July, 1963 COKVECTIVE

MASSTRAXSFER
IN DIAPHRAGM CELL
DIFFUSION 1469

were made for the known contributions to the ceric re-
duction. Corrections in the observed G(Ce+3) in-
cluded reduction of ceric ions by molecular and radical
radiolysis products, ttnd the reduction of the G(H2)
caused by the scavenging action of the nitrate ion for
hydrogen atoms. Isolation of a G(Ce+3) directly pro-
portional to the N a S 0 3concentration was accomplished
after these corrections were made. Excellent correla-
tion was obtained between the isolated G(Ce f3) which
is directly proportional to the NaN03 concentration,
the stoichiometrically equivalent G(Ce+3) as deduced
from the G(O2) measured in Ce+4-0.4 M HzSOpXaS03
solutions, and the stoichiometrically equivalent G(Ce+3)
calculated from the G(Oz) originating from the radia-
tion-induced decomposition of nitrate ion in enriched
oxygen-18 HzO-NaK08 solutions. This correlation
supports the over-all decomposition as N 0 3 - ~ - t
+
xo2- '/z 02.
Acknowledgment.-The author wishes to thank W.
Et. Ragland and co-workers of the Mass Spectrometer
Special Samples Laboratory for the mass spectrographic
analyses upon which the interpretation presented de-
pends. He also wishes to thank J. w. Boyle, C. J.
Hochanadel, H. W. Kohn, and P. S. Rudolph for their
critical evaluation of this work and their suggestions in
the preparation of the manuscript.

CONVECTIVE MASS TRANSFER I N A DIAPHRAGM DIFFUSIOX CELL

B Y JOHK
T. HOLMES,~ R. WILKE,-4ND DOSALDR. OLANDER
CHARLES
Department of Chemical Engineering, and the Lawrence Radiation Laboratory, University of California, Berkeley, Cal.
Received December 26, 1961

A fundamental assumption implicit in the analysis of a diaphragm diffusion cell is that the sole resistance
to transport resides in the porous glass disk, through which the solute moves by molecular diffusion. This paper
presents an experimental examination of the resistance to mass transfer in the fluid regions adjacent to either
side of the porous disk. The presence of an external mass transfer resistance has been observed by others who
have recommended that all diffusion measurements be conducted a t stirring speeds greater than an empirically
determined value where the cell constant becomes independent of the stirring rate. However, the external
mass transfer coefficients depend not only on the stirring speed, but also upon the viscosity and diffusivity of
the solute-solvent system as well. There is no justification for assuming that operation above the critical speed
found for the calibration fluid will eliminate the external mass transfer resistance in a system of larger viscosity
and small diffusivity. Both free- and forced-convection mass transfer characteristics of a vertical diaphragm
cell were investigated and the results correlated in terms of stirrer speed and the fluid properties. The data
indicate that operation above a critical speed is appropriate for a number of common systems but that significant
errors can arise for systems of high viscosity and lop; diffusivity and that for high reproducibility and accuracy,
cells stirred by free convection alone should not be employed.

Introduction mass transfer resistance in a system of larger viscosity

h fundamental simplification implicit in the analysis
of a diaphragm diffusion cell is the hypothesis that the
sole resistance to transport resides in the porous glass
disk, through which the solute moves by molecular dif-
fusion. More precisely, this model involves two inde-
pendent assumptions: first, that there is no bulk con-
vective flow through the pores of the disk, and second,
that the resistance to mass transfer in the fluid regions
adjacent to either side of the disk is negligible. This
paper presents an experimental examination of the
second assumption. Bulk convection through the pores
has been observed,2but mill not be considered here.
The presence of an external convection mass transfer
resistance has been observed by Stokesza and Lewis3
as an increase in the cell constant with the rotational
speed of stirring bars in the two compartments. Above
a certain speed, the cell constant becomes independent
of stirring rate and these workers recommend that all
diffusion measurements be conducted at speeds greater
than the empirical determined critical value. However,
the external mass transfer coefficients depend not only
on the stirrer speed, but upon the viscosity and dif-
fusivity of the solute-solvent system as well. There is
no justification for assuming that operation above t,he
critical speed found for the calibration fluid (generally
0.1 N KC1 in water at 25") will eliminate the external
(1) Brnonne National Laboratory, Argonne, Illinois.
(2) (a) R. H. Stokes, J . A m . Chem. Soc., 72,768 (1950); (b) A. Emaneel
and D. R. Olander, J . C h e m Eno. Data, 8,31 (1963).
(3) J. B. Lewio. J . A p p l . Chem. (London), I , 218 (1955).
and smaller diffusivity, e.g., solute dodecane in tetra-
decane at 15". Therefore, the free-and forced-convection
mass transfer characteristics of the vertical diaphragm
cell, shown in Fig. 1, were investigated and the results
correlated in terms of stirrer speed and fluid properties.
Experimental
Apparatus.-Ace Glass E porosity disks were employed in a
vertical position. The diaphragms were 5.0 cm. in diameter, 0.5
cm. thick, and with a nominal pore size range between 3 and 8
p . The cell compartments were each approximately 125 cc.
in volume and were stirred with 1-in. long Teflon-covered bar
magnets. The cells were calibrated with 0.2 AT HCI using the
data of Stokes28 as reference diffusion coefficients. Densities
were measured with a Westphal balance, and were reproducible
to 3~0.2%. Viscosities were measured with an Oswald visco-
simeter calibrated with distilled water and were reproducible to
3Z0.5y0. All data were taken a t 25.0 f 0.1". The four stirring
speeds obtainable with the equipment were measured with a
stroboscope. For additional details of the equipment and
experimental procedure, see ref. 4.
Effect of Fluid Properties and Stirring Speed.-So-
lute transfer from one compartment of the cell to the
other occurs in the following sequence: (a) convective
transfer through the boundary layer on the disk in the
compartment containing the concentrated solution;
(b) molecular diffusion through the sintered glass disk;
(e) convective transfer through the boundarylayer on the
disk in the compartment containing the dilute solutions.
Assuming pseudo steady-state operation, the mass
transfer rate is given by eq. 1
(4) J . T, Holmes, USAEC Report UCRL-9145 (1960).
1470 J. T. HOLMES,C. A. WILKE,AND D. R. OLANDER Vol. 67
GROUND
GROIINll where
1
p= -+-
i) 2D/kA + Z/Af (4)

ti
(;I

AC, and Act are the differences in the concentration be-

tween the two compartments initially and a t time t, re-
spectively. p is the experimentally determined cell con-
stant. Above the critical stirring speed, Z/Af >> 2D/
kA, and eq. 4 reduces to the standard expression for the
cell constant. The factor 2D/kA accounts for the ex-
ternal mass transfer resistance due to the laminar fluid
layers on the diaphragm cell.
Evaluation of the Mass Transfer Coefficients.-The
mass transfer coefficients required in eq. 4 have been
measured by electrochemical limiting-current experi-
\MAGNETIC /- ments in a half-cell identical with one side of the appara-
STIRRER BARS
tus shown in Fig. 1. This system is shown schemat-
Fig. 1.-The diaphragm cell. ically in Fig. 2. Wilke, et u Z . , ~ , ~ have shown that limit-
ing current experiments in copper sulfate and silver per-
chlorate solutions were diffusion controlled, and thus
I CELL
1 provided direct measure of the mass transfer charac-
teristics of the electrolytic cell. The rate of deposition
CURRENT of copper is given by
N = k(C
(5) - Ci) = (1 - T) I/xS
C - Ci is the concentration difference between the bulk
CATHODE liquid phase and the electrode surface, and for this
POLARIZATION case is equal to C. T is the transference number for
copper, I the limiting current, x the valence of the cat-

I
REFERENCE
/

CATHODE
ion, and 5 the faraday. Limiting currents were meas-
ured in solutions whose viscosity and diffusivity were
I
varied by the addition of glycerol. The mass transfer
ELECTRODE
coefficients computed from equation 5 were correlated
by the dimensionless relation
MAGNETIC
STIRRING BAR
Nu = 0.050Re0.7gSc3~38 (6)

c where N u is the mass transfer Kusselt number, kd/D,

2 CAPILLARY
TUBE
Pig. 2.-Electrochemical half-cell.
N = kA(C1 - CJ = DAf/Z (Ci, - C2J
kA(C*
where N is the molar transfer rate of the solute, 1: the
external mass transfer coefficieqt (assumed the same on
both sides of the disk) in cm./sec., A the gross area of
the disk, D the diffusion coeficient, and A/Z the ef-
fective area-to-length ratio of the pores in the disk.
Concefitrations involved are: C1,in the bulk of com-
partment one; C1, the edge of the diaphragm in com-
partment one; Cz,a t the edge of the diaphragm in com-
partment two; C2 in the bulk of compartment tmo. A
material balance for each compartment yields
where V1 and Va are the volumes of the two compart-
ments and t the time. Combining eq. 1 and 2 and inte-
grating
In (ACO/AC~)= PDt
Re a modified Reynolds number, n d 2 / v , and Sc the
Schmidt group, v/D. d is the length of the stirrer bar,
n, the stirrer speed, and v the kinematic viscosity. The
length parameter used in the Nusselt and Reynolds
numbers has been arbitrarily taken as the stirrer bar
length. Since this is not the only dimension of sig-
nificance in the system, nor was d varied in this study,
= its use in forming the dimensionless groups of eq. 6 must
- c2> (1) be regarded solely QS a matter of convenience in correla-
tion. Figure 3 presents a plot of eq. 6 and the data
from which it was obtained. Several free convection
experiments (no stirring) mere performed in the same
electrolytic half-cell. The resulting mass transfer CO-
efficients for the three solutions listed in Table I were
correlated by
Nuf = 0.57 [Xc.Gr] (7)
where Nu =k r / D and Gr is the Grashoff number,
[r3g(,, - is the radius of the disk, and P
pi)pavs]/p2ave,r
- pi the density differencebetween the bulk and the elec-
trode surface. Equation 7 agrees well with the relation
proposed by Wilke, et for natural convection mass
transfer from a free vertioal wall, except that their con-
stant was 0.66. The difference can be attributed to the
(5) C.R. Wilke, C. W. Tobias, and M. Eiseqberg, Chem. Enu. Progr., 49,
633 (1953).
(6) C. R. Wilke, M, Eisonberg, and C. W. Tobias, J . Electrochem. Sac.
(3) 100, 513 (1953).
July, 1963 MASSTRANSFER
CONVECTIVE IN DIAPHRAGM
DIFFUSIOX
CELL 1471

use of a circular rather than a square surface, as demon- 70 I I 1 I 1 1 1 1 I 1 8 8

strated in the Appendix.

50
TABLE I o S c : 2,520

FREE CONVECTION MASSTRaNSFER - A S c = 14,880

Solution I I1 111 30 - S c = 62,486
H 8 0 4 concn. (moles/l.) 1.495 0.745 1.143
cuSOc concn. (moles/l.) 0.259 0.380 0.587 20
Glycerol concn. (moles/
1.) 0.00 5.90 3.10
Density (g./cc.) 1.124 1.205 1.177 m
Viscosity (cp.) 1.457 9.310 4.093
D X 105 (cm.z/sec.) 0.513 0.122 0.234
Schmidt number (Sc) 2316 62,360 12,800 7.
Grashoff number ( G r ) 2.48 X lo6 8.67 X lo4 7.88 X 106
Nusselt number (IYU) 154 161 182 5
Nu/(Sc 0,556 0.592 0.574
Effect of the External Mass Transfer on the Cell Con-
stant.-Assuming the mass transfer behavior from a
copper surface to be identical with that for the glass disk,
eq. 6 and 7 permit the mass transfer coefficient k , and
hence the group 2 D / k A , to be evaluated for any solute-
3t I
2 3
I I
5
I ! I
7
1 1 1
IO
1
20 30 50

solvent system. Altlhough the absolute values of the Re x 10.

correction factors are limited to the particular geometry Fig. 3.-Forced convection mass transfer correlation.
of cell used in this study, the relative magnitudes of
2DllcA and Z/A and the variation of 2 D / k A with fluid
properties should be comparable in any diaphragm cell
(vertical or horizontal) of this General type.
The magnitudes of 2 D / k A for a variety of solute-sol-
vent systems and at several stitring speeds are presented
in Table 11. These figures should be compared to the
TABLE
11
CORRECTIOS
TO CELLCONSTANT DUE TO EXTERNAL MASS
TRANSFER
RESISTAXEFOR A DIAPHRAGM FOR WHICH1/A =
230 x 10-3 C M . - ~
Correction Z D / k A , om.- X 103
n=O
(Free n = 220 n = 350
Solvent Solute convection) r.p.m. r.p.m.
Water 0 . 1 N KC1 8.8 1.1 0.70
Water 0 . 2 N HC1 16.0 1.3 .85
Hexane Toluene .. 1.1 .77
Cyclohexane Toluene .. 1.2 .76
Decane Toluene .. 1.4 .80 Fig. 4.--l)ittgram of the conversion of a plate mass transfer
Tetradecane Toluene .. 1.5 .01 coefficient to that from a disk.

value of Z/A = 230 >: em.-* for a typical diffusion average difference (fourth column) is 6.4%, which coin-
cell (computed from the cell constant a t high stirring pares well with the 6.8y0 decrease predicted from the
speeds). Although the forced convection correction mass traiisfer coefficient given by eq. 7. The observed
factor varied by as much as 40% with the fluid proper- variations from cell to cell are believed t o be due to ran-
ties, it never amounted to more than 0.5% of l/A a t the dom mechanical vibrations in the apparatus. For
stirring speeds considered. Moreover, the sum 2 D / k A comparison, Stokes2a found a 6.0% difference between
+ VA, which is involved in the assumed constmcy of stirred and unstirred cell constants for 0.1 N HC1.
.(3, varied by less than (3.2% with fluid properties. Since I11
TABLE
the precision of the experimental method usually does EFIECT OF STIRRING SPEED UPON THE CELL C U S S T A N T FOR
not warrant correctiom of this order of magnitude, it V.4RIOUS DIAPHR~GXR
can be concluded that provided the critical stirring Cell constant, p, om.-% x 10%
speed is approached the cell constants obtained from n = O
KC1 measurements will be applicable to most other sol- Cell no. (Tree convection) n = 350 r.p.m. % 1)iBertance
vent-solute systems. For free convection, on the other 12 2.21 2.33 5 2
hand, 2 D / k A is not negligible compared to Z/A. Table 13 2.44 2.66 8.3
I1 indicates that there should be 3.8% decrease in the 14 2.27 2.45 7.3
unstirred cell constant for 0.1 N KC1 calibration and 25 1.85 1.94 4.6
6.8TGfor 0.2 N HCl. ,4iiother study of forced convection effects was re-
To verify the predicted effect of free and forced con- cently presented by Peterson and Gregor for an ion-
vection for HC1, the cell constants for four diaphragms exchange membrane system. Although their data are
were measured without stirring and with stirring at 350 (7) Rf. A. Peterson and H. P. Gregor, J . Electrochem. Soc., 106, 1051
r.p.m. These results are presented in Table 111. The (1959).
 1472 R. A. BONHAM,
T. IIJIMA, AKD T. ANDO Vol. 67

in qualitative agreement with the current study, they 2 ( -

are not complete enough to be expressed in the general
terms of eq. 6 and are therefore limited to the electro-
lytic solutions they investigated.
Conclusion
The data presented here indicate that cell constants
obtained from calibration with dilute KC1 or HC1 a t
stirring speeds in the neighborhood of the critical speed
will remain constant for most other solute-solvent sys-
tems of interest. However, if highly porous diaphragms
or fluid systems of high viscosity and low diffusivity are
employed, then the external mass transfer resistance
may be an appreciable fraction of the resistance of the
glass disk. In this case, use of the correction factor
2D/kA is required for precise measurements.
For high reproducibility and accuracy, cells stirred
by free convection alone should not be employed.
However, when somewhat lower accuracy is allowable,
it may be convenient experimentally to employ a free
convection cell and estimate the mass transfer effects by
the methods suggested above.
Appendix
The free convection mass transfer correlation for
square plates Z cm. on a side is5e6
k,l
NU = - = 0.66[Gr XC]~
D
where k , is the mass transfer coefficient for a square
plate, Xc is the Schmidt number, and the Gr is the Gras-
hoff number. For fixed values of the physical proper-
ties and the density riving force, k , - Cz-/4 where C is
the constant
~ pi)pavg~~~
C = 0.660
P2rW
Assume that this relation applies to the local mass
transfer coefficient on the segment of the circular plate
shown in Fig. 4. This assumption implies that the
parameter I is the height of the plate, that the above
correlation applies to rectangles as well as squares, and
the width of the rectangle is not significant.
The average mass transfer coefficient for a circular
disk of radius v is then
k=-=
sa L,dA
dA
C sa 1-I4 dA
rr
From Fig. 4, 1 = 2r sin ( 6 / 2 ) , x = r cos ( 6 / 2 ) , and dA =
I dx = -r2 sin2( 8 / 2 ) de. Inserting this into the integral
when r(n) denotes the complete y function of n.
Inserting the expression for C, the disk mass transfer
coefficient correlation can be written as
kr
NU - = (0.886)(0.66) [Gr XC]~
D
where Gr is based upon the disk radius T.
Thus, the varying height of the disk surface reduces
the average mass transfer coefficient from that which
would exist for a plate of uniform height r by a factor of
0.886. The combined constant in the above expression
is 0.58, which is very close to that observed (eq. 7).

THE THEORY OF ELECTRON SCATTER.ING FROM NOLECULES.

I. THEORETICAL DEVELOPMENT
B Y T. IIJIMA, R. -4.BOXHAM, AND T. ANDO
Department of Chemistrg, Indiana Uniuersity,Bloomington,Indiana
Received December 26,1962

The quantum theory of electron scattering from molecules in the gas phase is developed. Expressions which
include the effects of chemical binding are presented and the intensity averages to be expected for various types
of experiments are discussed in terms of the theory. The quantum mechanical average over the rotational
states of the molecule is shown to be reducible t o the classical method of averaging rotational motion except in
the case of extremely high energy resolution of the scattered electrons.

The scattering cross section of fast electrons exciting that of the final state is I), the incident wave vector is
a molecule from an initial state i to a final state f is given
by the formula2
cf
$ and is the scattered wave vector. The intensity of
electrons observed by a diffraction experiment is the sum
of l i f over all initial and final states of the molecule
rif = IgfI < + ILifl+f > < +f /Li,*l+ >//iii (1.1)
where according to the first Born approximation, L is
given as
(1.3)
Lif = (-exp[iktr]/4~) J u(<,
- .. . *. , 6) x -..
where w is the Boltzmann factor of the
-+ initial state i.
exp[i(ki - kf).;] drs (1.2)
Using the approximation /kfj = /kiI3 which is valid
with the interaction potential U(<, . . . ., G). The as long as the energy of the incident electron is large
wave function of the initial state of the molecule is J., compared with the loss of energy and as long as ex-
(1) Contribution Number 1109 from the Chemical Laboratories of Indiana tremely small scattering angles are not considered, the
University . summation over final states can be carried out siniply by
(2) L. Schiff, Quantum Abechanics, McGrarP-Hill Book Co., Inc., New
York, N. Y., 1955, p. 206. (3) P. M. Morse, Physik. 2..83, 443 (1932).