October, 1934 INDUSTRIAL AND ENGINEERING CHEMISTRY 1093

(8) Hinchley and Himus, Trans. Inst. Chem. Engrs. (London), 2, (17) Sherwood, Chemical Engineer’s Handbook, p. 1222, McGraw-
57 (1924). Hill Book Co., New York, 1933.
(91 Hine.
\-, - I~ -
Phvs. Rev.. 24. 79 (1924). (18) Stanton, Brit. Advisory Comm. Xironautics, Rept. & .)fern.,
94 (1913).
(10) Jurges, Beih. Gesundh. In;., 19 (1924).
(11) Kirkbride, IND. ENG.CHEM.,25, 1324 (1933). (19) Stauffer, Roberts, and Whitman, IND. ENG.CHEar., Anal. Ed.,
(12) Ibid.. 26, 425 (1934). 2, 88 (1930).
(13) Kirschbaum and Kranz, Chem. Fabrik, 7, 176 (1934). RECEIVED July 30, 1934. Presented as part of the Symposium on Diffu-
(14) Monrad and Badger, IND. ENG.CHEM.,22, 1103 (1930). sional Processes before the Division of Industrial and Engineering Chemlatry
(15) Prandtl, Physik. Z . , 11, 1072 (1910). a t the 88th AIeetmg of the Amerlcan Chemical Society, Cleveland, Ohio,
(16) Reynolds, Proc. Jlanchestw Lit.Phil. SOC.,14, 7 (1875). September 10 t o 14, 1934.

Diffusion of Vapors through Gas Films

T. K. SHERWOOD
AND E. R. GILLILAND,
Massachusetts Institute of Technology, Cambridge, Mass.

gas flow past the liquid or solid

D IFFUSION plays a tre-

mendously i m p 0 r t a n t
role in industrial proc-
esses because the capacity and
The nature of a gas f i l m is discussed briefly
and the application of the Stefan-Maxwtdl equa-
tion to diffusion in gas films is explained. T h e
results of experiments on rates of vaporization
phase, it seems probable that
there exists a thin layer of gas
moving in stream-line or viscous
motion over the surface of Ithe
consequently the fixed charges
on many types of i n d u s t r i a l of various liquids into air are reviewed, and rules other phase, and that the flow
equipment are determined by are given for estimating the diffusion rate of a breaks suddenly into turbulent
the rate of diffusion of heat or vapor through a gas film, o n the basis qf data motion beyond the outer
of material f r o m o n e p h a s e boundary of this viscous layer.
t o a n o t h e r . Diffusion in gas
on the diffusion rate f o r another uapor. Numeri- If this is the nature of the film, it
films is one of the most impor- cal examples illustrate the necessary culcula- seems probable that the thick-
tant technical problems which tions. ness of the laminar layer fluctu-
confronts the chemical engineer. Derivations of algebraic equations connecting ates rapidly and to a consider-
The rate of interaction of a gas the absorption coeficient Kca with the height of able degree, owing to the turbu-
with a l i q u i d o r solid m a y lent motion of the main gas cur-
be governed by the rate of a
packing equivalent to one theoretical plate rent. The experimental evidence
slow chemical reaction, or by the (H. E. T. P . ) are given, and the use of the latter apparently does not exclude the
slowness of diffusion t h r o ugh concept in the design of packed towers .for ab- possibility, however, of a con-
the liquid phase. In many -of sorption is discouraged. tinuous gradation in turbulence
the most i m p o r t a n t of s u c h from the surface of the solid or
operations, however, the rate liquid phase through the film to
a t which the operation proceeds is determined by the slow- the main body of the gas stream. I n the turbulent gas stream
ness of diffusion in the gas phase. This condition may be the movement of vapor through the gas is mainly by the mecha-
summarized by the statement that “diffusion through the nism of turbulent mixing or eddy diffusion. Eddy diffusion
gas film is controlling.” Such is the case in the absorption is very rapid, but the distances involved are much greater than
by liquids of soluble gases from mixtures with an inert gas; in the relatively stagnant film so that it is possible for the eddy
in adsorption of gases by solid adsorbents; in the air-drying diffusional resistance to be as great or greater than the re-
of wet solids; in vaporization of water or other liquids into sistance to molecular diffusion offered by the laminar film.
air, as in humidification; in condensation of vapors from mix- The total resistance to diffusion of the gas film may be con-
tures with noncondensable gases, as in dehumidification; in sidered to be the sum of the resistance of the turbulent layer
the evaporation of solvents, as in drying of lacquers; and in to eddy diffusion and the resistance of the laminar layer to
the combustion of solids a t high temperatures. molecular diffusion. The two diffusional mechanisms are
In interphase reaction, the distribution of diffusional quite different in nature.
resistance in the gas phase depends mainly on the velocity Since the nature of the film is not fully understood, the
characteristics of this phase. For the case of a quiescent attack on the problem of diffusion through gas f 3 m s must
gas phase, as in a bubble rising through a deep liquid layer, necessarily be empirical. This empiricism may be veiled by
the diffusional resistance is constant throughout. If the the introduction of the theoretical equations for diffusion in
gas phase is in laminar flow, the diffusional resistance is still stagnant gases, but appears in the treatment of the “effective
constant at all points, but the progressively lower mass ve- film thickness” involved in using this method of approach to
locity of the gas as the interface is approached causes a very the problem. For example, the Stefan equation for the
different distribution of the diffusing substance from that steady-state diffusion of one gas through a layer of a second
which would be encountered with a stagnant gas. In the stagnant gas is :
case of turbulent flow a large resistance to diffusion in the
gas phase is encountered in a narrow region adjacent to the
iquid or solid phase. This fact has been well understood
for a number of years, as evidenced by the widespread use of where N A diffusion rate per unit interfacial area, gram moles/
=
the phrase “gas film.” The physical nature of this film is, (sec.)(sq. cm.).
however, not well known, although it appears certain that D = diffusivity of system, sq. cm./sec.
it is not the simple layer of perfectly stagnant gas which P = total pressure, atm.
affords such a convenient, although erroneous, mental picture R = gas constant: (cc.)(atm.)/(gram mole)(’ K.).
T = abs. temp., K.
of the reason for the concentration of the diffusional resistance z = thickness of stagnant gas layer, cm.
near the phase boundary. Under conditions of appreciable k~ = film coefficient, grams/(sec.)(sq. cm.) (atm.).
 1094 INDUSTRIAL AND E N G I N E E R I N G CHEiMISTRY Vol. 26, No. 10
M A = mol. weight of diffusing gas only for the wetted-wall apparatus, and it may be that the
AI, P A 2 = partial pressures Of the diffusing gas or vapor at
the boundaries of the layer, atm. effect of D on ko for a packed tower Tvill be somewhat differ-
pel, p B 2 = partial pressures of the stagnant or non-diffusing ent. The exponent 0.56 for 1 would be unity if the
gas at the two boundaries of the layer, atm. mechanism were wholly molecular diffusion and would perhaps
pn.u = logarithmic mean of p e n and pel be zero for pure eddy diffusion. The observed fractional ex-
When this equation is applied to diffusion through a gas film, ponent is dependent on the relative resistance of laminar and
the thickness, 2, may be interpreted as the effective thickness eddy layers. That it is not sensitive to turbulence condi-
of the film. This thickness has no great theoretical signifi- tions, however, is indicated by the fact that it remained con-
cance, but it may be used empirically as are the various forms stant as the Reynolds number was varied over the range from
of gas film coefficients. Values of D for various gas systems 1800 to 26,000 in the wetted-wall column experiments. For
may be obtained from the standard tables of physical con- convenience, values of D for a number of typical systems are
stants or be estimated by means of an empirical correlation given in Table I.
published recently (1). I. DIFFUSIVITIES
TABLE IN AIR AT 30" C. AND 1 ATMOSPHERE
An experimental study of the application of Equation 1 to SUBSTANCE 0 3 0 SUBSTANCE n,,
diffusion in gas films has been described by the authors in c12 0.109" Methyl alcohol 0,140a
so2 0.119~ Ethyl alcohol 0.110a
another paper ( 2 ) . A wetted-wall column was used in these coz O.12sa Isopropyl alcohol 0.101b
NO2 0 , 138a n-Butyl alcohol O.088b
experiments; the liquid to be vaporized flowed in a thin film NO 0. 166a see-Amyl alcohol 0.072b
down the inner surface of a vertical tube through which air H C1 0.149" Ethyl acetate 0.089s
NH3 0.201" Chlorobenzene 0.075b
was forced, either parallel or countercurrent to the movement Hz0 0.2636 Toluene
Aniline 0.088b
Acetone 0.097n O.075b
of the liquid film. The rates of vaporization of nine liquids
were measured a t various temperatures, using various air a Calculated by empirical equation of Gilliland ( 1 ) .
b From experimental d a t a of Gilliland ( 1 ) .
speeds. The driving force (pal - P A * ) was varied by chang-
ing the temperature of the liquid circulated. The mean ILLUSTRATIVE PROBLEM 1
pressure of inert gas, P B M , was varied by operating the appa- A wetted-wall column operating a t a total pressure of 518
ratus a t pressures ranging from 110 to 2330 mm. of mercury. mm. of mercury is supplied with n-ater and air, the latter a t
The diffusivity was varied by using several liquids. The the rate of 120 grams per minute. At a mean driving force
effect of air turbulence was studied by varying the air velocity of 62.5 mm. and a calculated mean inert pressure of 449 mm.,
over a wide range. The data showed the rate of vaporiza- the rate of vaporization of water in the apparatus is 13.1
tion (1) to be directly proportional to the driving force, as cc. per minute.
called for by Equation 1; ( 2 ) to be inversely proportional to The same apparatus, now a t a total pressure of 820 mm. of
the mean pressure, P E M , of air in the gas film, as called for by mercury, is supplied with air a t approximately the same tem-
Equation 1 ; (3) to vary as the 0.83 power of the Reynolds perature as before a t a rate of 100 grams per minute. The
number for air flow through the pipe; and (4) to vary directly liquid vaporized is n-butyl alcohol, which is supplied a t such
as the 0.56 power of the diffusivity, D. The data were ex- a temperature that the mean driving force is 24.4 mm. and
pressed empirically by the equation : the mean inert pressure is 799 mm. The specific gravity of
= 0.023 (d ~ ) " * 8(3 the liquid is 0.807. The problem is to estimate the rate of
vaporization of n-butyl alcohol, as cubic centimeters per
X
where d = inside diam. of column minute.
u, p , = velocity, density, viscosity of turbulent gas stream, SOLUTION. From Equation 1 it is apparent that the weight
respectively rate of vaporization is proportional to k~ and to the driving
Each of the three groups in Equation 2 is dimensionless. force. Hence:
The relation between the rate of vaporization, or of the n-butyl alcoholvaporization = 13.1 X 1 0 24.4 &(ah.)
effective film thickness, 2, and the group p / p D is particularly 0.807 62.5 )-k
significant in that it suggests a method of prediction of the The ratio of ko(alc.)/kG(water) follows from the four rules'
performance of apparatus involving diffusion in gas films, given above:
on the basis of data on the same apparatus with a different
vapor. The familiar gas film coefficient, k G , represents the
rate of diffusion as weight per unit time per unit area, per
k c (alc .)
- =
0.83 74
(g) X - = 1.08
18
unit driving force. It is apparent from Equations 1 and 2 The ratio of Reynolds numbers is assumed to be the same as
that k~ varies : the ratio of air rates, since the apparatus was the same, and
(1) Directly as the 0.56 power of the product diffusivity times the air temperature approximately the same. Hence, the
total pressure. rate of vaporization of n-butyl alcohol will be:
(2) Inversely as the mean inert pressure ~ B M(the product
D P is independent of pressure). 1.0 24.4
13.1 X __ X - X 1.08 = 6.8 cc./min.
(3) Directly as the Reynolds number to the 0.83 power. 0.807 62.5
(4) Directly as the molecular weight of the diffusing vapor
(in addition t o the effect of molecular weight on D). The conditions given are those of actual experimental tests.
For the run on n-butyl alcohol the observed rate of vaporiza-
These rules may be used, for example, to predict the per- tion was 6.9 cc. per minute.
formance of a packed tower for the absorption on a soluble
gas such as acetone, provided data are available on the same ILLUSTRATIVE PROBLEM 2
packing used for the absorption of another soluble gas, such Assume, for example, that a test on a certain packed tower
as ammonia. They also suggest methods of correlation of absorbing ammonia in water a t 2 atmospheres and a t 25'
gas film coefficients for packed towers and other similar ap- C. gave a value of koa of 0.016 kg. per minute per cubic meter
paratus. For example, i t follows from Equation 1 that l / r per mm. when using a water rate of 78 kg. per minute per
is proportional to ~ G ~ B M T / D P andM A ,it seems probable square meter of tower cross section and an average gas rate
that values of this latter group might be correlated for -c.arious 1 Since t h e product D P is independent of pressure, rule 1 is equivalent to
gases. a statement t h a t lzo varies a s the 0 56 power of t h e diffusivity taken a t one
Unfortunately, the effect of diffusivity has been determined atmosphere.
 October, 1934 INDUSTRIAL AND ENGINEERING CHEMISTRY 1095

of 20 kg. per minute per square meter of tower cross section.
The tower reduces the ammonia concentration of the air
mixture from 20 to 1 per cent ammonia by volume. Using
these data, the problem is to estimate the value of ~ G Ufor the
absorption of acetone from air a t 0.5 atmosphere, using the
same type of tower packing, tem-
Lpo 1% perature, gas, and water rates as in
ciently good to bring the two streams in equilibrium. The gas
leaving plate CC, therefore, will be in equilibrium with the
liquid leaving the same plate. Consequently, for a column of
theoretical plates, it is possible to represent the relation be-
tween gas and liquid compositions leaving any plate by the
equilibrium curve for the system. The relation between the
gas and liquid compositions between any two plates-i. e., the

#
the test on ammonia. The concen- relation between the composition Y C of the gas leaving CC
A tration is to be reduced from 5 to 1 and the composition X B of the liquid leaving BB, is given by
per cent acetone by volume. the material balance,
r--0 SOLUTION.In calculating values
G(Yi - Yc) = L(X1 - X B )
-&--1
I (3)
’--<- .6----j of ~ B M the
, solutions may be con- where Y = weight ratio of solute to inert or carrier gas
sidered sufficiently dilute so that the X = weight ratio of solute to solvent in the liquid
D D vapor pressures of acetone and of
ammonia may be neglected. In the Figure 2 shows a diagram for this case with the “operating
case of the ammonia, in the main line” PQ based on Eauation 3. and the equilibrium curve OR.
XI YI
gas stream P B varied from 2.0-0.2 The operating line gives the’ relation
FIGUREZ X 2 = 1.6 atmospheres a t the gas between the composition of gas leav- TREATED
SOLVENT tAs
inlet to 2.0 - 0.01 X 2 = 1.98 atmos- ing a plate and the composition of
pheres at the gas outlet. At the liquid interface, P B = 2.0, liquid from the plate next above. The
since the back pressure of ammonia is neglected. At theinlet, vapor leaving any plate, CC, will be
therefore, P E X is the mean of 2.0 and 1.6, or 1.7‘3, and at the in equilibrium with the concentra-
gas outlet p n is~ the mean of 2.0 and 1.98 or 1.99. The tion, X C , of the liquid on the plate,
average value of p B . V is 1.89 atmospheres. For acetone, ~ B M its composition, Y c , will be deter-
at the gas inlet is practically constant a t 0.49 atmosphere mined by referring to point c on the
throughout the apparatus. equilibrium curve. The liquid leav-
From Table I the ratio of the diffusivities‘ for acetone and ing plate BB above mill have a com-
ammonia is 0.097 to 0.201, The ratio of the molecular p o s i t i o n determined by point b‘ on
nTeights is 58 to 17. Hence, for acetone: the operating line, corresponding to
the gas composition, Yc. The com-
~ Q = 0.016 X
0.097 O.56 129 58 - position of the gas leaving BB may
U
(Om) 0.49 17 - then be determined, and the equilib-
0.140 kg./min./cu. m./mm. rium curve and operating line may
be used alternately until point P is
CONCEPTOF THE THEORETICAL
PLATE reached, corresponding to conditions
Both packed towers and plate columns may be used for gas a t the top of the column. With any
absorption, just as both types of equipment are found ser- fixed operating lines, this s t e p w i s e
’ viceable in distillation practice. Rectifying columns for dis- calculation may be employed to de-
tillation are often of the plate type, and the traditional basis termine the composition of liquid and
. for the design of such equipment is the “theoretical plate” gas on the various plates and, what
concept. Absorption equipment is commonly of the packed is more important, t h e n u m b e r of FIGURE 3
tower type, and the design of such towers should be based on theoretical plates required.
capacity coefficients such as Koa (weight diffusing per unit
RELATION BETWEEN Kaa AND H. E. T. P.
time per unit volume of packing per unit of driving force ex-
pressed as pressure difference). Just as the equipment is in- I n order to apply the theoretical plate concept to a packed
terchangeable in practice, so the design methods for the two tower, it is convenient to picture a certain height of packing
processes have been interchanged, and the “theoretical plate” as accomplishing the same separation as one theoretical plate.
has been used as the basis for absorption tower design, or The height of packing equivalent to one theoretical plate ha5
capacity coefficients been termed by Peters (3) the H. E. T. P. and its numerical
have been used in value is an indication of the capacity of the apparatus, as is
rectifying c o 1u m n the capacity coefficient KGU. However, large values of KQU
design. correspond to small values of H. E. T. P.
The design proce- Let Figure 1 now represent a packed tower, and the pack-
dure based on the ing between BB and CC perform the same separation as one
theoretical plate theoretical plate. Let A B and CD represent other imaginary
concept may be fol- divisions of the column into theoretical plates. From the
lowed on Figure 1. definition of a perfect plate, the gas leaving section BC a t BB
The horizontal lines will be in equilibrium with liquid leaving the same section a t
A A , BB, etc., repre- CC. Analysis of the process on the basis of the theoretical
sent bubble-cap or X - SOLUTE CONCENTRATION IN LIQUID plate concept assumes the flow to be somewhat as shown in
other plates, L kg. KGS S O L L m / K G . M L V - Figure 3 . On each plate the liquid from the plate above and
per minute of sol- FIGURE 2 the gas from the plate below come together and are separated
vent overflow i n g a t the points circled, where the two streams are assumed to
from one plate to the next down through the column. The be in equilibrium. I n an actual packed column the flow is
gas to be treated, containing G kg. per minute of inert carrier countercurrent throughout, but the analysis based on the
gas, passes up through the column countercurrent to the flow theoretical plate concept does not introduce serious error if
of solvent, being brought into intimate contact with the solvent the sections are sufficiently small-i. e., if the H. E. T. P. is
by bubble caps or other devices on each plate. In a theoreti- small compared to the total height of the column. When the
cally perfect plate the contact between phases would be suffi- gas film resistance is controlling, the potential or driving
 1096 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 26, No. 10

forces a t BB will be represented on Figure 2 by b‘b. At CC
the corresponding potential will be represented by c‘c.
Assuming the equilibrium curye to be straight over the short
range, bc, the logarithmic mean may be used, and the equa-
tion written:
fusing per unit time per unit volume of packing per unit driv-
ing force expressed in terms of Y . The variable B is the ratio
of the mean driving force in pressure units to that expressed
in stoichiometric units. For very dilute gas:
B = M A / M E P where M A , M E = mol. weights of solute and
carrier gases, respectively
P = total pressure

where S, V = cross-sectional area and volume of the column, The derivation given above provides a relation between the
respectively capacity coefficient, Koa, and the H. E. T. P. The vaporiza-
tion data obtained in the wetted-wall column support the
application of the diffusion equation to an extent which indi-
V G In J cates that KGUis the more fundamental factor, and the
Then - = H.E.T.P. = BKGa(J - 1) (5) H. E. T. P. a more involved variable. Equation 7 shows that
S
the H. E. T. P. is dependent, not only on those variables which
Ifzm = ( Y c - Y B ) / ( X C- X E ) represents the slope of the affect Koa, but also on additional effects of gas and liquid
equilibrium curve over the range of concentrations of the plate weight velocities, G and L, and on the slope, m , of the equilib-
in question, and since the slope of the operating line is L;G = rium curve. Because of the influence of the latter variable,
( y o - YC)/(xC - XE), the H. E. T. P. may be expected to vary through the apparatus
with solute concentration. No such variations in Koa may
J = -mG be expected, unless there are large variations in temperature,
L
pressure, or EM. For these reasons it appears logical to dis-
Even when the slopes of the operating and equilibrium courage the reporting of data on gas absorption in terms of
curves differ considerably, it is usually allowable to employ values of the H. E. T. P. The value of the H. E. T. P. concept
the arithmetical in place of the logarithmic mean potential for rectification in packed columns may be somewhat greater,
in Equation 4, and so eliminate the logarithmic mean. The but even there the capacity coefficient Kca would appear to
result is : be a sounder basis for dealing with experimental data.
gv = H. E. T. P. = BKoa(J
2G
+
- 2GL
+
1) - BKGu(L mG) (7) LITERATTJRE
CITED
For the special case where J is substantially unity, both (1) Gilliland, IND. ENO.CHEM.,26,681 (1934).
(2) Gilliland and Sherwood, Ibid., 26, 516 (1934)
Equations 5 and 7 reduce to: (3) Peters, Ibid., 14,476 (1922).
RECEIVEID August 6, 1934. Presented as part of the Symposium on Diffu-
sional Processes before the Division of Industrial and Engineering Chem
istry a t the 88th Meeting of the American Chemical Society, Cleveland,
The term BKGa is defined by Equation 4 as the weight dif- Ohio, September 10 t o 14,1934.

The Drying of Solids. VI1

Moisture Movement by Capillarity in Drying Granular Materials
E. W.COMINGS
AND T. K. SHERWOOD,
Massachusetts Institute of Technology, Cambridge, Mass.

In the drying of many solids, particularly those which dry

D IFFUSION plays a complicated role in the drying of

solids because of the several diffusional resistances very slowly, the principal resistance is that offered by the
encountered by the moisture in passing from the in- solid itself to the movement of liquid water. The word
terior of the solid to the main body of the air stream employed “diffusion” must be used with care in referring to the move-
to carry away the water as vapor. At certain stages in the ment of water through a solid. Movement of liquid water
drying of many solids the water moves as a liquid part way to takes place under the influence of a pressure difference due
the solid surface and then diffuses as water vapor through the to gravity, an applied external force, or capillarity. I n the
air-filled openings in the porous solid near the surface. After drying of ordinary solid shapes, pressure differences due to
reaching the surface, the vapor must diffuse through the sur- gravity or similar forces are seldom encountered, and any
face air film and then be transferred by mixing or “eddy dif- liquid movement that does take place is apparently due to
fusion” into the main air current. Four diffusional resist- capillarity.
ances are encountered: the resistance to movement of liquid The mechanism of capillary movement of liquid water
in the interior of the solid. through a solid undergoing
the resistance to diffusion of 4 dryin; is well illustrated by
water vapor through the air- a s i m p l e experiment. A
illled passages, t h e r e s i s t - glass tube was drawn out
a n c e t o v a p o r diffusion E to form a tapered capillary
offered by the surface air s e v e r a l centimeters l o n g
film, and the eddy-dXu- (Figure 1). This was filled
sional resistance of the tur- FIGURE1. VAPORIZATION OF WATER FROM A TAPERED with water and to
bulent. air stream. CAPILLARY r e m a i n exposed to the air