December, 1924 INDUSTRIAL AND ENGINEERING CHEMISTRY 1215
ABSORPTION SYMPOSIUM
Papers presented before the Division of Industrial and Engineering Chemistry at the 68th Meeting of the American
September 8 to 13, 1924
Principles of Gas Absorption
By W. K. Lewis and W. G. Whitman
Massachusetts Institute of Technology, Cambridge, Mass,
information on.the operation of gas
is at present quite inadequate to
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absorption
ENGINEERING equipment
permit proper estimates and designs for new operations.
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Further progress in this field can be made most effectively
through a study of the mechanism of absorption phenomena
and of the factors which control them. When the basic prin-
ciples have been definitely established, they can then be
applied to specific problems by the engineer in the same man-
ner as he now employs heat transfer coefficients, friction
factors, and the like.
The object of this paper is to outline certain of the more
fundamental conceptions which have been developed from the
available data and from the general laws of reactions between
two phases.
The basis of all processes involving the absorption or the
escape of gas lies in the fact that a liquid-gas system which is
not in equilibrium tends to approach equilibrium conditions.
Thus, if the liquid is not saturated with gas under the exist-
ing conditions, absorption occurs, whereas if it is supersat-
urated the reverse is true. The escape of gas, as applied in
this case, is merely negative absorption, and for simplicity the
discussion will be confined to absorption alone.
Equilibrium or saturation represents the ultimate state
which the system tends to assume, and is the first of the pri-
mary characteristics of absorption phenomena to be consid-
ered. The other fundamental is the rate at which the sys-
tem approaches equilibrium, and in many cases the rate is
more important than the equilibrium itself. These two factors
are not independent of each other and, in general, the rate is
greater the further the system is from equilibrium.
Nature of Absorption Processes
Existing data clearly indicate that in almost all the cases
so far investigated the rate of absorption of a solute from a
gas by a liquid is limited by processes of diffusion. Any
other reactions which may take place are so rapid relative
to the speed of diffusion that they have no appreciable effect
upon the absorption rate. It is now becoming generally
recognized that wherever a liquid and a gas come into con-
tact there exists on the gas side of the interface a layer of gas
in which motion by convection is slight compared to that in
the main body of the gas, and that similarly on the liquid
side of the interface there is a surface layer of liquid which is
practically free from mixing by convection. This phenome-
non is frequently expressed by assuming the existence of
stationary films of gas and liquid respectively on the two sides
of the interface. This phraseology will be employed because
of its simplicity, although one should not infer that there is a
sharp line of demarcation between stationary liquid or gas
films on the surfaces and the major bodies of the fluids.
In the main body of either liquid or gas, except under spe-
cial conditions which will not be considered here, mixing by
convection is so rapid that the concentration of solute in the
Chemical Society, Ithaca, N. Y.,
fluid is essentially uniform at all points. (The exception
is illustrated in Becker’s paper, p. 1220 this issue, in experi-
ments with quiescent liquids. Differences in gas or liquor
concentration due to “channeling” in absorption apparatus
are not involved in this concept.) On the other hand, the
surface films are practically free from convection currents
and consequently any transfer of solute through these films
must be effected by the relatively slow process of diffusion.
These films, therefore, offer the controlling resistances to trans-
fer of a material from one phase to another.
Diffusion through the gas film proceeds at a rate that is
proportional to the difference between solute concentrations
in the gas on the outside and inside of the gas film. (Resist-
ance to diffusion due to a gas film is, of course, nonexistent
in the special case where an absolutely pure gas is being ab-
sorbed. This problem is very rarely encountered in prac-
tice, however, since the presence of very small amounts of
inert gas, which will concentrate at the liquid surface, is
sufficient to create an effective gas film.) Diffusion through
the liquid film, on the other hand, is controlled by the differ-
ence between the concentration of solute in the liquid at
the interface and its concentration on the other side of the
liquid film—i. e., in the main body of the liquid.1·* Since the
surface films are very thin, the actual amount of solute
contained in them at any one time is usually negligible com-
pared to the amount diffusing through them. It follows,
therefore, that all the solute which passes through one film
must also pass through the other, and the two films may be
considered as two diffusional resistances in series. Under
certain circumstances the importance of one of the films
may be so much greater than that of the other that the second
film may be neglected and the problem treated as if only one
film existed.
The concentration difference through either of these films
represents Aie potential or driving force that is causing
diffusion to take place. If the concentration differences be
expressed in identical units—e. g., gram mols per liter—it
is readily seen that the specific conductivity of the gas film
will be much greater than that of the liquid. The only
resistance encountered by the diffusing molecules is due to
their collisions with the interfering molecules of the gas or
liquid through which diffusion is taking place. Because of
the greater density of the liquid the collisions in the liquid are
much more frequent and the diffusional resistance is corre-
spondingly greater than in the gas. However, the resistances
to absorption are dependent also upon the film thicknesses.
It is to be expected that the gas film would be somewhat
thicker than the liquid, because under comparable conditions
of disturbance the major factor in determining film thick-
ness is probably the ratio of viscosity to density and this
ratio is greater for gases than for liquids. Despite this fact, the
greater specific conductivity of the gas film far more than
overbalances the greater film thickness, so that the actual
diffusional resistance encountered in the liquid film is much
greater than that in the gas.
The amount of solute absorbed per unit time by diffusion
through the two films is ^5·". (See table of nomencla-
* Numbers in text refer to bibliography at end of article.
1216 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 16, No. 12

ture for resumé of all symbols.) The amount of diffusion Effect of Solubility
is obviously proportional to the surface of the interface, A,
and it is therefore convenient to refer to the diffusional Certain simplifications of the general equation (1) are per-
missible when the conditions become such as to make one of
current density, This quantity is equal to the diffu- the two films negligible in importance as compared with the
sion coefficient per unit area (kg for a gas film or kL for a liquid other. Since these conditions are primarily determined by
film) multiplied by the concentration difference available as the solubility of the solute, it is desirable to consider as three
a driving force—i. e., separate cases the very soluble gases, the slightly soluble
gases, and those of intermediate solubility.
=
he(Pt -
Pi) =
kL(Ci -

CL) (1) Case I. Very Soluble Gases—The absorption of hydro-

where P =
gas concentration
C liquid concentration
=
and the subscripts g, i, and L refer respectively to conditions
at the outside of the gas film, at the interface, and at the inside of
the liquid film.
It is clear that the numerical values of the diffusion coeffi-
cients kQ and kL will depend upon the units in which the gas
and liquor concentrations are expressed. The choice of these
units, is purely arbitrary. In this paper solute concentration
in the gas is expressed as its partial pressure in fractions of
an atmosphere and concentration in the liquid as grams per
cubic centimeter because of the convenience of these units.
This makes the separate values of kg and kh of the same
order of magnitude for many cases and offers a good working
basis which will be employed throughout the paper.
Table op Nomenclature
W —
gen chloride in water is typical for the very soluble gases.
In dilute solutions this gas is so soluble that even a 20 per
cent solution (0.18 gram per cubic centimeter) exerts a
vapor pressure of hydrogen chloride of less than 0.2 mm. Hg
(0.00026 atmosphere) at 30° C. In this case the solubility
of the gas makes it possible to build up high concentration
gradients through the liquid film, although the concentration
in the gas at the interface may be very small. In other words,
once it reaches the interface, the hydrogen chloride is rapidly
sucked through the liquid film and the gaseous concentration
Pi is maintained at a very low figure. The absorption rate for
this extreme case will be determined almost solely by the rate
of diffusion through the gas film under a difference in gaseous
concentration substantially equal to Ps since the value of
Pi is negligibly small in comparison with Pa. The general
formula can therefore be simplified for very soluble gases to
the form
= kP
° s (4)

weight of solute, in grams AdQ

'=
time, in hours
dW and the problem treated purely as a case of gas film diffusion.
rate of grams per hour
„
— =
absorption, in
The same result can be reached by a more mathematical
dQ
A area of liquid-gas interface, in square centimeters
= treatment. Consider the absorption of hydrogen chloride by
kg diffusion coefficient through gas film
=
water from an air mixture in which the partial pressure of
kL diffusion coefficient through liquid film
hydrogen chloride is 0.1 atmosphere. The gas at this pres-
=

P concentration of solute in gas, in atmospheres

=

C concentration of solute in liquid, in grams per cubic centimeter

=
sure would be in equilibrium with a saturated solution con-
Subscript g applies to conditions in main body of gas taining 0.39 gram hydro-
Subscript i applies to conditions at liquid-gas interface gen chloride per cubic
Subscript L applies to conditions in main body of liquid centimeter at 30° C.
solubility coefficient = liquid concentration in grams per cubic
=

The liquid concentration

centimeter divided by equilibrium gas concentration in atmos-
pheres at the interface, Ci,
Kg over-all diffusion coefficient, based on gas concentration
=
would therefore be
Kl over-all
—
diffusion coefficient, based on liquid concentration somewhere between the
molecular weight of solute
=

limits of zero (that of

The data at present available indicate that at the true
the main body of liquid)
and 0.39 (that of a satu-
interface between liquid and gas the two phases are at sub-
rated solution). This
stantial equilibrium (Pi in equilibrium with Ci), even though
concentration would be
there may be rapid diffusion and therefore high concentra-
tion gradients through the films on the two sides of that inter- definitely fixed by Equa-
tions 2 and 3. For ex-
face. This fact puts us in a position to visualize clearly what
takes place in an absorption process. (Figs. 1 and 2) Con- ample, if the absorption
ditions at the outside of the gas film and at the inside of the
conditions were such
that kg fci, the equa-
=

liquor film are the same as those in the main bodies of gas and tions would be satisfied
liquid, respectively. Conditions at the interface are deter- 0.1 and Pi
mined by two factors: first, the equilibrium between gas and by Ct = =

0.000021; if kg 2kL,
=

liquor concentrations; and second, the fact that all the Ci =

0.2 and Pi =
solute diffusing through the gas film must also diffuse or íSoa </£/l /ry
0.00037; and if kB = /v/o/f
through the liquid film. Thus, 0.5 kj,, Ci 0.05 and
=
fact)
Fig. 1
Pi ñQ) =
(2) Pi =
0.0000054. It will
be observed that in the three examples the value of Pi is so
this function being the solubility relationship; and from
low compared to Ps that it can be neglected in the expression,
Equation 1 from (1)
UP, Pi) kL(Ci CL) ~ -
(3) -

dW
If the values of hg and of kL are known, the values of Pi and AdQ UP, Pi)
= -

Ci, the interfacial concentrations, are at once determined by and we may substitute the simpler form of Equation 4.
these two considerations. If, for example, ka should be Fig. 1 shows the film conditions diagrammatically, with the
just equal to U, (P, P<) would have to equal (Ci
—

CL) —
concentrations prevailing at the interface when kg kh. =

to satisfy Equation 3. The sudden rise in concentration at the interface is due to the
December, 1924 INDUSTRIAL AND ENGINEERING CHEMISTRY

solubility characteristics of this solute—i. e., a low partial or;

pressure in the gas is in equilibrium with a high liquid concen- dW =
KL(Cg -
CL) (8)
tration because the solute has a great affinity for the water Ade
phase. It will be noted that the concentration gradient and the over-all coefficients, Kg and Kl, can be obtained from
through the gas film is essentially the same as it would be if the individual film coefficients, kg and kz, by algebra, using
no liquid film existed. Equations I, 6, and 7 or 8. Thus
Case II. Gases of Low Solubility—With gases of low
HkLkg
solubility the rate of absorption is low because only very Ka =

HkL + kg
(9)
small concentration differences can be established across the
and
liquid film. The solute diffuses so slowly through the
Kg kL kg
liquid film that only a small concentration difference is re- _ _
~ _

Hkh + kg (10)
quired across the gas film. As a result the liquid at the
.

interface is substantially saturated with solute at the pres- From the nature of the over-all coefficients it will be seen
sure Pa and it is unnecessary to consider the gas film in the that the over-all coefficient Kj, can never be greater than the
calculations. liquid film coefficient kh, and similarly, that Kg can never
This may be shown mathematically for the absorption of be greater than kg. 0 099996-
0
oxygen at 0.1 atmosphere by oxygen-free water at 30 C. Sat- It should be noted that
uration under these conditions corresponds to only 0.0000037 theoretically the over-all 'Ell \
gram per cubic centimeter, and the value of Ci must there- Equations 7 and 8 can
fore be between this saturation value and the zero concentra- be applied only to iso-
tion of the main liquid. As in the earlier example, Ci is de- thermal absorptions,
termined by Equations 2 and 3. If k0 ki., Ci 0.0000037 = =
since the coefficient of
and Pi =
0.0999963; if ka 2kL, Ci 0.0000037 and Pi
= =
Henry’s law changes
=
0.0999981; and if kQ 0.5 kh, Ci 0.0000037 and Pi
= = =
with temperature. In
0.0999926. It is evident that in all cases Pi is essentially the practice, however, it is
same as Pg—i. e., the interfacial conditions are practically the permissible to employ
same as those existing in the main body of the gas. The value this method over narrow GAS
of Ci is therefore the same as that of a liquid saturated with ranges of temperature.
oxygen at Pg, and may be expressed as Cg. It then becomes The treatment for
possible to express the rate equation as soluble gases which do
not approximately obey
xL·
=
w -

^ <5>
Henry’s law over the
and eliminate any consideration of the gas film. range being studied, and
The film conditions for oxygen are represented in Fig. 2, yet are not soluble
with the concentrations prevailing when kg kh. The = enough to be treated
sudden drop in concentration at the interface is due to the low under Case I, may be-
come quite complicated. T
solubility of this solute—i. e., its slight affinity for the water In such cases, one must Ci 0.0000037
=

phase. It should be noted that the relative slopes of the gas Cases of Low Solubility
and liquid gradients are the same as in Fig. 1, since resort to the original (Oxygen)
equation and work out
W-f
- Cz£,
=
77
Kp
(= 1 for both figures) a method of integra-
Fro. 2

tion which is determined by the character of the solubility

In the diagram it is necessary to magnify the slopes of the
gradients, since they would appear as horizontal lines if drawn
to scale.
Case III. Gases of Intermediate Solubility—There
are many important cases where the gas is too soluble to per-
mit one to neglect the gas film (Equation 5), but is neverthe-
less not soluble enough to allow the liquid film to be disre-
garded (Equation 4). General Equation 1 must be used as
the basis of calculation for such gases.
Fortunately, however, an over-all coefficient, combining
the two film coefficients, may be used whenever Henry’s
law holds over the concentration range in question. The
concentration difference to be used with this over-all coeffi-
cient is the total difference between gas and liquid, expressed
in comparable units. Thus, if gaseous concentration is
expressed as partial pressure, Pg, the corresponding liquid
concentration must be given as the partial pressure, PL, in
equilibrium with the liquid concentration, Cl. Correspond-
ingly, the gaseous concentrations must be expressed as Cg
(the liquid in equilibrium with Pg) if the liquid concentra-
tion, Cl, is used.2-3·4
If the Henry’s law relation is shown
C HP
=
the absorption equation becomes
g; =
Kg(Pg-PL)
curve. The absorption of hydrogen chloride in solutions of
strong hydrochloric acid (which exert a vapor pressure of
HC1) represents this type of problem. Fortunately, most
industrial problems can be classified under one of the three
simplified treatments.
Other Variables
The discussion has so far considered only the effect of solu-
bility of the gas as affecting absorption rate per unit area.
The other important valuables are the diffusion coefficients
kg and kh, which can be varied considerably by the character
of the absorption process. Any factors which tend to cut
down the thickness of the surface films should increase the
coefficients and correspondingly speed up the absorption rate.
Thus, agitation of the liquid increases diffusion through the
liquid film, while higher gas velocities past the surface cause
more rapid diffusion through the gas film.
The effect of such factors will be somewhat dependent
upon whether the process is controlled by gas film or liquid
film diffusion. Thus, a change that decreased the thickness
as of the gas film but did not affect the liquid film would increase
the absorption of hydrogen chloride but would not affect the
(6)
rate of oxygen absorption.
Changes in temperature affect several factors, and it is
necessary to distinguish clearly between the effect of tempera-
(7) ture on the equilibrium and its effect on the coefficients of
1218 INDUSTRIAL AND ENGINEERING CHEMISTRY
diffusion. Increase in temperature makes the gas less solu-
ble, thus tending to lower the rate of absorption. The
diffusion coefficients themselves may, however, be either
raised or lowered by temperature, depending upon changes
in film thickness and in specific diffusivity. Liquid film
coefficients, kz, rise rapidly with increasing temperature,
both because of decreased film thickness due to lowered
viscosity and because of greater diffusivities. On the other
hand, Haslarn, Hershey, and Kean6 show that the gas film
coefficients, k0, decrease somewhat as the temperature rises
because the ratio of density to viscosity for the gas decreases
and therefore the gas film becomes thicker. Although little
is known regarding the effect of temperature on specific
diffusivities through gas films, it seems evident that this
effect is less than that due to an increase in the film thick-
ness.
A type of apparatus in which gas bubbles up through a
liquid would represent vitally different conditions from one
where liquid drops are sprayed through a gas. In the first
instance, a rising gas bubble would continuously expose
fresh liquid surface and the conductivity of the liquid film
would be high, whereas the gas film would be relatively
undisturbed. Such a device should therefore be most satis-
factory for absorbing the less soluble gases where liquid film
diffusion is controlling. In the other case, a falling drop
might be expected to have only a very thin gas film but a
fairly thick liquor film. Apparatus of a spray type might
therefore be well suited for absorbing very soluble gases.
From these suggestions it is evident that the ratio of film
conductivities varies with the type of apparatus and
with the conditions of operation. It is therefore quite possible
that the absorption of a gas of intermediate solubility might
be controlled primarily by liquid film diffusion in one piece
of equipment and by gas film diffusion in another. This
point is illustrated later by the case of sulfur dioxide, which
is almost entirely governed by the liquid film when passed
over a free surface of liquid, but which is largely affected by
the gas film when absorbed by bubbling through water.
It is possible to predict comparative performances of dif-
ferent solutes in the same equipment on the basis of this
general concept. Under similar operating conditions the
effective film thicknesses will in most cases be independent of
the solute that is being absorbed.
It has been shown6 that for low concentrations of the
diffusing component there is a definite relationship between
the coefficient of diffusion of material through a gas film and
the coefficient of diffusion of heat through the same film. In
the units here employed this relationship requires that the
gas film coefficient be proportional to the molecular weight of
the diffusing substance. The total gas pressure and charac-
ter of the inert gas are also involved in such a way that the
coefficient varies inversely with the product of the molecular
weight of the inert gas and the total pressure. This relation-
ship is based upon a thermodynamic analysis, which is be-
lieved to be valid so long as the- concentration of the diffusing
component relative to that of the interfering gas is low. In
other words, we have dependable information as to the
change of the gas film coefficient with changes in solute,
inert gas, and total pressure. Furthermore, the influence of
such other variables as velocity, temperature, and the like
must be identical for different diffusing substances.
Our knowledge as to liquid film coefficients is incomplete.
It is known that as the molecular weight of the diffusing
material becomes high its diffusivity decreases, but the data
show clearly that the change in diffusivity is small com-
pared with that in molecular weight. In the absence of
more definite information the authors have elected to assume
Vol. 16, No. 12
that the liquid film coefficient follows the same rule as that
just given for the gas film. In the units here employed
this means that the liquid film coefficient, kz, under condi-
tions of equal film thickness, is the same for all substances.
This approximation is somewhat justified by the fact that
diffusivity data given in the literature show a surprisingly
small variation for various weak electrolytes and other
aqueous solutions of low molecular weight.
Correlation of Data
Certain of the published data on absorption rates illustrate
the applicability of these principles and the effects of certain
factors and types of apparatus. The experimental methods
employed may be grouped in two general classes—those in
which the gas was bubbled through the liquid, and those in
which the gas was passed above the liquid surface. Since
there is a marked difference in the absorption characteristics
under these conditions, the discussion will consider each one
separately.
For purposes of comparison, wherever possible, results are
expressed, not only as diffusion coefficients, but also (for
liquid film processes) in terms of effective film thicknesses.
The calculation of film thickness is based on Hufner’s data for
the specific rate of diffusion of oxygen through water. Huf-
ner’s figures show that 0.067 gram of oxygen diffuse per hour
through an area of 1 sq. cm. when the diffusion layer is 1 cm.
thick and the concentration difference between the ends of
this layer is 1 gram per cubic centimeter. The effective film
thickness in centimeters for an absorption layer is then cal-
culated by dividing Hufner’s figure of 0.067 by the value of kz.
Gas Bubbled through Liquid—Adeney and Becker7
studied the absorption of oxygen, nitrogen, and air by water
from gas bubbles. The solubilities of these gases are so low
that they may be classed under Case II as examples of liquid
film diffusion. The absorption rates in these experiments were
very rapid, giving values of kz as high as 60 (Equation 5)
expressed as grams absorbed per hour per square centimeter
when the concentration difference is 1 gram per cubic centi-
meter. This kz of 60, obtained at 20° C. with an elongated
bubble about 15 cm. long, offering 20.5 sq. cm. of surface area,
corresponds to a film thickness of 0.0011 cm. The largest
bubble used in their work had about three times the surface
area of the one noted above and gave a coefficient of 43
corresponding to a film thickness of 0.0016 cm. The effect
of increasing temperature was to increase the coefficient
almost linearly owing to greater fluidity; thus the value of
kz doubled in going from 0° to 35° C.
Ledig and Weaver,8 absorbing a bubble of carbon dioxide
in water, report results from which the calculated value of
kz is about 80, corresponding to a film 0.0008 cm. thick. This
coefficient is greater than the maximum obtained by Adeney
and Becker, but the carbon dioxide bubble was much smaller
and was nearly spherical. As Adeney and Becker intimated,
the coefficient should be greater under these conditions.
Perman9 studied rate of escape by bubbling air through
solutions of ammonia, chlorine, bromine, sulfur dioxide, and
hydrogen sulfide in similar experiments. The data are too
incomplete to permit a calculation of specific absorption
rates, as the rate of air flow and size of bubbles were not
recorded. His work, however, allows a comparison of rates
between gases which vary widely in solubility. Berman’s
data are shown in Fig. 3, in which the logarithm of the liquor
concentration is plotted against the time of bubbling air. The
significance of these data may be analyzed by computing
the over-all diffusion coefficients for the whole apparatus,
AKz and AKa (Equations 8 and 7). If the values of AKl
should be constant for the five gases it would mean that the
process is substantially liquid film diffusion alone for all of
December, 1924 INDUSTRIAL AND ENGINEERING CHEMISTRY 1219

them and hence that the over-all coefficient KL is practically
identical with the film coefficient kL. On the other hand,
if the values of AKg were nearly constant, varying only with
the molecular weight as previously noted, it would indicate
that gas film diffusion controls in all five cases, the over-all
the most soluble gas, ammonia, the process is largely con-
trolled by the gas film.
The validity of this reasoning may be checked in a semi-
quantitative way by assuming that the chlorine and hydrogen
sulfide diffusions are entirely liquid film (AKL AkL) and=

coefficient Kg being equal to the film coefficient kg. that the ammonia diffusion is entirely gas film (AK„ =

The values of AKL in the second column of Table I were de-
termined directly from the slopes of Fig. 3, with the addi-
Akg). The values of AkL and Akg may be taken in round
numbers as 1170 and 2.1 X M, respectively, and used in
Equation 10 to predict the over-all coefficients AKL for the
other gases.
AkLk„ 1170 X 2AM
L
HkL + k„ X 1170 + 2AM
The coefficients figured from this formula are given in the
sixth column of Table I and show a reasonable agreement
with the experimental values of AKh in the secohd column.
Gas Passed oveb Liquid Subface—Adeney and Becker10
studied the aeration of quiet columns of pure and salt water.
They found coefficients, kL, for the relatively insoluble at-
mospheric gas of about 0.4 for pure water and 0.5 for salt water
at 15° C., corresponding to film thicknesses of 0.17 and 0.13
cm., respectively. These rates obtained with quiet liquid
surfaces are about one-hundredth of those realized with gas
bubbles.
When the liquid is stirred the rate, of course, is greatly
increased. Thus Becker11 obtained coefficients of 5 at 150
r. p. m. of his stirrer and of 15 at 1000 r. p. m. in another set of
experiments with air. Bohr2 studied both absorption and escape
of carbon dioxide by passing gas over a liquid surface, and the
coefficients calculated from his data give a value of about
7.5 at 250 r. p. m. He also found that the coefficients for
absorption approximately checked those for escape. Davis12
passed oxygen gas over water and obtained a value of kL of
about 3.3 at 60 r. p. m.
The effect of velocity on the liquid film is shown in a
qualitative way by the table of results by different investi-
gators.

thickness
R. p. m. Investigator Gas kjj Cm.
At rest Adeney and Becker Oe, N2 0.4 0.17
60 O2 3.3 0.020
150 Becker o2, N2 0.013
250 Bohr co2 7.5 0.009
1000 Becker o2, n2 15 0.0045

tional information that 50 cc. of liquid were employed in It is somewhat fortuitous that the order of absorption rates
each experiment. The third column gives the solubility so closely follows that of the rates of stirring when different
coefficient H under the experimental conditions. Values of types of vessel and stirrer were employed by the various
AKg were calculated by multiplying AKh by H (Equation experimenters. Becker’s own data on rates of stirring,
10), and these values are divided by M in the fifth column however, show in a more quantitative way that the coeffi-
to compensate for the effect of molecular weight on the gas- cient increases almost proportionally to the 0.8 power of the
eous coefficient. velocity of rotation.
Davis also absorbed more soluble gases under conditions
Table I
A Kg A Kl caled,
similar to those of his oxygen runs. He found the following
AKl H A Kg M as below over-all rate coefficients KL and K„:
cn 1340 0.0096 12.9 0.18 1090
HiS 1000 0.0048 4.8 0.14 1090 Table III
Bra 490 0.238 117 0.73 640
SOa 380 0.199 76 1.2 430 KL Kg
NHa 19 1.90 36 2.1 19 O2 in water 3.3 0.00014
SO2 in water 3.6 0.47
NHa in water 1.6 1.5
Since neither the values of AKL nor those of are con- HC1 in water 0.29 4.0
NHS in 2.3 N HC1 2.4
stant, it is evident that neither gas nor liquid film alone con-
trols the diffusion for all five gases. The coefficients AKL Just shown with Permán’s data, the values of KL de-
as was
decrease with increasing solubility, showing that the least crease and those of Kg increase with increasing solubility.
soluble gases (chlorine and hydrogen sulfide) most nearly Assuming that the absorption of ammonia in hydrochloric
approach purely liquid film diffusion. For example, ammo- acid solution is controlled entirely by gaseous diffusion in this
nia could escape much more rapidly than it actually does if case (Kg kg), and that oxygen absorption is a purely liquid
=

only the liquid film had to be considered, since the value of film phenomenon (KL kL for O2), one may calculate how
—

AKl for ammonia would be at least as high as 1000. The rapidly sulfur dioxide, ammonia, and hydrogen chloride,
which are between these two in solubility, should be absorbed
values of increase with solubility, indicating that with
by water. In a more complete discussion of this work, to
1220 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 16, No. 12

be given in a later paper, it is shown that the predicted ab-
sorption rates check the experimental rates within 15 per
cent for all three gases.
It is of interest to note that the ratio of liquid to gas film
kl
coefficients j- is roughly about 15-30 to 1 in the
of gas
case
bubbles (estimated from Perman’s data); whereas the ratio
is only about 1 to 1 for gas passed over a liquid surface (using
Davis’ data). This difference can probably be attributed
more to the exceedingly thin liquid films obtained around gas
bubbles than to any marked change in gas film thickness.
Conclusions
Rate of absorption is controlled by rate of diffusion of so-
lute through the surfac'e films of gas and liquid at the gas-
stirred as rapidly as possible without causing splashing, the value
of the rate of solution was only about half the value obtained
when the absorption took place from a bubble rising through the
liquid. A further important point is the form of the bubble,
as this determines the area it exposes for a given volume, and also
the rapidity with which the film surrounding it is renewed as it
rises in the liquid. From previous experiments it has been
found that the most effective form is that of a cylindrical bubble
ascending a fairly narrow tube, as this gives the maximum of
mixing of the liquid for a given speed of rise.
The remarkable effect of very slow stirring of the liquid in re-
ducing the effective thickness of the film is of great importance
when circumstances are such that a relatively insoluble gas has
to be absorbed without bubbling the gas through the liquid, as
by this means it is possible to obtain a very large increase in the
rate of solution with the expenditure of very little power. Thus
a stirrer running at only 60 r. p. m. increases the value of kt for
oxygen about twenty-five times, as compared with stationary
water.

liquid boundary. The relative importance of the two films is

determined primarily by the gas solubility and to a lesser
degree by the conditions of operation.
Gas bubbles give very thin liquid films and are therefore
particularly adapted to the absorption of the less soluble
gases. On the other hand, the rates for the more soluble
gases are limited by slow diffusion through the gas, and this
effect becomes increasingly evident with gases above sulfur
dioxide in solubility.
Absorption through free liquid surfaces is enormously
increased by stirring the liquid. The same general con-
siderations hold as for gas bubbles, but the liquid film is
thicker relative to the gas film. For this reason the effect
of the gas film is less noticeable with sulfur dioxide, although
with more soluble gases it comes into prominence.
Bibliography
xl:—Whitman, Chem. Met. Eng., 29, 146 (1923).
2— Bohr, Ann. Phys. Chem., 68, 500 (1899).
3— Lewis, J. Ind. Eng. Chem., 8, 825 (1916).
4— Donnan and Masson, J. Soc. Chem. Ind., 39, 236 (1920).
5— Haslam, Hershey, and Kean, Ind. Eng. Chem., 16, 1224 (1924).
6— Lewis, Mech. Eng., 44, 445 (1922).
7— Adeney and Becker, Phil. Mag., 38, 317 (1919); 89, 385 (1920).
8— Ledig and Weaver, J. Am. Chem. Soc., 46, 650 (1924).
9— Perman, J. Chem. Soc. (London), 67, 868 (1895),
10— Adeney and Becker, Phil. Mag., 42, 87 (1921).
11— Becker, Ibid., 46, 581 (1923).
12— Whitman and Davis, Ind. Eng. Chem., 16, 1233 (1924).
Discussion
In the discussion following this paper, R. E. Wilson sug-
gested that the general absorption equation could be expressed
using partial pressures multiplied by the solubility coeffi-
cient in place of liquid concentrations for diffusion through
the liquid film. Dr. Lewis pointed out that, although this
was quite permissible in those cases where the solubility
followed Henry’s law, it did not really simplify the problem
and could not be used when the solubility relationship was
not linear. The chairman noted that this method of presen-
Mechanism of Absorption of Moder-
ately Soluble Gases in Water
By H. G. Becker
Standard Oil Company op New Jersey, Elizabeth, N. J.
When the Liquid Is Mixed
liquid and a moderately soluble gas are al-
a
WHEN lowed tocome in contact and the liquid is kept
thoroughly mixed so that it may be regarded as of
uniform composition at all points, the rate of solution of the
gas varies directly as the degree of unsaturation of the liquid.
This has been shown experimentally by following the course of
the absorption of oxygen and nitrogen in air-free water by a
method which allowed the liquid surface to remain unbroken
although the liquid was vigorously mixed.1 The method used
consisted in allowing a large, cylindrical bubble of the gas to
pass up through a tube full of water which was initially air-
free, and measuring the reduction in pressure which resulted in
the bubble, due to the absorption of a portion of the gas. After
each traverse of the bubble, the pressure could be restored to
its original value by connecting the
gas space with an air res-
ervoir by means of a special tap. The process of absorption
could thus be followed step by step from zero concentration of
dissolved gas to saturation.
The curves shown in Fig. 1 which are for oxygen, show the
regular way in which the percentage saturation of the liquid
with the gas increases with time, and it is found that when the
rate of solution at various points on the curve is plotted
against the corresponding gas content of the liquid a straight
line results. The rate of solution can therefore be expressed
in the form
Integrating,
m a/b ce~u — =

tation wa§ employed in a later paper (by Professor Haslam)

and that the choice between the two systems of expressing For the experiments with air-free water,
liquid concentration would be primarily determined by con- When< 0, w
=
0, c a/b
= = —

venience in using the equations. Therefore w a/b (1 =

e~ht) —

Dr. Becker communicated tjhe following discussion: and when t infinity, a/b
= w w„ the saturation value
= =

Hence, w =
iv, (1 —
e~M)
It should be pointed out that the film theory can apply only cubic centimeter of liquid at
when the liquid is mixed and in fact that it will have its most where weight
w = of gas per
precise application when the conditions on both sides of the time, t
interface are distinctly turbulent. When the gas and the liquid hi, weight of gas per cubic centimeter of liquid at
—

are not kept in motion other factors appear to become of greater equilibrium
importance and the values of the absorption rates are not then When the initial gas content w, is not zero, this expression
always proportional to the solubility of the gas. becomes
The conclusion that for the absorption of less soluble gases a
bubble rising through the liquid is the most efficient device is
borne out by my experiments on stirring. When the liquid was 1
Adeney and Becker, Phil, Mag., 38, 317 (1919); 39, 385 (1920).