CORROSION AND POLARIZATION CHARACTERISTICS

OF ZINC IN NEUTRAL-ACID MEDIA - II.

EFFECT OF NH,+ IONS AND THE ROLE OF
BATTERY ZINC ALLOYING CONSTITUENTS

L. M. BAUGH
Beret Group Ltd, Group Tcchniral Cmtre, St Ann’s Road, London N15 3T1, England

(Aeceirred 3 I October 1978)

w - The corrosion and polarization cbaractistics of zinc have been studied in molar, quiescent
solutions of NH&lo,, (NH&SO+, NH&l and NH,Br in the pH range 3.8-5.8. Corrosion rates have been
determined by the Tafel line extrapolation procedureand the polarization resistance. method where possible.
Numerical values of the corrosion currents are compared. The role of NH: ions, anions, pH and battery zinc
alloying constituents on the nature of the rate controlling anodic and cathodic processes are discussed.

INTRODUCIION obtained with other ammonium salts, eg NH&IO,,

In the previous communication[ 1] it was shown that
the corrosion and polariultion characteristics of pure
zinc in quiescent, molar solutions of various sodium
salts are strongly dependent upon the solution pH in
the range 3.8-5.8 and the nature of the anion present.
In this paper the work has been extended to a study of
the corrosion behaviour of zinc in NH,Cl which is
commercially important because it forms the major
ionic component of the electrolyte in LeclanchC bat-
teries. Several other ammonium salts have also been
investigated. In addition, the effect of replacihg the
pure zinc electrode with one consisting of com-
mercially used battery zinc alloy is also examined.
EXPERIMENTAL
The battery zinc alloy disc electrodes consisted of
1.03% Pb, O.&Q Cd, 0.001% Fe and remainder Zn.
The pure zinc electrodes, electrode construction, sur-
face preparation, cell, electrode assemblies, instrumcn-
tation and experimental procedure have been de-
scribed previously[ 11.
Solutions were made up from AnalaR grade salts
with triply distilled water. Variations in pH were
effected by the addition of small quantities of HCl or
NH40H.
The reference electrode was a 1 N calomet All
experiments were duplicated and carried out at room
temperature (25 f 2’C).
BWULTS AND DlSCUSStON
Effect of NH: ions on the general polarization charac-
teristics of pure zinc
Figure 1 shows the effect of pH in the range 3.8-5.8
on the general polarization characteristics of zinc in
molar NH,Cl solutions. It can be Seen that this change
in the bulk proton concentration has little influence
upon the polarization curves except at low cathodic
overpotentials where proton reduction occurs. How-
ever, the &ect is small considering the two order
change in proton concentration. Similar results were
(NH&SO+ and NH,Br. These results indicate that
the surface concentration of protons is not appreciably
influenced by changes in the bulk concentration in
weakly acidic ammonium salt solutions and therefore
the source of the surface protons must lie elsewhere.
Figure 2 compares the polarization curve for NH&I
at pH 3.8 with that for NaCl at the same pH. Although
the anodic curves have an identical slope (approx.
25 mV per decade) both anodic and cathodic currents
are higher in the ammonium salt solution and the
cathodic curve for the latter solution deviates mark-
edly from that for NaCl. Previously it was de-
monstrated[l] that oxide film formation on zinc is
inhibited in solutions at pH 3.8 and therefore the
differences shown in Fig. 2 cannot be attributed to the
influence of such films. It was also shown that in simple
salt solutions like NaCl the current between points A
and B of Fig. 2 is due predominantly to diffusion
controlled proton reduction and that between points B
and C to water reduction. In ammonium salt solutions
the situation is more complex. The steepness with
which the cathodic current initially rises suggests that
in the region D-E in Fig. 2 hydrogen evolution occurs
under near activation (charge transfer) controlled
conditions. Also, since the current in this potential
region is considerably higher than the limiting
diffusion current at pH 3.8 (approx. 10 PA cm-‘) and
because a water reduction process would not be
expected until more cathodic potentials (line B-C), it is
necessary to make one of two alternative assumptions.
Firstly, that the NHi ions themselves are electroactive
NH:+e+NH,+H (1)
followed by
H+H,O* +e--rH,+H,O (2)
or
H+H+H,, (3)
or secondly that their rate of dissociation in the double
layer is sufficiently fast to establish a constant con-

669
670 L. M. BAUGH

Fig. I. Polarization
curves for pure zinc in molar NH&l solutions, (0) pH 5.8, (Cl) pH 3.8.

centration of protons at the outer Helmholtx plane
irrespective ofcurrent and thus maintain an activation
controkd situation :
NH: + H,O= H1O+ + NH3
2H,O+ + 2e + H, + 2H,O.
The difference between the rate controlling mech-
anisms for hydrogen evolution at low overpotentials
displayed in Fig. 2 can therefore be attributed to the
f%ct that in the NH,Cl solution the reaction occurs in
an unsupported electrolyte system whereas in NaCl it
occurs in a supported electrolyte system. As a general
conclusion it may be stated that in ammonium salt
solutions the double layer at cathodic potentials will
consist predominantly of NH: ions which may be
directly (reactions (l)-(3)) or indirectly (reactions (4)
and (5)) ekctroactive. Any tendency for the con-
centration of these ions to become reduced as a
consequence of their electroactivity will be com-
pensatcd by electrical migration in addition to
diffusion and probably some convection produced as a
result of hydrogen gas bubbling on the electrode
surface. The concentration of ammonium ions at the
(4) outer Helmholtz plane will therefore tend to remain
(5) effectively constant at low overpotentials and the
hydrogen evolution reaction will be activation con-
trolled. This corresponds to a situation where there is
negligible depletion of the equilibrium double layer
structure as a consequence of current Bow. In sodium
salt solutions and other simple non-electroactive salt
solutions, however, protons can only arrive at the
electrode surface by diffusion and convection because
the large excess of supporting electrolyte prevents
transport by migration. In such solutions under neut-
ral and near neutral pH conditions hydrogen evol-
ution is diffusion controlled.
The simple model proposed above accounts for the
observations at low overpotentials. However, it can be
seen from Fig. 2 that hydrogen evolution in NH,Cl

E/V
Fig. 2. Polarization curves for pure zinc in molar solutions at pH 3.8, (m) NaCl, (a) NH*Cl.
 Corrosion and Polarization charsoteristics of zinc in neutral-acid media - II
I I
-HO
II - 1.20
L
-1.30
Fig. 3, Polarization curves for pure zinc in molar solutions at pH 5.8, (0) NaCI, (0) NH&l.
becomes diffusion controlled at higher potentials (line
E-F] just prior to the influence of water reduction on
the net current (line F-G). The Tafel line for the latter
process would be expected to follow the line B-C
irrespective of which solution is considered. Subtrac-
tion of the limiting current (E-F) from the line F-G
for the ammonium salt solution produced a line
showing good agreement with that of B-C at high
overpotentials.
Figure 3 compares the polarization curve for NH4CI
with that for NaCl at pH 5.8. The shape of the curve in
NaCl has been attributed to the presence of an oxide
on the zinc surface[l]. In particular, this causes the
anodic branch of the curve to be steeper than expected
and the cathodic branch to exhibit a peak at - 1.32 V
for the reduction of the oxide. It can be seen that the
polarization curves for NH.&1 have none of these
features. The anodic branch has a slope of about
25 mV per decade and no reduction peak is discernible
on thecathodic branch. Thus the NH: ions present in
Fig. 4. Anodic polarimtion curves for the active dissolution
of ure zinc in molar solutions at pH 3.8 (open symbols and
p R 5.8 (closed symbols), (0) (NH&SO+ (0) NH& 1O+
671
/
-1.40
/
- 1.50
E/V
the double layer have the ability to inhibit oxide film
formation. This effect was demonstrated previously by
differential capacitance measurements[2] and gives
support to the theory that in ammonium salt solutions
the local pH at the zinc surface is sufficiently low to
inhibit film formation. It is difficult to understand how
this could be achieved in the absence of an appreciable
surface dissociation of NH; ions and this observation
may lend support to the view that hydrogen evolution
in ammonium salt solutions under near neutral bulk
pH conditions occurs by a process involving the prior
dissociation of NH: ions (reactions (4) and (5)).
Despite thefact that theNHt ion isonlyaweak acidin
bulk solution (pK, = 9.24) it is possible that di-
ssociation of these ions at the outer Helmholtz plane is
enhanced by the negative charge on the electrode
surface which pertains in the potential region where
hydrogen evolution occurs.
I I I
-1.05 -1.10 -1.15
E/V
Fig. 5. An& polarixat.ioa curves for the active dissolution
of pure zinc in molar soIutions at pH 3.8 (open symbols) and
pH 5.8 (closed symbolsX (0) NH&l, (0) NH4Br.
672 L. M. BAWH
Eflect of anions on the anodic dissolution of zinc
Figure 4 shows the effect of pH on the anodic
polarization curves for molar NH,ClO* and
(NH&SO4 solutions and Fig. 5 shows the same effect
for NH&l and NH,Br solutions. In Fig. 4 the Tafel
slopes are close to the value 2.3 x 2RT/3F in agree-
ment with the results obtained for the equivalent
sodium salts at pH 3.0 and representative of irrever-
sible dissolution involving two consecutive charge
transfer reactions[l]. The pH dependence of the
curves for (NH&SO4 with the dissolution rate in-
creasing with pH can also be explained in a similar way
to that for the sodium salt analogue in terms of the
participation of ion pairing[l]. The lack of a de-
pendence of the magnitude ofthe Tafel slopes upon pH
in the range 3.8-5.8 is, however, in contrast with that
observed for the equivalent sodium salts. In the latter
salt solutions the slopes were affected by the presence
of the oxide film formed at the higher pH values. The
results in Fig. 4 therefore confirm the absence of such
films at pH 5.8 in ammonium salt solutions. Further
confirmation comes from the lack of a significant
dependence of the dissolution current upon pH in
NH+CIOa. This is in contrast with that observed in
NaClO, in the pH range 3.8-5.8 where the anodic
dissolution current fell by over an order of magnitude
(cf[l, Fig. 11).
In the case of NH&I and NH& solutions it can be
seen that there is little dependence of either the
magnitude of the anodic slope or the magnitude of the
dissolution current upon pH. The anodic slopes are
close to the value 2.3 x RT/2F in agreement with that
for the equivalent sodium salts at pH 3.0 and repre-
sentative of reversible dissolution involving com-
plexed ainc-chloro or zinc-bromo species which
diffuse slowly away from the electrode[l]. These
results also confirm the absence of oxide films in the
pH range studied.
Fig. 6. Cathodic polarixationcurves for hydrogen evolution on pure zinc in molar (NH&%& solutions, (a)
pH 5.8, (0) .pH 3.8.
E.ct of anions on the cathodic hydrogen evolution
reactions
Figures 6, 7 and 8 show the effect of pH on the
cathodic polarization curves in (NH&SO~,
NH&IO, and NH4Cl together with NHIBr, re-
spectively. All these curves have a very similar shape
except for the case of NH,ClO, and (NH,),SO, at
pH 3.8. The latter anomaly can be explained by the
participation of HSOi ions[l] but it is not clear at
present why the former curves should exhibit such a
gradual rise at low overpotentials. This suggests that in
this potential region the proportion of the cathodic
current due to proton reduction is suppressed in the
NH&IO, solution.
The higher cathodic currents observed at high
overpotentials in the NH+Br solution (Fig. 8) suggests
the influence ofBr - specific adsorption upon the water
reduction reaction. Of all the anions studied it is likely
that only the Br- ion is likely to be specifically
adsorbed to any appreciable extent in the potential
range studied.
Determination of corrosion rates
Tables 1 and 2 show the corrosion rates for zinc in
the various ammonium salt solutions at pH 5.8 and
pH 3.8, respectively. Corrosion rates are shown as
determined by the Tafel line extrapolation procedure,
i:::,, and the polarization resistance method, i::,,
where possible. The details of these determinations
were discussed in the previous communication[l]. The
data for NaCl is also added for comparison with that
for NH&l.
In order to determine the corrosion rates it was
necessary to know the magnitude of the Tafel slopes b,,
and b, for the partial anodic and cathodic processes,
respectively. The anodic slopes are well defined but the
cathodic slopes are less so because of the influence of
concentration polarization. This is particularly pro-
 Corrosion and polarization characteristics of zinc in neutral-acid media - II 673

-I .I0 -1.15 4.M -1.25 -1.30 -1.35 - 1.40 - 1.45 -1.50

E/V
Fig. 7. Cathodicpolarizationcurves for hydrogen evolutionon purezinc in molar NH&IO4 solutions,(I)
pH 5.8,(D) pH 3.8.

loo -

I
-1.15 -1.20 -1.25 -1.30 -1.35 - I.40 - 1.45 -1.50

E/V
Fig. 8. Cathodic polarizationcurves for hydrogen evolution on pure zinc in molar solulions at pH 5.6 (closed
symbols) and pH 3.8 (open symbols), (0) NH,CI, (0) NH,Br.

blematic at pH 3.8 where the corrosion rate appears to
be in a state of transition from pure activation control
to pure diffusion control by the cathodic process. Thus
the rate of hydrogen evolution which occurs as a
consequence of the diffusion of protons from the bulk
of the solution becomes rate controlling as the pH of
the solution is lowered. This can occur when the bulk
concentration of protons exceeds the surface con-
centration maintained as a consequence of the dis-
sociation of NH: ions situated in the double layer. It
is also possible that at pH j.8 the buffering action of
NH: ions within the diffusion layer causes an effective
decrease in its thickness in a similar way to that
postulated for H!SOi ions at the same bulk pH
value[l]. The corrosion current at PH. 3.8 can there-
fore be represented _ passive state) the !J, values are very close to
%-
LOW= iz” = ~a+. (0)
This situation is exemplified by large slopes for the
cathodic polarization lines in the majority of the
pH 3.8 solutions (Table 2) having magnitudes 00 >> b,
> 2.3 x2RT/F_ The absence of a limiting current
throughout the entire low overpotential range, how-
ever, infers that despite the diffusional transport of
protons towards the electrode, their smface con-
centration approaches zero rather slowly as the poten-
tial is made more cathodic. These complications
invalidate the corrosion rate analysis by the polari-
zation resistance method which can only be used under
pure activation (b, = 120 mV per decade) or pure
diffusion (b, = a~) controlled conditions. However
Table 1 shows that for the pH 5.8 solutions (with the
exception of NaCl where the zinc surface is in a pseudo
2.3 x 2RT/F for all the salts studied. This indicates that
674 L. td. BAUGH

Table 1. Corrosion rates for pure zinc in various molar ammonium salts at pH 5.8
Eleotrolyte - R,,,Iv Rpffl cm’ bJmV bJmV it&/@ cm-s i;&/pA cm-r
NaCl I.114 1385 tz a, 2:: 6.9
1.117 2778 cc 5.0
Average 1.116 2082 15 co 4.1 5.9
NH&t 1.161 819 :: 120 12.8 16.2
1.161 610 124 16.5 18.2
Average 1.161 745 29 122 14.7 17.5
NI&Br 1.160 !Z If 122 12.4 15.8
1.157 120 12.4 15.6
Average 1.158 796 28 121 12.4 15.7
NH&IO, 1.143 1127 z 150 13.6 15.9
1.142 1106 150 13.8 14.9
Average 1.142 1117 46 150 13.7 15.4
W-LWO~ 1.179 592 z; 120 21.6 24.9
1.180 571 127 22.7 29.8
Average 1.179 577 39 124 22.2 27.4

at this pH value the corrosion current can
represented
- -
‘C.&W,
= 1~~ = iNH: (7)
with the cathodic process occurring under activation
control.
Despite the fact that the true Tafel line for hydrogen
evolution by proton reduction is only realized in the
pH 5.8 solutions there is still some curvature in the line
at higher overpotentials as the limiting current E-F of
Fig. 2. is approached. This curvature indicates that
true activation control of the cathodic process is
closely approached only near to the corrosion poten-
tial. Therefore the true cathodic slope pertaining at this
potential could only be. determined indirectly. Anodic
Tafel lines were first extrapolated to the corrosion
potential and a value for the corrosion current was
obtained. A line was then taken from this point to meet
the cathodic polarization curve tangentially and the
slope determined. It was observed that this line passed
through several cathodic points. The slopes so de-
termined are quoted in Table 1 where it can be seen
be that they are all close to the theoretical value of
120mV per decade. Any deviation between the true
slopes and the experimentally determined vatues
would be expected to be small and cause negligible
change in the corrosion rates determined by the
polarization resistance method. The slopes quoted for
the pH 3.8 solutions were taken directly from the
polarization curves. It can be seen from Table 1 that
the corrosion rates determined by the polarization
resistance metbod are lower than those determined by
extrapolation iiithough it is not clear why the discrep-
ancy should arise.
The way in which the corrosion current changes as a
function of the nature of the anion is a reflection of the
relatively complex changes which occur in the in-
dividual anodic and cathodic polarization characteris-
tics shown in Figs 4-8. Irrespective of pH, however, the
corrosion current decreases in the order SO:- > Cl-
> Br- z ClO;. The corrosion current for
(NH&SO4 solutions is highest at pH 3.8 because of
the participation of HSO; ions in the cathodic rs
action. The corrosion rate is highest in (NH&SO, at

Table 2. Cormsion rates for pure zinc in various molar ammonium salts at pH 3.8

Electrolyte - R&V Rp/fI cm’ bJmV b,/mV it$/pA crnm2 tz/pA cme2

NaCl 1.152
1.147 2078
2360 ;; 00
03 2: :::
Average 1.150 23 co 4.6 7.8
NH&I 1.147 169 -
1.150 169 5:::
Average 1.148 24 169 21.4
NH*Br Lf52 128 - 16.0
1.148 :: 125 - 14.4
Average lJS1 25 127 - 15.2
NH&IO, 1.143 234 18.2
1.143 z 234 - 17.6
Average 1.143 44 234 - 17.9
W-f,MQ 1.152 254 - 37.8
1.158 z 254 - 37.9
Average 1.155 363 40 254 - 37.9
 Corrosion and polarization
100
F
5
a
?
._
IO
Fig. 9. Comparison of polarization characteristics in molar NaCl at pH 3.8, ( x ) pure zinc, (0) battery zinc
pH 5.8 because of the probable influence of ion pairing
on the anodic dissolution reaction. Du$ to the fact that
the anodic dissolution current is lowest in NH4C104
solutions, ie the corrosion potential is the most anodic,
the corrosion current is smallest in this solution. The
corrosion rates for zinc in NH,Cl and NH,Br so-
lutions would appear to lie in between the two
extremes set by (NH,)#O, and NH,C104.
Comparison ofthe corrosion characteristics of pure zinc
and battery zinc alloy
The zinc used to produce the anode cups in Le-
clanchl batteries contains Pb which is added as a grain
retier and Cd which is added to increase the hardness
of the metat Both of these added metals have a higher
hydrogen overvoltage than zinc. It was therefore of
interest to compare the corrosion and polarization
characteristics of the battery alloy with that of pure
zinc in order to reveal any corrosion inhibiting
capability of the alloying constituents.
Figure 9 compares the general polarization curves
for pure zinc with those for battery zinc alloy in molar
NaC!l at pH 3.8. Very similar curves were obtained in
molar NaCI04 at the same pH. It can be seen that
although the anodic dissolution branch is not affected
n:
ci
a
*
1
IO -
Fig. 10. Comparison of polarization characteristi~i~~~o;ar Na2S04 at pH 3.8, ( x ) pure zinc, (a) battery
LA.24/6-p
characteristics of zinc in neutral-acid media - II 675
alloy.
by the presence of the alloying constituents the
cathodic hydrogen evolution reaction is considerably
retarded. Further, it can be seen that it is the water
reduction reaction and not the proton reduction
reaction which is inhibited. This is in contrast with the
results shown in Fig. 10 for molar Na,SO+ where it can
be seen that there is an inhibition of both reactions.
The steepness with which the cathodic current rises at
low overpotentials on the battery alloy electrode in
Na2S04 also suggests that the proton reduction
occurs under activation controlled conditions in this
solution. Some of the factors determining whether an
electrochemical process occurs under activation or
diffusion control have been discussed previously. In
the unsupported electrolyte situation, in addition to
diffusion and convection, the transport of reactants
towards the working electrode can be aided by mi-
gration which promotes an activation controlled
process. However, even when a supporting electrolyte
is present and diffusion plus convection are the only
modes of transport it is still feasible for the reaction to
proceed under activation control. Two factors must be
considered. Firstly, pure activation control is favoured
in the case when the intrinsic rate of charge transfer is
small, ie when the exchange current, P, is small.
676 L. ht. k4UGH

E/V
Fig. 11. Comparison of polarization characteristics in molar NaCl at pH 5.8, ( x ) pure zinc, (e) battery zinc
alloy.

Secondly, pure activation control is favaured when the
rate of diffusion of electroactive species towards the
electrode is large. This would be experimentally ma-
nifest by the observation of high limiting current
values, i,. Thus the process is activation controlled
when io << iL and diffusion controlled when i” >> iJ3].
These considerations can probably explain the diverse
behaviour shown in Figs 9 and 10. It is a combination
of increased limiting current and decreased exchange
current for proton reduction which allows the acti-
vation controlled hydrogen evolution at low over-
potentials to be realized on battery alloy zinc in the
Na,S04 solution. In the NaClO, and NaCl solutions
the limiting current is signiticantly less than that in
Na,SO, and apparently too small for similar results to
be observed. In contrast, on pure zinc electrodes,
because of the very much larger exchange current, only
diffusion controfled proton reduction processe scanbe
realized. As a consequence of these considerations, the
corrosion current in NaC104 and NaCl is changed but
little by the presence of the alloying constituents but a
considerable decrease in the corrosion rate is effected
in a Na2S04 solution. Also, as expected, the magni-
tudes of the limiting diffusion currents shown in Figs 9
and 10 are largely independent of the nature of the
electrode material.
Figure 11 compares the general polarixation curves
for pure zinc and battery zinc alloy in molar NaCl at
pH 5.8. At this pH the electrodes are both oxide
covered as evidenced by the cathodic reduction peaks.
It can be seen that the anodic curve is little affected by
the process of alloying except at low overpotentials
where a larger slope is exhibited. However, cathodic
currents are considerably smaller on the alloy elec-
trode throughout the entire pohuization range. This
gives some credence to the suggestion made in[l] of
this investigation that water reduction constitutes the
hydrogen evolution process irrespective of cathodic
potential in quiescent simple salt solutions at pH 5.8.
Figure 12 compares the general polariz&ion curves
for pure zinc and battery zinc in molar (NH&SO4 at
pH 5.8. Again it can be seen that there is little influence
of the alloying constituents upon the anodic disso-
lution but there is an overall lowering in tbe.rate of
hydrogen evolution. This can arise as a consequence of
the influence of the high hydrogen overvoltage alloy-
ing constituents on both the water reduction process
(high overvoltages) and the proton reduction process
(low overvoltages) since the former is activation
controlled and the latter is activation controlkd over
the initial part of the polarization curve. As a result the
corrosion current is lowered by a factor of two.

Fig. 12. Comparison of polarization ~hara&ristic~ in molar (NH&SOI at pH 5.8, I x 1 pure zinc, I*)
battery zinc alloy.
 Corrosion and polarization characteristics
CONCLUSIONS
In contrast with the behaviour of the equivalent
sodium salts, the corrosion and polarization charac-
teristics of zinc in quiescent molar solutions of
NH4C104, (NH.)$404, NH4Cl and NH4Br are not
markedly affected by pH in the range 3.8-5.8. This can
be explained if it is assumed that the dissociation of
NH: ions within the double layer increases the local
acidity at the electrode surface. The low surface pH
prevents the formation of an oxide film even at the
relatively high bulk pH value of 5.8 and permits the
hydtogen evolution reaction to proceed under acti-
vation control at the corrosion potential. At the lower
pH value (3.8) the hydrogen evolution rate in am-
monium salt solutions is also influenced by diffusion of
protons from the bulk solution. At higher cathodic
potentials a limiting current is observed prior to the
onset of water reduction irrespective of the solution
PH.
The effect of the anions ClOi, SO;-, Cl- and Br-
on the magnitude of the anodic dissolution current and
anodic Tafel slope in ammonium salt solutions is
similar to that observed for the active dissolution of the
metal in the corresponding sodium salts in more
strongly acid (pk 3.0) solutions. The cathodic polari-
zation characteristics are not markedly affected by the
nature of the anion present.
The presence of the high hydrogen overvoltage
constituents Pb(O.l%) and Cd(O.O49/,) causes a re-
duction in the corrosion rate of zinc by a factor of
of zinc in neutral-acid medii - II 677
about 6 in molar Na$04 solutions at pH 3.8 where
the limiting cathodic current is high. However, in
molar Nail and NaC104 solutions at the same pH
little inhibition is observed. This is explained by a
consideration of the relative magnitudes of the limiting
diffusion currents and the exchange currents which
only favows an activation controlled corrosion rate on
the alloy electrode in the Na,SO, solution. At the
higher pH value of 5.8 where the cathodic process is
water reduction the corrosion current in a NaCl
solution is reduced by a factor of about 5 by alloying.
In (NH&SO+ solutions at pH 5.8 where the cathodic
processes are more complex due to the electroactivity
of NH: ions the corrosion rate is reduced by a factor of
2. However, the presence of the alloying constituents
has virtually no effect upon the anodic dissolution of
zinc irrespective of the nature of the solution.
Acknowledgements - The author wishes to thank Mr S. W.
Roes and Mr G. R. Durham for carrying out the polarization
measurcmtnts and the Directors of the Beret Group Ltd, for
permission to publish this work.
REFERENCES
I. L. M. Baugh, Electrochim. Acta 24, 657-667 (1979).
2. L. M. Baugh and J. A. Lee, .I. eiectr~nal. Chem. d8, 55
(1973).
3. P. D&bay, Double Layer and Electrode Kinetics, p. 167.
Mm-science, New York (1965).