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Oc = _ div(Uc grad r + div(D grad c) -- V grad c [2] Consider a cell containing at one end a vertical plane
at cathode upon which metal ions are being deposited. Assume
where t = time, sec. The potential q) must satisfy the Poisson that due to mechanical stirring the concentration is uniform
equation (1), and the velocity vector V the three Navier- at "dl distances from the floor of the cell at any particular
Stokes equations. Thus a set of nonlinear differential equa- dist:mee x away from the electrode. For the species deposited
tions is obtained which has been solved only f m ' a rehtively a concentration profile through the main body of solution up
few cases. to the electrode-solution interface may prevail as illustrated
In a fluid in which turbulence has been induced by stirring in Fig. 1. The exact shape of the profile will depend upon the
or pumping, transfer by diffusion is augmented by eddy mass transfer mechanism predomina~ting at a w place. As-
diffusion resulting from turbulent pulsations. Analytical solu- stone further that the concentration in the main body of
tion of the convection-diffusion equations for such systems is solution remains constant. In view of the complicated nature
in general impossible at the present time. of the problem it is sometimes convenient to express the
over-all mqss transfer process by equations of simple empirical
Equations for Steady State Mass Transfer form which relate the mass transfer rate to the difference
between the mixed-mean or average concentration of the
The term "mass transfer" will be used to denote the trans-
transferred species in the nmin body of fluid and the concen-
port of ions or molecules by the combined effects of diffusion,
eddy diffusion, and convection, excluding the contribution of tration at the electrode-solution interface.
(A) Mass transfer coefficient: the rate of transfer may be
migration to the process. The mass transfer process is com-
expressed by a coefficient, /eL, defined as follows:
monly designated as "forced convection" when the system
is mechanically agitated by stirring or pumping, and as
Na = kL(cb -- c~) [5]
"fi'ee convection" when mixing is induced as a result of
density differences accompanying concentration differences where: Nd = mass transfer rate at any particular point on
from point to point within the fluid. Mass transfer in the the electrode, gram mole/cm2-sec; kL = mass transfer co-
steady state implies that the transfer rates, current density, efficient, cm/see; c~ = average concentration in bulk fluid,
concentrations, temperature, and other variables associated gram mole/cnr~; and c~ = concentration at interface.
with cell operation are independent of time at any particular (B) Equivalent fihn thickness or diffusion layer: this
point in the system. concept expresses the mass transfer process by the rate equa-
~Department of Chemistry and Chemical I",ngineertng, tion for steady state diffusion from concentration ca to cl
University of California, Berkeley, California. This work has over a hypothetical layer of stagnant fluid of thickness ~.
been supported by the Office of Naval Research. The diffusional term of equation [1], i.e., Fick's first law, is
360C JOURNAL OF THE ELECTROCHEMICAL SOCIETY December 1952
integrated for this case to give the relation which defines Concentration polarization.--During the passage of current,
the equivalent film thickness: the concentration of metal ions at the solution-electrode
interface changes from the value at rest, cb, to ci. The corre-
D(cb - c3 sponding shift in electrode potential, AEo, the concentration
Nd -- [61
polarization, is equal to the emf of a concentration cell with
transference, in which the electrodes are in contact with
where ~t = equivalent film thickness. solutions of concentrations Cb and c~, respectively. If transfer
This general mathematical formulation was originated by by migration of the potential determining ion is negligible,
Nernst (2) who termed ~t the "diffusion layer," a name which and the ratio of ionic activity coefficients is assumed to be
has been used widely throughout the electrochemical litera- unity,
ture. The term "equivalent film thickness" has been used
extensively in chemical engineering writings. fi T c,
~Ec = ~ h~ - [10]
(b
I/]
l~J The dependence of concentration polarization on current
EQUIVALENT CONCENTRATION density for any current, I, can be found by combining equa-
PROFILE tions [9] and [10]: 2
AEc = ~ - ~ l n 1 -- ~ . [111
==
Unsteady State Diffusion
The relation between current density, concentration and elec- Upon integration of equation [12] with the boundary condi-
trode potential.--Taking the example of the deposition of an tions as given below Sand obtained the result expressed by
n valent metal in the presence of a large excess of "inert" equation [13].
electrolyte which takes no part in the electrode process, Oc
equation [6] can be expressed as: A t x = 0, N~ = D ~ x x ; a t t = 0, betweenx = 0
andx ~ oo c ~ Cb
I _ D(cb -- m)
nF
[71
By means of equation [14] Sand was able to determine across which mass transfer is possible only by diffusion and
diffusion coefficients in electrolytes by observing the time migration. The magnitude of 8 depends only on hydrodynamic
interval necessary for a given current density to cause an ion conditions (r~te of stirring, rotation, etc.) and the viscosity
depletion at the cathode to zero concentration, i.e., to reach of the solution.
limiting current density. Sand realized that this procedure In the steady state the concentration gradient in this
is not rigorous on account of the variations in transference "diffusion layer" is constant, and the rate of diffusion is equal
numbers with concentration. However, on the basis of to the rate of the electrode process. Thus for the case of metal
Kohlrausch's work (6) he found that such variations result deposition, equation [7] applies. For any particular solvent,
in an error not exceeding 2.5 per cent for the systems in- geometryand rate of stirring, 8 is a constant, and can be deter-
vestigated.
An extension of the work of Weber and Sand was given by
Rosebrugh and Miller in 1910 in an excellent paper on the
mathematical treatment of electrolysis with direct and suc-
cessive currents (7). A cell of uniform cross section provided
~y,
with identical metal electrodes at both ends served as the
model. The electrode reactions were assumed to be identical
but opposite in sense (at the cathode, metal depositing; at
the anode, metal going into solution, both with 100 per
cent current efficiency).
Equation [12] was solved for the boundary conditions
Oc 0 =Y
at x = 0 (at half distance between the electrodes) - 0
Ot
DIRECTIONOF// DIRECTIONOFFLOW
art =0 --0c = 0 . DIFFUSIO?/
Ox
Under steady state conditions the increase in concentra- which upon integration yields:
tion of a volume element dx.dy.dz due to convection will be
F~
balanced by a decrease of concentration due to diffusion in a I~;;]-' (~: D1 -- n2D2) c* grad ~b
direction (x) perpendicular to the electrode.
By solving the differential equation for diffusion and
[251
convection q- F(D1 -- D2) grad c* ~- 3
I l l 7l 2
T &' 02c
~I l X ~ = D &--~ [20] wherej represents the vectors of current density and R = gas
constant.
with the boundary conditions: at x = 0, c = 0; at x = * , The solution of equation [25] allows the determination of the
c = c~; where W, denotes the constant fluid velocity unit exact relation betwcen the potential across the electrolytic
distance away from the electrode plane, the following expres- cell and the current. This import'mr separation of the convec-
sion was obtained for the total linfiting current: tive diffusion from the potential distribution has been shown
to be possible also for a tervalent system when the concentra-
iL = 77,800 hcb "~/D"g{IV~. [21 ]
tion of one kind of ions is low compared to that of the other
Dividing both sides of equation [19] by the surface area two kinds.
A = h-y~ yields the average limiting current density along A number of solutions for specific cases of definite geometric
the electrode. The result indicates that I~.=~g decreases with systems and hydrodynamic conditions were given as reviewed
the .~i power of the length of the electrode in the direction of below.
a flow, and increases proportional]y to D 2ja. This conclusion A fiat infinite disk rotating with a constant angular velocity.-
is also supported by the expression obtained for the average Using yon Karman's solution for the hydrodynamics of fluid
thickness of the diffusion layer: motion about such a rotating disk the following result was
obtained for steady state conditions in the discharge of one
8,,~ = 1.24 ,a/DYe-. [22] ion of a binary system:
'V W1
distribution so that the local limiting current density (IL)x In general Cz depends upon the shape of the surface, rough-
varies in the x-direction according to the equation: ness, and Reynolds number so that no complete generaliza-
tion is possible.
~FDco !~ *FDcb ". As a more general relation for turbulent flow Levich
(I~)~ = ~ = ~x [30]
suggests:
This is valid if the flow past the electrode and the electrolysis
IL = nFClcouor Re)
begin at the same point. Upon integration for an electrode of
width b and length L the total limiting current is found to be: where: ~o(Sc, Re) is a function which must be determined
v ~L .~ experimentally; Sc = v/D, the Schmidt number.
iL = ,~.~ nFDcb D -v b. [3t] Alternate expressions could be based upon the treatment of
yon Karman (6) for heat transfer. For low Schmidt numbers
I t should be noted that the development of the Prandtl equation [32] agrees well with a formula obtained by Prandtl
hydrodynamic boundary layer at the plate cannot go on 08) for the corresponding case in heat transfer.
indefinitely in an apparatus of finite size. How far in the x-(ti- At high turbulence the thickness of the diffusion layer will
rection its formation will extend, until a steady state boundary be practically constant over most of the electrode, and the
layer of constant thickness is formed, depends not only upon current and potential distribution will be correspondingly
the geometry of the entire cell (presence of any close parallel uniform.
wall, for instance) but also upon the length of the electrode. In a subsequent paper (15) Levich extended the treatment
Levich's equation [29] is acceptable from the hydrodynamical of turbulent flow to nonstreamlined electrodes (cylinder
viewpoint only for a short electrode at a relatively low fluid placed perpendicularly to the electrolytic flow) and to elec-
velocity and in the absence of any close parallel boundary. trodes of rough surfaces.
The problem of current distribution is also complicated. Along the lines suggested by Agar (19), Putnam, et al.
First, because near an electrode edge submerged into an dec- (20) correlated limiting current densities for the inner elec-
trolyte the current distribution will be nonuniform and the tro(te of an annular cell, with the mass transfer heat transfer
equipotential surfaces by no means parallel to the electrode an'dogy. Mass transfer correlations were obtained in terms
surface. Second, due to depletion of the ions, as the fluid of equivalent film resistances using experimental data ob-
moves along the electrode the electrode-potential changes tained from measurements with four different electrode reac-
continuously in the x-direction. This nonuniform potential tions. The electrolytes were passed through an annular elec-
is, in turn, responsible for a nonuniform current distribution trode system at various constant rates of flow. The experi-
throughout the electrode. These possible limitations should ments covered viscous and turbulent regions (Re =
be considered in the general application of equations [30] 59-30,000).
and [31]. From the measured limiting currents and the inlet concen-
Turbulent flow over a fiat plate electrode.--Levich considered trations to the cell, the mass transfer coefficient was obtained
the boundary layer (region of disturbed velocity) developed as follows:
over the plate to be divided into three regions with respect
to transfer of mass and momentmn. In region 1, immediately = ( (d.~ - - d~)'~ in - - Co
]CL \ 4dlL ] c, -- 4i/nF(d~ -- d~)V [33]
adjacent to the surface, turbulent pulsations are sufficiently
damped out so that transfer of momentum occurs by viscous
where: kL = mass transfer coefficient; d,d2 = diameter of
shear and transfer of mass occurs by molecular diffusion. In
inner and outer electrode, em; L = length of electrode, cm;
region 2, adjacent to region l, turbulent pulsations are large
Co = concentration of inlet stream gram mole/cc; I = limit-
enough to cause the transfer of mass to be predominantly by
ing current, amp; n = number of electrons per molecule or
eddy diffusion or turbulent pulsations, but because of the
ion reacted at the electrode; F = Faraday; and V = velocity
relatively high kinematic viscosity of the liquid, momentum is
transferred predominantly by viscous shear. In region 3, the
tin/see.
For the systems investigated in the laminar flow region the
magnitude of turbulent pulsations is sufficient to cause trans-
Leveque ai)proximatiou (21) can be applied in the following
fer of both momentum and mass to occur by turbulent pulsa-
form:
tions. Within these assumptions by application of the nmss
and momentum transfer analogy an equation was derived
which may be presented in the following expression for limit- 1) \pDL] \ L ] [34]
ing current density:
where: & = equivalent diameter, d2 - d~ cm; D = diffusivity,
nFCf7lo Co [32]
cmUsec; G = nmss velocity, gram/cm2/sec; and p = density
IL = 2[A q-(aSca/4--A)B%//(~fl
of electrolyte, gram/cc.
The agreement of experimental data with the Leveque heat
where: CI = coefficient of resistance, or friction factor; transfer equation was found to be satisfactory (within about
uo = velocity of flow past the plate; Co = bulk concentration ~=3%).
of transferred species; and A, B, a = constants to be evalu- The mass transfer under turbulent flow conditions was
ated experimentally. For tm'bulent flow over a flat plate correlated in terms of the jv parameter, defined by Chilton
at ordinary Reynolds numbers the coefficient of resistance is and Colburn (22) as:
given by:
CI = 0.07 Re -c 2
where Re = Reynolds nmnber for flow. where V = velocity, cm/sec, and t~ = viscosity, gram/cin/sec.
5 This equation is essentially equivalent to (12'), p. 287 in A satisfactory correlation of jD as a function of Reynolds
original reference. number was obtained. The function was found to agree
364C JOURNAL OF THE ELECTROCHEMICAL SOCIETY December 1952
rather closely with the friction factor data of Carpenter, Natural convection has also been treated by Agar (19)
Colburn, and Wurster (23), i.e., who utilized a theoretical solution for the heat loss from a
vertical plate derived by Schmidt, et al. (26) and obtained a
j o = f = 0,023 I36] result which may be expressed for limiting current density
2 as follows:
where f = friction factor.
However, it is doubtful that great significance can be (IL)x = 0.394 nFD \ re] X -~ Cb~. [401
attached to this apparent agreement between momentum
transfer and mass transfer in view of the high values A further expression was derived by Keulegan (17), which
of Schmidt numbers prevailing in liquid systems, and possible yields for limiting current density:
differences in surface roughness.
The correlation should be ve~T useful in predicting mass (It.)x = 0,471 nFD X -~ cb~. [41]
transfer behavior in electrolytic cells, under flow conditions, \.']
in presence of a large excess of indifferent electrolyte.
On the basis of experimental studies for deposition of
Natural Convection CuSO4 from sulfuric acid solutions the authors (27) have
Natural convection or "spontaneous stirring" results when found the following equation to be applicable:
density changes accompany concentration changes in the
region of the electrode. Fluid motion thus induced aids the (IL)x = 0.505 [g(p0 --e,)r X-" [421
mass transfer process by supplying fresh electrolyte from the \1)] L J
bulk solution. where
For a vertical plate electrode Levich 05) derived the fol-
lowing relation for the local limiting current density at any ,0-
p~
p, - ~r - ~so~
[Douso,
r.+ LbH~j [43]
height X on the electrode surface:
(IL)x = 0.3S2 nFD cb' where ac~so~ and an2so ~ = density coefficients for CuS04 and
H2S04 respectively; and VH+ = transference number for
hydrogen ion.
where: a = density coefficient (defined by equation [38]);
Thus it may be seen that all of the theories agree in es-
g = acceleration of gravity; and c0 = bulk concentration of
sential form, differing primarily by a numerical constant. It
species reacting.
should be noted that only equations [39] and [42] include the
The density coefficient, a, relates density changes to con-
effects of migration of nonreacting species on the density
centration changes:
difference established between the bulk solution and the
l(Op) Pb--Pl interface.
[381
=
po Oc
- -
po(cb - cD
- - - -
I t is unfortunate that the theory of Prandtl's boundai~ 4. J. N. AGAR AND F. P. BOWOEN,Proc. Roy. Soc., 169A,
layer, patterns of velocity distribution, and other aspects of 2O6 (1938).
hydrodynamic theory have not been introduced into the field 5. H. J. S. SAND, Z. physik. Chem., 35, 641 (1900).
of electrochemistry until recently. Mass, heat and momentum 6. B. KOHLRAUSCH,Wied. Ann., 62, 209 (1897).
transfer analogies, and dimensional analysis are valuable 7. T. R. ROSEBRUGH AND L. MILLER,J. Phys. Chem., 14, 816
(191o).
tools in the development of modern theories of electrolysis.
8. L. V. REDMAN,J. Phys. Chem., 29, 548 (1925).
The use of concentration instead of activity in the electro- 9. J. T. BURT-GERRANS, J. Phys. Chem., 30, 396 (1926).
chemical equations may lead to serious errors due to large 10. W. NERNST, "Theoretische Chemie," 15th ed., p. 454,
changes of the activity coefficients with concentration. The Enke, Stuttgart (1926).
form of some equations, e.g., those accounting for diffusion l l . E. BRUNNER,Z. physik. Chem., 47, 56 (1904).
only, may still be acceptable if one merely considers the 12. W. NERNST AND E. S. MERRIAM, Z. physik. Chem., 53, 235
symbols for concentration as representing activity. However, (1905).
when mass transfer analogies are carried over to electrolysis, 13. S. GLASSTONE ANI) A. HICKLING, "Electrolytic Oxidation
the distribution of concentration is obtained. Therefore, the and Reduction," pp. 81-85, Chapman and Hall, Ltd.,
prediction of the concentration polarization (which is a func- London (1935).
14. A. EUCKEN, Z. Elektrochem., 38, 341 (1932).
tion of the activities) is not possible unless the activity co-
15. B. LEVICH, Acta Physicochim. U.R.S.S., 19,117 (1944).
efficients are known for the entire range of concentrations. 16. B. LEVICH, Disc. Faraday Soc., 37, (1947).
A further major difficulty arises from the fact that the meth- 17. G. H. KEULEGAN,J. Res. Natl. Bur. Standards, 47, 156
ods available at present for activity measurements yield (1951).
the mean activity coefficients and not the activity coefficient 18. L. PRANDTL,Physik. Z., 29, 487 (1928).
of the potential-determining ion. The appreciation of these 19. J. N. AGAR, Disc. Faraday Soc., 26 (1937).
facts is essential for future theoretical and experimental 20. C. S. LIN, E. B. DENTON, H. S. GASKILL, AND G.
developments in this field. L. PUTNAM,Ind. Eng. Chem., 45, 2136 (1951).
The variation of the diffusion coefficient with concentration 21. J. LEVEQUE, Ann. mines, 13, 201 (1928).
22. T. H. CHILTON AND i . R. COLBURN, Ind. Eng. Chem., 26,
becomes a serious matter when high currents are applied. For
1183 (1934).
this reason the validity of the now available relations for 23. E. G. CARPENTER, A. P. COLBURN, AND A. WURSTER,
limiting currents, derived with the diffusion coefficient as- Trans. Am. Inst. Chem. Engrs., 42,165 (1946).
sumed constant, is subject to question. For a given system 24. C. WAG~ER, J. (and Trans.) Electrochem. Soe., 95, 161
the functional dependence of D on concentration can be (1949).
established in general only by experiment. Such diffusivity 25. TH. VON KARMAN,Z. angew. Math. u. Mech., 1,244 (1921).
measurements must be performed under conditions where 26. M. TEN BOSCH, "Waermeuebertragung," p. 159, Springer,
only the potential-determining ion diffuses under its own Berlin (1936).
concentration gradient. 27. C. R. WILKE, C. W. TOBIAS, AND M. EISENBERG, paper pre-
In conclusion it may be stated that the recent developments sented before the Philadelphia Meeting of The Electro-
chemical Society, May 5, 1952.
which have been reviewed in this paper represent a major
28. S. GLASSTONE,"Introduction to Electrochemistry," pp.
step toward establishment of quantitative theoretical methods 445-458, D. Van Nostrand Co., Inc., New York (1942).
for the prediction of mass transfer effects. This in turn should 29. G. KORT~L~[AND J. O'M. BOCKRm, "Textbook of Electro-
facilitate a more complete understanding of other aspects of chemistry," Vol. II, pp. 400-408, Elsevier Publishing
electrolysis. Co., New York (1951).
30. T. TSUKAMOTO, T. KAMBARA,AND I. TACHI, J. Eleclrochem.
REFERENCES
Assoc. Japan, 19, 311 (1950). (Subsequent to the prepara-
1. B. LEvicn, Acta Physicochim. U.R.S.S., 17,257 (1942). tion of this manuscript the author's attention was called
2. W. NERNST, Z. physik. Chem., 47, 52 (1904). to recent experimental and theoretical work dealing with
3. H. F. WEBER, Wied. Ann., 7,539 (1879). the problem of the rotating electrode.)