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12
ELECTROCHEMISTRY
OF IONIC
CRYSTALS
359C
IN ELECTROLYSIS-REVIEW
ay + Vc
Ill
cnl/see.
The three terms on the right represent, respectively, the
contributions of migration, diffusion, and convection. When
transfer is not unidirectional corresponding equations nmy be
written for each coordinate axis.
For unsteady state processes, changes of concentration
with time must be considered, and the general transfer equation becomes (1)
Oc = _ div(Uc grad r
at
[2]
[31
1(l
-- F)
nF
[4]
[5]
360C
JOURNAL
OF THE
ELECTROCHEMICAL
D(cb -
c3
[61
SOCIETY
December 1952
[10]
(b
I/]
l~J
EQUIVALENT
PROFILE
CONCENTRATION
1 -- ~
[111
==
Unsteady
Q:Ci.
l-
I
i , , / ~I
D IFFUSION
LAYER
Z
(3
Z
0
(..)
,-- 8 - , , . I
I
X
DISTANCE
FROM
Diffusion
I-
I-
State
ELECTRODE
r = D -O~c
Ot
Ox2"
The relation between current density, concentration and electrode potential.--Taking the example of the deposition of an
n valent metal in the presence of a large excess of "inert"
electrolyte which takes no part in the electrode process,
equation [6] can be expressed as:
Upon integration of equation [12] with the boundary conditions as given below Sand obtained the result expressed by
equation [13].
D(cb
--
Cb.
[S]
--
~1
DnFcb
- -
oo
Cb
[71
Oc
N~ = D ~ x x ; a t t = 0, betweenx = 0
andx
m)
nF
I~ -
A t x = 0,
[12]
----
I
IL"
[9]
[14]
DIFFUSION
V o l . 9 9 . N o . 12
AND CONVECTION
Oc
Ot
- 0
--0c = 0 .
IN ELECTROLYSIS
361C
0
DIRECTIONOF//
DIFFUSIO?/
~y,
=Y
DIRECTIONOFFLOW
Ox
where: y -
8 m__~l. 1 e_m%t
~
[15]
= ,~ --~
m
~r2D
nFD
=-/L
[I6]
X
FIG. 2. Laminar flow past an electrode (Eueken)
~__ 1.129 % / D t .
[17]
(b.
[18]
8 = R~/--%
[19]
where: R = rate of stirring (rotation), rpm; and a = a constant for a given solvent, geometry, temperature.
In moderately stirred solutions in a number of experiments
8 was found to be 0.02-0.05 mm (11, 12). Glasstone (13)
suggested that a = 0.05 gives a fair agreement with experimental findings?
Brunner realized that the assumption of a stagnant layer of
electrolyte of 8 thickness at the interface is physically incorrect. He also found that 5 depends on the diffusion coefficient. His mass transfer experiments were carried out in a
system of impractical geometry, and, therefore, only qualitative deductions can be made for different experimental
conditions.
Methods of hydrodynamics were applied first by Eucken
(14) to predict the effect of forced convection on mass transfer
rates to electrode surfaces (Fig. 2). The limiting current in
case of laminar flow in the y direction past an electrode of
height h and width yl was evaluated for cases when
the velocity of flow increases linearly with the distance from
the electrode plane.
a In equation [19] 8 is expressed in cm if used with a = 0.05.
Conditions for application of this equation, such as rotor size,
solution properties, etc., are not stated in reference.
362C
JOURNAL
OF THE
ELECTROCHEMICAL
Under steady state conditions the increase in concentration of a volume element dx.dy.dz due to convection will be
balanced by a decrease of concentration due to diffusion in a
direction (x) perpendicular to the electrode.
By solving the differential equation for diffusion and
convection
T
&'
~I l X ~
02c
= D &--~
[20]
[21 ]
[22]
0c*
~- q- (~'~grad) c* --- DV2c *
Cl
-
n2
December t 9 5 2
[251
q- F(D1 -- D2) grad c* ~- 3
I l l 7l 2
W1
where c* -
SOCIETY
[23]
where: 6
effective
viscosity
second.
Thus for
Cln2/sec
0 00647
Using the above value for 6, equations [8] and [11] may be
utilized to give limiting currents or concentr'~tion polarization. Equivalent expressions are presented by Levich.
Flow past a fiat electrode set into a landnar flow of liquid.-Levich developed a general theory of the laminar boundary
layer by considering the analogy of the convective diffusion
equation:
Ox q- V O!j = D \ a x e q- ay'- ]
[281
nl
[24]
8 = 3 D
LUJ
DIFFUSION
AND CONVECTION
~FDco
~
!~ *FDcb
~x
".
[30]
This is valid if the flow past the electrode and the electrolysis
begin at the same point. Upon integration for an electrode of
width b and length L the total limiting current is found to be:
iL
,~.~ nFDcb D
~L
-v
b.
.~
[3t]
IN ELECTROLYSIS
363C
In general Cz depends upon the shape of the surface, roughness, and Reynolds number so that no complete generalization is possible.
As a more general relation for turbulent flow Levich
suggests:
IL = nFClcouor
Re)
= ( (d.~ - - d~)'~ in - Co
\ 4dlL ]
c, -- 4i/nF(d~ -- d~)V
[33]
tin/see.
For the systems investigated in the laminar flow region the
Leveque ai)proximatiou (21) can be applied in the following
form:
1)
\pDL] \ L ]
[34]
~=3%).
of transferred species; and A, B, a = constants to be evaluated experimentally. For tm'bulent flow over a flat plate
at ordinary Reynolds numbers the coefficient of resistance is
given by:
nFCf7lo Co
IL = 2[A q-(aSca/4--A)B%//(~fl
[32]
CI = 0.07 Re -c 2
where Re = Reynolds nmnber for flow.
5 This equation is essentially equivalent to (12'), p. 287 in
original reference.
364C
I36]
Natural Convection
Natural convection or "spontaneous stirring" results when
density changes accompany concentration changes in the
region of the electrode. Fluid motion thus induced aids the
mass transfer process by supplying fresh electrolyte from the
bulk solution.
For a vertical plate electrode Levich 05) derived the following relation for the local limiting current density at any
height X on the electrode surface:
cb'
l(Op)
po Oc
Pb--Pl
[381
po(cb - cD
-
I
(IL)x = 4FD(cb)~ X-I
01np
126-D,vOcc.so, --
1.422 01up ~I
3
~,~o,j
\ re] X -~ Cb~.
[401
\.']
X -~ cb~.
[41]
(IL)x = 0.505
\1)] L
[421
where
,0-
p~
p,
~r
~so~
[Douso,
r.+ LbH~j
[43]
(IL)~ = Xoo
(I~.)x dz =
(IL)~.
[44]
Conclusion
or in a general form
December 1952
SOCIETY
~ Ki OciO
In p Il ]
[39]
DIFFUSION
AND CONVECTION
IN ELECTROLYSIS
365C
(191o).
8. L. V. REDMAN,J. Phys. Chem., 29, 548 (1925).
9. J. T. BURT-GERRANS, J. Phys. Chem., 30, 396 (1926).
10. W. NERNST, "Theoretische Chemie," 15th ed., p. 454,
Enke, Stuttgart (1926).
l l . E. BRUNNER,Z. physik. Chem., 47, 56 (1904).
12. W. NERNST AND E. S. MERRIAM, Z. physik. Chem., 53, 235
(1905).
13. S. GLASSTONE ANI) A. HICKLING, "Electrolytic Oxidation
and Reduction," pp. 81-85, Chapman and Hall, Ltd.,
London (1935).
14. A. EUCKEN, Z. Elektrochem., 38, 341 (1932).
15. B. LEVICH, Acta Physicochim. U.R.S.S., 19,117 (1944).
16. B. LEVICH, Disc. Faraday Soc., 37, (1947).
17. G. H. KEULEGAN,J. Res. Natl. Bur. Standards, 47, 156
(1951).
18. L. PRANDTL,Physik. Z., 29, 487 (1928).
19. J. N. AGAR, Disc. Faraday Soc., 26 (1937).
20. C. S. LIN, E. B. DENTON, H. S. GASKILL, AND G.