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NAME AND ADDRESS DATE

 NORTHWESTERN UNIVERSITY

“GAS ABSORPTION"

A STUDY OF THE VARIABLES AFFECTING

MASS TRANSFER

A DISSERTATION

SUBMITTED TO THE GRADUATE SCHOOL IN

PARTIAL FULFILLMENT OF THE REQUIREMENTS

for the degree

DOCTOR OF PHILOSOPHY

DEPARTMENT OF CHEMICAL ENGINEERING

by

HAROLD ARTHUR BLUM

EVANSTON, ILLINOIS

JUNE, 19 50.
 ProQuest Number: 10060983

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For her patience and encouragement

this dissertation is dedicated to

my wife.
 ACKNOWLEDGEMENT

The author thanks Dr. L# F* Stutzman for his encouragement and

guidance. He also wishes to express appreciation to his colleagues,

Howard A. Koch, Jr., Le Roi E. Hutchings, Wayne S. Dodds, Thomas A.

Peake, and Paul G. Reis for their critical review and aid in the pre­

sentation of this dissertation. Finally the author wishes to thank

the United States Office of Naval Research for making this work possi-

ble.
 TABLE OF CONTENTS

Acknowledgement

List of Tables and Illustrations • • • • • • * • « « » • • • • 3

Nomenclature • • • • • • • • • • • ....... • • • • • • • • • • U

Summary................................................... 7

Part I - Absorption of Carbon Dioxide from Air by Alkaline

Solutions • © ....... ....................... 7

Part II - Gas Film Transfer Coefficient • • • • ........ 7

Historical ...................... ©9 . •

Part I - Absorption of Carbon Dioxide from Air by Alkaline

Solutions

Introduction • • • » .......... ...... 9

Film Theory ......... . 9

Packed Tower Absorption « ............... 11

Theoretical............. .............. 13

Part II - Gas Film Transfer Coefficient

Introduction • • • • • • • • • • • • « • * « 1$
Diffusivity , . . . ..................... 15
Two Film Theory * • ..................... 15
Evaluation o f k a ....................... 16
g
Effect of Variables o n k a . © . . © * . © . 17
g
Generalized Correlations • • • ....... • • 20
Statement of Problem « • • • • . . . • ........ . . . . . . . 22

Part I - Absorption of Carbon Dioxide from Air by Alkaline

Solutions ................... . . . . . . . . . 22

Part II - Gas Film Transfer Coefficient.............. . 23

Experimental . . . ....................... .............. 25
Part I - Absorption of Carbon Dioxide from Air by Alkaline
Solutions
 Introduction . . . . . . .................. 25

Equipment • ..................... . . . . . 25

Flow System ........... 27

Experimental Procedure 30

Analysis of Gas and Liquid................. 30

Experimental Data .......................... 31

Part II - Gas Film Transfer Coefficient

Equipment • 40

Experimental Procedure ..................... 42

Equilibrium Data ......... 43

Experimental Data • * . * . . ................ 4-3

Correlation and Interpretation of Data • • . • • • • • • • • • • • 4-6

Part I - Absorption of Carbon Dioxide from Air by Alkaline

Solutions

Introduction • • • • © ..................... 46

Correlation of Overall Gas Transfer Coefficients46

Use of K* as Correlating Factor . . • • • • • • 5 3

Interpretation of Data © ............. 57

Part II - Gas Film Transfer Coefficient

Effect of Liquid Rate • • • * . • • • • • • . . 68

Generalized Correlations • • • • • • • • . . . .72

Conclusions • • • • • • • • . . .......... . . • • • • • • • • . 78

Part I - Absorption of Carbon Dioxide from Air by Alkaline

Solutions • • • • • • • • • ..................... 78

Part II - Gas Film Transfer Coefficient.................. . 7 9

Bibliography • ..... 81

Appendix

Development of A Gas Film Transfer Coefficient (k a) . • * . 84.

S
 *>
Relationship between Overall Transfer Coefficient (Kga) and
Film Transfer Coefficients k a and k_ & • • • • • • • • • • • 86
g 1
Use of Log Mean Driving Foice for the Calculation of K a in
the absorption of Carbon Dioxide from Air by Sodium Snd Po­
tassium Hydroxide Solutions ............................ 87

Use of Log Mean Driving Force for Calculation of k a in the

vaporization of pure liquids * * ............. g............ 88

Gilliland Equation and Application to This Study • • • » » • * 89

Characteristics of Ceramic Raschig Rings 92

Sample Calculations * ....................................... 93

V i t a ............................................................ 97
 TABLES

I* Estimated Errors of Experimental Measurements..............32

II. Absorption Data - Carbon Dioxide from Air by Alkaline Solu­

tions .............................. 34

III. Deviations from Correlation . * ........................... 56

IV. Solubility of Carbon Dioxide in Various Salt Solutions . . . 62

V. Data on Vaporization of 1-Propanol into Some G a s e s ......... 45

VI. Calculated Vaporization Data for the Van Krevelen-Koftijzer

Correlation * • • • • . . ............. . . . 73

VII. Calculated Vaporization Data for the Koch Correlation . . . 75

VIII. Physical Constants for Air, Carbon Dioxide, and Helium . . . 76

ILLUSTRATIONS

1. Absorption Apparatus (Glass Tower) Flow Sheet ............ 26

2. Absorption Apparatus (Steel Tower) Flow Sheet • • • • • • • • • 28

2a. Absorption Apparatus (Vaporization of 1-propanol).............. 41

3* K a versus L - Steel Tower ....................... /$

g
4. K a versus L - Glass T o w e r .......................... 49
.
g
5. K a versus L - Potassium Hydroxide - Steel Tower.......... 50
g
6. K a/ ••^versus L - Effect of Carbonate Concentration .......... 51
g y
7. K* versus L - Air-Carbon Dioxide-Hydroxide Solutions . . . 55

8. C versus /u1 ............................... .... 60

9* k a versus L (air, log mean driving force)• • • • • . . • • 69

g
10. k a versus L (air, arithmetic mean driving force).. 70
g
11. Atomic Volume versus Atomic Weight • ......... . . . . . . . 91
 NOMENCLATURE

A packing area - sq. ft,

a transfer area (specific) sq, ft./cu.ft.

a^ Dry actual specific packing area area of packing/ volume of packing

C C - a(pure water)/a(solution) (Table IV)

Concentration of carbon dioxide in liquid (Equation 2)

c1^ Average concentration of reactive component (lb, moles/cu. ft,)

D Diffusivity of diffusing component in gas (ft.2/hr.)

G
Dl Diffusivity of diffusing component in liquid (ft.2/hr.)

d Diameter of packing (ft,) or equivalent diameter of sphere having

same surface area as packing

G Total gas rate (lb. moles/hr, sq, ft.)

G1 Inert gas rate (lb. moles/hr, sq. ft,)

g acceleration of gravity 32.2 ft./sec2

h height of packing (ft.)

H HenryTs Constant (y/x)

K a Overall gas transfer coefficient (lb. moles/hr.-cu.ft.-atm.)

6
»1,0^ x, _ x
K* Defined as NA fj /h(OB“)(CO^)

kj First order reaction velocity constant

kjp Second erder reaction velocity constant

k Gas film transfer coefficient (wetted wall column) lb. moles/hr.-sq.ft.-atm.

k^ Liquid film transfer coefficient (wetted wall column) lb.moles/hr.-sq.ft.-

lb. moles
cu.ft.

k a gas film transfer coefficient (packed towers) lb.moles/ hr.-cu.ft.-atm

0
k a liquid film transfer coefficient (packed towers) lb.moles/hr. cu.ft. lb.moles
1 cu.ft.
L Liquid rate (lb* moles/hrv-sq. ft.)

Mm mean molecular weight of inert gas

N Normality of solution (Equivalents per liter)

N moles transferred (lb. moles/hr.-sq. ft*)

P Total pressure (atm.)

p<l partial pressure of diffusing component at the bottom of the column

(atm.)

p2* partial pressure of diffusing component at the top of the column (atm.)

vapor pressure of diffusing component at the bottom of the column

(atm*)

p2^ vapor pressure of diffusing component at the top of the column (atm*)

q Hydroxide ion concentration Equation 2

x. Concentration of diffusing component at the interface of the liquid

1 film, (mole fraction)

x^ Thickness of liquid film (ft.)

y mole fraction of component in gas

y mole fraction of diffusing component at the interface of the gas film

i
y-i mole fraction of diffusing component in gas at the bottom of the tower

y2 mole fraction of diffusing component in gas at the top of the tower

y mole fraction of diffusing component in equilibrium with main body of

liquid

Y-j mols of diffusing component in gas at bottom of tower per mols of inert
gas

Y 2 mols of diffusing component in gas at the top of tower per mols of inert
gas

A Y (Y2 -Y,)

(0H“) Arithmetic average (top and bottom of column) normality of hydroxide

(COj) Arithmetic average (top and bottom of column) normality of carbonate

fji viscosity of gas (lb./ft.-hr.)

jLt* ionic strength 1/2 cz2), where c is arithmetic average concentration

(moles/liter) and z is charge on the ion
/° Density (lbs./cu. ft.)

f>% Density (lb. mols/cu. ft.)

 SUMMARY

I* Absorption of Carbon Dioxide from Air by Alkaline Solutions

A study was made of gas absorption where chemical reaction is in­

volved. The systems studied were air-carbon dioxide-sodium hydroxide

(solution) and air-carbon dioxide-potassium hydroxide (solution). A

glass column (3 inch diameter) and a steel column (A inch standard) were

employed in which packing heights varied from 2.8 to A*33 feet. l/A*

3/8, and 1/2 inch ceramic Raschig rings were used. Liquid rates varied

from 13 to 185 lb. mols/hr*-sq. ft. and gas rates ranged from 2.9 to 18

lb. mols/hr.-sq. ft. Mol fractions of carbon dioxide in air entering the

column were between 0.03 and 0.28. Normality of hydroxides entering the

system varied from 0.07 to 3*90, while the average (arithmetic) carbo­

nate concentrations ranged from 0.02 N to 0*65 N* The pressure on the

towers for all runs was essentially atmospheric and the gas and liquids

were in general within 5°F of room temperature. A mechanism for this

absorption is proposed and the use of the overall gas transfer coeffi­

cient (K a) for correlation in this study is discouraged. The 191 runs

presented are correlated in the following equation.

N = K*h (OH")(COp
A

where K* = 0.0176L

II* Gas Film Transfer Coefficient

A study was made of the effect of liquid rate, gas rate, and inert

gas on the gas film transfer coefficient, k a. Experiments were run for

the vaporization of 1-propanol into air, carbon dioxide, and helium. A

2.75 inch I. D. pyrex glass column, packed with 6 mm. beads to a height
of 0*198 feet, was used. Liquid rates varied from 0*9 to 26.8 lb. moles/

hr.-sq. ft. and gas rates ranged from 2.5 to 17.9 lh* moles/hr.-sq. ft.

It was found that as liquid rate increases k^a increases at low

liquid rates* At higher liquid rates (below flooding), however, there

is no appreciable increase of k a with increase of liquid rate. The

B
Van Krevelen-Hoftijzer equation1 which correlates transfer area with li­

quid rate was an improvement over previous work but was far from satis­

factory in this respect.

The effect of inert gas on k a was predicted by two generalized

o
correlations although air was the only inert gas used before this study.

The Van Krevelen-Hoftijzer correlation1 fits the data remarkably well in

form considering the large variation in the properties of the gases used.

On the other hand the correlation of Koch2 did not fit the data satisfacto­

rily in this respect.

While it was possible to study the comparative effects of liquid

rate and inert gases on k a, the absolute values of k a should not be

considered as final since end effects are probably significant in this

study.

1. Van Krevelen, D. W., and Hoftijzer, P. J., Chem. Eng. Prog.. AA, 529-
536, I948.
2. Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern University,
(1949).
 HISTORICAL

Absorption of Carbon Dioxide from Air by Alkaline Solutions

INTRODUCTION - Several investigators have studied the absorption of

carbon dioxide by caustic solutions. The true mechanism of this re­

action has not been determined since the effects of physical diffu­

sion and chemical reaction are difficult to separate. For example,

if the concentration of the base is increased, the rate of chemical

reaction will increase but the viscosity will also increase thereby

decreasing the ease of the diffusion of molecules. Sherwood in his

book1 reviews the work done in the field up to that time. This work

and the more recent investigations are summarized here.

FILM THEORY - The basis for the theory on gas absorption and chemical

reactions was postulated first by Brunner2 who pictured a double film

in the liquid in which the reacting gas molecule dissolves, passes

through a liquid film, and finally reacts in another film with the re­

acting molecule contained in the solvent. This reacting solvent mole­

cule comes from the main body of the liquid. The product (assumed

non-volatile) moves into the main body of the liquid. Weber and

Nilsson3, Hatta*, and Davis and Crandall5 extended and developed this

concept further.

1. Sherwood, T. K., Absorption and Extraction. McGraw Hill, New York,

1937.
2. Brunner, E. Z., Phvsik. Chem.. A7. 67 et seq. (190A)«
3* Weber, H. C., and K. Nilsson, Ind. Eng. Chem.. 18. 1070 (1926).
A. Hatta, S., Tech. Rep. Tohoku Imp. Univ.. 8 , 1 (1928-1929).
5 . Davis, H. S., and Crandall, G. S., Am. Chem. Soc.. 52. 3757,
3769 (1930).
 Assuming that the equation representing absorption of carbon di­

oxide by sodium or potassium hydroxides is of the form

A + B -«► AB (i)
An equation was developed (1) which assumes equal molal diffusion rates

in the liquid:

where D is the diffusivity, x^ the thickness of the liquid film, Ci the

concentration of carbon dioxide in the liquid, and q is the OH concen­

tration in the main body of the liquid*

This equation was partially supported in batch experiments where

the carbon dioxide pressure was one atmosphere and the normality of the

base was not greater than two1. Above two, the rate of absorption falls

off. This fact was likewise noted by the batch experiments of Mitsukuri2

and Ledig and Weaver3.

Hatta^ found when using air-carbon dioxide mixtures that the rate

of absorption is proportional to the residual base concentration under

large gas concentrations of carbon dioxide but this was not true when

the concentrations of gas ranged from 2 to 38 per cent. He explained

his results on the basis of the two zone film theory previously men­

tioned* The reactions which he believed important are:

C02 + OH" HC03“ (3)

HC03“ + OH = H20 + C03^ (4)

1. Hitchcock, L. B., Ind. Eng. Chem. 2£, II58 (1934-).

22, 461 (1935).
27, 728 (1935).
Trans* Am* Inst. Chem. Eng*. 36, 347 (1935)*
2. Mitsukuri, S., Sci* Ren. Tohoku Imp. Univ.. 18, 245, (1929).
3 . Ledig, P. G*, and E. R. Weaver, Am. Chem. Soc.. 46. 65O, (1924).
4 . Hatta, S., Tech* Rep. Tohoku Imp. Univ., 8 , 1 (1928-1929).
 The latter equation is supposedly the rapid reaction$ therefore,

the first equation represents the rate determining chemical step.

According to Hatta1 the gas film resistance is controlling or Kg, the

gas transfer coefficient, is independent of normality and other condi­

tions of the liquid. Jenny2 presented data on the absorption of car­

bon dioxide from air by sodium hydroxide which disagreed with that of

Hatta1• He claimed that the liquid film is important since Kg is lower

than that of ammonia for the same apparatus. In his experiments he

found as Hatta Kg independent of normality between 1 and 2N, but there

was a definite effect on Kg below IN. Jenny2 thought that the main

error in the Hatta1 theory lay in the assumption that the reaction

was instantaneous in the film. Sherwood3 concluded that until more

is understood about the mechanism and kinetics of the reaction between

carbon dioxide and caustic, the real understanding of the absorption

process will have to be postponed.

PACKED TOWER ABSORPTION - Tepe and Dodge^ in a flow system studied the

effects on Kga of sodium- hydroxide and sodium carbonate concentrations in

the liquid, gas and liquid rates, and liquid temperature. They studied

this absorption of carbon dioxide in a six inch diameter column packed

with half inch carbon Raschig rings. It was found that Kga increased

with increasing normality up to a sodium hydroxide normality of two

and decreased when the normality was greater than two. They also found

that Kga decreased linearly with sodium carbonate concentration, in-

1* Hatta, S., Tech.Rep. Tohoku Imp. Univ., 8, 1 , (1928-1929).

2. Jenny, F. J., Thesis, M. I. T., 1936.
3. Sherwood, T. K., Absorption and Extraction. McGraw Hill, New York,
1937.
£. Tepe, J. B., and B. F. Dodge, Trans. Am. Inst. Chem. Eng.. L2. 827-
m > (1946).
 1

creased to the 0.28 power with liquid rate, and increased with the

sixth power of the absolute liquid temperature. The effect of gas

rate was found to be negligible. Their data was correlated graphi­

cally. It was concluded, contrary to Hatta*s1 work, that the gas

phase resistance 'is negligible and that the values of the overall

coefficients are higher than those reported for absorption of car­

bon dioxide in aqueous solutions of either sodium carbonate or die-

thanolamine. Spector and Dodge* studied the removal of carbon di­

oxide from atmospheric air by aqueous caustic solutions. They em­

ployed a twelve inch diameter tower, used 3/ 411 Raschig rings and 1"

Berl saddles, and packing heights of 7.8, 16.0 and 10 feet. The

data were represented by equations of the form

log Kga *= 0.20 log L - K (5)

They found that Kga increases with the gas rate to the 0.35

power for rates up to 500 lb/hr/sq.ft. and to the 0.15 power at flow

values around 1000 lb/hr/sq.ft. Studies on potassium hydroxide so­

lutions gave values of K a 20 to 30 per cent greater than those for

an aqueous sodium hydroxide solution of equal normality at the same

operating conditions. The effect of pressure was determined and it

was found that Kga decreased to the 0.5 power of the absolute tower

pressure. Their results indicate that Kga is approximately 20 per

cent higher with a packed height of 7.8 feet than a height of 16 feet

whereas K ga is slightly lower for a packed height of 10 feet compared

to the height of 16 feet. In discussing the mechanism, Spector and

1* Hatta, S., Tech. Ren. Tohoku Imp. TJniv.. 8, 1 (1928-1929).

2. Spector, N. A. and B. F. Dodge, Trans. Asu Inst. Chem. Eng.. 42.
827-848, (1946).
Dodge stated that it was necessary to use overall absorption coeffi­

cients to calculate the performance of absorption equipment since

nothing is known about the transfer mechanism in the liquid phase.

The fact that Kga varied to the 0*35 power of the gas rate instead

of the 0.8 power indicated to.the authors that this is not a system

where the gas film controls, but that it offers considerable resist­

ance to transfer.

THEORETICAL - Van Krevelen and Hoftijzer* derived the following equa­

tions for absorption in packed towers

M = c (_2_) °*8 (— tL_)V3

■f- ( ) (/OD ) (6)

kL( e*/>) = C» ( L )2/3 (__tt)l/3

D ( sfx ) {pn ) (7)

Stationary diffusion through a stagnant liquid film can be des­

cribed by

N = _D_&C
A at (8)
where D = diffusivity

= thickness of layer

AC = driving force (concentration gradient through the

layer)

For chemical absorption and a first order reaction, the following

equation was derived by Hatta2

-A ■ * 4 ° !
[ W h ^ j (9)

1 , Van Krevelen, D* W. and P. J* Hoftijzer, Chem. Eng. Prog.. AA.

529-536, 19/18 .
2. Hatta, S., Tech. Rep. Tohoku Imp. Univ.. 10. 119, (1932).
The difference between the physical diffusion and chemical absorption

is the factor in brackets in equation (9)*

By analogy a semi-empirical equation was developed for packed

towers even though there is no stagnant layer and though the probable

mechanism of the reaction is more likely second order rather than

first. This equation considers the effect of chemical reaction as

well as physical diffusion

1/3 ^ -1 0£)l/3 (kXI c 'r )1/2

( gf>2) = C'( L )2/f (u±/3 (gtf (----— )
kL
D J (ui) ( k n c O l / 2
tan h( gfi ( p ) (10)

The advantage of this equation is that it reduces to that of physical

diffusion in packed towers when kjj c1^ approaches zero. When kjj cTR

is relatively great, the "chemical group" becomes approximately

(tsL)V3
(uD- (kn c 'r )1/2
igfl*)
( D )
so that the rate of absorption will be proportional to the square root

of the concentration of the reactive liquor component. In considering

the absorption of carbon dioxide by sodium hydroxide Van Krevelen ard

Hoftijzer claimed the determining reaction was

C02 + OH” HC03~ (11)

They used the data of Tepe and Dodge1 and reaction velocity constants

of Payne and Dodge2# The ir constant was calculated and averaged 0,0189

with an average deviation of 22 per cent.

While there have been several reactions postulated concerning the

1# Tepe, J, B* and B# F, Dodge, Trans, Am, Inst. Chem. Eng,. 42. 827-
848, (1946).
2. Payne, J, W# and Dodge, B. F ., Ind. Eng# Chem.. 24. 630 (1932).
chemical absorption of carbon dioxide by alkaline solutions1, there is

no general agreement concerning the mechanism or kinetics of this pro­

cess#

2# Gas Film Transfer Coefficients

INTRODUCTION - kga, the gas film transfer coefficient used in absorp­

tion calculations, corresponds to conductance (the reciprocal of re­

sistance) in electricity. It was developed to facilitate design of

commercial gas absorption units. This coefficient is used in the foll­

owing equations

Na = kga h P(y - y±) (12)

The design problem usually involved is to find h, the height of the

packed section in an absorption tower.

DIFFUSIVITY - Equation (12) was developed from the basic diffusion

equation of Maxwell2 and the simplification of Stephan3 (See appendix

"Development of kga"). In this development an important characteristic

of a substance is defined, namely the term "diffusivity" (D). Quali­

tatively this term is a measure of the tendency of one substance to

diffuse into another. This term is not limited to gas diffusing in gas

but applies to other diffusion phenomena such as liquid-liquid, solid-

solid, and gas-solid diffusion. Gas diffusivities for some substances

are known and can be calculated for others4'.

TWO FILM THEORY - The term "gas film" in gas absorption comes from the

-^widely accepted "two film" theory of Whitman5. This theory hypothesizes

1. Payne, J. W. and Dodge, B. F., Ind. Eng. Chem.. 24. 630, (1932).
2. Maxwell, J. C., Phil. Trans. Roval Soc.. 157. 49* (1866).
3* Stephan, J., Wien Akad. Sizungsber. 63* (1871).
4. Gilliland, E. R., Ind. Eng. Chem.. 26 . 681, (1934).
5. Whitman, W. C., Chem. Met. Eng.. 29."No. 4, July 23, (1923).
eume chanism of mass transfer in gas absorption, in which two stagnant

films are in contact with each other (a gas film and a liquid film)*

The diffusing gas passes through the gas film across a gas-liquid

interface, through the liquid film, and finally into the main body of

the liquid* Most of the resistance to transfer occurs in these films.

Thus the reciprocal of the resistance across the gas film is called

kga, the gas film transfer coefficient.

EVALUATION OF k a - In most gas absorption work, it is not possible to

evaluate kga directly because the composition of the diffusing comp-

nent at the gas-liquid interface (yjJ is a function of the composition

of that component in the liquid film (x^)* Neither of these can ordi­

narily be obtained experimentally$ therefore, use is made of an overall

gas transfer coefficient (Kga) which is a conductance type term that

includes both liquid and gas film resistances. Instead of y^ in equa-

sk
tion (12) y is used (composition of gas in equilibrium with the main

body of liquid)*

Na = Kga P h(y - y* ) (13)

A relationship has been established between the overall gas transfer

coefficient and the gas and liquid film coefficients. Where Henry*s

Law applies the following equation applies (See Appendix "Relation be­

tween overall gas transfer coefficient and individual film coefficients1')

1 = H + 1
Kga P kiap' k a P (14)

The two terms on the right hand side of equation (14) might be

considered as the liquid and gas resistances respectively. In order to

study the effects of vard^ables on k^a, the liquid resistance term must

be negligible, or, there must be no liquid film such as in the ease of

vaporization of pure liquids into an air stream. In these two cases

the gas film transfer coefficient is equal to the overall coefficient.

Effect of Variables on kga

The variables affecting kga which have been investigated are gas

rate, liquid rate, gas diffusivity, humidity, packing size, and tempera­

ture.

The effect of gas rate on kga has been widely investigated. Has-

lam, Hershey, and Keani found that k varies as the 0.8 power of the
§>
gas rate in their studies of the absorption of ammonia and sulfur di­

oxide in a wetted wall column. Cogan and Cogan2 report the same expo­

nent in their studies of ammonia absorption. Hollings and Silver3,

however, found that for ammonia absorption G is raised to the 0.6 power.

In a spray tower Haslam, Ryan, and Weber'*’ report that kga varied to the

0.8 power of gas velocity (linear). Ammonia absorption in a spray tower

gave the same results for G in one case^ while in another6 kga varied

G to the 0.7 power.

In a packed tower there has been more evidence to show that kga is
0.$
a function of G • Sherwood and Gilgore7, Gill8, and Chilton, Duffey

and Vernon9 on ammonia, Schiebel and Othmer10 on several methyl ketones,

1. Haslam, R. T., Hershey, R. L., Kean, R. H., Ind. Eng. Chem.. 16. 1224.,
(19U ) .
2. Cogan, J. C., and Cogan, J. P., Thesis, Chem. Eng. M. I. T., (1932).
3. Hollings, H*, and Silver, L., Trans. Inst. Chem. Eng.. (London), 12,
49, (1934).
4. Haslam, R. J., Ryan, W. P., and Weber, H. C., Trans. Am. Inst. Chem.
Eng.. 1£, 177,. (1923).
5* Hixon, A. W., and Scott, C. E., Ind. Eng. Chem.. 27. 307, (1935).
6. Kowalke, 0* L., Hongen, 0. A., and Watson, K. M., Bull. Univ. Wis.
Eng. Exp. Station, 68, (June 1923).
7. Sherwood, T. K., and Gil gore, A. J., Ind. Eng. Chem.. 18, 744, (1928).
8. Gill, K. S., Dissertation in Chem. Eng., Northwestern Univ., (I94S).
9. Chilton, T. H., Duffey, H. C., and Vernon, H. C., Ind. Eng. Chem.. 29.
298, (1937).
10. Scheibel, E. G., and Othmer, D. F., Trans. Am. Inst. Chem. Eng.. 40.
611, (1944)-
 13

Hutchings, Stutzman and Koch1 on acetone, and Koch2 on water, methanol,

propanol, 1-butanol, 1-pentanol, and tolnene-air systems* Dwyer and

Dodge3 reported that the exponent on G varied inversely with packing

size from 0.72 - 0*90 for three different size Raschig rings. Sher­

wood and Holloway^ reported Kga varied to the 0.5 power of G for ab­

sorption of ammonia in one inch carbon Raschig rings. Adams5 absorp­

tion studies on sulfur dioxide indicated a variation of K a -with G to

o .8 g
the 0*9 power, Gill6 reported G , and Whitney and Vivian7 report

G°'\

The effect of liquid rate on kga has not been definitely estab­

lished. While most investigators report no effect of liquid rate there

are some who have found an effect. Kowalke, Hougen, and Watson6 found

that in spray towers K a increased with liquid rate for ammonia absorp-
u
tion up to 500 lbs./hr.-sq.-ft. and then remained constant with further

increases in rate. Hixon and Scott9 reported K^a varied directly with

liquid rate for ammonia absorption and independent of liquid rate in

absorption of sulfur dioxide. Kowalke, Hougen, and Watson6, in packed

tower studies on ammonia, indicate no effect on k a of liquid rate.

Pwyer and Dodge3 correlated k„a with L to the 0.2 or 0.39 power.

1. Hutchings, L* E. Stutzman, L* F., and Koch, Howard A., Jr., Chem.

Eng. Prog., 45, 253, (194-9).
2. Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern Univ.,
(194-9) •
3. Dwyer, D.E., and Dodge, B. F., Ind. Eng. Chem..33. 4.85,(1941).
4« Sherwood, T. K., and Holloway, F. A* L.,Trans. Am. Inst. Chem. Eng.«
15, 177, (1923).
5. Adams, F. W., Trans. Am. Inst. Chem. Eng.. 28. 162, (1932).
6 . Gill, K.S. Dissertation in Chem. Eng., Northwestern Univ., (1948).
7. Whitney, R. P., and Vivian, J. E., Chem. Eng. Prog*. 45. 323 1949.
8 * Kowalke, 0* L., Hougen, 0. A., and Watson, K. M*, Bull. Univ. Wis.
Eng. Exp* Station, <S8 (June 1923).
9. Hixon, A.W., and Scott, C. E., Ind. Eng. Chem..2£, 307, (1935).
-Hutchings, Stutzman, and Koch1 reported that kga varied as the 0.6

power of liquid rate in their acetone studies. Whitney and Vivian2

found k a varied with the 0.25 power of L.

g
The effect on kga of gas diffusivity has been studied by Gilli­

land and Sherwood3 in a wetted wall column. They found kg varied

to O .56 power with Dg. This was verified by Hollings and Silver*♦

Hixon and Scott5 also correlated their spray tower studies with di­

ffusivity to the O .56 power* Investigators studying this effect on

packed towers vary considerably in what they report* Mehta and Parekli6

found the exponent on D to be 0.17 in the vaporization of water, metha-

O
o. S'
nol, benzene and tolnene into air. Scheibel and Othmer? reported D
6
1,0 a
and Dg • They indicated more faith in Dg to the first power. Koch8

found that k^a varied with 0.5 power of Dg*

Dwyer and Dodge9 and Chilton, Duffey, and Vernoni studied the

effects of humidity on the overall gas transfer coefficients. Their

experiments indicated the Kga is independent of humidity. This work

is important because all gas absorption studies in air assume that

1* Hutchings, L. E*, Stutzman, L. F., and Koch, Howard A., Jr., Chem.
Eng. Prog.* 45, 253, (1949).
2. Whitney, R. P*, and Vivian, J. E., Chem. Eng. Prog.. 45. 323, 1949*
3. Gilliland, E. R», and Sherwood, T. K., Ind. Eng. Chem.. 26. 516,
(1934).
4. Hollings, H., and Silver, L., Trans. Inst. Chem. Eng.. (London),
12, 49, (1934).
5. Hixon, A. W., and Scott, C. E., Ind* Eng. Chem.. 27. 307, (1935).
6 * Melita and Parekli, S. M. Thesis, M. I. T*, (1939).
7. Scheibel, E. G., and Othmer, D. F., Trans* Am. Inst. Chem. Eng..
40, 611, (1944).
8 . Koch, H. A., Jr., Dissertation Chem. Eng., Northwestern Univ.,
(1949).
9* Dwyer, D. E., and Dodge, B. F., Ind. Eng. Chem.. 33. 4&5> (1941)*
10. Chilton, T. H., Duffey, H* C., and Vernon, H. C., Ind. Eng. Chem.
22, 298, (1937).
water vapor transfer is not important*

Kowalke, Hougen, and Watson* reported that in absorption of ammonia

k a was independent of packing size. Chilton, Duffey, and Vernon re-

o

ported kga varied as the 0*6 power of the dry specific packing area

(sq* fty/cu. ft.)* Dwyer and Dodge^ obtained the same results^ Hutchings,

Stutzman, and Koch* found that k a varied with 0.7 power of the nominal
o
packing diameter.

Gill^ reported that k a was independent of temperature for ammonia

and sulfur dioxide absorption in a tower packed with 1/4- inch Raschig

rings. Kowalke, Hougen, and Watson* and Dwyer and Dodge3 reported that

K_a decreased with air increase in temperature for ammonia absorption.

o

4* Generalized Correlations

If an equation could be developed for kga that would tie all systems

together, an extremely useful tool would be available, k^a could be cal­

culated from equation (14), if Kga were known since kga could be calcu­

lated independently. On the other hand, if k ^ were known and kga could

be estimated by a good general equation, Kga could be calculated and

gas absorption columns could be designed without previous pilot plant

studies.
Van Krevelen and Hoftijzer* derived such an equation in terms of

1. Kowalke, 0. L., Hougen, 0. A., and Watson, K. M., Bull. Univ. Wis.
Eng. Exp# Station, 68, (June 1923)#
2* Chilton, T. H., Duffey, H. C., and Vernon, H. C., Ind, Eng* Chem.,
22, 298, (1937). '
3. Dwyer, D. E., and Dodge, B. F., Ind. Eng. Chem., 33. 485, (1941)*
4* Hutchings, L* E., Stutzman, L. F., and Koch, Howard A., Jr., Chem.
Eng* ProgjL. 45,, 2$3, (1949). _
5* Gill, K. S., Dissertation in Chem. Eng., Northwestern Univ., (1948).
6. Van Krevelen, D. W*, and Hoftijzer, P. J., Recueil des Trav. Chain,
des Pavs Bas, 66, 49, (1947).
Cg. (Equation 6)
0.8
k-d = C(_G_) ( u )l/3
D (a n ) ( /> D ) (6)

Kochi developed from dimensional analysis the following equation.

0.0A3u (Mrt G)°'8

kga = M rtP A ( ix ) ( M- ) (15)
or for air

0.0154 o .S
kga = A Dg G (16)

These equations are very similar. For example, for air and the

same packing, the Van Krevelin-Hoftijzer equation becomes

0.8 0*447
kga^ = 0,0 D ( 17)

Koch!s development becomes

o.8 o.S , v
k a = C2G D (18)

1. Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern Univ., 1949.

 STATEMENT OF PROBLEM

1. Absorption of Carbon Dioxide from Air by Alkaline Solutions

There has been only one article1 published on the design of ab­

sorption towers when chemical reaction and physical diffusion are pro­

ceeding simultaneously* This excellent study by Spector and Dodge

was limited to the absorption of carbon dioxide in atmospheric air.

The nearest theoretical approach to this problem2 is still empirical

and difficult to handle* The absorption of carbon dioxide from air

by alkaline solutions is an excellent system for studying the above

mentioned problem.

The only investigations of the absorption of carbon dioxide from

air by alkaline solutions in packed towers are those of Tepe and Dodge3,

and Spector and Dodge1• These studies were summarized in the previous

section. Their approach to this problem was to analyze K a as a func-

tion of liquid rate, gas rate, carbonate concentration, and hydroxide

concentration. They did not develop an equation which could be useful

for design.

The above mentioned investigations did not include certain impor­

tant variables such as packing size and partial pressure of carbon di­

oxide in air. The effect of these variables on carbon dioxide transfer

1. Spector, M. A., and Dodge, B. F,, Trans. Am. Inst. Chem. Eng.. 42.
827-848, (1946).
2. Van Krevelen, D. W., and Hoftijzer, P. J., Chem. Eng. Prog.. /,/,,
529-536, 1948.
3. Tepe, J. B., and Dodge, B. F., Trans. Am. Inst. Chem. Eng.. 42.
827-848, (1946).
must be known in order to establish a useful design* The packing

size effect on transfer should be known because packing is involved

in two important design costs which are (1) Initial cost and (2)

Pressure drop costs. The effect of partial pressure of carbon di­

oxide on transfer should be known so that a range of problems can be

handled by one equation or method. For example it is much more useful

to develop a correlation which will apply to flue gas or process gas

which contains 20 per cent carbon dioxide as well as to a closed at­

mosphere gas which might contain three per cent carbon dioxide.

It is the object of this study, therefore, to do the following:

1. Investigate the effect of the important variables on

the transfer of carbon dioxide.

(1) Liquid rate

(2) Gas rate

(3) Partial pressure carbon dioxide

U) Packing size

(5) Height
(6) Concentration of base

(7) Base (KOH or NaOH)

(8) Concentration of carbonate

(9) Ionic strength

(10) Type and diameter of column

2. Correlate the data obtained into an equation which is

general and which could be useful for design.

2. Gas Film Transfer Coefficient

In the section on backgroundt the importance of the gas film trans­

fer coefficient (k a) was mentioned. It is no wonder, therefore, that

o
much work has been done both on specific systems and on general correlat-
 ■chkj

ing equations* One of the variables whose effect on k^a has not been

generalized is the liquid rate. (See ’’Effect of Variables on kga”).

The general equations used to correlate k a1*2 (Equations (6) and

O
(15)) have both considered that the effect on kga of liquid rate is

negligible* These equations contain in them functions of properties of

the inert gas. Hutchings, Stutzman, and Koch3, however, indicated that

their equation for k a might be applied to other air systems than ace-

tone-air-water if a diffusivity term were introduced. Their equation

includes a liquid rate effect on kga and should be confirmed. While

there is no limitation about which gas can be employed as the inert

one in equations (6) and (15)> in practice air, and air alone has been

used. There are two important factors, therefore, which must be estab­

lished before a generalized correlation can be successfully applied.

These are (1) the effect of liquid rate on kga and (2) the effect of

using another inert gas than air for absorption.

It is the object of this study to do the following:

1* For the vaporization of 1-propanol in an air stream in a

packed column, investigate the effect of liquid rate and
gas rate on kga.

2* To check the general correlation of Koch1 it is proposed

to vaporize 1-propanol in a packed column in a stream of
helium and carbon dioxide.

1* Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern Univ.,

(1949)•
2. Van Krevelen,D. W., and Hoftijzer, P. J., Recueil des Trav. Chim.
des Pavs Bas. 66. 4-9* (194-7)*
3* Hutchings, L* E., Stutzman, L. F., and Koch, Howard A., Jr., Chem.
Eng. Prog.. 45, 253, (1%9).
 EXPERIMENTAL

I. Absorption of Carbon Dioxide by Alkaline Solutions

INTRODUCTION - The absorption of carbon dioxide was performed in two

absorption columns, one glass and the other steel, both packed with

Raschig rings* Runs 1-114 were made in the glass tower and runs 115“

191 were made in the steel column • The correlation obtained after

the first 115 runs suggested those which were made subsequently (See

Correlation and Interpretation of Data). This study consisted of ab­

sorbing carbon dioxide from air in sodium hydroxide, sodium hydroxide-

sodium carbonate, potassium hydroxide, potassium hydroxide-potassium

carbonate, and sodium chloride-sodium hydroxide solutions. Conditions

which were varied were liquid rate, gas rate, partial pressure of car­

bon dioxide, packing size, normality of base, height of packing, and

normality of carbonate.

EQUIPMENT - For runs 1-114 on the carbon dioxide-air-hydroxide solution

system a glass tower three inches O.D. was erected. The glass tower

was approximately four feet long and about 2.8 inches I.D. It was

packed with one-half inch Raschig rings to a height of 2.82 feet, and

the rings were supported on a wire screen. The air introduction system

consisted of a 1/2” copper tube inserted in the center of a rubber stopper

with a small inverted cup of metal protecting the outlet of the tube

from the down coming liquor. Another copper tube in this stopper served

as a liquid outlet, and a small glass tube in the stopper was used as

a sampling point. A second rubber stopper was inserted in the top of

the tower and a copper tube was used as an air outlet. Liquid was in-
 FIGURE 1

Sketch, of Absorption Apparatus (Glass Tower)

 5
o
_l
£ *
U z
> <

SHEET
|x}

FLOW
a: o
Id to
I- CD
Id <
IE

HYDROXIDE
< to ^ Ld
CO O q <2
z < -J CO
O Ld
(J I to o

- SODIUM
£ □

- AIR
< Ll.

o ^
J” o
DIOXIDE
CARBON

tviZ
° f*
U I”

w -J
o >-
u u
troduced at the top of the packing by means of a spray coil. A ther­

mometer was inserted through the stopper and was used for measuring

temperatures of the outlet vapor* The system is presented in Figure 1*

A steel absorption column was used in runs 115-191* This absorp­

tion column was a four inch carbon steel, schedule 40 pipe, 84 inches

long packed to varying heights. The base of the packing was 11 inches

above the base of the column. The gas inlet was a standard one inch

opening below the base of the packing. The liquid outlet was a standard

one-half inch opening in the bottom flange. A standard two inch connec­

tion in the top flange was the gas outlet. The liquid inlet was through

1/32 inch drilled holes in a quarter inch coiled copper tube placed

slightly above the top of the packing. This tube entered the column

through a standard one-half inch nipple on the wall of the column above

the packing.

The pressure differential over the column and over the orifice

meter was measured with a regular liquid manometer filled with.827 Sp.

G. red oil.

Air was introduced into the system by means of a gear blower powered

by a one third horsepower motor. This system is shown in Figure 2.

FLOW SYSTEM - In the glass column where data were taken for runs 1-114,

the flow was as follows. A solution of the desired strength was mixed

and stored in the water surge tank. The solution was pumped from the

water surge tank by a centrifugal pump to a constant head tank from

which the excess passed down to the overflow tank where it was picked

up by the same centrifugal pump. The liquid entering the column passed

from the bottom of the constant head tank through a small globe valve

to the copper tube which served as a liquid distributor. The outlet

of the tube was in the forsa of a ring, and eight small holes in the

ring distributed the solution over the packing. The solution passed

out the bottom of the column through a liquid seal which consisted of

a glass tube, 1 1/2*' I.D., fitted with a two hole stopper at the bottom.

This liquid seal served as a safety valve on the glass tower and also

indicated the pressure at the bottom of the tower. A sample of the

inlet liquor was taken from the overflow tank, and a sample of the out­

let liquor was taken from the bottom of the tower.

The air was obtained from the building*s compressed air line and

it was filtered to remove oil and dirt. The air rate was measured by

means of a gas rotameter calibrated against a dry test meter. Carbon

dioxide was introduced into the air stream just before the air filter.

The carbon dioxide came from a surge tank through a pressure regulating

valve. The pressure in the surge tank was kept constant by the attached

carbon dioxide cylinder and the throttling valve on the cylinder. A

sample of the inlet vapors was taken by means of an Orsat apparatus1*2

from the line connecting the rotameter to the air introduction system.

The outlet vapors were sampled from a point in the exhaust line (See

Figure 1).

The flow system whereby carbon dioxide was absorbed from an air

C02 mixture ty a sodium hydroxide solution or a potassium hydroxide

solution in a four inch carbon steel packed column was as follows:

The air C02 mixture entered the column near the base and was

exhausted from the top to the atmosphere. The air feed was taken from

1* Schimpf, H. W., ,fManual of Volumetric Analysis," Wiley and Sons,

New York, Fifth Ed. (1909).
2. Scott, W. W., "Scott’s Standard Method of Chemical Analysis",
D. Van Nostrand and Co., Fifth Edition, (1939)*
 FIGURE 2
Sketch of Absorption Apparatus (Steel Tower)
 THERMOMETERS 2 :

VAPOR O U T L E T ABSORPTION COLUMN

(§) VAPOR INLET
_________ -TXT
VAPOR OUTLET
£
LIQUID INLET
VAPOR —(XI—
SA MPLING LIQUID OUTLET
LINES
VENT

MAN OMETERS
CD COLU MN PRESSURE DROP
WATER
ORIFICE PRESSURE DROP SURGE
ORIFICE UPSTREAM TA NK
PRESSURE DW
O
-{XJ—h

©
0
@ § -K

vJ: ip i— 4*— t.
" ^ HOT COLD
ROTAMETER ^ WATER WATER
t LI QU ID
OUTLET
CXI— y — IX-
r»,
O R IF IC E
?— *__ JLrU
CENTRIFUGAL PUMP

C02 SURGE TANKS GEAR BLOW ER

CYLINDER
the room and blown with a gear-blover through an orifice meter, mixed

with C02 and then passed throughthe column.

The C02 was obtained from a regular cylinder, fed into two 100

gallon surge tanks maintained atconstant pressure and temperature.

From these tanks the carbon dioxide passed through a rotameter into the

air line, entering the air line between the orifice meter and the column

at a point sufficiently upstream for adequate mixing.

The absorbing solution was made up in a holding tank and pumped

with a centrifugal pump, through a rotameter into the column near the

top, spraying into the column a minimum distance (approximately two

inches) above the packing. It discharged through a liquid seal out

the bottom of the column.

Provisions were made for continuously observing inlet and outlet

temperatures of the gas and liquid stream and for measuring the pressure

drop across the column. The flow system is shown in Figure 2.

EXPERIMENTAL PROCEDURE - Liquid from the surge tank was pumped through

the tower and air was mixed with the desired amount of carbon dioxide

and likewise sent through the tower. Twenty minutes were allowed for

equilibrium. After this time, the pressure drop across the column,

the pressure drop across the orifice, pressure drop from the atmosphere

to upstream of the orifice, liquid and gas temperatures, and rotameter

readings were recorded. Gas samples for analysis were drawn from the

system at points indicated in Figure 1. Liquid was taken from the

bottom of tower and from the surge tank and analyzed. The liquid

rate was measured by weight.

GAS AND LIQUID ANALYSIS - 100 mis. gas samples were d r a m into an

Orsat apparatus. From there, these samples were sucked into an evacuated
 a:
bottle containing 50 mis of standard barium hydroxide. The contents

of the bottle were shaken and then analyzed with standard hydrochloric

acid for the remaining hydroxide1,2* This, combined with knowledge of the

pressures and gas temperatures permitted calculation of compositions.

(See Appendix - "Sample Calculations")*

Liquid samples were analyzed by pipetting them into bottles con­

taining 50 mis of standard barium hydroxide solutions and backtitrating

the base with hydrochloric acid. The purpose of the hydroxide in this

analysis was to precipitate the carbonate formed in the absorption

column*

EXPERIMENTAL DATA - A total of 191 absorption runs were made-. 115 were

made in the glass tower and 76 in the steel column. Liquid rates varied

from 13 to IS5 lb. mols/hr.-sq.ft. Gas rates ranged from 2*9 to IS lb.

mols/hr.-sq.ft. Mol fractions of carbon dioxide in air entering the

columns were between 0.03 and 0.2S. The normality of hydroxides entering

the system varied from 0*07 to 3*90. Normalities of carbonates entering

the system varied from 0.0 normal to 0*44 normal while the average carbo­

nate concentrations (arithmetic mean between top and bottom of the tower)

ranged from 0.02 normal to O .65 normal. Gas temperatures were between

72°F and 92°F and most of the runs were between 75°F and S5°F. Liquid

temperatures varied between 65°F and 95°F but again most of the runs

ranged between 75°F and 85°F. The pressure on the towers for all runs

was essentially atmospheric.

Material balances showed an average deviation of 10 per cent and a

maximum deviation of 37 per cent.

1. Schimpf, H* W., "Manual of Volumetric Analysis," Wiley and Sons,

New York, Fifth Ed. (1909).
2. Scott, W. W., "Scott!s Standard Method of Chemical Analysis", D. Van
Nostrand and Co., Fifth Edition, (1939)*
 While this deviation seems large, it is within the calculated

experimental error* This is true because in many cases differences

were taken between two values which were very nearly the same.

The calculation of maximum experimental error employed the method

used by Sherwood and Reed1• The estimated errors, inherent in the

measurements which lead to the calculations for material balances,

are listed below in Table I*

TABLE I

Experimental Item Estimated Error

100 cc gas sample 0.25 cc

Liquid sample 0.02 ml
Gas-Rotameter (including graph) 0*5 lb. mol e/hr. /sq.ft.
Barometer
50 ml Ba(0H)2 0.03 ml
Gas and Liquid Titrations 0.2 ml
Liquid Rate (Precision) 3 %

The data for these 191 runs are presented in Table II.Included

in this table is sufficient information to calculate K 1 and Kga* The

following items are listed.

1• Run number

2. Liquid rate - L*

3* Air rate - G*

4* Carbon Dioxide composition in (mol fraction)

5* Carbon Dioxide composition out (mol fraction)

6. Normality of sodium hydroxide in entering liquid (gram

equivalents per liter)

7. Average normality of sodium hydroxide (or potassium hydroxide)

1# Sherwood, T* K*, and Reed, C. E., “Applied Mathematics in Chemical

Engineering1', McGraw Hill, New York, 1939*
 ■

(arithmetic mean between top and bottom of absorption column).

8. Average normality of sodium (or potassium) carbonate.

9- Mols of carbon dioxide transferred (absorbed), (based on the

liquid analysis and liquid rate)

10. K a
g
11# Average gas temperature °F
/.09 %
12. jLt* where juf is the ionic strength (£.(1/2 cZ. ), where c is

concentration in mols/liter and 2 is the charge on the ion.

This term is used in a correlating equation presented in the

section on Correlation and Interpretation of Data.

13* K 1 exp is used in a correlating equation presented in the

section on Correlation and Interpretation of Data. It is

calculated from data mentioned above.

1A* K 1 calc is the theoretical constant taken from a correlation,

presented in the section on Correlation and Interpretation

of Data.

15. Per cent deviation is

100 - K» exp , (100)

K* calc
 TABLE II 34

DATA ON RATE OF ABSORPTION OF CARBON DIOXIDE FROM AIR

SODIUM HYDROXIDE: 2,75 Inch Glass Column, 1/2 Inch Raschig Rings, Height of Packing 2.87 Feet

1 2 i 3 4 5 6 7 8 9 10 11 12 13 14 15
1■

Run ltu moles H^G lb, moles air Gas Composition Normality Normality Transfer K a TegP. °P 1.09 K* exp. K* calc, % Devi,a
hr. sq. hr. sq. ft. mole fraction NaOH N&2CO3 lb. moles lb, moles Ji
av# \
. L» 1
G* in av. av. hr.sq.ft* hr.cu.ft.&tm.
y? & ,L,„ II| I,
a ■ !
'
6P2 .0681
75 .0485 0.53 0.42 0.13 0.160 0.97 75 0.560 0.560 0.655 -14
;2 ' 23 ' 6.2 .0695 .0583 0.53 0.32 0,21 0.080 0.44 75 0.608 0.252 0,248 •
’1 2
3 37 !("• 6.1 .0611 ,0468 0.49 0.34 0.15 0.102 0.67 76 0.535 0.367 0.367 \ 0
4 \ 123 6.1 .0611 .0350 0.49 0.42 0.08 0.178 1.38 76 0.502 0.925 1.000 - 7
5 \ 91 6.1 .0611 .0374 0.49 0.40 0.09 0*155 1.19 76 0.508 0.736 0.780 .- 6
6 t 17 10.3 .0424 .0383 0.48 0.33 0.15 0.046 0.41 75 0.525 0.171 0.193 \ -11
7 75 10.3 .0422 .0333 0.48 0.41 0.07 0.097 0.93 75 0.485 0.556 0.655 \-15
8 \ 134 10.3 .0439 .0308 0.48 0.42 0.06 0.143 1.40 75 0.473 0.949 1.080 V-12
9 ' 35 13.1 .0485 .0438 0.47 0.34 0.13 0.084 0.52 73 0.508 0.327 0.343 ,•4 5
10 60 13.1 .0489 .0406 0.47 0.38 0.09 0.102 0.82 73 0.488 0*490 0.548 \1*\-11
11 104 '13.1 .0674 .0536 0.47 0.38 0.09 0.170 1.02 73 O .486 0,834 0.870
12 47 13.1 .0643 .0568 0.47 0.34 0.13 0.113 0.67 73 0.508 0*443 0.450 Ml
13 63 7.5 .0770 .0572 0.57 0.47 0.10 0.110 0.60 "75 0.591 0.495 0.582 -is
14 54 11.0 .0306 .0224 0.57 0.47 0.10 0.094 1.28 75 0.590 0.423 0.500 -15
15 59 12.9 .0531 .0411 0.57 0.44 0.13 0.134 1*04 75 0.606 0.509 0.535 - 5
16 62 4.9 .0680 .0420 0.57 0.43 0.14 0.161 1.07 75 0.615 0.564 0.585 - 4
17 60 6.0 .0587 .0369 0.57 0,43 0.14 0*247 1.13 75 0.612 0.529 0.548 - 4
18 47 8.8 .0400 .0272 0.57 0.43 0,14 0.121 1.31 75 0.615 0.426 0.450 - 6
19 54 8.6 .0760 .0604 0.74 0.55 0.19 0.186 0.99 75 0,822 0.508 0.510 0
20 71 8.6 .0797 .0574 0.74 0.57 0.17 0*213 1.14 75 0.810 0.626 0.630 - 1
21 86 8.6 .0809 .0569 0.74 0.60 0.14 0*219 1.16 75 0.795 0.719 0.740 - 3
22 97 8.6 .0776 .0556 0.74 0.60 0.14 0*239 1.32 75 0*792 0.800 0.820 - 3
23 141 8.6 .0790 .0456 0.74 0.63 0.11 0.269 1.60 75 0.776 1.080 1.120 - 4
24 69 8.6 .0728 .0500 0.74 0,51 0.17 0.206 1.23 75 0.810 0.603 0.610 - 1
25 72 8.6 .0503 .0434 0.77 0.62 0.16 0.166 1.17 75 0*836 0.616 0.650 - 5
26 28 8*6 .0607 .0485 0.77 0.54 0.23 0.117 0.77 75 0.875 0.287 0.290 - 1
27 46 8.6 .0585 .0464 0.77 0.61 0.16 0.135 0.92 75 0.841 0.396 0.440 -10
28 50 8.6 .0605 *0455 0.77 0.61 0.16 0.146 1.01 75 0.840 0.433 0.470 - 8
29 178 8.6 .0599 .0357 0*77 0.70 0.07 0*219 1.70 75 0.790 1.270 1.380 - 8
30 101 8.6 .0607 .0395 0.77 0.67 0*11 0.195 1.43 75 0.810 0.779 0.840 - 7
31 38 8.6 .0421 .0180 1.20 0,93 0.27 0*131 2.28 72 1.364 0.344 0.373 - 7
32 65 8.6 .0372 .0161 1.20 0.99 0.21 0.244 3.49 72 1.335 0.551 0.590 - 6
33 71 8.6 ,0406 .0161 1.20 0.99 0.21 0.266 3.61 72 1.335 0.601 0.640 - 6
34 121 8.6 .0453 .0062 1.20 1.03 0.17 0*369 6.75 72 1.312 0.970 0.980 - 1
35 169 8.6 .0506 .0180 1.20 1.06 0.14 0.412 4.66 72 1.295 1*280 1.300 - 1
36 43 8.6 .0573 .0372 1.20 0.93 0.27 0.214 1.65 72 1.373 0.404 0.418 - 3
37 51 8.6 .0722 .0549 1.51 1.24 0.27 0.251 1.42 72 1.720 0.446 0,480 - 7
$ 66 8.6 .0740 .0525 1.51 1.34 0.17 0*260 1.49 72 1.665 0.659 0.595 10
115 8.6 .0757 .0452 1.51 1.37 0.15 0.307 1.86 72 1.650 0.872 0.940 - 7
 TABLE II (CONTINUED)

2 3 4 5 6 7 8 9 10 11 12 13 14

.moles H-,0 lb. moles air Gas Composition Normality Normality Transfer ,Kga Temp. °F 1.09 K 1 exp. K 1 calc
sq.ft. hr.sq.ft. mole fraction NaOH N&2C0 3 lb. moles lb, moles Gas
L* av. p
G* in out in av. hr.sq.ft. hr.cu.ft.atm. av.
yi
149 8,6 .0629 .0442 1.51 1.39 0.12 0.319 1.97 72 1.634 1*100 1.180 6
170 8.6 .0624 .0306 1.51 1.41 0.10 0.308 2.42 72 1.624 1.255 1.310 4
56 8.6 .0609 .0406 1.51 1.32 0.20 0.198 1.39 72 1.676 0.449 0.515 13
31 8.9 .0748 .0585 1.51 1.19 0.32 0.179 0.95 72 1.751 0.283 0.310 9
51 9.0 .0710 .0504 1,94 1.66 0.29 0,261 1.53 73 2.220 0.427 0.473 10
95 9.0 .0741 .0438 1.94 1.76 0.19 0.324 1.97 73 2.162 0.750 0,810 7
110 9.0 .0732 .0425 1.94 1.78 0.17 0.333 2.07 73 2.151 0.850 0.910 6
169 9.0 .0738 .0388 1.94 1.87 0.12 0.379 2.44 73 2.129 1.280 1.300 1
26 9.0 .0708 .0545 1.94 1.52 0.43 0.203 1.15 73 2.306 0.252 0.275 8
a 8*6 .0745 .0626 0.71 0.50 0.22 0.157 0,81 72 0.802 0.409 0.400 2
90 8.6 .0757 .0552 0.71 0.56 0.15 0.244 1.33 72 0.768 0.774 0.770 1
130 8,6 .0713 .0512 0.71 0.60 0,11 0,260 1.51 72 0.747 1.020 1.040 2
190 8.6 .0784 .0600 0.71 0.64 0.08 0.260 1.32 72 0.727 1.375 1.440 5
44 8.6 .0737 .0610 0.71 0.49 0.23 0.180 0.96 72 0.808 0.462 0.428 8
28 8.6 .0795 .0674 0.71 0.46 0.25 0.129 0,62 72 0.822 0.320 0.290 10
34 8.8 .0680 .0556 0.73 0.53 0.20 0.122 0.69 77 0.810 0.330 0,341 3
90 8.8 .0700 .0451 0.73 0.57 0.15 0,248 1.55 77 0.785 0.775 0.770 1
113 8.8 .0706 .0456 0.73 0.60 0.13 0.262 1.62 77 0,773 0.918 0.920 0
154 8,8 .0786 .0482 0.73 0.61 0,11 0.310 1.76 77 0.764 1.192 1.210 •1
36 8.6 .0755 .0657 0.73 0.56 0.18 0.115 0.58 78 0.806 0.330 0.360 8
119 8.6 .0744 .0447 0.73 0.60 0.13 0.287 1.72 78 0.781 0,990 0.970 2
51 8.7 .0879 .0810 0.24 0.15 0.10 0.088 0.36 75 0.256 0.569 0.478 18
76 8,7 .0879 .0775 0,24 0.15 0.09 0.123 0.51 75 0.255 0.806 0.670 19
109 8.7 .©893 .0709 0.24 0,17 0,08 0.147 0.64 75 0.247 1.018 0.900 13
142 8.7 .0879 ,0667 0.24 0.18 0.07 0,167 0.76 75 0.242 1.240 1.120 11
169 8.7 .0886 .0698 0.24 0.18 0.07 0.192 0.85 75 0.242 1.420 1.300 9
35 8.8 .0844 .0776 0,24 0.13 0.11 0.068 0.29 74 0.262 0.434 0.350 22
50 8.8 .0838 .0754 0.24 0.15 0.09 0.035 0.37 74 0.255 0.550 0.470 16
70 8.8 .O844 .0742 0,24 0.15 0,09 0.109 0.48 74 0.256 0.730 0.620 17
85 8.8 .0844 .0722 0.24 0.16 0,08 0.126 0,57 74 0.251 O .846 0.730 16
87 7.6 .0702 .0637 0.07 0.04 0.03 0.049 0.26 80 0.072 0.930 0,755 22
127 7.6 .0691 .0625 0.07 0.05 0.03 0.061 0.33 80 0.070 1.200 0.960 23
89 7.6 .0689 .0622 0.07 0.04 0.03 0.049 0.27 80 0.072 0.929 0,760 20
69 7.6 .0311 .0276 0.07 0.05 0.02 0.030 0.36 80 0,068 0.595 0.610 •2
64 7.6 .0771 .0728 0.07 0.04 0.03 0.040 0.19 80 0.074 0.762 0.583 30
25 7.1 .0720 .0654 0.07 0.04 0.03 0.014 0.13 77 0.073 0.276 0.262 5
44 7.3 .0809 .0436 1.51 1.17 0.34 0.268 1.57 92 1.762 0.411 0.420 .2
42 7.3 .1030 .0633 1.51 1.08 0.44 0.330 1.34 92 1.815 0.480 0.401 18
it
42
§!& :858 * 1:51 l:tt m m 1:3? % 1:?H
1.872
8-M kB
0.410
i
9
8.6 .1605 .1410 1.51 0.97 0.54 0.412 1.03 92 0.444
45 7.A .1216 .0959 0.92 0.61 0.31 0.253 0.82 81 1.084 0.4.96 0.430 H
42 7.6 .$067 .0803 0.92 0.62 0.30 0.229 0,87 81 1.078 0.460 0.405 13
43 7.8 .0824 .0597 0.92 0.6? 0,27 0.204 1.02 81 1.058 0.430 0.410 5
 TA£I£ II (CONTINUED)

2 3 4 5 6 7 8 9 10 11 12 13 14

moles HoO lb. moles air Gas Composition Normality Normality Transfer
Nfc2C0„} 11. moles V Temp. °F 1.09 K r exp. K 1calc. iyij
•. sq. ft. hr. sq. ft. mole fraction NaOH lb. moles
G* in out in av. tv. hi .sq.ft. hr.cu.ft,atm. Gas
V yU
av.

43 7.9 .0677 .0500 0.92 0o69 C .23 0.179 1.08 81 1.039 0.405 0.410 ■1
45 8.3 .0452 .0325 0.92 0.74 C.18 0,141 1.29 81 1.010 0.374 0.425 •13
43 7.1 .1590 .1438 0.92 0.56 0.36 0.277 0.68 81 1.107 0.565 0.415 ■25
125 6.5 .2340 .1810 0.88 0.63 C.25 0.570 0.97 85 1.008 1.250 0.980 25
100 7.0 .1855 .1400 0.88 0,58 C.30 0.552 1.00 80 1.035 1.130 0.836 30
88 7.4 .1312 .0915 0,88 O .63 0.25 0.398 1,20 80 1.007 0.885 0.752 17
92 7.7 .1006 .0636 0,88 0,67 0.21 0.348 1.48 80 0.981 0.850 0.781 9
91 7.9 .0826 .0512 0.88 0.70 0.18 0,298 1.56 80 0.967 0,790 0.775 2
84 8.3 .0587 .0368 0,88 0.74 0.14 0,214 1.70 80 0.946 0.672 0,720 •7
104 6.5 .1490 .1238 0.35 0.23 0.13 0.237 0.62 84 0,386 1,110 0.870 12
101 6.5 .0873 .067.2 0.35 0.26 0.10 0.177 0.81 84 0.371 0.920 0,840 10
99 6.5 .0596 .0442 0.35 0.27 0.08 0.146 1.01 84 0.415 0,960 0,830 16
84 6.5 .2140 .1930 0,35 0.21 0.14 0.217 0.37 84 0.393 0.980 0.720 30
a 6.7 .2870 .2650 0,43 0.23 0.20 0.144 0.24 77 0.400 0.435 0.397 10
42 7.4 .1142 .1004 0.43 0.24 0.19 0.139 0.51 77 0.504 0.535 0,400 28
41 7.8 .1004 .0856 0*43 0*24 0.19 0.138 0.58 77 0.492 0.515 0.400 25
41 8.1 .0805 .0531 0.43 0.24 0.19 0.138 0.58 77 0.492 0.515 0.400 25
41 8.1 .0713 .0531 0.43 0.27 0.16 C.II9 0.72 77 0.480 0,458 0.400 15
38 7.9 .0889 .0776 0.41 0.23 0.18 0,122 0.52 80 0.473 0.475 0.365 26
33 8.4 .0413 .0282 O.4I 0.27 0.14 C.085 0.83 80 0.452 0.347 0,330 5
42 8.6 .0438 .0319 0.41 0.27 0.15 C.109 1.02 80 0,455 0.461 0.400 16
65 7.0 .1562 .0944 2.02 1.52 0.50 C.585 1.65 86 2.445 0.652 0.585 12
66 7.0 .1578 .0925 2.02 1.54 0.48 0.575 1.74 86 2.435 0,655 0.595 10
95 7.0 .1598 .0874 2.02 1.59 0,44 C .650 1.96 86 2.410 0.789 0.800 •1
175 7.0 .1590 .0696 2.02 1.77 0.25 C *791 2.64 86 2.300 1.390 1.320 5
79 7.0 .1558 .0899 2.02 1.59 0.43 0.608 1.79 86 2.405 0.742 0.686 8
44 7.0 .1673 .1068 2.97 2.29 0,<& 0,543 1.50 84 3.690 0.448 0.432 4
62 7.0 .1688 .0996 2.97 2.42 0.^5 (.613 1.74 84 3.620 0.580 0.575 1
83 7.0 .1700 .0940 2.97 2.54 0.44 ^ 0.650 1.96 84 3.540 0.725 0.725 0
108 7.0 .1700 .0865 2.97 2.63 0.15 C .670 2,21 84 3.490 0,900 0.895 0
185 7.0 *1688 .0764 2.97 2.71 O Mi) : 0.878 2.56 84 3.430 1.460 1.395 5
i
 TAEJ&II (CONTINUED)
37
SODIUM HYDROXIDEj 4.. Inch Tower, 3/8 Inch Raschig Rings, Height of Packing 4.30 Feet

1 2 3 4 5 6 7 8 9 10 11 12 13 U 15

Run lb. moles H^O lb, moles air Gas Composition Normality ifortR&lity Tra nsfer Ib.mola^ Temp. °F 1.69 K! exp. K fcalc. % Deviation
hr. sq. ft. hr.sq.ft. mole fraction NaOH Nk 2CO3 lb.moles hr.cu.fi /atm. Gas ^
L* in out in av. tv. hr,sq.ft. 4
G* v
ya

115 64 7.4 0,1572 0.1250 c.52 0.26 . 0.26 0.324 0.53 76 0.578 0.706 0,575 23
116 64 7.5 0.1558 0.1240 0.52 0.26 3-0.26 0,324 0.54 77 0.555 0.606 0.575 5
117 72 8.4 0.0950 0.0627 0.52 0.26 0*26 0.319 1.32 77 0.540 0.596 0.640 - 7
118 72 9.7 0.0917 O.C646 0.52 0,26 0.26 0.319 1*31 77 0.535 0.592 0.640 - 7
119 31 3.4 0.3669 0.1261 0.55 0.28 0,28 0.189 0.23 76 0.726 0.411 0.312 32
120 94 6.0 0.1581 0.1007 0.56 0.28 0.28 0.456 0.81 76 0.695 0.955 0.790 21
121 98 5.0 0.1799 0.1081 0.56 0.28 0.28 0.485 0,87 76 0.694 1.010 0.830 22
122 59 5.1 0.1771 0.1328 0,56 0.28 'C.28 0.319 0.48 76 0.729 0.700 0.535 31
123 59 6.7 0.1676 0.1325 0.56 0.28 0.28 0.323 0.50 76 0.727 0.707 0,540 31
124 88 3.9 0.1389 0.0400 0.61 0.32 C.29 0.465 79 0.744 0.583 0,760 12
125 96 3.4 0.1423 0.0221 0.61 0.33 0.29 0.491 79 0.738 0.898 0.810 11
126 47 12.0 0.0680 0.0499 0.61 0.32 0.29 0.246 0.97 85 0.741 0,451 0.440 2
127 46 12.0 0.0656 0.0481 0.61 0.32 0.28 0.238 1.07 84 0,734 0.440 0.435 1
128 88 12.8 0.0605 0,0348 0,61 0.38 0.23 0.364 1.78 85 0.708 0.678 0.760 -11
129 87 13.2 0.0605 0.0357 0.61 0.38 C.23 0.360 1,74 85 0.708 0.670 0.750 -11
130 26 10.2 0.0656 0.0473 1.07 0.62 C.45 0.210 0.86 79 1.325 0.216 0.268 -19
131 62 9.9 0,0684 0.0344 1.07 0,73 C.33 0.374 1.76 77 1.259 0.448 0.560 -20
132 71 9.1 0.0685 0.0309 1.07 0.77 0.29 0.379 1.87 79 1.245 0.482 0.630 -24
133 106 10.3 0,0705 0.0282 1,07 0,82 C.25 0.481 2.48 79 1.214 0.661 0.885 -25
134 69 9.1 0.0693 0.0322 1.07 0.77 0*30 0.374 1.72 79 1.242 0.467 0.610 -23
135 42 14.9 0.0705 0.0504 0.77 0.42 C.35 0.265 1.02 79 0.942 0.393 0.400 - 2
136 49 13.4 0.0694 0.0419 0.77 0.45 0,32 0.280 1.17 81 0.926 0.417 0.457 - 9
137 26 12.5 0.0647 0.0489 0.77 0.40 *•3* 0.176 0.72 84 0.946 0.260 0.268 - 3
138 34 15.7 0.0793 0.0622 0.77 0.39 C..39 0.235 0.77 84 0,962 0.354 0.334 6
139 152 13.7 0.0882 0.0305 0.77 0.51 C«26’ 0.704 3.02 83 0.892 1.210 1.200 1
340 50 10.0 0.0610 0.0514 0.26 0.15 0.12 0.108 0.45 76 0.295 0.422 0,468 -10
HI 85 12.7 0.0602 0.0481 0.26 0,15 0,11 0.172 0.74 77 0.290 0.671 0.740 - 9
142 25 10.3 0.0588 0.0540 0.26 0.14 C.12 0,056 0.23 79 0.296 0,220 0,260 -15
143 21 7.5 0.0457 0.0403 0.26 0.14 0.12 0.045 0.24 79 0,296 0.180 0.218 -17
144 150 5.8 0.1063 0.0673 0.26 0.15 0.11 0.304 0.84 78 0.291 1.200 1.180 2
145 77 12.5 0.0670 0.0534 0.28 0.14 0.24 0.193 0.74 80 0.317 0.737 0.670 K)
146 342 18.8 0,0710 0.0570 0.28 0.17 0.11 0.301 1.09 79 0.296 1.133 1.130 1
147 18 8,6 0.0625 0.0388 3.90 3.25 0.65 0.226 1.04 82 4.620 0,115 0.195 -41
148 46 10.9 0.0628 0,0273 3.90 3.39 0,51 ' 0.424 2.31 84 4.540 0.259 0.431 -40
149 71 1C.9 0.0639 0.0222 3.90 3.53 0.37 , 0.498 2.94 $4 4.450 0.394 0.650 -39
150 105 11.2 0,0625 0.0195 3.90 3.62 0.28 • 0.526 3.34 81 4.400 0.531 0.880 -4.0
151 22 9J 0.0646 0.0383 1.98 1.33 0,65 0.263 1.19 85' 2.480 0.176 0.237 -26
 STABLE II (CONTIMJED) 3B

SODIUM HYDROXIDE: 4 Inch Tower, 1/2 Inch Raschig Rings, Height of Packing 4,33 Feet
rr4r

1 2 3 A 5 6 7 8 9 >
10 11 12 13 14 15

Hun lb.moles HoO lb.moles air Gas Composition Normality Normality Transfer lb. moles Temp, °F 1.09 K ! exp. K ‘ calc. % Deviation
hr.sq.ft. hr.sq.ft. mole fraction NaOH Na2C03 lb. moles hr. cu. ft..atm. Has
I* G* in out in av. av. hr.sq.ft. M'
, v
y*. y^
/
155 27 A.9 0.0679 0.0572 0.38 0.20 0.18 0.093 0.3A 80 0.440 0.280 0.278 1
156 58 2.9 0.0857 0.03A7 0.38 0.22 0.15 0.170 0.69 81 O.A33 0.535 0.530 1
157 86 11.1 0,0500 0.0337 0.38 0.26 e.i2 0.197 1.09 79 O.AIO 0.7A0 0.740 0
158 116 9.6 0.0633 0.036A 0.38 0.25 0.13 0.28A 1.32 80 O.All 0.960 0.905 6
159 30 A.3 0.0336 0.0291 0.08 0.0A 0.04 0.022 0.16 73 0.080 0.305 0.302 1
160 81 12.6 0.0360 0.0320 0.08 0.0A O.OA 0.056 0.38 81 0.080 0.630 0.720 -13
161 120 9.A 0.0A61 0.0381 0.08 0.0A 0.0A 0.082 0.A5 81 0.080 0.990 0.990 0
162 69 10.1 0,0A18 0.0317 0.08 0.0A O.OA 0.052 0.35 82 0.080 0.610 0,610 0
163 115 6,6 0.0726 0.0612 0.08 0.0A O.OA C.087 ' 0.30 82 0.080 0.650 0.950 0

l/A Inch Raschig Rings, Height of Packing 3.02 Feet

16A 90 9.5 0.0578 0.0220 1.51 1.28 0.23 0.369 3.28 79 1.700 0.705 0.770 - 8
165 13 4*5 0.0548 0.0347 1.51 0.95 0.56 0.099 0.69 801 1.900 0.117 0.153 -23
166 128 7.5 0.0651 0.0178 1.51 1.3A 0.17 C .386 3.52 30 1.690 0.950 1.000 - 5
167 73 8.5 0.0619 0.0232 1.51 1.2A 0.27 0.360 3.02 79 1.725 0.615 0.650 - 5
168 48 8.2 0.0591 0.0380 0,55 0.3A 0,22 (.191 1.31 80 0,638 0.550 '■ 0.455 21
169 112 11.A 0.0650 0.0435 0.55 P.A2 0.14 0,224 1.67 80 0.596 0.777 0,920 -15
170 84 7,9 0.0615 0.0338 0.55 0.A0 0.16 0.2AO 1.65 30 0.607 0.777 0,740 5
171 28 12.5 0.0358 0.0287 0.55 0.36 0.19 0.096 0.95 33 0.624 0,287 0,285 1

SODIUM HYDHOXIDE-SODIUM CARBONATE MIXTURE: l/A Inch Raschig Rings, Height of Packing 3.02 Feet

172 15 4*9 0.1540 0.1500 0.65 0.37 0.28 0.075 1.68 76 0.762 0.183 0.172 11
173 55 A.9 0.15A0 0.1AA9 0.65 0.A8 0.17 0.176 3.83 76 0.818 0.580 0.530 11
174 89 A.9 0,1610 0.1A59 0.65 0.49 0.15 0.240 5.53 77 0.828 0.858 0.770 11

SODIUM HYDROXIDE-SODIUM CHLORIDE MIXTURE: l/A Inch Raschig Rings, Height of Packing 3*02 Feet

175 29 A.9 0.1A27 0.13710.44 0.29 0.15 0.083 1.86 77 0.802 0,505
176 57 A.9 0.1A02 0.1328 O.AA 0.3A 0.10 0.10A 2.57 78 0.773 0.778
177 70 A.9 0.1A06 0.1328 0.44 0.35 0.09 0,113 2.80 77 0.768 0.9A2
178 115 3.2 0.1362 0.131A O.AA 0.36 0.08 0.170 4*14 77 0.765 1.AA0
179 70 A.9 0.1389 0.1312 O.AA 0,35 0.09 0.110 2.56 77 0.766 0.917
 DCs

TA^Ll II (CONTINUED)

POTASSIUM HYDROXIDE: 4 Inch Tovfer, l/A Inch Raschig Rings, Height cf Packing 3.02 Feet

I 4 5 10 11 12 13 1A 15

Run lb.moles WoO lb.moles air Gas Composition Normality Normality Transfer lb. moles Temp. 1.09 K 1 exp. K* calc. % Deviation
hr.sq.ft. hr.sq.ft. mole fraction im lb.moles hr.cu,ft.atm. Gas
V r»t in out in av. av. hr.sq.ft. K a av. M
Jti-
180 29 11.8 0.0530 0.0389 0.704 0.38 o;3'2 0.167 1.26 80 0.852 0.344 0.295 17
181 63 9.2 0.0570 0.0307 0,704 0.49 0.21 0.243 1.93 80 0.796 0.611 0.570 7
182 72 8.9 0.0591 0.0284 0.704 0.49 0.21 0.274 2.27 82 0.794 0,670 0.640 5
183 133 7.5 0.0710 0.0216 0,701 0.55 0.15 0.372 3.12 82 0.764 1.100 1,070 3
184 76 8.7 0.0555 0.0445 0.193 0.11 0o08 0,111 0.74 80 0,205 0.831 0.670 24
185 119 7.4 0.0633 0.0450 0.193 0.12 0,07 0.151 0.92 80 0.200 1.160 0.980 18
186 186 5.0 0.0906 0.0471 0.193 0.12 0.07 0,248 1.19 80 0.202 1.880 1.420 32
187 51 7.1 0.0571 0.0466 0.193 0.10 0.09 O.O84 0,53 81 0.208 0,620 0.440 41
188 92 7.9 0.0594 0.0442 0.193 0.11 0.08 0.134 0.81 81 0.205 1.020 0,790 29

POTASSIUM HYDROXIDE-POTASSIUM CARBONATE MIXTURES: 4 Inch Tower, 1/4 Inch Raschig Pings, Height of Packing 3.02 Feet

189 a 10.7 0.0620 0.0509 0.363 0,18 0.43 0.134 0.74 80 0.683 0.374 0.395 - 5
190 87 8.7 0.0714 0.0465 0.363 0,19 0.43 0.244 1,28 80 0.683 O .684 0.750 - 9
191 H9 6.1 0.1000 0.0455 0.363 0.19 0.43 0.386 1.70 82 0.681 1.070 1,180 - 9
 EXPERIMENTAL

II. Gas Film Transfer Coefficient

EQUIPMENT: The absorption system used for the vaporization of 1-propanol

into air, carbon dioxide, and helium is shown in Figure 2a.

A four foot pyrex glass tubing (2.75 inch I.D.) was used as the ab­

sorption column. The top of the column was closed by means of a No. 14

rubber stopper through which two holes were made. One hole contained

a 1/2 inch copper tube for a gas outlet while the other took a 1/4 inch

copper tube which was part of the liquid introduction system.

The liquid distributor was a shower head type constructed from a 1 1/2

inch bell reducer to which was soldered a perforated steel plate. It was

located about 1/2 inch above the packing.

At the bottom of the column was another No. 14- rubber stopper through

which holes were drilled for a 1/2 inch copper tube gas introduction pipe,

a 15 non. O.D. glass tube for liquid outlet, and an 8 mm. 0. D. glass tube

for a thermocouple well.

The 6 mm. glass bead packing was supported on a fine wire mesh placed

about two inches above the gas inlet tube. This wire mesh was connected

to the umbrella on the gas introduction tube by means of three steel strips*

Gas was introduced through a vertical 1/2 inch copper tube in which

were drilled 1/64 inch holes. The top of the tube was protected by a

metal shield (umbrella) to prevent the downcoming liquid from going into

the gas tube.

The liquid outlet was attached to 8 mm. glass tubing through a rubber

stopper. This tubing (as shown in Figure 2a) leads into a constant head

tuba (2 inch 0. D. pyrex glass tube) which provides the liquid seal for
 FIGURE 2a
Sketoh. of Absorption Apparatus (Vaporization Experimenta)
 1

LEGEND
A LIQ U ID ROTAMETER
B 2.75*1.0. PYRE X G L A S S C O L U M N
C PACKED SEC TIO N
D PACKIN G SUPPORT
E L I Q U I D S E A L T A N K 2*1. Q G L A S S
F L I Q U I D S U R G E , 15 M M . G L A S S j
G G E A R T Y P E PUMP
H \/A C O P P E R T U B I N G
I LIQ U ID O U T L E T , I 5 M M G L A S S
4 0 J GAS IN T R O D U C T IO N S Y S T E M
K THERMOCOUPLE WELL
L L IQ U ID IN T R O D U C T IO N SYSTEM
M GAS O U T L E T PIPING
N THERMOMETER WELL
O 8 M M PYREX GLASS T U B IN G
P L I Q U I D FEED I N T R O D U C T I O N
Q NO. 10 R U B B E R S T O P P E R
R NO. 14 R U B B E R S T O P P E R
S VA PO R V E N T

2 10
 ‘at A

the absorption column (prevents-1gas from blowing out of the liquid out­

let tube). This 2 inch tube also receives liquid from the column and

acts as a feed for the surge tube in the column.

The surge tube, constructed of 15 mm. 0. D. glass tubing was connected

by a rubber stopper to 1/4 inch copper tubing which led to the liquid pump.

Liquid was pumped through the rotameter and into the liquid distributor

by means of a gear pump.

Air was obtained from the building compressed air line. It was lead

through a rotameter (calibrated by a dry test meter) to the tower.

Carbon dioxide was introduced into two evacuated eighty gallon surge

tanks from the carbon dioxide cylinders. From these tanks thegas was led

into the system in the same manner as air. The reason for not using the

carbon dioxide cylinders directly was that the throttling caused the valves

and line to freeze which in turn made the flow irregular.

Helium was introduced directly from a cylinder controlled by a regu­

lating valve.

The liquid rotameter was calibrated by measuring the time for a defi­

nite volume of liquid to pass through it.

Thermocouples were placed in the system for the measurement of the

temperatures of the gas out, liquid in, and liquid out. The gas temperature

(in) was measured by a thermometer placed in the incoming gas line.

EXPERIMENTAL PROCEDURE: 1-propanol was introduced into the system and the

pump started. The liquid was circulated in the system until the level in

the surge tube did not change. If runs were started before this equili­

brium existed it would appear as if more propanol was evaporated than

should be, since part of the inventory change would be due to filling

voids in "the system rather than-in vaporization.

The gas was then brought into the-system* As vaporization occurred,

the level in the surge tube became lower and it was necessary to add

more liquid to maintain the reading on the liquid rotameter* About

1/2 inch above or below the top of the guide tape on the surge tube did

not affect the rotameter reading appreciably. When the temperatures did

not change, the system was considered in equilibrium. 1-propanol was

added so that the liquid level was above the top of the guide tape. When

the liquid level was even with the top of the tape a stop watch was started

and rotameter readings and temperatures were recorded. Liquid (1-propanol)

from a burette placed above the liquid seal tube (E, Figure 2a) was intro­

duced to keep the liquid level up. When the desired volume was added to

the system the liquid level was observed until it was even with the tape.

At this point the stop watch was stopped.

EQUILIBRIUM DATA: With the liquid in and liquid out temperatures known

it was possible to find and p2 • For 1-propanol this equilibrium

data is presented in an article by Stull1.

EXPERIMENTAL DATA: The data presented consists of 46 runs which are summa­

rized in Table V. They'cover the vaporization of 1-propanol into air

(24 runs), carbon dioxide (13 runs), and helium (9 runs). Liquid rates

varied from 0*9 t 26. B lb. moles/hr.-sq. ft. and gas rates from 2.5 to

17.9 lb. mols/hr.-sq. ft. The total pressure on the system was essentially

atmospheric.

Table V contains sufficient information to calculate k a* The columns

g
In this table are described below.

-1. Stull, D.-R #* Ind.. Eng. Dhem.a 39. 5l7'(1947).

Column

1 Run number

2 Liquid Rate (L1)

3 Gas Rate (GT)

k Mols 1-propanol transferred per hour per square

foot cross section area (tower), (N )

5 Barometric pressure (P)

6 p2 partial pressure of 1-propanol in gas stream

at the top of the column, (p-j - partial pressure
at bottom equals zero).

7 t2 temperature liquid in
JL
8 p2 vapor pressure of 1-propanol at top of column

9 ^ temperature of liquid out

10, p ^ vapor pressure of 1-propanolat bottom of column

11 Temperature of gas in

12 Temperature of gas out

13 Gas film transfer coefficient (k a)

Calculated by means of a log meaS driving force
/ * N / * N
i.e. z^PoJ.-," J B?,-J&? )
In (Pt*- p O
(P>- Pa)

Ik Gas film transfer coefficient (kgft)

Calculated by means of an arithmetic mean driving
force
fe *i(
i*e* A Pm = (p_i - Pi) pg - Pa)
2
 TABLE V

DATA ON RATE OF VAPORIZATION OF 1-PROPANOL INTO SOME GASES

6 Eam. glass beads, 0.198 feet packing height

1 2 3 4 5 6 7 8 9 10 11 12 13 14
Hun No. L* G! na P P2 t2°c ti°c Pi* t°C kgfl kga
P2* t°C
lb. moles lb. moles lb. moles baro. mm. Hg liq. in Vapor Pres, liq. out Vapor Pres, gas in gas out lb. moles (arith. mean
hr.sq.ft. hr.sq.ft. hr.sq.ft. mm. Rg ip* Hg___ mm. He hr.cu.ft.atm. driving force)

AIR
1 7,9 8.5 0,158 750 13,9 22.2 16.4 18.2 12.7 28.3 24.1 96.8 79.9
;2 4,3 8,5 0.138 750 12.2 22.0 16.2 16.8 11*7 28.3 24.0 73.7 68.4
3 2.9 8.5 0.096 750 8.4 18.1 12.7 15.9 10.9 28.3 24.0 51.4 48.5
4 19.3 4.2 0.109 747 18.6 26.5 21.3 25.3 19.9 28.6 24.3 48*8 37.1
5 11.7 4.2 0.099 747 16.8 26.2 20.9 24.7 19,1 28.6 24.1 39.1 32.8
6 7.4 4.2 0.096 747 16.2 26.2 20.9 24.3 18.7 28.6 24,1 36.2 31.3
7 3.5 4.2 0.080 747 13,6 25.5 20.0 21.9 16.1 28.6 24.0 29.2 27.3
8 13.0 3.8 0.095 750 19,0 26.4 21,3 25.7 20.2 31.1 29.5 44.3 32.5
9 9.5 3.8 0.097 750 19,4 26.9 21.9 25.7 20,2 31.1 29.5 44.1 32.9
10 5.3 3.8 0.084 750 16.7 27.6 22.9 25.9 20.6 31.0 29.7 26.7 23.9
11 1.8 3.8 0.065 750 13.0 26.9 21,9 21.5 15.7 31.0 29.6 20.7 20.2
12 16.7 7.4 r4175 751 17.7 23.9 18.0 23.6 18.0 28.8 26.6 - 74.5
13 12.1 7.4 0.145 751 14,7 23.3 17.5 20,4 14.3 28.8 26.0 79.0 65.3
14 7.4 7.4 0.135 751 13.7 23.4 17.3 19.3 12.4 28.8 26.0 73,0 64.8
15 4.0 7,4 0.114 751 13.6 24.0 18.0 17.7 12.1 28.8 26.0 48.8 47*4
16 19.5 4.9 0.118 751 17.7 23,9 18.0 22.6 17.7 28.8 26.6 52.7
17 11.6 4,9 0.106 751 15.9 23,8 18.0 22.5 15.9 28.8 26.6 60.0 48.2
18 2.2 5.3 0.063 749 8.9 21,1 15.2 17.7 12.1 27.7 26.0 27.0 26.1
19 0.9 5.3 0.043 749 6.1 16.6 11.4 17*5 12.1 27.7 24,9 19.9 18.9
20 4 26.8 5.3 0.122 743 16.6 22.4 16,6 20.9 15*2 25.8 22.8 - 62.0
21 20.0 5,3 0.119 743 16.7 22,9 17.0 21.5 1602 25.8 24,9 - 55.5
22 14.0 5.3 0.108 743 15.1 22.9 17,0 21.2 lr).2 25.8 24,9 64,4 48.3
23 9.9 5.3 0.103 743 14,5 22,9 17.0 20.8 14.8 25.8 24.9 57.3 48.1
24 5.0 5.3 0.095 743 13.3 23.3 18.0 20.3 14.3 25.8 24.9 42.2 38.4

CARBON DIOXIDP
25 13.6 3.1 0.113 749 26.8 30.5 26.8 29.5 25.6 32.0 31.0 34.0
26 6.6 6.1 0.163 749 20.0 27,8 23.2 23.8 18.2 32.0 29*5 72.7 53.6
27 3.7 7.2 0.190 749 19.8 26.7 21.6 22*2 16.3 32.0 28.4 110.0 80,5
28 3.7 6.8 0.374 749 19.1 28.8 21.6 22.2 16.3 32.0 30.5 91.0 71.0
29 17.3 4.9 0.146 750 22.4 26.0 21.8 21.3 16.0 27.5 26,6 - 70.3
30 8.2 3.2 0.085 750 19.7 24,9 19.5 23.3 17.5 "27.5 26.6 - 37.4
31 7.0 4.9 0.143 750 21.7 25.0 19.5 21.1 15.3 26.5 25,5 - 71.6
32 3.2 4.8 0.089 750 13.9 25,5 20.0 20.0 15.2 26.5 25*5 34.1 29.2
33 6.3 5.9 0,142 750 18.1 23.9 18.3 18.8 13.0 25.0 26.0 — 84.0
34 4.4 4.8 0.113 750 17,7 26.0 20.7 21.1 15*3 27.0 26.6 57.7 47.6
35 2.9 3.0 0.078 750 1919 25.5 20.0 21.1 15*3 27.0 26.6 - 39.3
36 1.7 3.0 0.073 751 18.6 25,0 19.5 20.6 14*9 28.3 27.7 - 35*1
37 1.7 2.8 0.064 751 17.2 26.1 20.7 20.6 14.9 28.3 27.7 31.1 26.6

HELIUM
38 14.5 6.5 0.205 751 23,0 24.6 19.0 23.4 17.7 31.0 28,4 90.0
39 15.7 11.8' 0.222 751 14,1 22.6 16.7 20.0 14.8 31.0 28.4 121.0 104.0
40 15.7 4.2 0.110 751 19.6 24.5 18.9 21.6 15.7 31.0 28U - 54.0
a 15.7 9.9 0.189 751 14,3 24.4 18.8 a.i 15.3 31.0 28.6 82.5 73.5
42 24.2 9.9 0.222 751 16.7 24.5 18.9 21.1 15.3 31.0 27.2 126.0 98.0
43 2.3 6,4 0.075 751 8.8 27.1 22.1 19.5 18.9 29.0 28,4 18.1 18.0
44 4.3 6.4 0.154 751 18.1 27.1 22.1 21.7 20.8 29.2 28.4 58.0 48.0
45 0.9 2.5 0,042 751 12.9 25,5 20.0 21.1 15.3 28.5 27.7 15.1 14.4
46 2.9 17.9 0.271 751 11.5 25.5 20.0 17.1 11.8 28.5 27.8 104.0 102.0
 CORRELATION AND INTERPRETATION OF DATA

Absorption of Carbon Dioxide from Air by Alkaline Solutions

INTRODUCTION - The correlation of the data presented in the previous

section has been done in following ways: (1) calculations of the over­

all gas transfer coefficients and studying the effects of the variables

on them, and (2) is a study of the mechanism of this absorption result­

ing in a design equation which can be satisfactorily used in the range

of the experimental data.

CORRELATION OF OVERALL GAS TRANSFER COEFFICIENTS - Calculations of K_a

o
were made using a log mean driving force and assuming a zero back pressure

of carbon dioxide. As long as the concentration of carbon dioxide in air

is low and there is no back pressure the use of the log mean driving

force is permissible (See Appendix f,Use of log mean driving force for

calculation of K^a in the absorption of carbon dioxide from air by hy-

droxides,,)• The equation used for this calculation is given as follows:

Kga = G > A Y
Ph(y,-y»)
InZt
7z (19)

where K a is lb. moles transferred (overall mass transfer coefficient)

hr. cu. ft. atm

g' = lb. moles air or (rate of air flow)

hr. sq. ft.

P = pressure in column (atm)

h = height of packed section

y1 = mol fraction of carbon dioxide entering column

^ “ mpls carbon dioxide in

mols air in

y2 = mol fraction of carbon dioxide leaving column

 Yz ~ mols carbon dioxide out
mols air out

While Kga has heen of practical value in the design of many columns,

it should not be considered fundamental for design at this time since

its development has been largely empirical. It is natural, however,

since this coefficient is used and understood by engineers, to employ

it wherever possible. For this latter reason K„a has been presented
O
in the data and correlated graphically. (Figures 3-6).

The data are plotted in Figures 3 to 6 as Kga (overall gas trans­

fer coefficient) versus liquid rate (lb.-mole/hr.-sq.ft.). All curves

show that Kga is independent of gas rate. It can also be seen that the

transfer coefficient increases with liquid rate but that this effect

becomes less as the liquid rate increases. In one series of runs (Fig­

ure 4-, curve 5), K a reached a maximum and then decreased as the liquid
o
rate was further increased. This is not obvious from the above men­

tioned curve but there are two points not shown there (Runs 3U and 35

in Table II), which bear this out. An examination of Figure 3 indicates

that K a increases with normality of sodium hydroxide up to 1*51 normal

€
and then is not affected by further increase in the base concentration.

This is indicated in curves 1, 3, 4-, 5, 6? 7, and 8 of Figure 3 (all

at approximately the same average partial pressure of carbon dioxide.)

The effect on K^a of average partial pressure of carbon dioxide was

a function of normality of the base. At high normalities (above 1.51)

Kga decreased as the average partial pressure increased up to a value

of about 0.06 atmospheres. A further increase in partial pressure

had no noticeable effect on Kga. At lower normalities (i.e. N - 0.88)

K a decreased as the partial pressure increased (at same gas and liquid

rates) throughout the range of the experimental data (i.e. 0.05 - 0.20
 *4
atmospheres). A comparison of curves 2_and 6 in Figure 3 shows how the

partial pressure of carbon dioxide affects K a* In curve 2 the hydroxide

S
normality ranged between 0.52 and 0*56 and the partial pressure (average)

was approximately 0.12 atmospheres while in curve 6 the hydroxide nor­

mality was 0*55 and the average partial pressure 0-05 atmospheres. Curve

5 whose normality is 0.614 (same range as curves 2 and 5) is even better

for comparison because the average carbonate concentrations were the

same as in curve 2. The data represented in Figure 3 have in general

lower average partial pressures than in Figure 4> therefore for the same

normality range, the curves in Figure 3 are higher than those in Figure

4* A major exception is curve 6 of Figure 4 where the average partial

pressure of carbon dioxide is approximately 0.025 atmospheres at an

average normality of 1.20. Another exception is one point in curve 1

of Figure 4 whose average partial pressure is 0.03 atmospheres compared

with 0*065 for the rest of that series. This point would fit well on

curve 1 of Figure 3 where the average mol fraction (approximately numeri­

cally equal to partial pressure) is 0.03 and the normality is approxi­

mately equal to that in curve 1 of Figure 4* It would be expected that

the normalities represented by curve 5 of Figure 4> being above I.5N

should lie on the same line providing the partial pressures of carbon

dioxide were about the same since it was true in the case of the points

represented on curve 8 of Figure 3* In this case, however, the average

partial pressure of carbon dioxide is approximately 0.12 atmospheres

for the 2.02 normal solutions and 0.055 for the 1.94 normal hydroxide

solutions. The carbonate concentration in the former case is higher

than in the latter. It would seem therefore that Kga is not affected

appreciably by partial pressures (average) above 0.06 atmospheres. On

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ilH HI ii’ v111- hi; Hfr 1 1st i Hi h TS* Ho.
iif f i uili. i
fft
IW
ift f t I T i l Hit rlti j.ijf Tt itii i-it
itti

iT)
%SS e m t tS ft: i|T nr 8
O lO
ro oj CJ>
 FIGURE 6
0.45
Kffa/y,av. VS. L
EFFECT OF CARBONATE CONCENTRATION

l ;:: 1 r

•> , s ■. ioo 8 -■ t ' •

L ( LB. MOLS / HR. S(J. FT.)

C0HVE % a O H IN % a 2C03 Av*

1 0.77 0.34
2 0.65 0.20
the other hand in runs 87-92 where the normality of base entering is

0.88, as the partial pressure (average) increases K a decreases at the

e
same liquid and gas rates, for the entire partial pressure range from

0.20 to 0*05 atmospheres* It can be seen therefore that the partial

pressure of carbon dioxide has a complex effect on K a, an effect which

o
is a function of normality.

As the average carbonate concentration increases K a decreases.

o

Figure 6 shows two series of runs where the entering hydroxide concen*-

trations are O .65 and 0.772N. In this range of normality K a varies

o
with -0*45 power of yaV (Runs 87-92) therefore Kga/y^15 is plotted

against liquid rate for two different average carbonate concentrations*

The results show that Kga decreases with increase in average carbonate

concentration. In the case of curve 2 in Figure 6, the entering car­

bonate concentration was 0 .14N while in curve 1 the entering carbonate

concentration was zero.

The fact that potassium hydroxide is a better absorber than sodium

hydroxide can be seen by comparison of Figures 5 and 3* For example in

curve 3, Figure 5 the entering potassium hydroxide normality was 0.70

with an average partial pressure of 0.045* K^a (s) for the same liquid

rate and average partial pressure were greater than those shown on curve

7, Figure 3 where the entering sodium hydroxide normality was 1.069*

There was no noticeable effect of packing size on Kga. 1/4? 3/8?

and 1/2 inch ceramic Raschig rings were employed. Characteristics of

these Raschig rings are given in the Appendix (’’Characteristics of Ras­

chig Rings")*

USE OF K* AS CORRELATING FACTOR - From the observations of the variables

affecting the overall gas transfer coefficient? it can be seen that no

simple equation can represent the-data* Besides indicating the com­

plexity of a correlation of Kga, the effects of these variables lead

to the belief that there is no particular reason to correlate with the

overall gas transfer coefficient. For example the complex effect of

partial pressure of carbon dioxide on Kga which in itself is another

function of partial pressure indicates that the use of an overall gas

transfer coefficient for correlation can be justified only by tradi­

tion. The "a11 term in K^a was introduced to convert K in wetted wall
o e
columns for use in packed towers. This term considers the surface

effect of the packing employed. Since there was no apparent effect of

packing size on K a, the lack of justification for its use is borne

E
out. Furthermore the fact that K a is independent of gas rate implies

that the important resistance to transfer is in the liquid and that a

useful correlating factor might be found by placing more emphasis on

what goes on in the liquid rather than the gas.

In this study such a correlating factor was found. It is defined

in the following equation, represented in Figure 8.

K«h (QHH c o J
A
JLt' 1#°9 (20)

where K f = 0.0176L*®1* (21)

The average deviation for all runs (187) except those where sodium

chloride was added to the incoming hydroxide solution is 11.1 per cent

with a maximum deviation of 32 per cent.

A summary of the net and mean deviations for the various condi­

tions employed is presented in Table III.

When sodium chloride was added to the entering sodium hydroxide

solution, equation (20) did not apply. The effect of liquid rate how­
 54

TABLE III

Mean Net
______ Condition Deviation j. Deviation ^

OVERALL - 187 RUNS 11.1 1.4

GLASS COLUMN
1/2 inch Raschig Rings -
2.82 feet packing height Runs 1-114 9*1 3*3

STEEL COLUMN
3/8 inch Raschig Rings —
4*30 feet packing height Runs 115-154 17*4 -6.8

1/2 inch Raschig Rings -

4*33 feet packing height Runs 155-163 2.0 0.0

1/4 inch Raschig Rings -

3*02 feet packing height Runs 164-171 10.0 -4*0

1/4 inch Raschig Rings -

3*02 feet packing height Runs 172-174
Sodium carbonate in entering solution 11.0 11.0

1/4 inch Raschig Rings -

3.02 feet packing height Runs 180-188
Potassium hydroxide solution 20.0 20.0

1/4 inch Raschig Rings -

3.02 feet packing height Runs 189-191
Potassium hydroxide and carbonate in
entering solution 23 -23
 tjt)
K' rs. L
(ALL Rt'us) *

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4_r7 L :.. ---— ■
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■I
.Hxx+xr XXxxx; j -V ■j!'- ' 'X'
,: 1
■1 i 1;
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xXjxx iX
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0 * 1 ’- x j ■

L (LB. MOLS j HR. SQ. FT.)

FIGURE 7
* x - SODIUM CHLORIDE
» - ALL OTHER RUNS
ever was "the same as found in the above mentioned equation* As with

Kga, K f was found to be independent of gas rate and Raschig ring size.

"While there was an effect of partial pressure of carbon dioxide on K ’,

this effect was small and varied with different solutions. It was

possible to correlate the data without considering this effect. There

was a trend noticeable with normality of base. K 1 tended to increase

slightly with normality up to about 1.5 normal and then decrease as

the normality was further increased. Potassium hydroxide as indicated

by the net deviation from the correlation is a better absorber than

sodium hydroxide.

INTERPRETATION OF DATA - Since it is believed as previously mentioned

that the overall gas transfer coefficient is not a satisfactory correlating

factor in this study, interpretation of the variables affecting it is

pointless.

It is interesting to note that the development of equation (20),

in which K f is prewent, preceded its application to the data. The basis

for this equation is an assumed mechanism of transfer.

This mechanism assumes that the rate of transfer is dependent on

the rate of chemical reaction. The reactions which are believed to occur

are given as follows:

OH” + C02 -■>- HC03~ (22)

OH” + HC03“ HOH + CO3 (23)

CO3 + C02 + HOH ->* 2HC0J (2A)

The first and third reactions are believed to be slow ones since

they involve the combination of an ion and a non ion. On the other hand

the second reaction is believed to occur rapidly since it is a reaction

of ions. Bicarbonate (HC03) is not found in solution with sodium hydroxide

present therefore in this proposed mechanism it is considered as an

intermediate ion. Without hydroxide present the third reaction occurs

but is reversible.

It is assumed then that the pound mols of carbon dioxide trans­

ferred per hour per square foot of tower crossectional area (N^) is

proportional to the concentration of ions and non ions which tend to

remove carbon dioxide. From the left hand side of the first and third

reactions listed above, the following equation can therefore be written.

Na o. (0H")a (COj)b (C03=)C (H20)d (25)

The concentration of water does not change appreciably therefore it

can be considered as constant. The concentration of carbon dioxide

in solution cannot be experimentally determined by ordinary analysis

but its concentration can be expressed as a function of physical con­

ditions. Some of these are listed below

1^
■
(C02) = f( ionic strength(juf), G* (inert gas rate),

L(liquid rate), Packing Size, temperature, absolute

pressure, partial pressure of carbon dioxide, viscosity

of solution (m -)> packing height (h), etc. (26)

It was decided to consider ionic strength as a factor since it is known

that carbon dioxide at one temperature is less soluble in aqueous salt

solutions than in pure water. The resulting equation became (when ex­

ponents are assumed to be equal to one)

N„ = K'h (QH~)-(.CCU= )
A (20)

Experimentally it was found that this equation fits the data best when
o.94>
m = 1.09* It was also found that K T = CL « Since all the runs

are approximately at one temperature and absolute pressure, these vari­

ables mentioned had no apparent affect on K*.

 The effect of liquid rate on the concentration of carbon dioxide

in solution can be explained on the basis of holdup. Jesser and Elgin1

found that holdup is proportional to liquid rate to the 0.6 power for

1/2 inch rings. The amount of holdup or liquid inventory in a column

is dependent on the liquid rate. Effectively this means that when the

liquid rate is increased, the size of the reactor is greater therefore

more contact between carbon dioxide and the liquid is possible which in

turn accounts for the increase in transfer.

The fact that sodium chloride addition to the entering solution

caused a serious deviation from the correlation can be explained by the

fact that the effect of concentration on the solubility of carbon di­

oxide is different with different salts. This can be seen by analyz­

ing some data presented in the monograph on carbon dioxide2 • In this

book is presented the solubility of carbon dioxide in salt solutions

of different concentrations. From this data the ionic strength was

calculated and then plotted against ”C” which is now defined as the

solubility of carbon dioxide in pure water divided by the solubility

of carbon dioxide in the given solution. These data and calculated ”C”

values are presented in Table IV and are represented graphically on

Figure 8. It can be concluded therefore that the exponent on the

ionic strength term in equation (20) is a function of the salts in

solution and therefore the use of ionic strength in the above mentioned

equation is specific for the absorption of carbon dioxide, from air by

1. Jesser, B. W., and Elgin, J. C., Trans. Am. Inst. Chem. Eng.. 39.
277, 19-43*
2. Quinn, E. L., and Jones, C. L., "Carbon Dioxide”, Reinhold, New
York, 1936.
hydroxides. It was to determine this fact that sodium chloride was

used in the solutions entering the absorption column. (Runs 175-179).

 GO

o
I

TiaURE 8

C VSyU«

CURVE SOLUTION

1 NH.C1
4
2 KC1

3 NaCl

4 MgSO^
 61

TABLE IV

Comparison of effect of different salts on the solubility of

C02 in water.

In pure water at 15°C a = 1*019 where a is vol. of gas reduced

to standard conditions which at the temperature of the experiment is

dissolved by a vol. of the solvent (i.e. ccfs gas dissolved in 1 cc.

of water) gas partial pressure = 760 mm.

Sodium Chloride
(ac pure water)
_______ N-= U r a__________ a_________________

15*0°C 1.170 .755 1.35

15.0°C 1.253 .735 I .385

15.0°C 2.400 •557 1.828

15.0°C 3.344 •431 2.36

15.0°C 3.407 .442 2.30

15.0°C 5-312 .297 3-43

15.2°C 0.220 .978 1.041

15*2°C 1.094 .760 1.340

15.2°C 2.188 •580 1.757

15*2°C 3.282 •466 2.18

15.5°C 1.000 .708 1.44

Magnesium Sulfate
Moles At._____ Ul______ a______ C

15.2°C .220 .440 .901 1.13

15.2°C .660 1.320 •669 1.52

15.2°C 1.320 2.640 .441 2.26

15.2°C 2.641 5.280 .188 5.42

 b<;
Magnesium Sulfate
lioles/Lt. ... u* a C

15.5°C 0.2$0 0.50 .816 1.23

15-5°C 0.500 1.00 .688 1.45

15*5°C 1.000 2.00 .447 2.24

15*5°C 2.000 4.00 .355 2.82

Ammonium Chloride
N = LL» a C

15.0°C 1.233 .825 1.23

15*0°G 1.707 .791 1.29

15*0°C 2.505 .798 1.28

15*0°C 4*856 .738 1.38

15*2°C 0.019 1.013 1.005

15.2°C 0.187 .985 1.032

15.2°C 0.965 .941 1.080

15.2°C 3.216 .819 1.245

15.2°C 4-822 .770 1.32

Potassium Chloride
N = Lt» a C

15.0°C 0.50 .925 1.1

15.0°C ,.828 .777 1-31

15.0°C 1.00 .850 .1.20

15.0°C 1.22 .770 1.32

15.0°C 1.732 .720 1.41

15.0°C 67 .571 1.78

15.5°G 1.00 .818 1.25

 Sodium Sulfate
MolesA t , U' a C
r
15*2°C ,0.100

o
o
•950 1.07

•
15.2°C 0.668 2.004 .620 1.64
15*2°C 2.000 6.000 .234 -4•35
 The fact that K f is independent of gas rate confirms the assumption

that the important resistance to transfer is not in the gas but in the

liquid*

A serious doubt exists here that the widely accepted mechanism of

gas transfer in the liquid phase in packed columns, namely, the film

and zone theory, is valid. This theory is based on two assumptions which

are (1) concentration gradient across the liquid film and (2) that there

is a stagnant layer of liquid with respect to velocities normal to flow

at the gas-liquid interface. The fact that Raschig ring size does not

affect transfer indicates that the surface area is not important* Accord­

ing to the film picture of transfer, this area is very important. The

fact that Hutchings, Stutzman, and Koch1 found this to be important in a

case where the gas film is controlling indicates the plausability of the

gas film theory. On the other hand in this study and that of Koch, Stutz­

man, Blum, and Hutchings2 where there is no packing size effect there

is a serious doubt that the important resistance to transfer lies in a

liquid film. Furthermore it is believed that in packed columns there

is no stagnant surface layer but that there is an unsteady state condi­

tion at the surface so that there is no appreciable concentration gradient

in the liquid. This latter belief is based on general observations of

liquids falling through packed columns and the fact there is no back pressure

of carbon dioxide from hydroxide solutions. It is believed that the

function of packing in a column is to distribute the gas so that it is

1. Hutchings, L. E., Stutzman, L. F., and Koch, Howard A., Jr., Chem.
Eng. Prog.. 253, (194-9)*
2. Koch, H. A., Jr., Stutzman, L. F., Blum, H. A., and Hutchings, L. E.,
Chem. Eng. Prog., to be published in 1949 •
in good contact with the liquid so that it can truly be said there is

no appreciable gas film resistance.

The peculiar effect of normality of base on K 1, in which K 1 in­

creases with normality until about 1*5N and then decreases with any

further increase in normality can be explained within the assumed mech­

anism. There are probably two opposing forces, namely the hydroxide

concentration which according to the proposed mechanism will remove

carbon dioxide, and some physical property of the solution which tends

to prevent carbon dioxide from entering the solution. This property

might be viscosity or some other one not considered here.

Since neither the correlating equation nor the mechanism on which

it is based referred specifically to sodium hydroxide, runs were made

(180-188) in which potassium hydroxide was the absorbent. A trend in

the data indicated that potassium hydroxide was a better absorber than

sodium hydroxide. If fit the correlation reasonably well. One expla­

nation for its better absorption might lie with the viscosity effect.
{ov this
possible reason^is that the potassium ion is a larger ion

than sodium therefore tends maaici to form covalent bonds than does sodium.

In water this tendency shows up as hydration. If there is a greater

^obdi^y <W\c|
amount of hydration with the ion, it means less rminr in n_~
Viscosity
^atien -ao -
free water-thoroforo the effective concentration "of the hy-

rfrnTriiidn wnrld—1" r"■■**-»-

The previous work of Tepe and Dodge1 did not check this correlation*

No satisfactory explanation has been found to account for this disagree-

1. Tepe, J. B., and Dodge, B. F., Trans. Am. Inst. Chem. Eng.. £2, 827-
8^8, (194-6).
 66
ment. Comparing runs in the above mentioned study with similar runs made

here, it seems that the absorption of carbon dioxide was less efficient

in those of Tepe and Dodge1 . For example Run 20 in their work where

G = 6.6 lb. mols./hr.-sq.ft., L = 84. lb.mol s/hr.-sq.ft., average

partial pressure of carbon dioxide = 0.0135 atmospheres average nor­

mality of sodium hydroxide = 1*33, average normality of sodium carbo­

nate = 0.13, height of packing = 3 feet, (jl1 raised to the 1.09 power =

1.63, and = 0.1 lb.mol/hr.-sq.ft., K 1 = 0.314* In Runs 33 and 34

of this study where conditions are comparable (liquid rates are 71 and

121 lb.mols/hr.-sq.ft., the K* values are much higher and fit the corre­

lation (Equation 20) within -6 and -1 per cent respectively. It may be

that the low partial pressures used by Tepe and Dodge1 account for this

but their data does not correlate even by itself. Of course, the fact

that the data does not fit equation 20, even in form, does not imply that

the data is at fault but puts a temporary limit on equation 20.

In general, it can be concluded that while the mechanism proposed

may not be the true one, there is much evidence to confirm it and the

explanations of the effect of variables on K 1 do not contradict it in

any way.

1. Tepe, J. B*, and Dodge, B. F., Trans, Am. Inst.. Chem. Eng., ^2, 827-
848,?(1946).
 b *
II*. G&s Film Transfer Coefficient-

EFFECT OF LIQUID RATE ON k a: It was mentioned previously that the effect

o
of liquid rate on kga was uncertain since there is much disagreement in

the literature concerning this variable* In this research the effect

of liquid rate was studied carefully for the vaporization 1-propanol

in air and briefly checked in the vaporization of this solvent in helium

and carbon dioxide. In Table V kga is presented in two ways. The first

employs a log mean driving force (column 13, Table V) which is rigorous

for this case (See Appendix ’’Use of Log Mean Briving Force for Calculation

of k a”). The second uses an arithmetic mean driving force forAPm in

the equation k a = __
h APm (27)
The reason for using such an average driving force is that .many runs which

were made at high a liquid rate as possible without flooding were almost

saturated. This means that/^p2 or (p2 - p2) is very small which in turn

means that the reliability of this term as a factor is not very great

since the difference taken between two quantities which are very close

in value, yieldsanerror (maximum) which is very large. In Pi0g mean =

&Pf - Ap, »A P 2is^°° small for accurate evaluation of this driving

In &pi
*p 2
force in several cases where the column is operating at maximum transfer

efficiency (near flooding). In order to consider these runs, It was de­

cided to correlate on the basis of an arithmetic mean as well as a log

mean driving force. Figures 9 and 10 show the difference between a

plot of k a versus liquid rate when employing a log mean driving force
g
and an arithmetic mean driving force. In Figure 9 the log mean is used

while in Figure 10, the arithmetic mean is used. It can be seen that

while the curvesinFigure 10 are lower than those in Figure 9 the form
 63
of the curve is approximately the same.

It can be seen from both Figures 9 and 10 that for one gas rate,

^creases with liquid rate at low liquid rates and is not appreciably

affected by liquid rate at higher ones (up to flooding).

Explanation for this effect can be offered by examining the work

of Mayo, Hunter and Hash1• These authors found that even though there

was excellent liquid distribution (They used a perforated plate (shower

head) liquid distributor.) that 9 inches below the top of their tower,

the percentage wetting went down to ^0 per cent. They employed a red

dye and 1/2 inch Raschig rings made from paper to show the percentage of

wetting. They also found that the percentage of surface wetted increased

with liquid rate up to flooding and that gas rate had no effect on wetting.

It is the authorJs belief therefore that liquid rate affects the

transfer area only and therefore k a but that under efficient wetting
6
conditions (high liquid rates below flooding) k a is independent of li-

quid rate.

Van Krevelen and Hoftijzer2 considered this effect of liquid rate

in the following equation

In a~ - a = -c L
a0 p' (28)

Knowing the liquid rate and density of the liquid, one can calculate

ua.u from the above equation. By experiment kga can be obtained and then

converted to k by dividing by "a". Using this method to obtain k and

6 £
2
then applying it to the Van Krevelen-Hoftijzer equation taking into

consideration that the packing size is constant, equation (6) becomes

1. Mayo, F., Hunter, T. G., and Nash, A. W., J. Soc. Chem. Ind., 375T
(1935)•
2. Van Krevelen, D. W., and Hoftijzer, P. J., Chem^ Eng. Prog.. 529-
536, 194-^•
 FIGURE 9
k„a VS. L
l-PBBPANOL AIR

6 8 10 IS 14
L (LB. MOLS/ HR. SQ. FT)
 FIGURE 10
kga Vs, L (Arithmetic Hean Driving Force)

4i

■: | !i. i:■ ■; j. ’. ::: I"i::•!" .1:.

nrrr-^t :4:~4:!

L (Ik* sols / Hr. 8q, Ft)

 v^ G '
This calculated data is presented in Table VI (based on a log mean driv­

ing force). The Van Krevelen constant generally increases with increase

in liquid rate at the same ga.s rate. In other words while equation (28)

which relates transfer area to liquid rate is an improvement over work

done previous to it, it should not be accepted as a general equation

when there is considerable effect of liquid rate.

It is interesting to note that Koch1 found no appreciable affect

of liquid rate on k^a. He investigated the effect of this variable on

water and 1-butanol systems. Applying the Van Krevelen-Hoftijzer2 equa­

tion to his data (vaporization of organic liquids into air), it was found

tha "S'p11 approximately equaled tlaM for all runs. In the experiments pre­

sented in this study (Tables V and V^) there is in general a considerable

difference between "a” and This means that Koch’s run£ were in the

range where liquid rate has'little effect on k a (Flat portion of curves

g
in Figures 9 and 10).

GENERALIZED CORRELATIONS: The effect of inert gases on k a has been pre-

g
dieted in two generalized equations. One of these is the Van Krevelen-

Hoftijzer equation which was mentioned above. It was hoped to test this

equation for the vaporization of 1-propanol in air, carbon dioxide, and

helium. The results are given in Table VI. (Using log mean driving force).

In order to compare the effect of these gases without considering the

liquid rate effect in this comparison, runs were selected which were in the

1* Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern University,

(1949).
2. Van Krevelen, D. W. and Hoftijzer, P. J., Recueil des Trav. Chim. des
Pays Bas, 66, 4-9* (194-7)*
 TABLE VI

APPLICATION OF VAPORIZATION DATA TO VAN KREVELEN-HOFTIJZER CORRELATION

Run No. 0.35L* W p D)iA £LIMbi Cyan K.

& ______UL______________
AIR
1 2.77 286 0.3 38 1.182 5660 1000 0.00812
2 1.51 230 0.320 1.182 5660 1000 0.00770
3 1.02 194. 0.265 1.182 5660 1000 0.00636
4 6.80 305 0.160 1.182 2800 570 0.00678
5 4.11 300 0.130 1.182 2800 570 0.00550
6 2.59 282 0.128 1.182 2800 570 0.00542
7 1.23 2l6 0.135 1.182 2800 570 0.00572
8 4.57 302 0.147 1.182 2530 520 0.00682
9 3.32 294 O.I50 1.182 2530 520 0.00697
10 1.86 192 0.139 1.182 2530 520 ' 0.00645
11 O .515 123 0.168 1.182 2530 520 0.00780
13 4.25 301 0.262 1.182 4940 890 0.00707
14 2.59 280 0.261 1.182 4940 890 0.00705
15 1.40 230 0.212 1.182 4940 890 0.00572
17 4 ..08 300 0.200 1.182 3260 640 0.00755
IB 0.773 165 0.163 1.182 3530 680 0.00580
19 a. 315 83 0.240 1.182 3530 680 O.OO850
22 4.92 304 0.212 1.182 3530 680 0.00754
23 3.46 296 0.194 1.182 3530 680 0.00689
24 1.75 252 0.168 1.182 3530 680 0.00597

CARBON DIOXIDE
26 2.31 275 0.264 1.000 7520 1280 0.00670
27 1.29 222 0.495 1.000 9000 1460 0.00962
28 1,29 222 0,410 1.000 8500 1390 0.00837
32 1.12 206 0.165 1.000 6000 1050 0.00447
34 1.54 240 0.240 1.000 6000 1050 0.00649
37 0.597 142 0.219 1.000 3490 680 0.00915

HELIUM
39 5.52 305 0.396 1*57 1050 257 0.00876
41 5.52 305 0.270 1.57 1120 278 0.00552
42 8.50 305 0.413 1.57 885 223 0.01054
43 0.658 147 0.123 1.57 571 160 0.00437
44 1.51 230 0.252 1.57 571 160 0.00895
45 0.315 83 0.182 1.57 224 72 0.01435
46 1.02 196 0.531 1.57 1600 360 0.00795
 ■ri'-i
* *J
flat portion of the curves in Figure 9 Tor air* For the other gases

(helium and carbon dioxide) the liquid rate effect was not studied as

carefully as with air. As a result it was attempted to make all runs at

the highest possible liquid rate for all gas rates. This accounts for the

several runs for which k a (log mean driving force) could not be calculated

since the liquid rates in these cases were high enough to make^p 2 mean­

ingless* For air the constant in the Van Krevelen-Hoftijzer equation

averaged 0.00731 for runs 1, 4, 8, 13, 17, and 22. For carbon dioxide

this constant averaged 0.00807 for runs 26, 27, 28, 34, and 37. For

helium the constant averaged 0.00863 for runs 39, 41, 42, 43, 44, 45 and

46. It seems to the author that for this choice 01 gases which are so

far apart in their properties that the agreement is remarkable.

The other generalized equation which predicted the effect of inert

gases on k ga is that of Koch1• His equation, when the total pressure

and packing is constant, becomes as follows

kga - ^Koch-11- M )
g Mm ( M ~ ) (30)

In order to remove the effect of liquid rate from this comparison there

was a selection'made of runs from Table V which were in the range where

liquid rate did not appreciably affect k a. Furthermore in order to ob-

g
tain a large number of runs as possible the arithmetic mean driving force

k a (s) were used. The results are given in Table VII. It can be seen
g
that for air the constant (Cgocjj) applies fairly well but for the other

gases there is a wide variation. Furthermore it can be seen that the

constant for helium is far below that of carbon dioxide and air. The log

1 . Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern University,

(1949)•
 -TABLE VII

APPLICATION OF VAPORIZATION DATA TO KOCH CORRELATION

Run No. kga Dp M £G-Mm

sa* CKoch
_ LL 11 a LL
AIR
1 79-9 0.0015 5660 1000 17.6 4.19 12.7
4 37.1 0.0015 2800 570 17.6 4.19 10.4
8 32.5 0.0015 2530 520 17.6 4.19 9.9
12 74-5 0.0015 4940 890 17.6 4.19 13.3
13 65.3 0.0015 4940 890 ' 17.6 4.19 11.7
14 64.8 0.0015 4940 890 17.6 4.19 11.6
16 52.7 0.0015 3260 640 17.6 4.19 13*1
17 48.2 0.0015 3260 640 17.6 4.19 12.0
20 62.0 0.0015 3530 680 17.6 4*19 14.2
21 55.5 0.0015 3530 680 17.6 4.19 13.0

CARBON DIOXIDE
25 34.0 0.0008 3880 730 44.1 6.65 8.8
29 70.3 0.0008 6130 1060 44*1 6.65 12.4
30 37.4 0.0008 4000 750 44*1 6.65 9.4
31 71.6 0.0008 6130 1060 44.1 6.65 12.7
33 84.O 0.0008 7390 1220 44.1 6.65 12.9
37 26.6 0.0008 3500 680 44*1 6.65 7.4

HELIUM
38 90.0 0.0112 580 160 1.03 1.015 4.95
39 104.0 0.0112 1050 257 1.03 1.015 3.54
40 54.0 0.0112 375 112 1.03 1.015 4 .24
42 98.0 0.0112 885 223 1.03 1.015 3.87
45 14 *4 0.0112 224 72 1.03 1.015 1.76
46 102.0 0.0112 1600 360 1.03 1.015 2.49
mean driving force k^a (s) show a similar trend. It can be concluded,

therefore, that the above mentioned generalized correlation is not satis­

factory except when applied to air. In the case of air it should be ex-
0*6 6,5
pressed as k a = G G D
g
Average values of P , ju, D , and M , which were used are given in
G m
Table VIII. D^, was calculated from the equation proposed by Gilliland1

(See Appendix ’’Gilliland Equation1’). In this equation V represents molecular

volume which is the volume of one cubic centimeter of the liquid at its

boiling point. This information was not available for helium but a plot

of the logarithm of the atomic volume versus the logarithm of the molecular

weight gave a straight line for the elements whose atomic volumes were

listed1• These elements were hydrogen, carbon, nitrogen, and sulfur. He­

lium was assumed to lie on this line.

TABLE VIII

' /3(lbs./cu.ft7) Lt(lb. ) Drift*?) M (lbs.~ )

(ft.-hr) ( hr.) m (lb. mole )

Air 0.0750 0.0435 0.352 29

Carbon Dioxide 0.1140 0.0350 0.308 44

Helium 0.0103 0.0448 1.120 4

In this study of the gas film transfer coefficient the height of

packing was only 0.198 feet. This was a compromise between a larger

height of packing in which end effects are minimized and a composition

of exit gas which is so close to the vapor pressure of the 1-propanol that

calculations of a log mean driving force are Impossible. It should be

pointed out therefore that while these experiments showed the effects of

liquid rate and inert gas on k^a, the absolute value of k^a should not be

1. Gilliland, E. £., Ind. Eng. Chenu, 26, 681 (1934) ♦

considered as final since end effects were probably significant.
 CONCLUSIONS

Absorption of Carbon Dioxide from ^ir by Alkaline Solutions

1* The overall gas transfer coefficient (K a) should not be used as a

o
correlating factor because it has no theoretical or practical meaning in

this study*

2. The following observations concerning this coefficient are given be­

low.

a. K a is independent of gas rate

o
b. Kga is independent of packing size

c. K a increases with liquid rate but this effect becomes less as

liquid rates become high

d. K a increases with normality of sodium hydroxide up to I.5IN

a^ter which it decreases

e. K a is a function of partial pressure of carbon dioxide which de-

pinds on the normality of the base used

f. Kga decreases as the average carbonate concentration increases

g. K a (s) for potassium hydroxide absorption of carbon dioxide are

greater than those of sodium hydroxide.

3* A correlating equation based on an assumed mechanism of transfer fits

all the data as indicated in Table III.

N
A (20)
o. 34.
■where K' = 0.0176 L (21)

4.. The following observations concerning K* are given below.

a. K ’is independent of gas rate

b. K 1is independent of packing size

c. K f is very nearly independent of thepartialpressure of carbon

dioxide within the range of the experimental data

d. K 1increases with normality up to I.5N beyond which itdecreases

 ^lightly. This seems to indicate the necessity for an additional
physical correlating factor such as viscosity. Within the range
of the experimental data, however, the effect of normality is
not too great.

e* K* (s) are higher with potassium hydroxide than with sodium hy­
droxide.

5* With the addition of an inert salt into the absorbing solution the

correlation fails. The effects of liquid and gas rates on K 1, however,

are the same as that mentioned in 4-a- and c* This was explained ("Corre­

lation and Interpretation of Data") by showing how the effect of ionic

strength on the solubility of carbon dioxide is different for different

salt solutions. In other words the use of the ionic strength factor in

the above correlating equation is specific for this system.

6. It is believed that these experiments and those of Koch, Stutzman,

Blum, and Hutchings1 raise some doubts concerning the validity of the li­

quid film hypothesis in gas absorption.

II. Gas Film Transfer Coefficient (Vaporization of 1-propanol)

1. As liquid rate increases k a increases at low liquid rates. At higher

g
rates there is no appreciable effect of liquid rate on k^a. This is in­

terpretsted to mean that liquid rate affects the transfer area ("a") in

k a.
g
2. Application of the Van Krevelen-Hoftijzer2correlation to these data

removes some of this liquid rate effect but is still not satisfactory in

this respect.

3. The effect of different inert gases (air, carbon dioxide, and helium)

on k a has been studied and it was found that the Van Krevelen-Hoftijzer2
g
correlation fits the data remarkably well. On the other hand, the Koch

1. Koch, H. A., Jr., Stutzman, L. F ., Blum, H. A., and Hutchings, L. E.,

Chem. Eng. Prog, to be published in 1949*
2. Van Krevelen, D.W., and Hoftijzer, P. J., Chem. Eng. Prog.,44l, 529-
536, 194-8.
 79
correlation, which also predicts the effect of inert gases on k a does
g
not.
 BIBLIOGRAPHY

1. Adams, F. W., Trans. Am. Inst. Chem. Eng.. 28, 162 (1932).

2. Brunner, E. Z . , Physik^ Chem.. 42, 67 etseq (1904).

3. Chilton, T. H., and Gilgore, A. J., Ind. Eng. Chem.. 18, 744 (1928).

4* Cogan, J. C., and Cogan, J. P., Thesis, Chem. Eng., M. I. T. (1932).

5. Davis, H. S., and Crandall, G. S., J. Am*. Chem. Soc.. £2, 3757, 3769
(1930).

6. Dwyer, D. E., and Dodge, B. F., Ind. Eng. Chem.. 33. 485 (1941).

7. Gill, K. S., Dissertation in Chem. Eng., Northwestern University,

(1948).

8. Gilliland, E.R., Ind. Eng. Chem.. 26. 681 (1934)*

9* Gilliland, E*R., and Sherwood, T. K., Ind. Eng. Chem.. 26. 516 (1934).

10. Haslam, R. T., Hershey, R. L*, Kean, R. H., Ind. Eng. Chem.. 16. 1224
(1924)*

11. Haslam, R. T., Ryan, W. P., and Weber, H. C., Trans. Am. Inst. Chem.
Eng.. 1£, 177 (1923).

12. Hatta, S., Tech. Ren. Tohoku Imp. Univ..8, 1 (1928-1929)*

13. Hatta, S., Tech. Rep. Tohoku Imp. Univ..10. 119 (1932).

14* Hitchcock, L. B., Ind. Eng. Chem., 26, II58 (1934)*

22, 461 (1935)*
22, 728 (1935)*
Trans. Am. Inst. Chem. Eng.. 36. 347 (1935)*

15. Hixon, A. W., and Scott, C. E., Ind. Eng,. Chem.. 22, 307 (1935)*

16. Hollings, H., and Silver, L., Trans. Inst. Chem. Eng.. (London), 12,
49 (1934)*
17. Hutchings, L. E., Stutzman, L. F., and Koch, Howard A., Jr., Chem.
Eng. Prog.. 45. 253 (1949).

18. Jenny, F. J., Thesis, Massachusetts Institute of Technology, 1936.

19. Jesser, B. W., and Elgin, J. CL., Trans. Ann Inst. Chem. Eng., ^2,
277 1943.
20* Koch, H. A., Jr., Dissertation in Chem. Eng., Northwestern University,
(1949).
 $-i

21. Koch, H. A., Jr., Stutzman, L. F., Blum, H. A., and Hutchings, L. E.,
Chenu Eng. Prog, to be published in 1949.

22. Kowalke, 0. L., Hougen, 0. A., and Watson, K. M., Bull. Univ. Wis.
Sb s .". Station, 68, (June 1923).

23* Ledig, P. G., and Weaver, E. R., J^ Am^ Chem. Soc.. 4£, 650 (1924).

24. Maxwell, J. C., Phil. Trans. Royal Soc.. 157. 49 (1866).

25. Mayo, F., T. G. Hunter, and Nash, A. W., J^ Soc. Chem. Ind.. 54, 375T

26. Mehta and Parekli, S. M. Thesis, M. I. T. (1939).

27. Mitsukuri, S., Sci. Rep. Tohoku Imp. Univ.. 18, 245, (1929).

28. Payne, J. W., and Dodge, B. F., Ind. Eng. Chem.. 24, 630 (1932).

29. Quinn, E. L., and Jones, C. L*, "Carbon Dioxide", Reinhold, New York,
1936.

30. Scheibel, E. G., and Othmer, D. F., Trans. Am. Inst. Chem. Eng., 40,
611 (1944).

31* Schimpf, H. W., "Manual of Volumetric Analysis", Wiley and Sons, New
York, Fifth Ed. (1909).

32. Scott, W. W., "Scotty Standard Method of Chemical Analysis", D. Van

Nostrand and Co., Fifth Edition, (1939).

33* Sherwood, T. K., Absorption and Extraction. McGraw Hill, New York,
1937.

34* Sherwood, T. K., and Gilgore, A. J., Ind. Eng. Chem.. 18, 744 (1928).

35* Sherwood, T. K., and Holloway, F. A. L., Trans. Am. Inst. Chem. Eng..
1£, 177 (1923).

36. Sherwood, T. K., and Reed, C. E., "Applied Mathematics inChemical

Engineering", McGraw Hill, New York, 1939*

37. Spector, N. A., and Dodge, B. F., Trans. Am. Inst. Chem. Eng.. 42.
827-848, (1946).

38. Stephan, J., Wien Akad. Sizungsber, 6£, (1871)*

39. Stull, D. R., Ind. Eng* Chem., 517 (1947).

40. Tepe, J. B. and Dodge, B. F., Trans. Anu Inst. Chem., Eng., 42, 827-
848, (1946).

41. Van Krevelen, D. W.,and Hoftijzer, P. J., Recueil des Trav. Chim.
des Fays Bas, 66, 49 (1947)•
 82
4*2. Van Krevelen, D* W., and Hoftijiser, P. J,, Chem* Eng* Prog* * LL*
529-536, 19-48.

4-3* Weber, H. C,, and Nilsson, K., Ind* Eng. Chem*. 18, 1070 (1926).

4A* Whitman, W. C*, Chem. Met. Eng., 29, No. 4., July 23 (1923).

4-5* Whitney, R. P., and Vivian, J. E., Chem. Eng. Prog.. 323, 1949.
APPENDIX
 83
Development of A Gas Film Transfer Coefficient (k a)

The gas film transfer coefficient kga has been developed from basic

diffusion equations. It is a conductance term for mass transfer across the

gas film in packed towers. Transfer of one component through a stagnant

film is described in detail in Sherwood's "Absorption and Extraction"1.

For diffusion to take place, the frictional resistance must be over­

come by a partial pressure drop of the diffusing component. This is the

basis for the further development of the equation below. Assumptions made

in this development are (l) ideal gas laws apply, (2) steady state flow,

(3) one component diffusion, (4-) single phase in film and (5) two film
theory.

% = 22---- (Pag - Pai)

RTxPbm
where R is gas constant

x thickness of gas film(effective)

D diffusivity

T Absolute temperature

Pbrn l°g value of the partialpressure of the inert gas

p partial pressure of diffusing component in the gas stream

pfll partial pressure of diffusing component in gas at the film

interface

In many cases the inert gas partial pressure approximately equals the total

pressure in which case the above equation becomes

2* NA = kg(pag - Pal)
if thetemperature and x are constant. It can be seen therefore that there

1. Sherwood, T. K., Absorption and Extraction. McGraw Hill, New York, 1937*
 84
are many assumptions which go into this development.

The equation mentioned above assumes a knowledge of* the transfer area*

This is not known accurately. Therefore, a device was suggested to enable

the application of this diffusion equation to packed towers. The above

equation applies only to one plane in a column. If a section height dh

is used then the total transfer in this height is G' dY where G* is

av av
the average gas velocity in lb. mols per hr.

3. Then dANA = G*aVdY = kg(p&g - Pai)dA

where A Is the transfer area in this section. If dA = adV where

a 1 is a constant, called the specific area then the above equation be-
comes

'mean &&
where dV is the volume of the section. Since the crossectional area

of a column Is constant, dV = A*dh where A T is crossectional area of column

Equation 4 becomes

kga (pag “ pai^m^fen

Let GJ.av be termed G* where G* is the inert gas rate in lb. mols/hr.-sq.ft
A
(crossectional area of column).

The result is an equation which can be used for design purposes.

G*dY = k a(p - p ) dh
& ag ai mean
 85

RELATIONSHIP BETWEEN OVERALL TRANSFER COEFFICIENT K a AND FILM TRANSFER

COEFFICIENTS kga AND k1& g

1* For steady state conditions where the rate of transfer of the diffusing

component is equal in each film, the following equations can be written

= G*dY = K aP(y - y*)dh

6
= G*dY = kgaP(y - yi)dh
na

= G»dY = k^ajf?*(x^ - x)dh

na
2. Rearrangement of above equations yields the following

a* (y - y*) = G_*dY
K_aPdh
g
b. (y - y±) = G ’dY
k„aPdh
e
c. (x± - x) = G ,dY
k-|_a^fdh

3* If Henry*s Law applies

y. = Hx. (interfacial equilibrium)

I r
y* = Hx* (y is defined as the composition (mol fraction) in
equilibrium with the main body of the liquid)

A. Substituting the above for x and x_^ in equation 2c and rearranging

y. - y * = G*dYH
1 k1ap,dh
5. By addingequation A to 2b andsubtracting theresult from 2a, the

following is obtained.

0 =
G*dY - GVdY - G*dYH
K aPdh k aPdh k ap*dh
g g 1
6. By rearrangement and dividingeach term by G*dYthe final relation-
dh
ship is obtained.

1 = 1 + H
K a P k aP k-jap*
g g
 86
Use of Log Mean Driving Force for the Calculation of K a in the Absorption
of Carbon Dioxide from Air by Sodium and. Potassium Sydroxide Solutions

1* The basic design equation is given below

G'dI = K aP(y - y*)dh

g
where Y = y
l - y

2. dY = dv
(i - y)2
3* Substituting in 1 and rearranging, the following is obtained

G ’dy = K aPdh
(i - y)*(y - j*) g

A* In the carbon dioxide absorption by sodium hydroxide y = 0 since

there is no measurable back pressure of carbon dioxide in a sodium hydroxide

solution.

if (i - y) approximately equals one such as in the case of very

low mol fractions of carbon dioxide in air, equation 3« becomes

G fdv = KgaPdh
y
5* Integrating from top to bottom of column where subscript one applies

to terms at the bottom and subscript two applies to the top

G*ln Xi. ~ K aPh (This' assumes K a and P are constant through

y2 ® tower) ®

6. Multiplying bothsides of equation 5 by (yi - yz)

G»(yi - y2) = K aPhfy, - y,)

In
Jz

7* This becomes

N = G = G fA Y = K aPhAy
A e m
where A ym is log mean driving force.
 8(

Use of Log Mean Driving Force for Calculation of k a in the Vaporization

of Pure Liquids 6
1. The basic design equation is

G !dY = ^ga(Pi “ p)dh

wlici*o
Pj_ is the interfacial partial pressure of the diffusing

component and in this case equals p since there is no concentration gra

dient in a pure liquid.

2. As in the previous derivation Y = y and equation 1 becomes

1 - y
G*dy = k adh
(1 - y)2(p* - p) g

3* y is usually less than 0*02 in these experiments therefore 1 - y = 1

Also P(y* - y) = (p* -p)

G fdv = k aPdh
(y* -y) g

A» If the liquid temperature is approximately constant, then Y is

constant and integration over the entire column yields the following

G'ln(y * - Vi) - k^a Ph

(y* “ Yz)

5. Multiply both sides of equation A by (y - y,) - (y -y2)

6. G !(y* -y-,) - (y*-y2) = kgaPh„(ylt -j;±)zLj*L-Ya.)

In .(y,„ . z J i l , -

7 -Yz
7. This becomes on simplification

Na = G ' & y = G ' A Y = kgaPh(y* -y)lm

 88
Gilliland Equation1 and Application to This Study

In the correlation of the gas film transfer coefficient (k a)

g
with several systems, it is necessary to know the gas diffusivity

(Dq ). When this is not available from experiments, it is necessary

to calculate it. The Gilliland equation1 is widely used and has been
applied to this problem*

D = °*00^ tV* \f 1 + i
P(Va 1/3 + V b 1/3)2 ^ m a Mb

D = diffusion coefficient, cm2/sec

T = absolute temperature, °K

Ma , M b = molecular weights of the two gases

P = total pressure, atmospheres

V Vg = molecular Volumes

To convert D to Dq in English units the following factor is used

D x 3600 x______ = 3*88

2.54 x 2.54 x 144

In the case of helium the atomic volume was not -available • A plot

of the logarithm of atomic volume versus logarithm of molecular weight

yielded a straight line (Figure 11) . Helium was assumed to be on

this line.

Example - 1-propanol in air (25°C)

D = 0,00A 3 x 5180 x 0.224 x 3,88 = 0*352 ft*a

G 55 hr

where

V(l-propanol)

1. Gilliland, E. R., Ind. Eng* Chem. * 26, 681, (1934)*

 O »jr,brsry
3 C A4-.4-

o 7.4

8 H 29*6
81*4.

V (air) given as 29*9.

ATOMIC VOLUME VS. ATOMIC WEIGHT

ATOMIC WEIGHT

FIGURE 11
 qr>

CHARACTERISTICS OF CERAMIC RASCHIG RINGS

Nominal Size f Free Space Surface Weight Number Units

sq.ft * lb. per per cu. ft.
cu. ft. cu. ft.

1/4- 52 200 67 45000

3/8 53 148 65 26000
1/2 53 1H 65 10700
 SAMPLE CALCULATIONS

K a and K 1
g
Run No* 90 Date - 6/9/48
Gas Sample - 100 c. c
Barometer - 747 mm. Hg
Packing Height - 2.83 feet
Packing size - 1/2 inch Raschig Rings

Liquid

Na2C03 - 0.00N
HC1 - 0.107N
Ba(0H)2 - 0.0465N (50 ml. in sample bottle)

Gas IN OUT

HC1 final 14.16 31.08

HC1 initial 00.00 14.16
mis. 14*16 16.92
meq. Ba(0H)2 2.320 2.320
meq. HC1 lf513 1.811
meq • C02 0.807 0.509
y 0.1006 0.0636
Y =___ __ 0,1120 0.0680
1 - y

&Y 0.0440
G ' & Y (G» = 7.72) 0.3390

Liquid
mis. HC1
Ba(0H)2 + NaOH 38.2 (50 mis Ba(0H)2 + 20 mis NaOH)
Ba(0H)2 (from standardization) 21.7
NaOH 16.5
20 mis. sample

HC1 final 7.80

HC1 initial 0.00
mis. 7.80
mols C02 transferred/
mol solution 3.76 x 10 3 ( A x)
L f£ x 0.348

Conversion Factors

meq. (milliequivalents) of carbon dioxide to mole fraction

For 100 mis. sample, correct to standard conditions and convert to

mols (gram)

y = moles carbon dioxide

moles gas
 ~ — x__ t x (460*+ t) x 76*0 x 224.60 =
2 x 1000 x 492 x Barometer x 100
(cm. Hg)
1*73 x 10"2 (4.60 + t) (meq.)
p
barometer
t = temperature of gas (°F)

Volume of HC1 from liquid titration to pseudo mole fraction of car­

bon dioxide in solution.

mis.. x NHC1 = mols carbon dioxide

1000 x 2

20 = mols of solution (assume all water)

18

(20 ml. sample)

Ax(change in mole fraction) = mis. x .107 x 20 = 0.0594 x 10“3

1000 x 2 x 18

K a =N . (based on liquid) where N - LAx

8 A PhAy A
m
K a = - x .348 x ■ = I .48
g 1 x 2.83 x .0806

A = *1006 - .0636 = 0.0806

In .1006
•0636

k * =
h(0H )(C0f)

NtNaOH)^ = 16.5 x 1.07 = 0.88N

x 20

N(NaOH)out = (16.5 - 7.8) 1.07 = O.465N

20

(0H”)av# = 0.88 +0.4.65 = 0.672N

2

N(Na2C03)in = 0.00N

N(Na2C03)o„t = 7.8 x .107 = 0.4UN

x 20

(C0J)av. = °-207N
Ionic strength (ju1) ~ £.(1/2 cZ.2)
 95
l|a + - 1 /2 x 0 .8 8 x I 2 = ~ 0 .4 4 0

0H“ - 1/2 x 0*672 x l2 = 0.336

CO3 - 1/2 x 0.207 x 22 = 0.207

2 0.9&3
f.0<)
M* = 0.981

K* = 0.3A8 x 0.981 x - = 0.855

2.83 x 0.672 x 0.207

2. k a
-g-
k a - NJL

Date 7/7/49

System - 1-propanol-air

Run No. 1 Barometer - 750 nmu

Height of Packing - 0.198*
Type and Size of Packing - 6mm. glass
beads
Column Diameter - 2.75 inches

Time Run (min.) 5!22,,j 5*28" (checked all runs)

Vol. Absorbed (mis.) 20

Rotameter Liquid - Reading 35

Rate 7*9 lb. moles/hr. sq. ft.

Gas Rotameter - ReadingO .46

Rate 8.5 lb. moles/hr. sq. ft.

Temperatures - (°C)

Gas in - 28.3 Liqiiid in - 22.2

Gas out - 24.1 Liquid out - 18.2

Calculation
N = 20 x 0.8 x 60 x _x ...— .. = O.I58
A x 60 x 5*43 x 454 x .0412

= mis, x grams x x min_._x grammole x .lb.moles__

x mis. x min. x hr. x grams x gram moles x sq.
ft
- lb. moles
hr.sq.ft.

G = 8 .5, &y = A Y = N, = 0.0186, y2 = 0.0186

OT
 %
Pi 12.7 ram. p2* 16*4 ram.
Pi o»o P2 13*9 = Py2
12.7 2.5

A Pm = 12_._7 - 2.5 = 6.27

In 12.7
2.5

~ 0.158 x 760 = 96.8 lb. mols

0.198 x 6.27 hr .cu. ft. atm.
 9.

VITA

Harold Arthur Blum

Born: April 19, 1921, New York City, New York

Educations Primary and Grammar Schoolss Jersey City,New Jersey

1925 1934
- .

High Schools Dickinson, Jersey City, New Jersey

1934-1938

Rensselaer Polytechnic Institute, Troy, New York

1938-1942, B. Ch. E.

Northwestern University, Evanston, Illinois

1946-1947, M. S. (Chemistry)

Northwestern University, Evanston, Illinois

1948- , (Chemical Engineering)

Employments Philadelphia Signal Corps Procurement District and

Chicago Signal Corps Inspection Zone - Engineer
1942 (June) - 1943 (December)

Army of the United States Signal Corps.

December 194-3 - May 1946

Northwestern University - Teaching Assistant (Chemistry

Department), 1947

Northwestern University - Research Fellowship sponsored

by United States Office of Naval Research
1948-1949

Professional Societies: American Chemical Society

American Institute of Chemical Engineers (Junior

Member)

American Association for the Advancement of Science

Sigma Xi

Phi Lambda Upsilon

Professional Engineer, State of Illinois