D = diffusion coefficient [m2/s]

Gz = Graetz number (= uAh2/DAxL) [-]

h = depth of liquid phase [m]
å ^aoi>^sni = equilibrium constants for each step in
Fig. 3 [m3/mol]
Kdnl = equilibrium constants for desorption step
in Fig. 3 [mol/m3]
k°dnl = reaction rate constants for desorption step
in Fig. 3 [mol/(m2-s)]
u = averagelinear velocity [m/s]
Sh = dimensionless average mass transfer rate
( = (A CAuAh2/DAxLCA0)) [-]
x =contact length [m]
a. = (CA0/CB0) [-]
Fig. 6. Relations between logklnl and logKdnl.
P = (DJDB) [-]
both cases, the calculated results agree well with a = mean deviation [-]
experimental values. Thus, the above inter facial re- (Subscript)
action model can be adopted as the most suitable A = acid
model to express the experimental results. a = adsorption
In are
Fig.plotted
6, values of logk° B = amine
dnl against d = desorption
logKdnl for propionic acid and acetic acid systems.
ij = A^Bj species
The value of rate constant, k°dnl, for each desorption s = surface reaction
step increases with the equilibrium constant, Kdnl. 0 = initial
The linear logarithmic relationships involving the rate
constants and equilibrium constants of the same Literature Cited
reaction series have been obtained in the homo- 1) Danckwerts, P. V.: "Gas-Liquid Reactions," McGraw-Hill
geneous reaction,2) that is, hydrolysis of ester. Co., New York (1970).
However, the detailed discussion of the linear loga- 2) Hammett, L. P.: "Physical Organic Chemistry," McGraw-
Hill Co., New York (1970).
rithmic relationships for the inter facial reaction have 3) Kawano, Y. and F. Nakashio: Kagaku Kogaku Ronbunshu, 3,
been left as an unsolved subject to be studied in 393 (1977).
future. 4) Kawano, Y., K. Kusano, T. Takahashi, K. Kondo and F.
Nakashio: Kagaku Kogaku Ronbunshu, 8, 404 (1982).
5) Kawano, Y., K. Kusano, K. Kondo and F. Nakashio:
Acknowledgment
Authors would like to acknowledge the continuing guidance of Kagaku Kogaku Ronbunshu, 9, 44 (1983).
Professor F. Nakashio in Kyushu University. 6) Kawano, Y., K. Kusano and F. Nakashio: Kagaku Kogaku
Ronbunshu, 9, 211 (1983).
Nomenclature 7) Wilke, C. R. and P. Chang: AIChEJ., 1, 264 (1955).
C = concentration [mol/m3]

A DIMENSIONLESS EQUATION FOR GAS DIFFUSION IN

MICROPOROUS MEDIA IN KNUDSEN'S REGIME

Yuji SHINDO, TOSHIKATSU HAKUTA, Hiroshi YOSHITOME AND HAKUAI INOUE

Process Research and Development Div., National Chemical Laboratory for Industry, Tsukuba, Ibaraki 305

by the authors3):
1. Dimensionless Diffusion Equation
QVMr=-K^+^/fcr+«{exP(8*/feT)-l}] (1)
A diffusion equation for gas permeation through a
porous mediumin the Knudsenregime was proposed
Received January 10, 1983. Correspondence concerning this article should be addressed This equation was obtained theoretically as a function
to Y. Shindo. H. Inoue is at Dept. ofChem. Eng., Univ. ofTokyo, Tokyo 113. of temperature, taking into account the effect of the
VOL. 16 NO.6 1983 521
 surface potential energy, i.e., interaction energy be-
tween a gas molecule and the surface of a porous
medium. Here, two reduced values are defined as
follows.

Q = Q^MT/K (2)
f= ^r/£* (3)
With these reduced values, Eq. (1) can be rewritten as
e=irW+a{exp(1/f)~1} (4)

This dimensionless equation suggests that all gases

obey the same diffusion equation when expressed in
terms of reduced values.
Permeabilities for several gases through a micro-
porous Vycor glass membranewere measured by the
authors3) and Hwang et al.2) Porous Vycor glass has Fig. 1. Plotting ofQ vs. f, from data by the authors.3*
been quite popular for diffusion studies because of its
usually narrow pore size distribution and repro-
ducible surface and physical properties. Figures 1 and
2 show the plotting of the reduced permeability Q
against the reduced temperature f. The real lines in
Figs. 1 and 2 are the curves calculated from Eq. (4).
The data in Fig. 1 were obtained by the authors.3) The
data in Fig. 2 were obtained by Hwang et al.2) The
parameters K, a, /? and e* were calculated in the
previous paper.3) Figures 1 and 2 show that all
permeability data are expressed fairly well by one
curve. One can comprehensively understand thereby
the relation between permeability and temperature for
gases. The increase of Q at high temperatures is
caused by the relative decrease of interaction energy
between a gas molecule and the solid surface, cor-
responding to the kinetic energy of the gas molecule.
On the other hand, the increase of Q at low tempera- Fig. 2. Plotting ofQ vs. f, from data by Hwang et al.2)
tures is due to the increase of surface flow molecules.
2. Temperature Minima for the Permeabilities
Figures 1 and 2 show temperature minima, Tm, for f.'(i+W-gexp"/t)=o (6)
Q. theIt istemperautre
approximatelyrangeconsidered that gas diffusion in
above fm is almost gas-phase The temperature minimumpoint for each gas Tmis
flow and that gas diffusion is accompanied by a derived by use of Eq. (3).
surface flow at temperatures below fm. It must, of Tm = fme*/k (7)
course, be noted that a small amount of surface flow The relation between £* and the intermolecular poten-
is still present at high temperatures above fm. The
tial energy £ has been obtained3) as
minimumpoint of temperature Tmroughly indicates e*/& = £l8/yfe (8)
whether there is a surface flow or not. Surface flow
increases exponentially below fm. The values of Tm Inserting Eq. (8) into Eq. (7) gives the relation
can be obtained theoretically from Eq. (4). Dif-
between Tmand s.
ferentiating Eq. (4) by T, T^ k^e/k (9)
^=WTW~^exp(1/T) () The values of a=0.246, fi=0.606 and ^=2.26 were
obtained by experiments of gas permeation through a
fm satisfies the following equation: microporous Vycor glass membrane.3) The value of
Tmcan be calculated from Eq. (6) with the values of a
522 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
 ed1} that there are proportional relationships among
them, roughly estimated to be as shownbelow.
e/k=0.llTc (ll)

e/k= 1.15Th (12)

By use of these relations, proportional relationships

between Tm and certain physical properties of gases
are derived. For example, on inserting Eq. (ll) into
Eq. (10) we obtain
Tm=4.02Tc (13)
The values of 7^ are plotted against Tc in Fig. 4.
Close agreement between observed and calculated
values was obtained. Once the values of K, a, /? and
kl9 which depend on the geometrical structure of the
Fig. 3. Relationship between temperature minimum
porous mediumor on the nature of the surface, are
determined we can predict the permeabilities as a
and intermolecular potential energy e/k. function of temperature for other gases. We can
obtain e* or Tmfor any unknowngas from its physcial
properties by use ofEqs. (8), (9), (ll) and (12).
Nomenclature
K = diffusion coefficient defined by
Eq. (1) [mol1/2 à"kg1/2 à"K1/2/(mà"sà"Pa)]

k = Boltzmann constant [J/K]

kx = constant defined by Eq. (8) [-]
M = molecular weight [kg/mol]
Q = gaspermeability [mol/(m à"s à"Pa)]
Q = reduced permeability [-]
T = temperature [K]
Th = boiling point [K]
Tc = critical point [K]
Tm = temperature minimumfor Q^jMT [K]
f = reducedtemperature [-]
Tm = minimum point of f [-]
a = constant [-]
Fig. 4. Relationship between temperature minimum Tm ft = constant [-]
and critical point Tc. s = intermolecular potential energy of two
identical gas molecules [J]
s* = effective potential energy between a gas
and /? by a computer. The result is Tm=2.31. Inserting molecule and the solid surface [J]
the values ofk1 and Tm into Eq. (9), one obtains
Tm= 5.22e/k (10) Literature Cited
1) Hirschfelder, J. 0.5 R. B. Bird and E. L. Spotz: J. Chem.

The observed temperature minima Tmwere read off Phys., 16, 968 (1948).
from the figures reported.2'3* The values of Tm are 2) Hwang, S. T. and K. Kammermeyer: Can. J. Chem. Eng., 44,
82 (1966).
plotted against s/k in Fig. 3. The experimental values'
3) Shindo, Y., T. Hakuta, H. Yoshitome and H. Inoue: /. Chem.
agree well with the theoretical results. Eng. Japan, 16, 120 (1983).
Gases have many physical properties, such as in-
termolecular potential energy e, critical temperature (Presented in part at the 16th Autumn Meeting of The Society of
Tc, boiling point Th, and the like. It has been suggest- Chemical Engineers, Japan at Toyota, October 1982.)

VOL 16 NO. 6 1983 523