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J. N. AGAR
27
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.
McAdams, Heat Transmission (McGraw5 Rayleigh, Natuve, 1915,95, 66.
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.
28
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.
l1)
(za)
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).
J. N. AGAR
29
It will be assumed that c, has the same value at all points on the electrode. 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 electrolyte 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.
-+
3%
3U
=o
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
and Agar (in course of publication).
Modern Deueloflvzents in FZuid Dynamics (Oxford, 1938). Lamb,
Hydrodynamics (Cambridge, 1932).
l 7Hoar
l8 Goldstein,
30
pol
and (7)
TABLE I.
Transfer of Heat.
Transfer of Solute.
Symbol.
Quantity.
ce -c,
=@
D
V
Dimensions.
Quantity.
ML-2T-1
ML-3
L2T-'
L
LT-I
M-1L4 T-1
(Gravity x thermal
expansion coefft.)/S
J. N. AGAR
31
of j , I/, V , I, D and (c, - c,,), and the analogous variables which occur in
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 :
Re
Reynolds number :
Nusselts number :
Pr
Prancltls number :
uz
=-
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 :
Grashofs number :
z3ga0
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 :
(12)
1922,44,
926.
2o
32
(12)
(forced convection)
(14)
(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 concentration 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 concentration 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 :
and
s -- G(Gr, Pr)
or
F(Re, Pr) = B
. (Re)a(Pr)b
(16)
J. N. AGAR
33
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, moreover, 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 =
cm.2 sec.-l and v = 1 0 - 2 cm.2 sec.-1 (see Table 11), he finds :
IO-~
0'022
. 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 :
a=
(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-
34
istic length I, the experimental heat transfer curve for long horizontal
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
(b)
0'1
40x10~
IO-~
IO-~
IO-~
4x102
26.3
3-24
0.038
0.031
.
.
J. N. AGAR
35
SO
"
7,
>
RT
or V , = V, I - . g l n ~
(21)
-.-1nn -/- I ZF I,
nS-1
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 overpotential, and the potential is thus controlled by the concentration of
rlc
sign.
25
sse.g.Wilson and Youtz, Ind. Eng. Chem., 1923, 15, 603. Collenberg and
36
N. or
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
Summary.
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 unstirred 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 between 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.
I.
R6sum6.
( I ) Lanalyse dimensionnelle est appliqube d la diffusion et & la convection, 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 certaine variation en fonction de la diffkrence de concentration ; les changements 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 berechne te Dicke der biff usionsschicht an einer vertikalen Elektrode in einer
ungeruhrten Losung stimmt gut mit den beobachteten Werten iiberein.
J. N. AGAR
37
Elektrode in einer geriihrten Losung unabhangig vom Konzentrationsunterschied 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.