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DIFFUSION A N D CONVECTION A T ELECTRODES.

BY J. N. AGAR.
Received 5th March, 1947.

Movement of solute between the bulk of the liquid phase and the
electrode/solution interface is an essential feature of all electrode re-
actions ; dissolved reactants must be supplied to the interface or products
must be removed. This movement can occur in three ways: (i) by
diffusion ; (ii) by convection (i.e. movement of the liquid containing the
solute) ; (iii) by ionic migration. Migration and convection cannot
account for the whole of the material required or produced by the reaction,
and the co-operation of diffusion is always necessary ; the concentrations
at the interface must therefore differ from those in the bulk of the solution.
Such concentration differences are responsible for concentration over-
potential 1 and limiting currents, and have an important influence on the
kinetics of electrode reactions generally.
These effects are usually discussed in terms of the Nernst diffusion
layer hypothesis (see next section), which can hardly be considered a
satisfactory theoretical treatment of the subject. I n this paper a different
method is adopted ; the variables involved in the problem are found by
inspection of the fundamental equations and certain properties of the
relations between these variables are then derived by dimensional analysis.
Further information can be obtained by considering experimental and
theoretical results relating to the closely analogous subject of heat transfer.
It is necessary to restrict the discussion to systems in which the
transport number, T,, of the ion or molecule concerned is constant ; in
other cases, calculation of the effect of migration becomes too complicated.
T , is constant, or approximately constant, for :
(a) non-ionised solutes or ions in a large excess of some other electro-
lyte ( T , = o ; no migration) ;
(b) solutions containing only two ions (i.e. a single salt).
No more need be said about (a); in ( b ) , migration is responsible for a
definite fraction of the total transfer of solute, and the remainder is
transferred by diffusion and convection, which proceed as if no migration
were occurring.l* The transfer rate, j , defined below, always refers to
this latter fraction, due to diffusion and convection and not to migration.
The same transfer rate is thus relevant to non-electrolytic reactions a t
a solid/liquid interface.
It is sometimes possible t o ensure that the liquid containing the elec-
trode is stationary, so that there is no c o n ~ e c t i o n . ~But the liquid is
usually in motion, owing to (i) intentional stirring (forced convection),
Agar and Bowden, Proc. Roy. Soc. A , 1938,169,206.
a See Bridgman, Dimensional Analysis (Newhaven, 1931).
Roseburgh and Lash Miller, J . Physic. Ckern., 1910,14, 816; see also Levich
(ref.1l).
4e.g. Sand, Phil. Mug., 1901,I, 45.
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J. N. AGAR 27
(ii) gravitational motion due to variations in density associated with
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concentration changes (natural convection), (iii) evolution of gas at the

electrode, (iv) temperature gradients within the cell, and (v) adventitious
causes such as vibration. The present paper is concerned with (i) and
(ii) ; (iii) may be regarded as an extreme case of (ii), but probably in-
volves additional factors such as bubble size.
The complete calculation of the convective transfer depends on the
solution of intractable hydrodynamical problems, but a partial solution
can be obtained quite simply by dimensional analysis ; this method has
proved very useful in the treatment of thermal c o n ~ e c t i o n . ~The close
analogy between heat transfer and mass (solute) transfer has long been
known, and has been widely used in the study of mass transfer in gases6
The possibility of extending the analogy and the use of dimensional
methods t o mass transfer a t a solid/liquid interface has also been recog-
nised,'. but it does not seem that its implications have been fully
considered.
I t would, of course, be more satisfactory to obtain a complete solution
of the equations of hydrodynamics and convective transfer. Seveial
problems in thermal convection have been worked out in detail 1-mostly
in terms of Prandtl's boundary layer theory-and three important papers
by Levich 1 1 ~ l3 deal with convection a t an electrode Fn a similar manner.
l2S

But all such solutions are a t present limited to cases where the geometry
of the cell and electrode is simple, and restrictions may also be imposed
on the size of the electrode. In practice, the design of cells and electrodes
is governed by factors other than geometrical simplicity, and electro-
chemical experiments are often carried out under conditions which, from
the hydrodynamical point of view, are impossibly complicated.

The Nernst Diffusion Layer.

Nernst l4 postulated a stationary layer of liquid in contact with the
electrode ; within the layer only diffusion is operative, while outside the
layer the concentration is maintained a t a constant value, c,, by con-
vection, and diffusion is negligible. If the electrode is plane, the steady
concentration gradient in the layer is linear and the rate a t which a solute
passes through i t (the transfer rate) is :

where D is the diffusion coefficient of the solute, c , and e, are respectively

the concentrations in the bulk and at the electrode and 6 is the thickness
of the layer.
I n practice, 8 is calculated by the formula

3
where is the mean value of j over the whole electrode (mean transfer
rate), and the same equation is used without modification for non-planar
electrodes.
5 Rayleigh, Natuve, 1915,95, 66. McAdams, Heat Transmission (McGraw-
Hill, 1942). ten Bosch, Wci'rmeiibertragung (Springer, 1936).
6 e.g. Shenvood, Absorption and Extraction (McGraw-Hill, 1937).
7 King and Howard, I n d . Eng. Chew., 1937, 29, 75.
SHixson, ibid., 1944, 36, 488. Hixson and Baum, ibid., 19411 33, 478;
1942,34, 120.
9 Uchida, J . SOC.Chein. I n d . .Ja?an, B , 1933,36,416 ; 1934,37,456. Uchida
and Nakayama, ibid., 1933, 36, 635.
See ten Bosch (ref.5) and Goldstein (ref.18),ch. 14.
l1 Levich, Acta Physicochinz., 1942, 17,257.
l2 Levich, ibid., 1944, 19, 117.
Is Levich, ibid., 1944, 19, 133.
I4Nernst, 2. physik. Chem., 1904,47,52.
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28 DIFFUSION AND CONVECTION AT ELECTRODES

Provided the transport number T , is independent of concentration
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(including the case where migration is negligible and T, = o), j is given by :

j- = I ( I - T,)
AzF
where I is the total current, A the electrode area, F the Faraday, z the
number of Faradays required per mole. reacting and T , the transport
number of the reacting ion.
I n reality the transition from diffusion alone a t the electrode surface,
t o convection alone in the bulk must take place continuously ; diffusion
and convection will be equally important a t some distance 6 from the
surface, where 6 is of the same order as 6. Any factor which increases
convection (e.g. increase of liquid velocity) will diminish 6 ; an increase
of the diffusion coefficient will enlarge the zone in which diffusion is
predominant and will thus increase 6. Similar changes in 6 are to be
expected.16
The experimental values of 6 are around 0.05 cm. for vertical surfaces
in unstirred solutions (natural convection) and 0.005 cm. or less in stirred
solutions, according t o the rate of stirring.ls It thus appears that forced
convection due t o the ordinary laboratory methods of stirring is much
greater than natural convection ; the latter can therefore be neglected in
stirred solutions, and the two types of convection can be considered
separately.

The Equations of Diffusion and Convection.

The rate of change of concentration, c, a t any point in the solution
is given by the differential equation :

or in vector notation (cf. Levich l1) :

-
3c = D div grad c - v grad c
3t
. . (za)
where t is time, D is the diffusion coefficient, and u, ZI and w are the x ,
y and z components of the velocity v a t the point x , y , z . The first term
on the right represents the effect of diffusion, which is assumed t o obey
Ficks law as in a stationary liquid ; the second term gives the change in
concentration due t o convection,
As the equation is linear in c, we can replace c by the concentration
difference 8 = c - c , ; hence :

At the electrode surface, u, v and w are zero and transfer is entirely

by diffusion, so we have the two boundary conditions :
c=c, or e = c , - c G o . * (4)
and

where j has the same meaning as in (I) and n represents distance from the
electrode measured normally t o the surface.
l6 King, J . Amer. Chem. SOL, 1935,57, 828.
I6Nernst and Merriam, 2. physik. Chem., 1905, 53, 235. Brunner, ibid.,
1904,47,. 56 ; and see the review of the subject by Glasstone and Hickling,
Electrolytzc Oxidation and Reduction (Chapman and Hall, 1935).
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J. N. AGAR 29
It will be assumed that c, has the same value at all points on the elec-
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trode. This is always true under limiting current conditions, when G , = O

over the whole electrode surface, but it is not necessarily true in other
cases. For a highly reversible reaction, c, will be related t o the metal/
solution potential difference, V , by the usual Nernst equation, but V
will vary from point to point t o an extent determined by the distribution
of current in and specific resistance of the electrolyte. The variation of
V and c, is probably negligible for relatively small electrodes in an electro-
lyte of high conductivity.17 Further complications arise if the electrode
reaction is irreversible.
The experimentally important mean transfer rate is given by :
j = -1J- 4jdA
A
where A is the area of the electrode.

The Equations of Motion.

The following brief discussion is given in order to show the factors
on which the motion depends. Full accounts are, of course, to be found
in standard works on hydrodynamics.l*
The components of velocity, u, v, w, in a liquid are determined by the
equation of continuity :

-+
3U
3% + =o

together with the three Navier-Stokes equations :

and two analogous equations in v and w. p, P and v are respectively

the density, total pressure and kinematic viscosity (i.e. viscosity/density),
and X is the x component of the extraneous forces acting on unit mass
of the liquid. The terms on the left, taken together, are the acceleration
of a particle of the liquid, and, after multiplying by p , (6) has the form:
density x acceleration = pressure gradient +extraneous forces
+ viscous forces,
The extraneous force to be considered is gravity, and, in a liquid of
constant density, it is balanced by the hydrostatic pressure, Po, so that
X may be omitted if P is replaced by p = P - Po. But if the density
is variable, the effect of gravity cannot, in general, be balanced by a
hydrostatic pressure, and the equation becomes :

where g is the acceleration of gravity and g(p - p,) is the excess force
resulting from variation in p, the x axis being supposed vertical.
In the present case, the variation in density arises from variations in
concentration, and if only one solute is concerned, we may put

(8)

where p o is the density a t concentration c,. The density coefficient

cc determines the change of density with concentration and is assumed
l 7Hoarand Agar (in course of publication).
Modern Deueloflvzents in FZuid Dynamics (Oxford, 1938). Lamb,
l8 Goldstein,
Hydrodynamics (Cambridge, 1932).
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30 DIFFUSION AND CONVECTION AT ELECTRODES

to be constant. p - p o will usually be small compared to pol and (7)
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thus becomes approximately :

As already stated, the effect of natural convection (i.e. of gravitational

motion) is negligible under forced convection conditions, and the gad
term may then be omitted.
Although pressure gradients and velocities appear in the equations of
motion, pressure and velocity cannot both be taken as independent
variables. It is usually most convenient to choose velocity as an inde-
pendent variable ; p is then, in principle, determined by the equations,
and no further consideration need be given t o it, nor to quantities such
as p o which appear only in conjunction with p .
In forced convection problems, some characteristic velocity U (e.g.
peripheral speed of a stirrer ; mean rate of flow through a tube) must be
specified. In natural convection, U may be put equal to zero (stirrer
stationary), and therefore does not appear as a variable. In addition,
the time, t, may be omitted from any relation that refers to a steady state
of diffusion and convection. It is worth noting, however, that in turbulent
motion the velocities fluctuate about a mean value, and similar fluctuations
must occur in c, j , etc. Experimentally, the important quantities are
the average values over a long period, and they will be independent of t.

Application of Dimensional Analysis.

( I ) Forced Convection.-The solution of the differential equations
is a function of the coefficients which occur in them and of the quantities
appearing in the boundary conditions. Hence j depends on U , V, D and
(G, - cO) ; i t also depends on the distance n appearing in (5) and on the
various spatial co-ordinates which determine the position and size of the
electrode (including its area A ) , and of the other boundary surfaces. All
these latter quantities can be expressed in terms of some characteristic
length I (e.g. the length of the electrode), together with dimensionless
ratios of the type x/Z. The problem thus involves six dimensional quan-
tities, j , U , Y , I, D and (c, - c,,).
It must be possible to express the relation between these six quantities
in a form which is independent of the units employed, i.e. as a relation
between dimensionless group^.^ Table I shows the dimensions and units
TABLE I.
-
Transfer of Solute. Transfer of Heat.
Symbol.
Quantity. 1 Dimensions. Quantity.

Mean transfer rate ML-2T-1 Mean transfer rate

(moles. /cm.2 sec.) (cal./cm.2sec.)
ce -c, Concentration difference ML-3 (Temp. difference) x S
=@ (moles./ ~ r n . ~ ) (~al./cm.~)
D Diffusion coefficient L2T-' Thermal diff usivity
(cm.2/sec.) (cm. /sec .)
V Kinematic viscosity (As for solute)
(cm.2/sec.)
I Characteristic length (cm.) L (As for solute)
U Characteristic velocity LT-I (As for solute)
(cm./sec.)
Gravity x density coefft. M-1L4 T-1 (Gravity x thermal
(cm. /sec.2)x (cm3/mole.) I expansion coefft.)/S
-
S = specific heat per unit volume.
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J. N. AGAR 31
of j , I/, V , I, D and (c, - c,,), and the analogous variables which occur in
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heat transfer problems.

Elimination of the three fundamental units M , L and T imposes three
conditions ; hence 6 - 3 = 3 independent dimensionless quantities can
be formed from the sis variables. They may be chosen in various ways,
but the following are most convenient :

Reynolds number : Re =-
uz
V

Nusselts number :

Prancltls number : Pr
D
=
where 0 = (c, - c o ) .
The nomenclature follows the usage of hydrodynamics and heat
transfer ; the nature of the corresponding thermal quantities will be clear
from Table 1. The relation between the six variables can thus be reduced
to :
Nu = F(Re, Pr) . * (10)
The form of the function F depends only on the shape of the apparatus.
(2) Natural Convection.-The characteristic velocity U does not
appear in natural convection problems, but the quantities g and a have
t o be included. They need not be considered separately, since only their
product (gu) occurs in the equations (see (91); the dimensions of (gm)
are given in Table I. From the six variablesj, I, V , D ,0 and (g.), three
dimensionless quantities can be formed ; the usual choice is Nzt and PY
as in forced convection, together with :
z3ga0
Grashofs number : GV = -
v2 *

We thus have :
NU = G(Gr, PY) . (11)-
where the form of the function G depends only on the shape of the apparatus.
Under certain conditions this equation can be simplified.lD If the
velocity of motion is small and steady, the acceleration of any element
of the fluid (i.e. the left hand side of ( 9 ) ) becomes negligible ; the pressure
gradient and gravity are balanced by viscous forces alone. (9) can now
be rewritten so that v appears only in the pressure terms, which are of
no further interest, and in a coefficient ( g m ) / v; in the final solution v
must therefore occur only in this form. This condition is satisfied by
introducing Gr and PY into the function G as their product GY . Pr, so that :

NU = G(GY,Pr) = G(Gr. Pv) = G - (12)

Heat transfer measurements show that the simplified equation holds

over a wide range of Gr and Pv.20
The discussion has so far been restricted to reactions where only one
solute is concerned (e.g. deposition of Cu from CuSO, solution). Many
electrode reactions, and other surface reactions, are more complicated,
since the density of the solution depends on the concentration of two or
more solutes. Examples are :
(i) reactions in which reactants and products are both in solution,
+
e.g. Fe+++ e- -+ Fe++ ;
(ii) deposition of, e.g., a metal from excess of indifferent electrolyte ;
there are changes in the concentrations of metal ion and of in-
different electrolyte.
Davis, Phil. Mug., 1922,44, 926. 2o See McAdams (ref.5), p. 243.
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32 DIFFUSION AND CONVECTION AT ELECTRODES

Assuming that the changes in density due to the various solutes,
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nuinbered I, 2, 3, etc., are additive, the term gas in (9) must be replaced
by g(cr,8,+ +
a,O, . . .), and there must be equations similar to (3),
(4) and ( 5 ) for each solute, involving its concentration and its diffusion
coefficient (Dl, D,,etc.). It does not seem possible to derive simple
expressions analogous to (11) and (IZ), but approximate values of Nu
will be given by

where D, is the arithmetic mean diffusion coefficient, The use of D m

can be justified on the grounds that the differences between the various
Ds are usually small and that the value of N u is not very sensitive to
changes in the variable Gr . Pr, as will appear later,
The effect of variations in density due t o temperature gradients is
probably small (see Levich l Z )and they have been neglected. Temperature
gradients may arise from the Joule heating effect of the current and from
the heat of reaction a t the electrode. The former will certainly be negligible
a t small current densities ; the latter may escape by conduction through
the electrode or, in other types of apparatus, may be transferred to the
solution, in which case heat may be treated as an additional solute.

Comparison with Experiment.

Equations ( ~ a )(IO),
, (11) and (12) show that the thickness of the Nernst
diffusion layer is given by
1

6 -
- F(Re, Pr)
(forced convection) . (14)
1
and s -- G(Gr, Pr) or (natural convection) . ( I 5)
G(Gr . Pr)
where the subscripts f and n show the type of convection.
I n forced convection, S, is independent of the concentration difference,
8 = c, - c,,, since neither R e nor Pr depend on 0 ; in other words, j is
proportional to c, - c,. This result is analogous to Newtons Law of
Cooling in the thermal case. In natural convection, on the other hand,
6, is a function of Gr = Z3ggm@/v2, and therefore varies with the concentra-
tion difference (or with the current density). It is obvious that there
must be some such variation of a,, since the velocity of motion depends
on the density difference. Both these conclusions are supported by
experiment, although 8, does not, in fact, vary much with the concentra-
tion difference and may often be considered constant.
Further information about the functions F, G and G has to be derived
from experiment (including heat transfer measurements) or from the more
complete theoretical solutions which have been obtained in certain simple
cases.
Forced Convection.-Assuming that F can be expressed in the form :
F(Re, Pr) = B . (Re)a(Pr)b - (16)
where B is a constant, we have :
1
6 - - (Re)-a(Pr)-*.
I - B

The effect of stirring velocity, U , on a,, in electrode and other surface

reactions, has been investigated by many authors, and the results have
usually been found t o obey a law of the form
6, = const. U--n
with values of m ranging from 0-5 t o x, according to the type of apparatus
and stirring.ll Comparison with (16) shows that 1 / y ~ = a.
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J. N. AGAR 33
There is little direct information about the value of b, which determines
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the effect of Pr (i.e. of D),or about the influence of changes in v and 1.

Hixson and Baum,* from the rate of solution of benzoic acid tablets in
stirred liquids of various v and in geometrically similar vessels of differing
sizes, found a 5 I and b = 0.5 ; King and Howard found b = 0'3 from
the rate of solution of metallic wires in various reagents, and b = 0-17
on the basis of earlier experiments. King and Howard also measured
heat transfer from electrically heated wires in the same apparatus and
showed that it could be correlated with the mass transfer observations
by an equation similar to (16).
The data derived from heat transfer measurements are much more
complete. For turbulent flow through long pipes, McAdams gives
Nu = 0.023 (Re)o.s ( P r ) O a 4 (17) *

using the mean velocity of flow (cc. per sec. per sq. cm. cross section)
and the diameter as the characteristic velocity, U , and length, 1. Similar
equations have been proposed for transverse flow past wires and pipes.
It should be possible to calculate diffusion layer thicknesses from equations
such as (17) (cf. King and Howard 7), and a rough calculation, using (17)
for a tube I cm. in diameter with U = IOO cm. per sec. and values of v
and D given in Table I1 leads to Sr fi 0 . 0 0 2 cm., which is of the order
commonly observed, although there do not appear to be any recorded
measurements of S for flow through tubes. Uchida has found, more-
over, that the rate of attack of copper tubes by ammonia solution is
proportional to the 0.79 power of the velocity of flow, and has drawn
attention t o the close agreement with the exponent 0.8 in (17). The rate
of attack is probably controlled by the rate a t which dissolved oxygen
reaches the surface of the metal.
Laminar flow along a flat electrode has been treated theoretically by
LevichJ1l and, with rather different approximations, by Eucken.22 The
general equation for convection in this case, if Pr > I,* has the form : 23
Nu = const. (Re)+(Pr)*.
Levich has also considered a rotating disc electrode; putting D = IO-~
cm.2 sec.-l and v = 1 0 - 2 cm.2 sec.-1 (see Table 11), he finds :
0'022
-
a= . cm.
drev. per sec.
Natural Convection.-A theoretical solution of the natural convection
equations for heat loss from vertical plates in air has been obtained by
Schmidt, Pohlhausen and Beckmann ; 2* when reduced t o the simplified
form ( IZ), i t becomes :
NU = G' (Gr . P Y )= 0.525 (Gr . P r ) ) = 0 - 5 2 5 -(z3fiB)f
(18)
and this equation should hold for other types of convection in other media.
N u is independent of the width of the plate provided i t is large compared
t o 6, and the relevant characteristic length to be used in (18) is the height.
A similar expression is given by Levich.12
Fig. I shows the theoretical relation between log Nu and log (Gr Pr) .
according t o (IS), and also according to data derived from heat transfer
measurements given by M ~ A d a r n s . ~ The two curves agree well from
Gr . Pr = 1 0 4 to Gr . Pr = 1oS. If the diameter is used as the character-
* Pr = v / D is of the order 1 0 3 for diffusion of electrolytes in aqueous solution
at room temperature. See Table 11.
21 Glasstone and Hickling, ref.16.
22 Eucken, 2. Elektrochem., 1932,38, 341.
23 See, e.g., Goldstein, ref.l*, ch. 14.
24 See ten Bosch (ref.5),p. 159.

B
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34 DIFFUSION AND CONVECTION AT ELECTRODES

istic length I, the experimental heat transfer curve for long horizontal
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wires lies very close t o that for vertical plates.

As already mentioned, the Gr . Pr product for convection in electrode
processes is often a rather complicated quantity. But in most cases the
various 0 ' s appearing in (13)are proportional to one another and roughly
equal numerically ; we can thus use the simpler expression (12) if a now
TABLE 11.

1
cm.

-- --- -
(a) 1'0 40x10~ IO-~ IO-~ IO-~ 4x106 26.3 0.038

(b) 0'1 40x10~ IO-~ IO-~ IO-~ 4x102 3-24 0.031

determined by- a differ-

ential effect-increase of
concentration for one
solute and decrease for
another. Y and D are
typical values for aqueous
salt solutions at room
temperature.
The values of N u =
.
G'(Gr Pr) corresponding
.
t o Gr Pr = 4 x 10-2 and
4 x I O - ~ are obtained
from the experimental
heat transfer curve,
Fig. I, and the thickness
of the diffusion layer is
calculated by (~5). It
will be seen that they
agree reasonably well
with the commonly ob-
served value 0.05 cm. ;
when i t is remembered
that the calculation is
based on heat transfer
measurements, mainly
FIG.I .-Natural convection for vertical plate. for large plates in air,
- - - - - Theoretical (eqn. 18). the agreement may be
Experimental (McAdams)(heattransfer). considered very satis-
factory. It is clear from
the graph that the theoretical equation (18) would give nearly the same 8 a t
Gr . Pr = 4 x 10-6 but a somewhat larger value at Gr . Pr = 4 x I O - ~ .
From (15)and (IS),it appears that :
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J. N. AGAR 35
SO that 6, should change appreciably with the concentration difference 0.
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It is often stated that 6, is independent of 8, and this seems to be par-

ticularly well established for the stationary platinum wire micro-
"

electrodes" used by Laitinen and K o l t h ~ f f . ~It~ is, however, to be

expected that 6, will be relatively insensitive to changes in @ when very
small electrodes are used ; there are two reasons :
(i) if the linear dimensions in all three directions of the electrode are
small, the mass transfer due to diffusion alone (without convection)
becomes appreciable ; for transfer of this type, 6 is constant;
(ii) the experimental heat transfer curves for wide plates and long
wires (Fig. I), where (i) is of no importance] flatten out at low
values of Gr .Pr, i.e. the exponent in (18)becomes less than $. Since
Gr . PY diminishes rapidly with the linear dimensions, a similar
effect may occur with Laitinen and Kolthoff's short wire micro-
electrodes.
AS regards larger electrodes, some of the available data 26 show a.
definite trend of 6, in the expected direction, although it is not as large
as predicted by (19). Further evidence on this point is given in the
following section.

Concentration Overpotential under Natural Convection Con -

ditions.
The variation of 6, with 0 which is to be expected under natural
convection conditions, has an effect on the relation between current and
concentration overpotential. Assuming that all the variables except
7, 6 and 6, remain constant, and that
.
NU = (Gr)" f (PY) . . (cf. (11))
we have

and
6, = k,O-n . -
(cf. (19))
I = k 2 j = k,8*+1
where I is the total current and R,, k , and k , are constants.* Assuming
further that the potential of the electrode is controlled by the concentra-
tion of only one solute and that diffusion potentials can be neglected, the
concentration overpotential, vC, is given by :

where I , = k s c , n f l . The positive sign is t o be used when c, > c, ; the

negative when C, < c,.
When c, >
c,, ( 2 0 ) becomes
RT I
-.-1n-
rlc =
I
n -/- I ZF I, nS-1
+
or V , = V, I - . g l n ~ (21) .
if V , is the potential measured against a standard reference electrode.
n can thus be determined from the slope of the potential - log (current)
curves.
With this object, some observations have been made on the deposition
of iodine from KI solutions, at flat vertical platinum anodes 1.0to 2-9 cm.
high and 1.0 cm. wide, in unstirred solutions at 21' c. Brunner 27 has
shown that iodine is liberated without any measurable activation over-
potential, and the potential is thus controlled by the concentration of
* 8,1 and 1, are to be taken as positive quantities, irrespective of their true
sign.
25 Laitinen and Kolthoff, J . Physic. Chem., 1941,45, 1061.
sse.g.Wilson and Youtz, Ind. Eng. Chem., 1923, 15, 603. Collenberg and
Bodforss, 2.physik. Chem., 1922, 1 0 1 , 117.
2 7 Brunner, Z.physik. Chem., 1907,58, I.
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36 DIFFUSION AND CONVECTION AT ELECTRODES

I,- in contact with the electrode. The concentration of KI was N. or
Published on 01 January 1947. Downloaded by University of Massachusetts - Amherst on 06/10/2014 12:27:23.

5 N., and the effect of changes in [I-] is negligible ; the concentration of

I,- in the bulk, i.e. c0, was zero. Under these conditions (21) should
hold, and, introducing the appropriate values of z, etc., it becomes

in volts. Measurements of the potential of the anode (against saturated

calomel) a t various currents showed that the relation between V , and
log I was linear ; the observed slopes ranged from 0 - 0 2 2 to 0.025 v. The
corresponding values of n are approximately 0-3 and 0.15, and may be
compared with the theoretical value 0.25 (equation (19)).

Summary.
I. The method of dimensional analysis is applied t o the diffusion and
convection processes which govern the transfer of a solute between an
electrode and the bulk of a solution, and the results thus obtained are
extended by consideration of experimental and theoretical work on the
closely analogous subject of heat transfer.
2 . The thickness of the diffusion layer at a vertical electrode in un-
stirred solution is calculated from experimental heat transfer data, in
satisfactory agreement with observed values.
3. It is shown that the thickness of the diffusion layer, 6, a t an electrode
in a stirred solution is independent of the concentration difference be-
tween the interface and the bulk of the solution. I n unstirred solutions,
some variation of 6 with concentration difference is t o be expected, and
the resulting changes in the relation between current and concentration
overpotential are briefly discussed.

R6sum6.
( I ) Lanalyse dimensionnelle est appliqube d la diffusion et & la con-
vection, qui rkgissent le transport dune substance dissoute entre une
blectrode et le corps de la solution; les rbsultats ainsi obtenus sont
&endus par comparaism avec des travaux expkrimentaux et thboriques
sur un sujet analogue, le transport de chaleur.
(2) Lkpaisseur de la couche de diffusion sur une klectrode verticale
en solution non agitke est calculbe B partir de valeurs expbrimentales
du transport de chaleur et se trouve en bon accord avec les rksultats
observbs.
(3) On prouve que lkpaisseur de la couche de diffusion, au voisinage
de lklectrode dans une solution agitke, est indkpendante de la diffkrence
de concentration entre linterface klectrode-solution et le corps de la
solution. Dans des solutions non agitkes, on doit sattendre B une cer-
taine variation en fonction de la diffkrence de concentration ; les change-
ments qui en rksultent dans la relation entre le courant et le survoltage
pax concentration sont brikvement discutks.

Zusammenfassung.
(I) Die den obergang von geloster Substanz zwischen einer Elektrode
und der Hauptmenge der Losung kontrollierenden Diffusions- und
Konvektionsprozesse werden mit Hilfe der Dimensionsmethode analysiert.
Die Erwagung von experimentellen und theoretischen Arbeiten auf dem
eng verwandten Gebiet der Warmeu bertragung ermoglicht eine Enveiterung
der so erhaltenen Ergebnisse.
(2) Die aus den Resultaten von W2rmeu bertragungsmessungen berech-
ne te Dicke der biff usionsschicht an einer vertikalen Elektrode in einer
ungeruhrten Losung stimmt gut mit den beobachteten Werten iiberein.
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J. N. AGAR 37
(3) Es wird gezeigt, dass die Dicke der Diffusionsschicht an einer
Published on 01 January 1947. Downloaded by University of Massachusetts - Amherst on 06/10/2014 12:27:23.

Elektrode in einer geriihrten Losung unabhangig vom Konzentrations-

unterschied zwischen der Phasengrenzflache und der Hauptmenge der
Losung ist. Fur ungeruhrte Losungen ist aber eine solche Abhangigkeit
zu erwarten und die dadurch hervorgerufenen Veranderungen in der
Relation zwischen Stromstarke und Konzentrationsiiberspaiinung werden
kurz besprocheii.
Laboratory of Physical Chemistry,
Cambridge.