6
encountered in continuous operation. It might be well to point impurity is present, by xnea,ns of a measurement of specific
out, however, that if somewhat higher conductivities are to be resistance alone.
measured, a frequency of 60 cycles second can be applied.
This modification leads to a considera le reduction in equipment, One additional fact should be noted concerning the calibration
since the alternating current power line can then be used directly points shown in Figure 3. Although a comparison of one set
instead of the oscillator. Increased sensitivity to changes of of samples (different sets are indicated by different symbols in
specific resistance a t lower levels can be obtained by suitably the figure) with another wa.s in error as much as 1.50/, a t high
shunting t,he voltmeter, thereby reducing the value of r in Equa-
tion 9. purities, the accuracy of the calibration for any one set was more
consistent. A change in purity was always accompanied by a
change of meter reading in the correct direction. Thus changes
in purity were indicated to an accuracy much better than 1 . 5 ~ o ,
and the indicated purity always varied as it should with changes
in still temperature and reflux ra.te.
98t
96-
It) is of interest tha,t. the conductance of methyl vinyl ether
measured under flow conditions was consistently lower than that
of an equivalent immobile sample. A t first this effect was as-
a cribed t o a cleansing of the cell by the flowing liquid, but the
Y findings could also be explained in wcordance with Plumley’s
Li 94-
F! theory ( 5 ) . If favorable orientation in the electric field counter-
52 92-
acts recombination of the ions formed by spontaneous dissociation
c
8
one may expect a lawer conductivity in a flowing medium since
Y the ions are being carried away by the moving liquid.
2 90-
ACK8OW LEDGMENT ,
88 - \
\ The authors would like to thank H. Beller, new products
A. \ mansger of the General Aniline Works Division and his associ-
ates a t the Graseelli plant, for their wholehearted cooperation ;
0 50 I00 150 200 250 3, they are also grateful to R. M. Fuoss who made several valuable
RECORDER DEFLECTION (ARBITRARY SCALE1
suggest,ions on reading the manuscript. The chemical analyses
Figure 3. Recorder Scale Calibration of the methyl vinyl ether eamplrs vere performed by S. Siggis
and R . 1,. Edsberg.
In the h a l installation provisions were made for continuous LITERATURE CITED
recording by modifying the output of the electronic voltmeter (1) Fuoss, R. M., J . Am. Chem. SOC.,55, 21 (1933).
so t h a t it actuated a conventional temperature recorder. Figure (2) Jones, G., and Josephs, R. C., Ibid., 50, 1049 (1928).
(3) Onsager, L., J . Chem. Phys., 2, 599 (1934).
3 shows the correlation between the readings obtained on the (4) Pao, C. S., Phys. Rel;.,64, 60 (1943).
recorder and the values for methyl vinyl ether content deter- (5) Plumley, H. J., Ibid.,59, 200 (1941).
mined by chemical analyses of identical samples. The methods (6) Rosenthal, R., Instruments, 23, 664 (1950).
described by Siggia (8) and Siggia and Edsberg (9) were used for (7) Schildknecht, C. E., Zoss, A. O., and McKinley, C . , IND.ENO.
CHEM.,39, 180 (1947).
these determinations. As shown in Figure 3, in most cases the ( 8 ) Siggia, S., Anal. Chem., 19, 1025 (1947).
correlation was found to be quite good, Of course, since the (9) Siggia, S., and Edsberg, R. L., Anal. C h m . , 20,762 (1948).
same effect of decreasing the resistance may be obtained from RECEIVEDOatober 23, 1950. Presented before the Gordon Research Con-
many different kinds of impurity, it is impossible t o tell which ference on Instrumentation (A.A.A.S.), New London, N. H. (Auguet 1950)
P. V. DANCKWERTS
UNIVERSITY D E P A R T M E N T OF C H E M I C A L E N G I N E E R I N G , T E N N I S C O U R T R O A D , C A M B R I D G E , E N G L A N D
D
T HE conventional picture of the process of absorption of a gas
into a n agitated liquid, under conditions such that (‘the liquid
film is controlling,” is t h a t there exists a stagnant “film” of liquid
R = - (c*
XL
- GO) (1)
at the interface, similar to the laminar sublayer formed when a where R is the rate of absorption per unit area, c, is the bulk con-
fluid flows past a solid. The concentration of the bulk of the centration of the solute, D is its diffusivity, and X L i? “the effec-
liquid beneath this film is kept uniform by turbulent mixing, while tive film thickness” (9).
the surface concentration has a t all times the saturated value c“. It seems doubtful, however, whether the conventional picture
The rate of absorption (per unit area) will then be given by the bearP a very close relationship to the actual mechanism of absorp-
expression tion. The conditions reauirrd to maintain a stagnant film at the
June 1951 INDUSTRIAL AND ENGINEERING CHEMISTRY 1461
free surface of an agitated liquid appear to be lacking, and it tested by experiment. It may well be found that the processes
seems more probable that turbulence extends to the surface and occurring in gas-absorption equipment are too complicated to be
that there is no laminar boundary layer. I n particular, if we treated successfully by such simple methods as those presented
consider the liquid flowing over the packing in an absorption here, but the author hopes that these may constitute a step in the
tower, it appears most unlikely that the surface layer of liquid right direction.
maintains its identity throughout all the discontinuities of flow.
ABSORPTION INTO A STAGNANT LIQUID
The fictitious nature of the “liquid film” is probably widely
suspected; nevertheless, it is constantly referred to as though it Consideration is limited in the first place to the case where
actually existed. This may be regarded, for many purposes, as a the surface of the liquid is at all timea saturated with the solute
harmless and convenient usage, as measured absorption rates gas, and there is no chemical reaction between solute and solvent.
appear to conform to the expression If the normal diffusion law is obeyed in the liquid, the rate of
* absorption (quantity per unit area per unit time) into a stagnant
R = ~ L ( c *- eo) (2) liquid of infinite depth is given by
where k ~the , liquid-film mass-transfer coefficient, is constant for a
pjven liquid and gas under given conditions. However, if the
$(e) = ( C * - e o ) (3)
U film model is in fact an un-
where 6’ is the time of ex-
realistic one, it may lead t o
T h e present theory of gas absorption is based on a pic- posure to the gas and the
erroneous results if it is used
as the basis for theories which ture of the absorption mechanism which is probably un- initial concentration is uni-
seek to relate k~ to the con- realistic. For many practical purposes this is nnimpor- formly equal to co (see dis-
ditions of operation. tant, but the theory is likely to be misleading when used cussion of derivations of R
It may be of value, there- to predict the behavior of systems for which no experi- below).
fore, to show t h a t the proved mental data are available. A more plausible picture of the I t can be seen that unless
usefulness of Equation 2 in absorption process is therefore suggested. the surface is renewed by
no way provides support for The usual assumption of a “stagnant film” of liquid at stirring or by convection, the
the stagnant-film hypothesis, the interface is abandoned. Instead it is supposed that rate of absorption becomes
as this expression can be the surface is continually being replaced with fresh liquid, v e r y slow a f t e r a time.
derived from what is con- and a theory of absorption rates is developed on this basis. Stagnant water will normally
sidered t o be a more realistic It appears to agree generally with experience, but it must absorb in 1 hour a quantity
picture of the processes occur- be regarded as tentative until confirmed experimentally. of gas equivalent to a satu-
ring during absorption into
an a g i t a t e d l i q u i d . T h e
treatmeDt is here extended to
If the detailed features of the theory are confirmed, it
offers a powerful method of predicting the performance of
absorption equipment. Failing this, it may still provide
(taking D -
rated layer about 2 mm. thick
sq. em. pcr
second). If the “depth of
cases in which gas-film resist- suggestions for a new method of approach to the subject. penetration” is arbitrarily de-
ance or surface resistance fined as the depth a t which the
plays a part. Provided no rise in concentration is l/loa
chemical reactions occur, the expressions derived for the rate of ab- that a t the surface, it will be equal to 3.6 d E (see Equation
sorption are similar in form to those based on the film theory, but 27), with a value of about 6 mm. at 1 hour. (In the case, for
a different significance is attached t o the liquid-film coefficient. instance, of carbon dioxide and water, $ will conform to Equation
On the other hand, when the absorbed gas undergoes a reaction in 3 only for small values of 8; thereafter convection currents will
solution, the two methods of treatment give different expressions arise because the density of a solution of carbon dioxide is greater
for the relationship of the rate of absorption to such quantities as than that of water, and the predicted values of $ will be exceeded.)
the liquid-film coefficient without reaction, the reaction-velocity Under certain conditions Equation 3 can be applied as a close
constant, and the diffusivities of the components of the system.’ approximation to: (a)liquid layers of restricted depth, and ( b )
The expressions derived in this paper for the rate of a b s o r p liquid moving parallel to the surface with a velocity that varies
tion, R, under various conditions contain a quantity, 8 , which with the depth. The necessary condition for ( a ) is that the time
. relates to the rate of renewal of liquid surface. A complete de-
velopment of the subject would require further discussion of the
of exposure should be so short that the depth of penetration is
less than the depth of the liquid; for ( b ) it must be so short that
relation of s to the hydrodynamics and geometry of the system. the depth of penetration is less than the depth at which the veloc-
For the present s is regarded as a quantity which must be deter- ity is appreciably different from that a t the surface.
mined experimentally for any given system. The various expres-
* sions for R in terms of s are thus likely to be of use mainly in com- ABSORPTION INTO SURFACE O F TURBULENT LIQUID
paring rates of absorption in systems of equal 8. For instance, When a liquid is in turbulent motion it is a mass of eddies
suppose the rate of absorption of carbon dioxide into water is which incessantly change their conformation and position.
measured in a packed tower. With the same packing and flow These eddies are pictured as continually exposing fresh surfaces to
rate, and with a liquid of virtually the same density and vis- the gas, while sweeping away and mixing into the bulk parts of
cosity, s will have the same value, and under these conditions it the surface which have been in contact with the gas for varying
may prove possible to use the measurements on carbon dioxide lengths of time. The assumption will be made that during the
and water to predict the rate of absorption of, say, sulfur dioxide time of exposure of any portion of the liquid it absorbs gas a t a
into water or carbon dioxide into dilute alkali. (The possibility rate given by Equation 3, as in case ( b ) above. This is equiva-
of doing so depends in part on factors discussed under “Nonhomo- lent to assuming that the “scale of turbulence” is much greater
geneous Distribution of Surface Ages.”) than the “depth of penetration” of the solute diffusing from the
No attempt has been made to compare the expressions derived surface, so that relative motion of the liquid a t different levels
here with published experimental measurements. I n spite of close beneath the surface may be disregarded. Velocity gradi-
the enormous number of these, very few are suitable for an analy- ents no doubt exist beneath the surface, but while an increase in
sis of this sort, and in any case a knowledge of some of the essen- intensity of turbulence will accentuate these, it will a t the same
tial physical constants is at present lacking (particularly of ks,the time decrease the depth of penetration by shortening the period
“surface resistance” coefficient). for which any part of the liquid is exposed to the gas before being
The theory must be regarded as speculative until it has been submerged once more.
1462 I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Vol. 43, No. 6
Consider a liquid which is maintained in turbulent motion by Equation 6 t h a t for a series of solutes 1 / k ~should be linear in
stirring a t a steady rate. The total area of the surface which is l/dB.
exposed to the gas will be taken as equal t o unit and the average
rate of absorption is uniform over the area. &e motion of the Further complications‘will be introduced if the solute undergocs
liquid will continually replace with fresh surface those parts
which are older, in the sense that they have been exposed for a chemical reaction in the liquid, or if there is a gas-film resistance
finite length of time, The mean rate of production of fresh sur- or surface resistance. These are considered in connection with
face will be constant and equal to s, and the chance of a n element absorption in packed columns, and the expressions obtainrd are in
of surface being replaced within a given time is assumed to be in- general applicable to stirred liquids also.
dependent of its age; hence the fractional rate of replacement of
the elements belonging to any age group is equal to s.
Let the area of surface comprising those elements having ages
between 0 and (0 +
de) be +(B)d6. At steady state this does not
vary with time. Hence in a short time interval equal to de the
PACKED ABSORPTION TOWERS
renewal factor, s, will in this case depend on the physical proper- values of k ~ but
, this requires confirmation. Further investiga-
ties and rate of flow of the liquid and the geometry and size of the tion may show the phenomenon to be one of considerable impor-
packing. If the rate of absorption into a stagnant liquid, nThich tance in determining rates of gas absorption.
has been exposed t o the gas for a time e, is denoted by $(e), the Until more information is available, it is not possible to say
mean rate of absorption per unit area of wetted surface in the whether ICs is a function of the age of the surface, although this
section of packing will be seems unlikely. Assuming it to be constant, we have by analogy
with Equation 9
(7) e* - eo
R =
1 1
when the value of s is not homogeneous. Thus even a system 3. First-Order Reaction between Dissolved Gas and Sol-
with constant flow conditions, and for which k a is known, will vent.
show no simple relationship between R and D . All t h a t can be c = ca,x > 0, e = o
said ie t h a t R/(c* - e,) will be a unique function of D for a series C,L)&+r”
ae ax
c = C * , X = 0, e> 0
of solutes if H / k c is kept constant, and t h a t it will be a unique c < c ~ , x =~ . , e > o
function of H/SGfor a series of systems in which D is constant If conditions are such t h a t the concentration of unreacted ab-
(liquid-flow conditions assumed constant throughout). Such sorbed gas in the bulk of the liquid is negligibly small (c, = 0),
considerations indicate a basis for the correlation of experimental the solution of the above is, as has been shown elsewhere (6),
results, but are not of great practical valut-. Similar conclusions
may be reached regarding systems of the types referred to in
Equations 10 t o 14.
whence
dERlVATION OF EXPRESSlONS FOR R IN VARIOUS TYPES OF
SYSTEM
Two methods may be used. One is to solve the appropriate This result could have been reached much more directly by the
partial differential equation to find +(e), the rate of absorption per
unit area of surface into a stagnant liquid which has been exposed application t o the eneral case where eo 0. *
Laplace transform method, which will be illustrated by ita
Multiplying eacx term in the differential equation by e -80,
to the gas for time e. $(e) may then be multiplied by se-sO and integrating with respect t o e between 0 and 03, and making use of
integrated. as already explained, t o give R. This method is the first boundary condition, TVC find ( 3 )
used in cases 1, 2, and 4 below. Alternatively, the Laplace
dzE
transform may be applied t o the diffusion equation and the re- sC - co = D-
dx2
- rC
sulting ‘*subsidiary equation” solved for i ( ~s), , the Laplace
transform of c ( r , e) ( 3 ) . R is equal to - D s ( d z / d x ) , = 0. The while the second and third boundary conditions become
latter method, which is illustrated in cases 3 and 6 below, is
generally considerably simpler than the former, but is applicable
only when the‘ diffusion equation is linear.
A general rule for the “addition of resistances” is derived be-
low, so t h a t it is not necessary to consider the effect of an added
gas-film or surface resistance for each type of system separately.
where C, the Laplace transform of c, is defined by
1. No Reaction. Surface Constantly Saturated.
C,= c,,, x >0, e= o
C = C * , X = O , B > O
c = c ~ , x =0 0 , e > o The solution of the above is
The solution t o t,his is (1) -8
c o t p * \ s )- ~._le . -
c = co + (e* - c,)er.fc [A]
2de0 e =
(r +4 (33)
whence Now $(e), the rate of absorption at time e, is equal t o
- D (z),
bC
= whence it can be seen from the definition of C that
equivalents per unit volume), and T ’ = the second-order reaction where k is the appropriate mass-transfer coefficient. This trans-
velocity constant, we have for a stagnant liquid forms to
c = C*,X = o,e > o
c = 0, x > 0, e = o
c=O,x= m,8>0
C’ = e;, x > 0,e = o The new solution for Cis
c’=c,I,x= m,e>O
dc’
-=o,x=o,~>o
dX
R = (c* - A ) B .\/B
( A and B being constants) when the surface is constantly satu-
R =
e* -A
10%: 1
G5’i
R1= sJdm e-%(e)de
CONCLUSION
JU The considerations advanced in this paper raise two distinct
questions, which can be answered only by experiment.
1. Is the surface-renewal mechanism here postulated closer t o
the truth than the conventional picture of an undisturbed layer
The value of the ratio is seen to depend both on c:/c* and on a t the surface of the liquid?
P’c:/s, but because interest centers on systems in which s and 2. If so, does the distribution of surface ages in absorption
T’c.) are of comparable magnitude-i.e., diffusion and reaction
play roughly equal parts in determining the absorption rate- equipment of practical interest approximate to Equation 41
we may put r‘c,/s = 1 for purposes of illustration. It is then It should be possible to shed some light on the hrst by qualita-
found that c : / c * > 50 if Equation 36 is to be complied with. tive observations on stirred and flowing liquids, without reference
6 . Rule for Addition of Resistances. I n all types of systems
considered here the equation for C(x,s),the Laplace transform of to absorption. If the answer should prove to be “yes,” then the
the concentration a t x, has the following form: conventional picture is misleading, and should not be used as the
basis for theories of absorption although its terminology would
dzE
_ - aE b probably be retained as a matter of convenience. As regards the
dx2 - D - 5 (37)
second, careful measurements of rates of absorption, and of the
where a and b are constants. I n the case where there is no surface relevant physical quantities, such as k s , would be required to
or gas-film resistance, so that the surface of the liquid is con- determine thP answer; it mould be convenient if this should
stantly saturated with the gas, the boundary condition a t the prove to be “yes,” because a precise mathematical treatment
surface becomes could then be employed, as described above. Should the answer
to the second question prove to be “no,” the predictions of the
theory lose a great deal of their precision and utility, but this in
itself would not be a valid reason for preferring the “stagnant
whence film” hypothesis as a basis for further theoretical developments.
. $”’
liquid
r = velocity constant for first-order reaction between absorbed
gas and liquid
velocity constant for second-order reaction between ab-
(2)Ibid., p. 53.
( 3 ) Ibid., p. 240.
(4) Danokwerts, P. V., Research, 2, 494 (1949).
sorbed gas and reagent in solution
(5) Danokwerts, P. v., Trans. Faraday Soc., 46,300 (1950).
(6)Ibid., p. 701.
s = fractional rate of renewal of surface of liquid (7) Higbie, R., Trans. Am. Inst. Chem. Engrs., 31, 65 (1935).
so = value of s for area a
(8) Perry, J. H., “Chemical Engineer’s Handbook,” pp. 1179. 1184,
f v = volume of liquid per unit volume of packing
X L = “effective thickness of liquid film” New York, MoGraw-Hill Book Co., 1941.
x = distance beneath surface of liquid (9) Sherwood, T. K., “Absorption and Extraction,” p. 61, New York,
B = quantity defined by Equation 16 McGraw-Hill Book Co., 1937.
e = time for which a liquid surface has been exposed to gas, (10) Ibid., p. 196.
“age” of surface (11) Ibid., p. 202.
* = rate of absorption into unit area of surface of stagnant
liquid RECEIVED
August 8,1950.