
!
_I--._ _ _ ~I ~

NA

Superficial gas velocity = 0.31 m/sec

Superficial liquid velocity = 1.4.
Temperature = 2OoC
K i i = 73 kgmoijmj atm

B = NH3
C = HSD = NH,+

m3
-_____
.I- m3
0.198 1 00462

Diameter of column = 0.026 m

Packing material: glass rings 5 X 5 mm

Height of column = 0.31 m

---I0 9 0 lo3

______

T a b l e IV.

Absorption of hydrogen sdphide b y ammoniacal ammonium sulphate solutions

RECUEIL 67 (1948

D. W .v a n

148

Krevelen,

P . J. Hoftijzer

and C. J. v a n

Hooren.

Table
Absorption of hydrogen sulphide in sodium
Packing material : glass rings 5 X 5 mm

Height of column = 0.15 m

Diameter of column = 0.030 m

B =C 0 3 ~
C = HS-

-- - 1

VG

Run

PGo
atm

rnlsec m/sec
__

D = HC0.rPGe

B L ~

atm

qmol/m3

. -~
-

~~

rgmol/sec

10-4

10-3
I 0.116 8.8 4.80
2 0.116
8.7 4.50
3 0 112
8.2 5.60
4 0.116
8 5 5.30
5 0.108 7.8 4.60
6 0.I08
9.3 4.80
7 I 0.107
8.5 4.60
8 0.157 8.5 4 84
9 0.109 8.1 9.70
10 '0.105f 12.6 5 00
1 1 /0.118 9.1 4.35
12 0.112 8.6 4.70
13 0.118 18.1 4.50
14 0.121 37.6 3.80
15 0.113 8.5 4 84
16 0.115 7.4 5.77
17 0.114 8.3 8 80

- --

0.90
I .50
1.20
0.90
1.10
0.84
1 .80
2.05
4 60
2.50
1.65
120

0.190
0 095
0.190
0.380

0.169
0.0212
0.0785
0.0167
0.165 I 0.0252
0.355 i 00250
0.360 1 0.0201
0361 I 0.0191
0.080
0.0149
0.0735
0.0215
0.0665
0.0865
0.0087
0.0805
00285
0.0145
0 361
0.0190
0.086
0 0089
0.0043
0 0905
0.0203
0.I70
0.0725
0.0227
0.0269
0.0131
~

0.095

0.380

,i

0.58
1.15 i
2.20
6.50

'1

0.0212
0.0167
0.0252
0 0250
0.0201
0.0191
0.0I49
0.021 5
0.0285
0.0087
0.0145
0.0I90
0.0089
0.0043
0 0203
0 213
0:3 13

0.ibO

0.095
0.040

Height of column = 0.085 m

Diameter of column = 0.032 rn

-.

0.190
0.300

-~___

.~---

I 0-7
1.12
0.87
1.23
1.27
0.94
1.06
0.755
1.10
1.38
0.655
0.79
0.975
0.965
0.97
1.04
1.01
0.65

Table
Absorption of hydrogen sulphide in sodium
Packing material: glass rings 5 X 5 ma

B= C03=C = HSD = HC03I

D L ~ I' DL?
NA
BL=
kgrnol/rn3 kgmol/m3 i kgmol,'m3 kgmol/m3 kgmol/m3 ' k g mol/sec
m*
!
_ B L ~I

BL~

2
3
4
5

0.194
0.163 ,
0.215 1
0.200
0.180 !
~

1.46
1.78
1.72
1.61
1.28

___ -

10-3
1.20
2 42
7.63
2.90
2.54

0.39
0.84
4.35
1.50
1.43

0.1885 1 0.184
,.
0.1825
0.1713
0.1446
0.1373
.,
0.1381

I
~

0.0045
0.0060
0.0172
0.0073
0.0065

-1

0.0045
00060
0.0172
0.1061 j 0.1134
0.1I26
-

,. I

I 0-7
0.700
1.145
3.16
1.263
0.892

SOO'O
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9'ZI
2-01 rl-01

b9'E
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b9 6
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LS 8
Zl'b
IZ'L
8-0 I

..

._

6E'L
E9'L
18'9

LbZ

*Is

II

j,
I11
:Z'il

,
SIZO'O 1065.0
SbZO'O 80'Z
610'0 I 61'5

100
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~

RECUEIL 67 (1948)
150

D. W . van

Krevelen,

_____

-.

P. J. Hoftijzer

C . 1. van Hooren,

and

_ _ .___

Third approximafion Bi2 = 0 at the bottom, BIY-Bi2 = 0 a t the top.

Sometimes at the bottom of the column the first approximation can
be used, but a t the top the second must be applied. In this case the
average R resulting from the values of both approximation methods
is used.
T h e solution of equation ( 7 ) is relatively easy when experimental
series a t equal gas and liquid velocities are available. T h e n from the
experimental data the average values of P, Q, R and S are calculated
(averaged between the values a t top and bottom).
W h e n the

kc
ratio ( = q ) can be estimated, k ,
kL
-

is found by

substitution:

kL = s
__
W h e n the

kG

+ Pq + q s t Pq)" T Q R q
~

2-Rq

-ratio-estimation would be difficult the equation can

-~

kL

be solved by a graphical trial and error method.

After estimation of k, we calculate y = Rk,; -S and x = Pko-Q.
Plotting of y against x must give a straight line through the origin it
the estimation of k, was correct. In most cases two or three estimations
of the k,-value are sufficient in order to make a n accurate interpolation.
W h e n no series a t equal gas and liquid velocities are available the
following method may be used.
T h e dimensionless equations for k, and kL are:

SO

that kc = c , T and

kL = c2 w

(-i-J (&) '

D vdp'08

where T = 3

/3

and 21' =

D !Lp)2h (
yQz2Y
I,D
-

ap

NOW:P' = Py
Q=Q
R ' = R VY.'
S' = sy,
(P. Q. R, S are calculated from the experimental d a t a ) .

,LL j''3

RECUEIL 67 (1948)
Studies of gas absorption.
_

T h e n c2 =

151

~~

Pq-Q

Rc, -S *
T h e performance of the calculation of cp is similar to that of k, in
the former case.

8. Application of equation (7) t o experimental data.

a ) Hydrogen sulphide absorption in ammonia solutions.
In table I11 the experimental data are represented.
In this series gas and liquid velocity were kept constant throughout
the whole series. Only the partial pressure of hydrogen sulphide and
the concentration of ammonia have been varied.
It proved that B, could always be neglected so that the first
approximation method was used. T h e average deviation in the
calculated k,,-values ( t h e results are given in table 111) is about 12 p .
In the calculation we used the equilibrium constant of the reaction:

H,S

+ NH, f HS

-t NH,

+ ,

b ) Htjdrogen sulphide absorption in ammoniacal ammonium sulphate

.solufioris.
Also in this series ( t h e results of which are given in table IV) gas
and liquid velocity were kept constant. Due to the effect of the
ammonium sulphate Po,? could not be neglected at the top of the column
so that the third approximation method was used.
T h e value of KH has been increased to 73 kgmol m 3 atm 1 due to
the increased ionic strength.
T h e average deviation in the calculated k,,-values is only 6 rh.
c ) Hydrogen sulphidc absorptiori in sodium carbonate-bicarbonate
solutions.

T h e experimental results are given in tables V and VI.

Gas and liquid velocities were not constant in these series, so that
c, and c2 had to be calculated. Bi could not be neglected. T h e third
approximation method was applied.
For the reaction I-I!,S 4- CO:,= 2 HS HC0,-- the equilibrium

constant KH =

(HS--)(HC03-)
tc(33-)PH2S
~

100 kgmol m

atm-1 was used.

T h e results are s a k f a c t o r y again. T h e average deviation in the

k,,-values is about 15 /c.

R E C U E I L 67 (1948

152 D. W. van Kreoelen, P . 1. H o f t i j x r and C. 1. van

-

____

Hooren, Studies, etc.

__-__

L E T T E R SYMBOLS.
m-.l
wetted area per unit volume . . . . . . . .
concentration of solute gas . . . . . . . .
kgmoles m--
concentration of reactive liquid component , . .
kgmoles m--S
dimensionless constant . . . . . . . . . .
id.
in dimensionless k,;-equation
id.
in dimensionless k,,-equation
packing diameter . . . . . . . . . . . .
m
diffusivity
. . . . . . . . . . . . . .
m2 secacceleration due to gravity . . . . . . . .
m s e c -:
Henry coefficient . . . . . . . . . . . .
kgmolrs m a atm-1
equilibrium constant . . . . . . . . . .
overall absorption coefficient . . . . . . . . . kgmoles sec -1 m -2 atm- 1
mass transfer coefficient in gas phase . . . . . kgmoles sec- 1 m-? a h - -
mass transfer coefficient in liquid phase . . . .
m secl
reaction velocity coefficient . . . . . . . .
kgrnolesr m3 sec-1
superficial liquor rate (mass) . . . . . . .
kgsec-1 m--L
superficial liquor rate (volume) . . . . . . .
m sec--
kgmolrs scc 1 m -:
rate of absorption . . . . . . . . . . . .
partial pressure . . . . . . . . . . . . .
atm

ratio kc
-

kt.

overall driving force

velocity . . . . . . .
film thickness . . . . .
R. S. P, Q, R. S, x, y
viscosity . . . . . . .
density
. . . . . . .

. . . . . . . .

8ec-l

. . . . . . . .
=

calculation factors

. . . . . . . .
. . . . . . . .

kg m

sec
kgm

Indices (Subscripts).

unit surface
gas
interface
liquid
logarithmic mean
reaction zone
inlet (initial)
outlet (end)

(Receiued Ocfober 16th 19.t7).

-I

-a