1

Adsorption at Solid Electrodes

BY P.J. MITCHELL, N. A. HAMPSON, A N D A . J. S. McNElL

1 Introduction
It is our intention to write a review of the literature on adsorption at solid
electrodes as it affects the technology of electrochemistry. This subject is relatively
clear at the smooth solid electrode, and following on the work of the well-known
pioneers relatively simple ideas of inner layer and diffuse layer structure, broad-
ened out by concepts of physical adsorption, specific adsorption, and chemi-
sorption, are generally sufficient to describe most of what might be termed the
thermodynamic behaviour. Parsons'.2 has recently commented upon this area and
these comments, written at the time that we began to tackle the emerging litera-
ture, formed a foundation on which our scholarship could develop. The Parsons
paper,' together with a subsequent article written from a slightly more technical
view2 put into perspective the relevant fundamental work on solid metal electrodes
of crystallographic uniqueness. The main features of this work have been fore-
shadowed by other scientifically less satisfactory work carried out in the 1960s and
1970s and it is useful to electrotechnologists, as well as electrochemists, briefly to
review these studies.
The first problems to be solved were concerned with the purity of materials. The
purity of electrodes has been completely solved by the use of such techniques as
zone refining, electrolysis, and various vacuum and melting techniques developed
for the semiconductor industry as well as for LEED studies of metal surfaces.
The metal surface must be structurally well defined as well as pure, and this has
necessitated the preparation of single crystal electrodes with crystallographically
defined planes exposed. Moreover, the surface must retain its unique identity
under the influence of the electrolyte solution. The primary hydration of the metal
electrode surface (with or without specific adsorption) is a spontaneous process
and there is clearly a chance that this surface hydration energy may cause some
reorganization of the electrode surface. Thus a conflict of desirable properties
exists; too low a melting point results in an electrode surface which is liable
to reorganization by hydration; high melting point refractory metals are more
difficult to process. This has resulted in the modern view of the characteristics
of solid metals being almost completely established on the metals Cu, Ag, Au,
and Pt.
On the electrolyte solution side pre-polarization techniques removed the ionic
impurities from solution but were largely ineffective with the non-ionic ones.
Adsorption of impurities on to charcoal3 or some highly porous active surface

R. Parsons, Progress in Electrochemistry Conference, see also R. Parsons, J. Electroanal. Chem.,

1981, 118, 3.
R. Parsons, Surf Sci., 1980, 101,316.
G. C. Barker, Atomic Energy Research Establishment, 1954, C/R 1563.

1
2 Eiectrochemistry

(e.g.platinum sponge) was the solution to this p r ~ b l e mThe

. ~ combination of these
two methods generally suffices to produce the ultra-pure solution demanded to
complement the electrode preparation.

2 Adsorption at the Solid Electrode

It has been well established that at each plane of the single crystal electrode a
unique double layer structure exists. This has been quantitatively demonstrated in
the case of silver5 where different low index planes cxhibit different potentials
characteristic of zero charge. This important difference has been confirmed6 for
copper and gold. Valette and Hamelin5 have further discussed the important
consequence of this difference and demonstrated that a polycrystalline electrode
exhibits a minimum capacitance in dilute solution near to the pzc of the lowest
charge density plane, which will be the one with the most negative pzc. The system
is an extremely complicated one, even for an electrode with the simplest double
layer structure. What has been done to analyse the data by the established
techniques7 for silver monocrystals indicates an inner layer capacitance,
~

like that on mercury, which is independent of concentration but with a peak

amounting to a maximum value of 120 pF cm-2 positioned close to the pzc (the
hump), probably explained by the process of reorientation of water molecules
adjacent to the metal surface. This view is confirmed by the close fitting of the
extrapolated inner layer capacitance curve with theoretical models. The re-
orientation of the surface water at such electrodes has not yet been satisfactorily
confirmed.
The effect of specifically adsorbed anions at crystallographically unique plane
silver electrodes has been studied in detail12- l4 and yields interpretable results for
the case of chloride ions. Three peaks in the differential capacitance curves occur
at low (lo%), medium, and almost complete coverage. The middle peak cor-
responds to the usual adsorption effect. The narrow positive peak is due to the
onset of chloride penetration to the inner layer water, and the most negative
peak marks the complete discharge in the monolayer adsorbed on silver. Thus
the general characteristics of the adsorption of C1- on low index planes on
Ag can be understood and extended to other face centred cubic metals. On higher
index planes the behaviour may be successfully approximated to a combination
of those of the low index steps and planes which go to make the whole
surface.I5- l 8
A. H. W. Atcn, P. Bruin, and W. de Lange, Red. Truv. Chim. Pajs-Bas, 1927,46417.
' G. Valette and A. Hamelin, J . Electroanal. Chem., 1973,45. 301.
'' J. Lecoeur, These, Paris, 1979.
G. Valette, J . Electrounal. Chem., 1981, 122, 285.
' G. Valette. J . Electroanal. Chem., 1982, 138, 37.
' D. C. Grahame, Chem. Rev., 1947,47,441.
R. Parsons and F. G. R. Zobel, J . Electroanal. Chem., 1965,9,333.
"
R. Parsons, Trans. Soc. Adv. Electrochem. Sci. Technol.. 1978, 13,239.
l2 A . Bewick, K . Kunimatsu, and B. S. Pons, Electrochim. Acta, 1980,25,465.
'' S. Vitanov and A. Popov, Trans. SOC.Adv. Electrochem. Sci. Technol., 1975, 10, I .
'' G. Valette, A. Hamelin, and R. Parsons, 2. Phys. Chem. (Frankfurt am M a i n ) , 1978, 113,71
l5 A. Hamelin and S.P. Bellier, Surf. Sci., 1978,78, 159.
l6 A. Hamelin, J . Electroanal. Chem., 1979,101,285.
" A. Hamelin and A. Katayama, J. Electroanal. Chem., 1981,117,221.
l8 A. Hamelin, A . Katayama, G. Picq, and P. Vennereau, J . Electroanal. Chem., 1980, 113,293
Adsorption at Solid Electrodes 3
The chemisorption of species at electrodes which involves the complete electron
transfer to form a bond has special importance in the hydrogen-platinum system.
Since Will19 made the original suggestion that different planes, (110) and (loo),
each contribute characteristic adsorption peaks in the voltammogram, other
have confirmed that this indeed is so, but surface and experimental
control were so difficult that quantitative agreement between investigations has
never been demonstrated satisfactorily until relatively recently. Clavilier et
ul.25-26have shown specific voltammograms characteristic of each of the (1 1 l),
(110), and (100) surfaces. The results of the other workers can be discussed in
relation to the Clavilier results and a measure of unification can be obtained.’ An
interesting point here is that the (1 1 1) electrode clearly showed evidence of surface
reorganization if the potential range included the formation and removal of the
oxide layer.
It is clear therefore that by 1980 a high level of success had been obtained using
very pure systems involving well-characterized electrodes of face centred cubic
metals such as Pt and Au. This has served to emphasize the very great complexity
of polycrystalline electrodes; indeed, bearing in mind the need for a generalized
treatment for monolayers at uniform electrode surfaces, a theoretically based
description of adsorption at a polycrystalline electrode appears to be beyond the
present state of the subject. In view of this, in our review we intend to concentrate
on the technological aspects of adsorption at solid metals although theoretical
aspects will be briefly treated inasmuch as papers published since the beginning of
1980 are noted; an in-depth review in this area is too large a task at present.
On the basic theory level Mohilner et al. have discussed the concept of congru-
ence or non-congruence of electrosorption with respect to the electrical vari-
able.27-29 They showed in the first contribution that congruence is both a
necessary and sufficient condition that the activity coefficients of the adsorbed
species in the inner layer are independent of the magnitude of the electric field
there. The theory of non-congruent electrosorption of organic compounds pro-
posed by Mohilner was shown to be quite general and an expression for the
electrosorption isotherm, expressed as a function of the excess electrochemical free
energy of mixing of the inner layer, was derived. Moreover, the general theory of
differential capacitance in the case of organic electrosorption was derived on the
basis of the non-congruent electrosorption. It was shown that the traditional
method of calculating electrosorption isotherms from differential capacitance is
incorrect. Tests were proposed for extrapolation to zero frequency. Parsons3’
l9 F. G. Will, J . Electrochem Soc., 1965, 112,451.
2o A.Hubbard, R.Ishikawa, and J. Katekava, J. Electrocmu/. Chem., 1978,86,271.
2 1 P. N. Ross, J. Electrochem. Soc., 1979, 126,67.
2 2 W. E. O’Grady, M. Y. C. Woo, P. L. Hogans, and E. Yeager, J. Vac. Sci. Technol., 1977, 14, 365; J.
Electrochem. Soc., 1978, 125, 348.
2 3 B. E. Conway, H . Angerstein-Kozlowska, and W. B. A. Sharp, Z . Phys. Chem. (Frankfurt am Main),
1975,98, 6 I .
24 K . Yamamato, D. M. Kolb, H. Kotz, and G. Lempfuhl, J . Electroanal. Chem., 1979,%, 233.
2 5 J. Clavilier, R.Faure, G. Guinet, and R.Durand, J. Electround. Chem., 1980, 107,205.
26 J. Clavilier, J . Electroanal. Chem., 1980, 107, 21 1.
’’ D. M . Mohilner and M . Karolczak, J . Phys. Chem., 1982,86,2838.
2 8 D. M. Mohilner and M. Karolczak, J. Phys. Chem., 1982,86,2840.
l 9 D. M. Mohilner and M. Karolczak, J . Phys. Chem., 1982,86,2845.
30 R.Parsons, Can. J . Chem., 1981,59, 1898.
4 Electrochemistry
has calculated the contribution to the capitance of an electrode from a species
adsorbed with partial charge transfer. A simple model was proposed in which the
degree of charge transfer changed rapidly with potential and as such was likely to
account for some of the sharp peaks observed experimentally.
Rangarajan et aL3’ have derived two- and three-state models for the adsorption
of organics and it is shown how these can be understood at the molecular level.
New isotherms are provided for three molecular description^.^^
There have been two important reviews during our review period. L a ~ i r o n ~ ~
has reviewed (257 references) the voltammetric methods used for the study of
~ ~ reported (304 references) much more
adsorbed species and R a r ~ g a r a j a nhas
generally on the double layer. The latter review gives an up-to-date account of the
concepts underlying the solvent structure of the interphase and the various
theories of adsorption and the reader is referred to this article for the theoretical
background to the present review. The Laviron article is effectively a complemen-
tary contribution to that of Rangarajan and emphasizes that adsorption is
necessary for electrodic transformation. Again the treatment is physicochemical
rather than electrotechnological and in view of this excellent treatment it is
intended here to review only the generalities of adsorption.
A brief mention here of some of the more outstanding theoretical papers
published during the last four years is justified on the grounds that it is neces-
sary to form a link between the highly developed theory of adsorption and the
profound effect of adsorption on electrode kinetics.
Myamlin and K r y 1 0 v ~have
~ obtained an expression for the adsorption of
charged and neutral species on the surface of an energetically non-uniform
metal electrode. In a following contribution, the same authors36 consider the
simultaneous adsorption of two sorts of species. The work provides a method for
finding the mechanism of complex formation from the experimental data for the
adsorption isotherms. For the dual particle adsorption, two types of adsorption
site are assumed present on the electrode, each characterized by a particular value
of adsorption energy. Equations for the adsorption isotherms are obtained using
statistical combinations. For the case of uniformly inhomogeneous electrode
surfaces, adsorption isotherms are established and analysed. Another paper37
describes procedures for calculating the adsorption parameters for the case of
two-dimensional adsorbate condensation at solid electrodes. The target was to
refine the calculation procedure for the case of a non-uniform surface. Specifically
the adsorption parameters of camphor on bismuth were calculated from differen-
tial capacitance curves. Capacity curves were calculated on the basis of a segmen-
ted electrode consisting of six equal areas. The results obtained indicated that
although this technique was satisfactory for use at a liquid electrode, it did not
necessarily apply at a solid electrode.

31 M. V. Sangaranarayanan and S. K. Rangarajan, J . Electroanal. Chem., 1981,130,339.

32 M. V. Sangaranarayanan and S. K. Rangarajan, Can. J . Chem., 1981,59,5072.
33 E. Laviron, Electroanal. Chem., 1982,12, 5 3 .
-’4 S. K. Rangarajan in ‘Electrochemistry’ Vol. 7, A Specialist Periodical Report, ed. H. R. Thirsk, The
Chemical Society, London, 1980.
’’ V. A. Myamlin and V. S. Krylov, Elektrokhimiya, 1980, 16,462.
36 V. A. Myamlin and V. S. Krylov, Elektrokhimiya, 1980, 16,467.
37 N. A . Paltusova. A. R. Alumoa. and U. V. Palm. Elektrokhimiya, 1980,16,1249.
Adsorption at Solid Electrodes 5
The non-local electrostatic approaches to interphasial structures has been
reviewed by Russian authors.38 In this method electric interactions are described
using the methods associated with plasma physics and solid state theory. This
review is interesting but does not contribute much to the technology.
There are a number of other papers which warrant a brief m e n t i ~ n . ~ ~ - ~ ~
K a r o l c ~ a ink~two
~ preliminary
~~~ papers considers generalized adsorption at elec-
trodes. Of the recently published equations for adsorption equilibria at electrodes,
two general equation^^^,^^ are compared which differ in the physical meanings
which are implicit in the respective meaning of the surface coverage, 8, and the
ratio of the partial molar areas, ‘n’. The contributions illustrate the deductions
that can be obtained from the interdependence of the measurable adsorption
charactcristics on the adsorbate coverage although, in common with other inter-
phasial problems, other interpretations may exist. In general, results must be
compared with calculations from the proposed model of the interphasial structure,
and good agreement between the two is generally taken as validation for the cor-
rectness of the argument. Damaskin et ~ 1 . analysed
~’ the energetic and geometrical
characteristics of the inner part of the electrical double layer in the presence of
specific adsorption of ions arising from the change in dielectric properties and
dimensions of the inner layer. For the specific adsorption of tetra-alkylammonium
cations on Bi in ethanol and in aqueous solution, good agreement between exper-
iment and the appropriate theory involving the Frumkin isotherm and the values
of the parameters was obtained.
The differential capacitance curves associated with organic adsorption have
recently been discussed in detail by Damaskin and c o - w o r k e r ~- 4. 7~ ~Congruence
of adsorption isotherms with respect to the charge or the potential implies a linear
relationship between 8 and either the potential or the charge q. For the latter
condition, the characteristics of differential capacitance curves are described for
the adsorption of an organic particle. For the adsorption of organics at constant
electrode potential, Damaskin and K a r p ~ vhave ~ ~ analysed the effect of the
diffuse layer on the form of the isotherm and the energetics of adsorption of
organics. The model approach applied to the adsorption of organics has been
explored in detail4* and formulae for the calculation of the differential capacitance
curves have been put forward. The theory predicts flat minima at high negative
charges, arising via the diffuse structure of the double layer, and these have been
verified on the liquid metal Hg and the low melting Bi. Moreover computer
calculations yield good agreement although these calculations demanded the use
of unrealistic interaction parameters.
38 A. A. Kornyshev and M. A. Vorotyntsev, Surf. Sci., 1980,101,23.
39 M. P. Karolczak, J . Electroanal. Chem., 1981,122,373.
40 M . P. Karolczak, J . Electroanal. Chem., 1981,122,377.
41 B. Damaskin, U. Palm, M. Vaartnou, and M. Salve, J. Electroanal. Chem., 1980,108,203.
42 Yu. I. Kharkats, J. Electroanal. Chem., 1980,115, 75.
43 R. Parsons, Croat. Chem. Acta, 1980,53, 133.
44 M. A. Loshkarev, A. F. Nesterenko, and E. V. Murashevich, Elektrokhimiya, 1981,17, 1477.
45 B. B. Damaskin, Elektrokhimiya, 198 1,17, 33 1.
46 B. B. Damaskin, Elektrokhimiya, 1982,18,3.
4’ A. F. Nesterenko, E. V. Marashevich, and M. A. Loshkarev, Elektrokhimiya, 1981,17, 1044.
48 B. B. Damaskin, S. Karpov, D. Dyatkina, U. Palm, and M. Salve, J. Electroanal. Chem., 1982, 136,
217.
49 R. Bennes, J . Electroanal. Chem., 1979,105,85.
6 Electrochemistry

The behaviour of a system of interacting adsorbed organic molecules present on

the surface of an electrode in such a way that two orientations are possible has
been studied by K h a r k a t ~With
. ~ ~ attraction constants defined for different orien-
tations the relationship between 8 and concentration is established. Depending on
the relative values of the isotherm parameters, one or two reorientation transitions
can be realized in the system. Qualitative similarities exist for the adsorption of
bipyridine isomers with the behaviours predicted by the author.
For the case of the co-adsorption of two organic substances Nesterenko et
ci1.47,48hage considered the differential capacitance-potential relationships. The
effect of the adsorption coefficients of the individual substances on the form of the
differential capacitance-potential curve is analysed in detail and it is clear from the
interactions that a wide and differing range of behaviours is possible. It is clear
from the theoretical papers concerned with the interphasial structure that this area
of understanding is far from complete. From the electrotechnologist's viewpoint
this is not likely to be a deterrent to his endeavours to achieve the desired modifi-
cation to electrode reactions, usually brought about by what are generally referred
to as solution additives.
A major area for the electrotechnologist is the inhibiting effect of organic
additives. Guidelli et 01.~' have produced a theoretical treatment of the inhibiting
effect of neutral organic surfactants at high surface coverages on simple electrode
reactions. The authors assume that the activated complex is specifically adsorbed
and use the absolute reaction-rate theory applied to a system in which the surfac-
tant is adsorbed under equilibrium conditions. A statistical treatment of different
models leads to an expression for the ratio of the rates of the inhibited to the
uninhibited reaction. The inhibitory effect of aliphatic alcohols on the kinetics of
the electroreduction of Cd2+ and Cu2+ is examined in order to verify the general
relationships which arise from the theory. The suggestion is that the iondipole
interactions between the charged activated complex and a neighbouring water
molecule are changed as we pass from a solvent-covered electrode to a surfactant-
covered one, and this is responsible for the inhibition. Damaskin and SafanovS2
have calculated the inhibition parameters at various degrees of electrode coverage
for the cadmium amalgam/cadmium(II) reaction using a method of least squares.
It was shown that the data treatment did not give an unequivocal choice between a
relationship containing three fitting parameters

ln(ko/kd)=In(l - e ) - ~ , e - ~ , o P (1)

and one containing only two inhibition parameters

ln(ke/ko)= r ln(l - 0) - se (2)

The most interesting effect of adsorption to the technologist is that on the

kinetics of reaction. A number of important theoretical papers have appeared in
this area over the last few years.

B. N . Afans'ev, B. B. Damaskin, G. J. Avilova, and N. A. Borisova, Efektrokhimiya, 1975, 11, 593.

'' R. Guidelli, M . L. Foreste, and M. R. Moncelli, J . Electroanal. Chem., 1980, 113, 171.
'* B. B. Damaskin and V. A. Safanov, Efektrokhimiya, 1980,16,1558.
Adsorption at Solid Electrodes 7
A f a n a s ’ e -~5~5 ~has proposed models for the inhibition of electrochemical reac-
tions. For the case in which the electron-transfer step is preceded by one in which
the reactant is penetrating a layer of water aggregates and adsorbate molecules, a
model is discussed53which shows that the charge transfer coefficient, a, is constant
provided that the penetration step is reversible. Lower apparent values of a arise
when the rate constant for the charge transfer and the penetration are comparable.
It was shown that this model applied to the electrode reduction of Cd” and Cu” in
the presence of surfactants. A later c ~ n t r i b u t i o nusing
~ ~ the same model described
methods that can be used to calculate parameters which describe the inhibited
reaction. These calculations involved the estimation of both the change in free
energy arising from reactant concentration changes in the surface layer and the
change due to surfactant adsorption. The methods used enabled the calculation of
the S and r factors in equations of the form of (2). For the parameter S, exper-
imental and theoretical values agreed for the electroreduction of Zn2+,Cd2, and
Cr2+ in the presence of n-butanol. A further paper55showed that the S parameter
agreement extended to T1+, EuSO,’, VSO,’, and S 2 0 B 2 - in the presence of
n-butanol. Further, the changes in S due to temperature, length of hydrocarbon
chain, and degree of coverage were calculated.
Agladze and Sushkova have examined the theoretical criteria for the analysis of
transient processes resulting from potential-step experiments in the presence of
adsorbed intermediate c ~ m p l e x e s .For ~ ~ -Temkin
~~ adsorption, an analysis of the
relaxation effects in the case of intermediate adsorption is also given.
Krylov and c o - w ~ r k e r -s 64~ ~have published a number of contributions con-
cerned with the effect of the adsorption of organic substances on electrode kinetics.
In the first of these the effect of local density changes of the adsorbed species is
estimated quantitatively. The calculations show that when the organic is adsorbed
with the positive pole towards the electrode, these molecules will not deviate
from their equilibrium position during the elementary act of the electrochemical
reaction. The positive ends of the organic must be closest to the activated complex.
It was not possible to draw unambiguous conclusions with the negative end
towards the electrode surface.
For the case of interaction of the reactant ions with specifically adsorbed
inactive ions, Fishtik and Kry10v~~ assumed a two-dimensional hexagonal lattice
as the adsorbed layer model and calculated the local density change occurring in
the specifically adsorbed charge at the interface due to penetration of the adsorbed
species and reactant ions into the double layer. It was shown that the change of the
‘adsorbed’ charge depended on the mutual deposition of the reactant ions and the
nearest adsorbed ions.
The inhibition of the discharge of ions by indifferent surface-active substances
has been considered quantitatively.60 The model used was that of the fixed lattice

53 B. N. Afanas’ev, Elektrokhimiya, 1980,16,296.

54 B. N. Afanas’ev, Elektrokhimiya, 1981,17,32.
’’ B. N. Afanas’ev, L. M. Kuzyakova, and I. A. Cherepkova, Elektrokhimiya, 1981,17,1198.
56 T. R. Agladze and 0.0.Sushkova, Elektrokhimiya, 1980,16,1377.
’’ 0 . 0 .Sushkova and T. R. Agladze, Elektrokhimiya, 1980,16, 1382.
58 I. F. Fishtik, V. A. Kir’yanov, and V. S. Krylov, Elektrokhimiya, 1980,16,416.
59 I. F. Fishtik and V. S. Krylov, Elektrokhimiya, 1980,16,641.
6o I. F. Fishtik, V. A. Kir’yanov, and V. S. Krylov, Elektrokhimiya, 1980,16,850.
8 Elect rochemist ry
developed by the authors, giving good agreement between the theoretically cal-
culated inhibition constant log(k,/k,) and the observed value for the discharge of
Zn2 inhibited by n-butanol.
+

The significance of linking of complexes to an electrode via an adsorbed ligand

has been considered.6' Thus this form of anion-induced adsorption may show
some considerable influence on the rate of a reaction. Using a numerical method in
order to calculate the significance of the constants in an adsorption isotherm
obtained from assumed equilibria between chemical potential in the bulk and the
adsorbed state certain conclusions were obtained. The most important of these are
that the adsorption isotherm is very sensitive to the values of the compact layer
parameters and to the configuration of the complex species and that there is a
strong dependence of the adsorption on the electrode potential. The calculation
emphasized that the presence of an excess of a particular component in solution
does not mean that this component would be adsorbed preferentially at the elec-
trode. The effect of specific adsorption of ions on the kinetics of electrode proces-
ses has been summarized by the Russian workers62who developed the framework
for a theory and applied it to the h.e.r. on Hg in the presence of halide ions. The
statistical averaging of the elementary act of the electron transfer at the interphase
in the presence of specifically adsorbed inactive ions was the method of attack.
Analytic expressions for the polarization characteristics of the electrode were
obtained for cases of the localization of centres of the ionic species in the reaction
state, both inside the compact part and in the diffuse part of the double layer. The
theory illuminates the problem of the decreased hydrogen overvoltage, implying
an increase in hydrogen-ion concentration near the mercury which is simply not
adsorbed. The idea of penetration of the hydrogen ion into the compact layer, as
suggested by Russian workers, removes this problem. Here the reactant centres are
located inside the compact double layer and the negative shift of the average
potential acting on the electron which is transferred to the hydrogen ion causes a
significant decrease in the overvoltage, but the outer phase potential remains
effectively the same. This theory thus reveals the mechanism of the influence of the
electric field created by the specifically adsorbed ions on the reaction rate. In con-
trast to the classical theory, the resulting rate of the electrode process thus becomes
determined by the so-called micropotential rather than the average potential of the
plane containing the reactant ions. K r y 1 0 v ~extended
~ the approach generally to
charged and neutral components of the solution when the electrochemical process
does not disturb the statistical equilibria with respect to either ionic reactants or
supporting electrolyte ions. The conclusion from this further consideration is not
unsurprisingly the same as the initial paper, that the resultant rate of an electro-
chemical reaction is determined by the local electrical potential rather than the
average potential corresponding to the continuously spread ionic charges. The
examples given in this paper are represented by Krylov and F i ~ h t i kin~a~con-
tribution on the kinetics of electrode processes in the presence of discrete layers of
specifically adsorbed substances. These examples, the discharge of Cd2 and +

'' I . F. Fishtik, I . I . Vataman, and V. S. Krylov, Efekrrokhimi-ya, 1980, 16,882.

'' V. S. Krylov, V. A. Kir'yanov, and I. F. Fishtik, J . Electroanal. Chem., 1980, 109, 1 1 5 .
hJ V. S. Krylov, J. Electroanal. Chem., 1981,123,95.
h4 1'. S. Krylov and I. F. Fishtik, Can. J. Chem., 1981,59,2026.
Adsorption at Solid Electrodes 9
Zn2+ into Hg on which adsorbed n-butanol acts as an inhibitor, demonstrate a
convincing proof of the correctness of the theory based on the statistical mechani-
cal approach and validates the conclusions of this work (v.s.). The important
conclusion that the micropotential is the crucial factor in determining the reaction
rate is emphasized in a paper by F a ~ c e t tHere. ~ ~ the location of the reaction site
and the discreteness-of-charge effect on the electrode kinetics is considered. An
expression for the local activity of the activated complex is derived and shown to
be a function of both the potential drop across the inner layer and the charge
density due to specifically adsorbed ions. The analysis is discussed in terms of the
electroreduction of the periodate ion and it is clear that further improvements in
the discreteness-of-charge effects are desirable in order for the totality of effects to
be properly explained. In addition to the static effect of adsorbed ions when
adsorption is localized, the dynamic effects which arise where equilibrium exists
between adsorbed ions and ions in the bulk has been discussed.66
Several papers have appeared which treat theoretical aspects of the effect of
adsorption on electrodeposition. C h e r n ~ vhas ~ ~formulated the relationships
governing an adsorption process which occurs at an electrode at which adsorbate
is consumed (by destruction, burial in the deposit, or whatever). It was shown that
adsorption always remains a transient process and equations given enable the
conversion rate constants to be estimated from experimental data. Krichmar6*
presents a solution to the equations representing the process of smoothing occur-
ring at a cathode at which Langmuir-type adsorption of an inhibitor material is
occurring. The rate of change of the heights of the two-dimensional microprofile
of the surface is expressed as a function of the relevant electrochemical constants
and the wavelengths of the microprofile. Four distinct types of smoothing rate-
current density curves were identified. It was shown that under favourable con-
ditions the smoothing velocity may exceed the maximum possible rate of negative
smoothing at limiting current. This conclusion is of some significance and the
conditions for this desirable effect are identified.
For electrochemical phase formation, Bosco and Rangarajan6’ propose a new
class of models which are based on adsorption, nucleation, growth, and their inter-
actions. The potentiostatic response of models that involve the development of a
new phase on a free area of the electrode are analysed for both instantaneous and
progressive nucleation. The interesting feature of this important contribution lies
in the fact that it leads to the prediction of certain experimental features in the
transient response to potentiostatic steps which have not been predicted hitherto
except by the assumption of additional processes. The important new feature
of the authors’ theory is an adsorptiondesorption step which depends on the
availability of unoccupied sites by the ordered phase.
L a v i ~ o npresents
~ ~ . ~ ~a theoretical study of simple redox systems with adsorp-
tion of reactants at a rotating disc electrode for the case where both the reactant

65 W. R. Fawcett, Can. J . Chem., 1981,59, 1844.

66 A, M. Kuznetsov and V. A. Kir’yanov, Elektrokhimiya, 1981,17, 1405.
61 B. B. Chernov, Eleklrokhimiya, 1981,17, 122.
68 S. I . Krichmar, Elektrokhimiya, 1981, 17, 1444.
69 E. Bosco and S. K. Rangarajan, J . Chem. Soc.. Faraday Trans. I , 198 1,77, 1673.
’’ E. Laviron, J . Electroanal. Chem., 1981,124, 19.
’’ E. Laviron, J . Electroanal. Chem., 1982,140,247.
10 Elt.ctrochernistrj2
and product can be adsorbed. A Langmuir isotherm is ascribed to the adsorption
and the adsorption rate is not considered to be a limiting factor. The relative
importance of the reaction in the adsorbed state and of heterogeneity are discussed
in terms of the characteristic process constants. It is shown that electrochemical
reaction should take place in most cases via the adsorbed species in aqueous
solution. For non-aqueous solution, reactions exist for which the influence of
adsorption is negligible. For diffusion-limited adsorption and activation-controlled
desorption, Laviron7’ shows that at low coverages the behaviour is similar to that
when adsorption equilibrium is assumed. At high coverages, reaction can be com-
pletely via the surface reaction. The disposition of the reaction between the various
paths is discussed together with auto-inhibition effects.
~ ~ presented calculations of the rate of
Recently Afanas’ev and K u ~ y a k o v ahave
electrochemical reactions in the presence of surfactants. The energies of inter-
action between a discharging ion and supporting electrolyte ions within the outer
Helmholtz plane are calculated for various degrees of coverage by adsorbate
molecules. It is shown that an increase in the negative charge on the surface causes
changes in the effective value of the transfer coefficient, which is compensated by
an increase in the dielectric constant of the double layer.

3 Corrosion
We consider in this section the work done in the last three years on the corrosion of
metals and its prevention or diminution by the addition of inhibitors. These corro-
sion studies are considered together because of their common electrochemistry
and because they constitute an important example of the electrotechnological
application of adsorption phenomena. Realistic corrosion situations are highly
complex, involving engineering, metallurgical, and chemical factors.
The studies considered in this section encompass a wide range of approaches,
from specific and detailed investigations of a single metal-inhibitor combination,
to general evaluations of a range of inhibitors. A great diversity of organic
and inorganic compounds have been evaluated as corrosion inhibitors. The dis-
tinction between studies of corrosion and of electrochemical dissolution may not
always be clear, and this section should be considered in conjunction with the
other sections on the individual metals.
Usually studies have considered the effect of inhibitors upon one particular
metal, but a few studies deal with corrosion inhibition for a wide range of metals.
Aramaki73.74has discussed the chemisorption of organic corrosion inhibitors in
terms of the hard and soft acid and base (HSAB) principle. A co-ordinate bond
is formed between the metal and the polar atoms of its inhibitor, which thus
act as Lewis acids and Lewis bases, respectively. A potentiostatic polarization
method was used to measure the inhibitor efficiencies upon various metals in
3M HClO, of compounds whose polar atoms belong to the IVA, IVB, VIB, and
VIIB groups. In terms of acid softness the metals can be ordered in the series

’’ B. N . Afanas’ev and L. M. Kuzyakova, Efektrokhimiya,1983, 19, 1107.

73 K . Aramaki, Ann. U n h . Ferrara,Sez. V ,Suppl., 1980, No. 7 , 267.
74 K . Ararnaki, S. Iizumi, and F. Nakagawa, Boshoku Gvutsu, 1980,29, 566.
Adsorption a t Solid Electrodes 11
A1 < V < Cr < Fe < Co < Ni < Cu < Zn. The inhibitor (soft base) was chemisorbed
on the metal (soft acid) by formation of both co-ordinated and block-co-ordinated
bonding between the polar atom and the metal. The inhibitor efficiency and
electronegativity of the polar atoms, as a measure of the softness of the bases, were
related by a Hammett-type equation.
Kuron et al.75 have reported the performance of a broad spectrum corrosion
inhibitor, ‘Prevent01 C1-2’, in aqueous and aqueous-alcoholic heat transfer
media, on a variety of metals (grey cast iron, carbon steel, copper, brass, and
aluminium alloys). Uniform layers 1@5-0 nm thick were found, and the rate of
weight loss was much reduced. Localized corrosion was observed on none of the
metals and the cavitation corrosion of grey cast iron was diminished.
Kuznetsov et al. 7 6 investigated a family of substituted phenylanthranilates as
corrosion inhibitors for a wide range of metals (iron, zinc, aluminium, and
alloys) by anodic polarization in buffered (pH 7.4-8.08) solutions containing
1&30 mM NaCl. The introduction of electron-acceptor substituents into the
phenyl ring in meta- or para-positions relative to the amino-group much improved
the inhibitor properties. More polar substituents modified the mechanism of
adsorption and caused a decrease in the protective efficiency. The inhibiting effect
of the phenylanthranilates increased in the order Zn < A1 < Fe.
Privalov et al.77 investigated various thiocyanate derivates as inhibitiors of
acid corrosion of steel, aluminium, and copper, using gravimetric and polariz-
ation techniques. Ten derivatives of 3-amino- 1,2,4-dithiazolidine-5-thione,a
condensation product of HSCN, showed strong inhibitive properties.
P o g r e b ~ v ahas
~ ~discussed the intramolecular synergism that can occur with
bifunctional corrosion inhibitors that bear amino-groups together with thiol or
oxonium groups. The presence of two substituent groups can produce stronger
adsorption, greater surface coverage, and increased corrosion inhibition.
Farr and Sare~lli’~ used potentiodynamic techniques to investigate the corro-
sion inhibition properties of a range of inhibitor compounds - molybdate,
1,2,3-benzotriazole and 1-hydroxyethylidene- 1,l-diphosphonic acid - on steel,
copper, aluminium, and tin in simulated cooling water.
Molybdate was found to be an effective corrosion inhibitor provided that
surfaces are allowed time to attain passivity. Moreover, there are beneficial
co-operative effects between molybdate and the other inhibitors which lead to
extended anodic limits of passivity.

Aluminium and its Alloys.-Considerable attention has been paid during the
review period to the corrosion of aluminium and its alloys. A wide range of
organic inhibitors have been studied, as well as a number of inorganic anions. The
field is further complicated by the variety of alloying constituents in use, which
have marked effects on alloy microstructure and corrosion behaviour.

75 D. Kuron, H. Grlfen, and J . J. Rother, Werkst. Korros., 1981,32,409.

76 Yu. I. Kumetsov, Yu. A. Filakov, L. I. Popova, and E. S. Endelman, Zushch. Mer., 1982,18,72.
” V. E. Privalov, V. E. Vail’, and A. M. Khanin, Zushch. Met., 1981, 17,295.
78 I. S. Pogrebova, Ukr. Khim. Zh., 1982,48,1198.
79
J. P. G. Farr and M. Saremi, .Surf. Technol., 1983, 19, 137.
12 Elect rochem is try

Kamel et a/. have studied the protective properties of the tertiary phosphate
(PO,,-) ionso and the chromate (Cr042-) ion" on pure aluminium in unstirred,
aerated, 0.1--0.5 M NaOH solutions. Under certain circumstances" with very
small additions of Na,PO, to dilute NaOH solutions, the presence of phosphate
could decrease corrosion rate. At higher concentrations ( N 0.05 M) the increase
in corrosion rate was attributed to the adsorption of N a + ions, accelerating
the cathodic reaction. The passivation current in the polarization experiments
decreased with increasing phosphate concentration, due to the replacement of
OH- by Po,3- at the metal surface and its large contribution to charge
transfer. In contrast,*I the chromate ion markedly promoted corrosion at low
concentrations, ( < to-, M), accelerating both anodic and cathodic reactions
-
and increasing the passivation current. Above lo-, M the Cr0,2- ion acted as
an inhibitor, ascribed to the formation of a protective layer of chromium oxide.
The promotion of corrosion at low Cr0,2 - concentrations was accounted
for by proposing that the protective chromium oxide film was formed by the
disproportionation of an intermediate adsorbed chromium species with a valency
less than 6.
Yadav et a/.82 included the CrOa2- ion in a study of the effect of 14 anions
(10-300p.p.m. concentration) on the corrosion of 3003 A1 alloy in chloride-
containing solutions of pH 1, using weight loss and polarization techniques. The
Cr0,2- ion was the most effective inhibitor in the group Cr0,2-, S 2 0 3 2 - ,
C 2 0 4 2 p , and NO,-. The ions W 0 , 2 - , B,0,2-, ClO,-, and VO,,- all
stimulated corrosion. The ions H 2 P 0 4 - , HPO,'-, -, and tartrate and
citrate inhibited corrosion at low concentrations and accelerated it at higher.
Polarization experiments indicated that the Cr0,2 - ion acted by polarizing the
cathodic reaction.
Sarnuels et a/.83 investigated four classes of compounds as inhibitors of the
corrosion of aluminium alloy 2024-T3 in NaCl solution: (a) various inorganic
oxyanions (Cr0,2-, NO,-, ClO,-, SO,2-), (b) sodium salts of citric acid and
tartaric acid, (c) the sodium salts of acetic, benzoic, and oxalic acids, and ( d )com-
pounds known to form stable complexes or compounds with aluminium, such as
benzotriazole, quinaldic and rubeanic acids. Inhibitor efficiencies were compared
for 14-day immersions and linear polarization measurements. In class (a) only
chromate gave complete protection, the other anions showing a range of effects
from inhibition to accelerated corrosion, depending on concentration. In class (b)
both acids produced accelerated corrosion at certain concentrations. Sodium
benzoate performed best in class (c) and the class (d)compounds offered only fair
inhibition. These results are interpreted in terms of the species formed with the
aluminium ion.
Singh et have investigated the inhibitive properties of various substituted
8o K. Kamcl, S. Awa, and A. Kassab, J . Electrounul. Chem., 1981, 127, 195.
'' S. A. Awad, K. Kamel, and A. Kassab, J. Electrounul. Chem., 1981,127,203.
'' P. N. S. Yadav. D. D. N. Singh, R. S. Chandhury, and C. V. Agarwal, fndiun J. Tcchnol.. 1981, 19,
461.
83 B. W . Samuels, K. Sotondeh, and R. T. Foley, Corrosion (NACE), 1981,37,92.
x4 D. D. N. Singh, M. M . , Singh R. S. Chandhury, and C . V. Agarwal, Elecfrochim. Actu, 1981. 26,
1051.
'' D. D. N. Singh, C. Chakrabarty, R. S. Chandhury. and C. V. Agarwal, J . Appl. Electrochem.. 1981,
11, 671.
Adsorption at Solid Electrodes 13

urea compounds - urea, thiourea, p h e n y l t h i o ~ r e a , ~a-naphthylthiourea,

~’~~
acetylthiourea, o-tolyl, m- and p-tolylthioureas and 1,3-diphenylthi~urea’~-
upon the corrosion of some aluminium alloys 5052, 3003, 1100,8s and 106084*85
in 20% HNO,. The effectiveness of all the compounds except urea increased
with temperature, and was attributed to their adsorption at cathodic sites. All
inhibitors except urea obeyed the Langmuir adsorption isotherm below a con-
centration of 300 ~ , p . m . , showing
’~ their maximum protective effects in the range
250-300 p.p.m.84,8sAt a concentration of 1.5%, urea accelerated corrosion and
also caused localized attack.85The additives85 were most protective of the 1060
alloy (Si 0.12, Fe 0.02, Mn 0.04%).85 The potentiostatic anodic polarization
curves were shifted towards lower current densities by the inhibitor^,^^ but there
was no proper correlation between the inhibition efficiencies and the current
densities required for the passivation of the alloys.
The same authors also investigated the effects of various azoles ( 2 5 4 0 0 p.p.m.
of 2-mercaptobenzothiazole, sulphathiazole, and 1,2,3-ben~otriazole),~~ and other
compounds [isatin, thiosemicarbazide, and their condensation product, isatin-3-
(3-thio~emicarbazide)~~] on the corrosion of the same aluminium alloys in 20%
HNO,. The azolesS6were most effective at 200 p.p.m. concentration, above which
their effectiveness was undermined by the formation of corrosive sulphide and
thiol species. The inhibition efficiency of the azoles decreases in the order given
above, increasing with temperature and reaching a maximum after 24 hours
immersion. The first two compounds inhibit corrosion by mixed control, and the
third by anodic polarization.86 The inhibition efficiencies of isatin and thiosemi-
carbazide were not as high as that of their condensation p r o d ~ c t . ~
All
’ these com-
pounds functioned predominantly by acting on the local cathodes, and the critical
passivation current density decreased in the same order as the inhibition efficiency
increased.
The same aluminium alloys as in ref. 85 were used by Chandhury et aLs8 in a
study of the interaction between tungstate ions and morpholine in pH 1 chloride
solutions. After 6 hours immersion in the presence of tungstate ions corrosion
rates can be 6-8 times higher, due to cathodic depolarization, than in its absence.
Morpholine polarized these cathodic sites to act as an inhibitor both in the blank
electrolyte as well as in the presence of tungstate ions. Tungstate ions were not
adsorbed on the metal surface in the presence of morpholine, and a synergistic
effect was found at high morpholine concentrations.
Desai et aLS9have reported the performance of several substituted aldehydes -
benzaldehyde, its 0-, m-, and p-derivatives, P-resorcaldehyde, anisaldehyde,
vanillin, and cinnamaldehyde - in corrosion protection of AI-56s alloy (Mn 0.3,
Mg 5.0%) in 0.5-4 M HCl. All compounds were cathodic inhibitors, with
anisaldehyde being the most effective. Among the monohydroxy benzaldehydes
the order of efficiency was o > p > m . The second -OH group on the benzene
nucleus was not favourable to the inhibitor action. These authors” also examined
86 D. D. N. Singh, R. S. Chandhury, and C. V. Agarwal, Indian J . Technol., 1980,18,392.
D. D. N. Singh, M. M. Singh, R. S. Chandhury, and C. V. Agarwal, J . Appl. Electrochem., 1980,10,
587.
R . S. Chandhury, P. N. S. Yadav, and C. V. Agarwal, J . Appl. Electrochem., 1983,15,807.
89 M. N. Desai, H. G. Desai, and C. B. Shah, J . Electrochem. SOC.(India), 1981,30, 31.
90 M. N. Desai, G.V. Shah, and M. M. Pandya, Trans. SAEST (India), 1981,16,221.
14 Elect rochemist r y

six azomethines (derived from salicylaldehyde, anisaldehyde, and cinnamaldehyde

using the amines ethylenediamine and aniline) under the same conditions, and
found all to be predominantly cathodic inhibitors. Talati and Joshigl studied the
aldehydes salicylaldehyde and a-furfuraldehyde as inhibitors of the corrosion of
alloy 3s (1.3% Mn) in NaOH solution. The efficiency of the first compound
increased with alkali concentration, whereas it fell for the second compound.
Immersion for longer periods of time improved this slightly. Both aldehydes were
inhibitors of a mixed type, with emphasis on the local anodes.
Talati et al.92 also considered a range of aminophenols (e.g. o-aminophenol)
as corrosion inhibitors of the 3s aluminium alloy, and other alloys; 2 s
(99.8% Al), B26S (3.9% Cu) and M57S (2.2% Mg), in phosphoric acid. The
aminophenols decreased corrosion rates with efficiencies increasing in the order
3s < B26S < 2 s < M57S.
Desai et derived Schiff bases from benzaldehyde and aniline, o-anisidine,
ethylene diamine, and methyl-, ethyl-, and propyl-amine, and used these as
inhibitors of the cofrosion of A1-51s (Si 1.0, Mg0.6%) in 0 . 5 4 M HCI. The
Schiff bases were better inhibitors than their corresponding amines, the ethylene-
diamine derivative being the most efficient. A mixed mechanism of inhibition was
proposed, with cathodic action being predominant.
Copper and Bras~.-Moreau~~has identified three regions in the oxidation-
reduction behaviour of copper in acid chloride solutions (0.1 M < [HCI]< 2 M). In
the first the redox system is Cu-CuCl,-. In the second, the analysis of corrosion
products identifies CuCl and CuCI,-, and where the current, I, is independent of
electrode potential and obeys the relation
I=constant x [Cl-] x (3)
where ~ iis) electrode rotation speed. Assuming the existence of an adsorbed species
CuCI,,, a multistep process comprising:
(charge transfer) Cu + C1- s C u Cl,,, + e -
(4)
(adsorption/desorption) CuCI,,,eCuCl (5)
( R W +
CuCl c1-eCuCI, - (6)
Here the kinetics are governed by diffusion to a uniformly reactive surface. In the
third current-potential region the corrosion behaviour of the copper is explained

Scheme 1
In terms of this model the kinetics are assumed to be governed by charge transfer
and diffusion to a non-uniformly reactive electrode surface.
Ezzat and E l - T a n t a ~ considered
y~~ the galvanokinetic behaviour of copper in
aqueous 0.1 M Na,PO, (pH 12.5) with and without the additions of NaC1.
Galvanostatic excursions in the absence of C1- displayed two distinct anodic tran-
sients, as well as a third ill-defined one, and two clear cathodic potential arrests.
91 J. D. Talati and N. H. Joshi, J. Electrochem. Snc. India, 1981,30, 253.
92 J. D. Talati, G . A. Patel, and B. P. Patel, Brit.Corr. J., 1980, 15, 85.
” M. N. Desai, M . M. Pandya, and G . V. Shah, Indian J . Technol.,1981, 19,292.
Y4
A. Moreau, Elecrrochim. Acta, 1981,26, 1616.
95 I. I. E7zat and Y. A. El-Tantawy, Brit. Corros. J . , 1981, 16, 172.
Adsorption at Solid Electrodes 15
The authors devised a simple method of calculating the quantity of electricity con-
sumed in each process. The addition of C1- increased the quantity associated with
the anodic processes. At 1 M C1- concentration, the passivating film did not resist
C1- attack and rapidly broke down. The effect of C1- was explained in terms of
adsorption, interactions with soluble copper-hydroxy intermediates, and finally
peptization of the deposited oxide.
A variety of compounds have been considered as corrosion inhibitors for cop-
per. Dinnappa et al. have investigated the effects of CN- ions96 and SCN-
ionsg7 upon the corrosion of copper in 0.1 M HClO,. Corrosion was accelerated
by traces to 2 . 5 ~ M) of CN-,96 and inhibited at higher concen-
trations ( > 5 x M). Maximum protection was attained at concentrations
> 5 x lO-,M, beyond which corrosion rate became independent of CN- con-
centration. The CN- ion acted as a mixed anodic and cathodic inhibitor at inter-
mediate concentrations with specific adsorption of CN - and the precipitation of
CuCN. At l o p 2M CN-, surface passivation was observed. In small
additions of SCN - ions markedly decreased the corrosion rate, giving maximum
protection at 1 mM concentration. The manner of protection was considered to be
analogous to that for CN- ions.
McCrory-Joy and Rosamiliag8 have evaluated three azole compounds, benzo-
triazole (BTA), imidazole, and benzimidazole as copper corrosion inhibitors in
acetate buffered aqueous media. Pre-treatment by dipping in the azole solution
forms surface copper films which can inhibit the anodic oxidation reaction,
decreasing in the order BTA > benzimidazole N imidazole. El-Taib Heakal and
H a r ~ y a m ashowed,
~~ using impedance techniques, that the copper-BTA surface
film was dielectric in nature ( E N 20), and that its thickness increased, with conse-
quent reduction in corrosion rate, with increasing BTA concentration or with
ageing. It was assumed that at the free corrosion potential the rate of dissolution
of the Cu-BTA film was balanced by the slow transport of copper ions through the
film.
Dinnappa and Mayanna"' examined the corrosion of copper in HClO, solu-
tions containing various (10- 7-10-4 M) concentrations of benzoic acid, and
related compounds, p-toluic acid, p-nitrobenzoic acid, phthalic acid, and tereph-
thalic acid. These compounds were found to act as corrosion inhibitors even in
trace concentrations, with weight loss and polarization measurements giving com-
parable results. Inhibition was attributed to adsorption of inhibitor, in terms of
the Bockris-Swinkels adsorption isotherm.
Nagoya and Ishikawa"' found potassium octylhydroxamate to be a good
anodic inhibitor of the corrosion of copper in chloride media (pH 6-8.6), with a
maximum efficiency at > 0.1 mM. The inhibition effect is mainly due to the forma-
tion of adherent films of Cu" - octylhydroxamate complex. Horner and Pliefke'02
found 2-aminopyrimidine to be an effective corrosion inhibitor for copper under
96 R. K. Dinnappa, H. B. Rudresh, and S. M. Mayanna, J . Electrochem. SOC.India,1980,29, 257.
9' R. K. Dinnappa, H. B. Rudresh, and S. M. Mayanna, Suif Technol., 1980,10,363.
98 C. McCrory-Joy and J. M. Rosamilia, J . Electroanal. Chem., 1982,136, 105.
99 F. El-Taib Heakal and S. Haruyama, Corros. Sci.,1980,20,887.
loo R. K. Dinnappa and S. M. Mayanna, J . Appl. EIectochem., l981,11,111.
lo' T. Nagoya and T. Ishikawa, Hokkaidn Daigaku Kogakubu Kenkyu Hokoku, 1980, NO.98,13.
lo' L. Horner and E. Pliefke, Werkst. Korros., 1982,33, 189.
16 Electrochemistry

various conditions, using several experimental techniques. The aminopyrimidine

formed a protective coating in conjunction with Cu' ions as they left the copper
surface. Raicheva et al. l o 3 evaluated the corrosion inhibiting qualities of
quinoline, 8-hydroxyquinoline and 2-methyl-8-hydroxyquinoline. Inhibition was
found to be greater on mechanically polished than on electrochemically polished
surfaces.
Two research groups have considered the corrosion of brass. Gupta ef aI.'O4
investigated the inhibitive action of pyridine and its derivatives [2-, 3-, and
4-picoline] for the corrosion of 70/30 brass in 1% H,SO,, using weight loss and
potentiostatic measurements in conjunction with solution analysis. All four com-
pounds obeyed the Langmuir isotherm up to their optimum concentrations, with
efficiencies in the order 2-picoline > 4-picoline > 3-picoline > pyridine. All com-
pounds except 3-picoline acted as mixed inhibitors. Dinnappa and Mayanna' O 5
found halogeno-acetic acids (chloro-, dichloro-, trichloro-, bromo-, and iodo-
acetic acids) to effect a significant reduction in the corrosion rate of copper in
HNO,. The cathodic drift of corrosion potential and the change in the cathodic
Tafel slope indicate these compounds to act on the local cathodic sites. The
thermodynamic parameters of adsorption obtained using the Bockris-Swinkels
adsorption isotherm revealed a strong interaction between the inhibitors and the
brass surface.

Iron.-We consider here studies of the corrosion of pure iron; studies of various
steels are considered in the next section.
Wieckowski et al. l o 6 investigated adsorption processes occurring at an electro-
deposited iron electrode in a neutral electrolyte saturated with l4C-1abelled CO,.
In addition to the incorporation of 14C-containing species in the iron electrode,
both reversible and irreversible adsorption of these species were observed. The
irreversible adsorption was attributed to incorporation of 14C-species (probably
HC0,- ions) in the passive layer. The reversible adsorption was attributed to
weak interactions of carbonic acid with the oxidized iron surface. Adsorption is
viewed in terms of Lewis acid and base concepts, and the r61e of reversible CO,
adsorption in the accelerated corrosion of steel is discussed.
In an interesting inversion of the normal experimental approach, Bech-Nielsen
et ul. O 7 have investigated the cathodic polarization of corroded iron electrodes in
de-aerated acid perchlorate solutions. While the steady-state cathodic reaction is
the hydrogen evolution reaction, the reduction of corrosion products formed by a
preceding anodic polarization, also occurs, in three distinct potential regions. In
the first potential region (i), just below the corrosion potential, the reaction is
influenced by potential and solution pH. In region (ii) at lower potentials the
rcaction is limited by diffusion of H + ions, the limiting current density being
determined by pH and electrode rotation speed. In region (iii) the current density
increases due to discharge of water molecules, and is pH and rotation-speed

103
S. Raicheva, E. Sokolova, and D. Zlateva, Ann. Univ. Ferrara, Sez. 5 , Suppl., 1980, No. 7 , 755.
P. Gupta, R. S. Chandhury, T. K. G. Namboodhiri, and B. Prakash, Brit. Corros. J.. 1982, 17. 193
105
R. K. Dinnappa and S. M. Mayanna, Corrosion ( N A C E ) . 1982,38,525.
A. Wieckowski and E. Ghali, Electrochim. Acta, 1983,28, 1627.
I07
B. Hakansson, N.-G. Vannerberg, and G . Bech-Nielsen, Electrochim. Acta, 19X3,28,451.
Adsorption at Solid Electrodes 17
independent. Short term experiments show that the behaviour in regions (i) and
(ii) depend on the preceding anodic treatment, and the oxidized forms of iron that
are created. A novel type of analysis of the cathodic reaction in (i) indicates a low
but constant coverage of the electrode by adsorbed hydrogen atoms, producing a
parallel combination of a Volmer-Tafel mechanism (the minor part) and a Volmer-
Heyrovsky mechanism (the major part) for the hydrogen evolution reaction.
Elewady and Lorenz108used a rotating disc electrode in the study of the corro-
sion behaviour of pure iron in 0.5 M Na,SO, solutions of pH 7-9. A membrane
inhibition effect was observed, caused by the time-dependent formation of three-
dimensional porous oxide layers on the electrode. This inhibition effect was greatly
improved by the addition of inhibition mixtures 'Prevent01 VP OC 2003' and
'Aktiphos' which caused the formation of more homogeneous and compact
surface oxide layers.
Aramaki and I c h i m ~ r a evaluated
'~~ 40 compounds as inhibitors of iron corro-
sion in 6.1 M HCl, including hydrocarbons, carboxylic acids, alcohols, ethyl
ethers, halides, mercaptans, and amines. Cathodic protection was stronger
than anodic protection, and generally the unsaturated compounds were better
inhibitors. The pattern of substituent behaviour showed that delocalized unshared
electrons of polar atoms and delocalized x-electrons of the double bond played an
important rBle in adsorption. Shigorin et al.ll0 have described a method using
polarization curves for estimating the amount of hydrogen adsorbed on an iron
electrode, and used this for determining the degree of adsorption of a corrosion
inhibitor, such as quinoline. Vdovenko et al.l 1 1 , 1 ' also used cathodic polariza-
tion measurements, on iron in 0.1-3 M HCl, to measure the degree of adsorption
of benzylquinolinium bromide and chloride (up to 0.5 M). Both compounds were
effective corrosion inhibitors (the former slightly superior) and increased the
hydrogen overpotential by 0.2 to 1 V. Both compounds were chemisorbed on the
electrode surface and partially hydrogenated by atomic hydrogen.
Ekilik et af.'13 made a voltammetric study of iron dissolution and hydrogen
absorption in aqueous methanolic solutions of H2S04 in the presence of
1 mM 2,4,6,-triphenyl-N-(R-phenyl)pyridiniumperchlorates (where R = 2'-Br,
2'-NH,, and 2'-N:NC,H,NMe,). The chemical dissolution of iron decreased and
the rate of hydrogen absorption increased, with increasing methanol concentra-
tions (up to 80%). Podobaev and Klimov'l4 observed a link between inhibitor
action and the hydrogen evolution reaction for iron in 0.5 M sulphate solutions
(pH 0.5-2.5) with addition of laurylpyridinium sulphate (3 g dm-3). The corro-
sion inhibiting properties, as shown by the slope of the anodic current-potential
curve, increased with increasing amount of adsorbed hydrogen. However, beyond
a critical current density the anodic process was activated, due to the removal of
atomic surface hydrogen.
lo' Y. A. Elewady and W. J. Lorenz, Muter. Chem., 1981,6,223.
Io9 K. Aramaki and M . Ichimura, Boshoku Gijutsu, 1980,29,437.
110 V. G. Shigorin, N. I. Fomina, M. R. Tarasevich, and V. A. Bogdanovskaya, Zushch. Met., 1982,18,
605.
'I1 I. D. Vdovenko, N. A. Perekhrest, A. 1. Lisogor, and V. I. Kovalevskii, Zashch. Met., 1981,17,744.
'I2 1. D. Vdovenko, A. I. Lisogor and N. A. Perekhrest, Ukr. Khim. Zhur., 1981,47,683.
'I3 V. V. Ekilik, V. P. Grigorev, S. P. Svirskaya, and A. I. Makhanko, Zh. Prikl. Khim. (Leningrud),
1980,53,1303.
N. I. Podobaev and G. G. Klimov, Zashch, Met., 1980,16,611.
18 Elect rochemist ry

Two groups of workers have investigated the corrosion inhibition properties of

a range of propargyl ethers for iron in HCI solutions. Allabergenov et al.' evalu-
ated 14 derivatives of propargyl phenyl ether, finding that all of them diminished
the double layer capacitance. The most effective compound was the propargyl
ether of o-aminophenol, which was adsorbed on the electrode at -0.2 to -0.9 V,
and gave a minimum capacitance value of 2.4 pF ern-,, which indicated the form-
ation of a polymeric adsorption film on the metal surface. Ivanov et a1.116 also
found strong adsorption of propargyl mono- and di-ethers of ethanediol, pro-
pane- 1,3-diol, and butane-2,3-diol to form dense layers which diminished the
transport of H,O+ ions to the electrode, and hence the corrosion rate.
Two studies of amine inhibitors have been found during the review period.
Szauer and Brandt' l 7 showed that the adsorption of amine salts of oleic acid on
iron in 0.5 M H,SO, occurs by the preferential bonding of the oleic acid at the
metal surface. The presence of more than two active groups in the molecule could
result in cross-linking, producing a compact multilayer film. The same authors' '*
also considered thi behaviour of triethanolamine salts of unsaturated fatty acids,
in terms of the competitive co-adsorption of the acid anions and the amine cations.
Measurements of diffuse double layer capacitance and iron dissolution kinetics
indicated the fatty acids to be preferentially adsorbed, their orientation being a
critical f x t o r in the formation of effective adsorbed films. The best films were
based on oleic acid molecules oriented perpendicular to the metal surface, with
salts of acids possessing a greater number of z-bonds being less effective. The main
r6le of the amine was to cross-link the acid chains adsorbed on the iron surface.
The remaining work considered in this section comprises unconnected studies of
a wide range of organic compounds. Proskurnaya et a1.'l9 found that, of a range
of 9-pyrazol derivatives, vinylmethylpyrazol iodoethylates were the most efficient
corrosion inhibitors for iron in 1 M H2S04, affecting both anodic and cathodic
processes. The influence of inhibitors such as but-2-yne-l,4-diol and trimethyl-
benzylammonium perchlorate was studied by Reshetnikov, 2 o who proposed a '
stepwise mechanism of iron dissolution, involving the formation of adsorbed
intermediates of the type [Fe(OH) (inhibitor)]. Kuznetsov et found that
the presence of AN, DMF, DMSO, methyl ethyl ketone, and ethylene glycol in
neutral borate buffer (pH 7.4) resulted in the inhibition of anodic iron dissolution
and a decrease in the growth rate of passivating oxide films. Passivation by adsorp-
tion from amphoteric solvents could be reached only by the addition of inhibitors
such as sodium benzoate or phenylanthranilate, whilst in aprotic solvents their
nucleophilicity was the determining factor. The same authors122also examinec
iron corrosion in borate buffer solutions containing 0.03 M Na,S04 and variouf

'I5 K . D. Allabergenov, F. K. Kurbanov, and A. B. Kuchkarov, Zashch. Met., 1980,16,620.

'Ih E. S. Ivanov, S. F. Karaev, E. A. Mamedov, and V. V. Egorov, Zh. Prikl. Khim. (Leningrad), 1981
54, 1955.
T. Siauer and A. Brandt, Electrochim. Acta, 1981,26, 1209.
T. Szauer and A. Brandt, Electrochim. Acra, 1981,26, 1219.
L. V. Proskurnaya, Yu. V. Fedorov, G. G. Skvortsova. and L. A. Yeskova, Zashch, Met., 1982, 18
930.
S. M. Reshatnikov, Zh. Prikl. Khim. (Leningrad), 1981,54,586.
121,
Yu. I. Kuznetsov, S . V. Oleinik, and I. L. Rozenfel'd, Elektrokhimiya, 1981, 17,942.
122 Yu. I. Kuznetsovand S. V. Oleinik, Zashch. Met., 1983, 19,92.
Adsorption at So lid Electrodes 19
arylcarboxylates. The efficiencyof inhibition correlated with the nature and pos-
ition of the substituent species, being increased by electron-donating substituents.
Donchenko et al.‘ 2 3 found mono- and di-methylthiourea, AN, and their mixtures
to decrease by a factor of 200 to 2000 the rate of iron corrosion in 6 2 4 % HNO,.
The presence of Ag ion could enhance this inhibition, producing passivation and
+

decreasing the corrosion rate by up to 105-times.

Eldakar and investigated the effects of benzotriazole and its 5-
substituted derivatives (-CH,, -NH,, -NO,, -C1, and -CO,H groups) in
deoxygenated 0.5 M H,SO,. With 0.1 mM concentration the inhibitors were
simply adsorbed during anodic dissolution, whereas at higher concentrations they
interacted with an intermediate iron species. Simple adsorption again interfered
with the hydrogen evolution reaction. Greater inhibition was obtained with
electron-accepting substituents than with electron-donors.

Steel.-Nearly 40 studies of steel corrosion have been found for the review period,
the great majority concerning carbon steel (generally low carbon mild steel, which
may also have a low alloy content), and the rest concerning stainless steels. Whilst
the steel type is generally indicated according to the prevailing National system of
coding, little mention is made of structural condition. We first consider the work
on carbon steels, and then the stainless steels.
A small proportion of the studies concern inorganic corrosion inhibitors for
steel. In a study of the corrosion behaviour of normalized low alloy carbon steel in
sulphate, acetate, and chloride media, Lubenski et al. 2 5 found that H,S produced
a decrease in the cathodic current density in the first two media, attributed to the
competitive adsorption of C1- and acetate ions on the steel surface. Singh et
were able to achieve =90% inhibition of a mild steel (ASTM 212) in 0.5%
NaF with 800 p.p.m. of Na,CrO,. Duprat et ~ 1 . found l ~ ~zinc monofluorophos-
phate to be a more efficient inhibitor than the potassium salt for 0.35% steel
(Norme AFNOR XC 38) in 3% NaCl solution. Rozental’ et a!.128used direct
corrosion measurement techniques and anodic polarization curves to show that a
combination of NaNO,( 1.5%) and surfactants (0.3%) could strongly inhibit
corrosion in concrete.
Lorenz and MansfeldI2’ have reviewed and discussed the use of electrochemical
d.c. and a.c. methods in the determination of corrosion rates. They present
experimental data on the corrosion of iron and type 4340 steel in sulphuric and
hydrochloric acid media in the presence of various inhibitors (triphenylbenzyl-
phosphonium chloride (TPBP), propargylic alcohol, but-2-yne-1,4-diol and
hexynol). With either no inhibitor or only TPBP present, the corrosion rate was
found to be correlated to the electrochemical d.c. measurements, and to the value
of the inductive loop in the a.c. data extrapolated to zero frequency. However, in
123 M. I. Donchenko, 0. G. Sribnaya, and Yu. Yu. Zheleznyak, Zashch. Met., 1981, 17, 156.
12* N. Eldakar and K. Nobe, Corrosion ( N A C E ) , 198 I,%, 27 1,
12’ A. P. Lubenskii, Z. P. Semikolenova, N. N . Zikeer, and L. S. Popova, Korroz. Zashch. Neftegasov.
Prom-sti., 1979, No. 12, 5.
126 P. R. Singh, S. S. Chouthai, and H. S. Gadiyar, Brit. Corros, J . , 1981,16, 198.
12’ M. Duprat, A. Bonnel, F. Dabosi, J. Durand, and M. Cot, J . Appl. Electrochem., 1983,13,317.
12’ N . K. Rozental’, A. V. Ferrouskaya, G. A. Koro’kova, E. I. Tupikin, and N. M. Kashurnikov,
Zushch. Met., 1981, 17,448.
129 W. J. Lorenz and F. Mansfeld, Corros. Sci., 1981,27,647.
20 E/ertrochemistry

the presence of the other inhibitors the corrosion rate cannot be correlated with
the polarization resistance because of an irreversible desorption of the inhibitor in
the vicinity of the corrosion potential.
Of all the organic compounds considered as corrosion inhibitors for steel, the
greatest attention has been paid to the family of amines of one type or another.
Duprat et ~11.'~'made a comparative study of a range of amino-alcohols and
diamines as corrosion inhibitors for a carbon steel in aerated and stirred 3% NaCl
solution, using measurements of steady-state polarization curves and of polariza-
tion resistance. Because most of these compounds are strongly alkaline in the
saline solutions they are characterized in terms of 'differential inhibitive efficiency'
which takes account of the rise in pH that they produce. 'The results of this com-
parative study are in accord with the concept of inhibition by surface chelate
formation. These authors'31 went on to study the combination of a fatty
polyamine, oleylaminopropyleneamine, and an aminophosphonic acid, aminotri
(methylphosphonic) acid. For an inhibitor concentration of 1 g dm- electro-
chemical tests indicated an efficiency of 80%, while long-term gravimetric tests
indicated 50%. The gravimetric tests, however, were conducted in a pilot-scale
circuit simulating the industrial conditions, and with a different hydrodynamic
flow pattern.
Marshall' 3 2 has characterized a synergistic nitrite-N,N-di(phosphonomethy1)
methylamine corrosion inhibitor, that is superior to nitrite, zinc chromate, and
zinc phosphonate. In aerated neutral solutions the inhibitor does not affect the
cathodic oxygen reduction reaction, but alters the processes of anodic dissolution
and passivation. It is suggested that the inhibition of corrosion is due to the repair
of the oxide film by anodically deposited ferric aminophosphonate, which forms a
better barrier to corrosion than the y-FeOOH produced by nitrite alone. How-
ever, when nitrite and the methylamine inhibitor are combined the passive film is
even thinner, more protective, and less prone to pitting corrosion.
Desai et u/.133,134compared the performance of various polyamines
(ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylene-
pentamine as inhibitors of mild steel corrosion in 1-6 M HC1. These compounds

-
acted as mixed inhibitors, mainly affecting the cathodic reaction, and giving
80-85% protection at concentrations of 4.3 cm3dm- 3, increasing at higher
concentrations. With increasing HCl concentration the inhibition efficiency
increases in the case of the last two compounds, but falls for the first two.
Efficiency generally improved with increasing time and temperature, and with
increasing polyamine chain length.
Szauer et proposed a model for the inhibitor action of oleates of various
amines in which the compound is adsorbed at the metal surface and there forms a
protective metal oleate soap coating. Fokin et found that the protective

13" M. Duprat and F. Dabosi, Corrosion ( N A C E ) , 1981.37,89.

131 M. Duprat, F. Dabosi, F. Moran, and S. Rocher, Corrosion ( N A C E ) , 1981,37,262.
13' A. Marshall, Corrosion ( N A C E ) , 1981,37,214.
133 M. N. Desai and M. B. Desai, J. Electrochem. SOC.India, 198 1,30, 345.
134 M. N. Desai and M. B. Desai, Trans. SAEST (India), 1981,16,77.
135 T. Szauer, Z . Klenowicz, and Z . Szklarska-Smialowski, Corrosion ( N A C E ) , 1980,36,400.
136
A. V. Fokin, M. V. Pospelov, A. N. Levichev, B. V. Bockarov, and 0.Cuskova, Zashch. Met., 1981,
17, 524.
Adsorption at Solid Electrodes 21
efficiency of a range of diethylalkylamines correlated with the surface activity of
these compounds. The increase in electron density on the N atom, due to the
effects of the substituents, had no influence on the protective properties.
Rozen’feld et al.13’ found that the deleterious effects of H,S - including
decreased surface plasticity and corrosion cracking - could be prevented by the
addition of various aliphatic amines. The combination’ 3 8 of 25-100 mg dm-3
K,CrO, with mono-, di-, or tri-ethanolamine afforded good protection to carbon
steel in 3% NaCl solution.
Range1 and scull^'^^ studied the inhibiting effects of quinoline on low carbon
steel in 0.25 M H,SO,, finding that the protonated form accelerated hydrogen
evolution while the free form inhibited it. The presence of C1- improved the
inhibiting efficiency for both anodic and cathodic polarizations. A.c. impedance
measurements indicated the formation of a metal-quinoline complex, the adsorp-
tion of quinoline being enhanced by the C1- ion. Shigorin and showed
that the incorporation of quinoline into polyepoxide-polyamide coatings for steel
markedly improved their protective properties. The quinoline is adsorbed at the
metal surface, suppressing electrochemical processes underneath the polymer
layer.
Desai and Desai141 used electrochemical and weight loss measurements to com-
pare various thiourea derivates (phenyl, diphenyl, o-tolyl, and p-tolyl thiourea) as
corrosion inhibitors of mild steel in 1-6 M HC1. All the compounds were mainly
cathodic inhibitors, with efficiencies increasing in the order given above, and with
time and concentration. Przewlccka and Bala142 have made a detailed study
of the influence of thiourea (0.003-0.4%) on the corrosion of carbon steel
(0.002-1.05%) in de-aerated 2 M H,SO,. Below a certain optimal concentration,
dependent on carbon concentration and on stirring rate, the thiourea suppresses
the corrosion process, but above it, corrosion is enhanced. In the absence of
thiourea the anodic and cathodic Tafel slopes were sensitive to the carbon content
of the steel, but this dependence disappeared in the presence of 0.01 and 0.1%
thiourea. The electrochemical data in conjunction with metallographic obser-
vations indicated that both the cementite and ferrite phases dissolve in the
presence of thiourea.
Driver and Meakin~’,~ compared four alkylquaternary ammonium compounds
n-alkyltrimethylammonium (TMA), n-alkyltriethylammonium (TEA), n-alkyltri-
propylammonium (TPA), and n-alkyltributylammonium (TBA) salts as corrosion
inhibitors for iron and steel in 0.5 M H,S04. For a given chain length the
efficiency generally increased in the order given above, although the transition to
TBA could have an adverse effect, attributed to disruption of the adsorbed film by
the large headgroup. These compounds performed better on iron than on steel,
possibly because the rest potential for iron lies closer to the pzc. Polarization
13’ I. L. Rozen’feld, L. V. Frolova, V. M. Brusuikina, N. E. Legezin and B. N. Altshuler, Zashch. Met.,
1981,17,43.
13* I. L. Rozen’feld, S. Ch. Verdiev, A. M. Kyaziniov, and Yu. Yu. Yusupov, Zashch Met., 1983, 19,
129.
13’ C. M . Raugel and J. C. Scully, Ann. Univ. Ferrara, Sez. 5 . Suppl., 1980, No. 7,961.
V. G. Shigorin and I. Yu. Molotov, Zashch. Met., 1980,16,454.
141 M. N. Desai and M. B. Desai, J . Electrochem. SOC.India, 1981,30,351.
H. Przewlocka and H. Bala, Werkst. Korros., 1981,32,443.
143 R. Driver and R.J. Meakins, Brit. Corros. J . , 1980,15, 128.
22 Electrochemistrj 9

measurements indicated these compounds to be predominantly anodic inhibitors

that actually stimulated the cathodic reaction at the lower levels of inhibition.
Mehta and S a ~ t r y 'observed
~~ the inhibition properties of the alkaloids
(brucine, quinine, and cinchonine) for mild steel in HCl to increase in the order
given. The inhibition was ascribed to chemisorption of the alkaloids, favoured
by the presence of N-heteroatoms and OMe groups. The same authors145also
found phenothiazines (hydrochlorides of promethazine, chlorpromazine, and
trifluoropromazine) to be effective inhibitors for mild steel in hydrogen-saturated
H2S04,with efficiencies increasing in the order given. Benzoic acid and its deriva-
tives have been found by Subramanyan et ~ 1 . tol act ~ ~as cathodic inhibitors for
steel in 2.5 M HCl with efficiencies increasing in the order nitrobenzoic < phthalic
< benzoic < salicylic cp-aminobenzoic < o-aminobenzoic < thiosalicylic acid. The
observations are discussed in terms of the structural characteristics, complex
formation, and adsorption of the substances.
Maitra et ~ 1 . ' ~concluded
' that dicyandiamide acted as an inhibitor of the acid
corrosion of low carbon steel by an adsorption mechanism, involving chemical
rather than physical factors. The application of the Langmuir isotherm gave
values for the activation energy and heat of adsorption to be expected for a process
in which the rate determining step is a surface reaction. V i g d o r ~ v i c h 'found
~~
propanol to inhibit both the chemical and electrochemical mechanisms of dissolu-
tion of iron and carbon steel in alcoholic HCl solutions, though with > 20% water
present only the electrochemical mechanism was suppressed. Shadrina et ~ 1 . ' ~ ~
found oxyethylated alkylphenols (containing three ethylene oxide units) to adsorb
on to steel from aqueous and oil solutions and to inhibit metal dissolution.
Phenylarsonic acid was observed by Reshetnikov et to stimulate the
anodic process at low anodic overpotentials but to inhibit it at high overpotentials,
while the cathodic process was always inhibited. These effects were attributed
to adsorption, and were dependent on pH and inhibitor concentration.
Ponomarenko et al. l 5 used double layer capacitance measurements to demon-
strate the adsorption of ferrocene derivatives [a-pyridyl, 1,l'-di-(a-pyridy1)-,
a-quinolyl-, and 1,l'-di(a-quinoly1)-ferrocene, and the products of their
photolysis] on steel in 1 M H,S04. The addition of KCl or KI containing
a-pyridylferrocene improved the degree of inhibition. Dhazilov et al. 1 5 2
have reported on the inhibiting properties of naphthenic acid hydrazide
[C,,H,CON(H):NH,] against steel corrosion by H2S. Trufanova et al. 1 5 3 com-
pared the protective properties of various nitro-derivatives using anodic and
144 G . N. Mehta and T. P. Sastry, J . Electrochem. SOC.India, 1981,30,284.
14' G. N. Mehta and T. P. Sastry, Foshoku Gijentsu, 1980,29,223.
146 N. Subramanyan, S. V. Iyer, and V. Kapali, Trans. S A E S T (lndiaj, 1980, 15,251.
147 A. N. Maitra, G. Singh, and K. Bhattacharyya, Trans. S A E S T (India), 1981,16,61.
148 V. I. Vigdorovich, Izv. Vyssh. Uchebn. Zaved., Khim. Khim. Tekhnol., 1981,24, 1399.
'41 A. N. Shadrina, N. M. Nikolaeva, Yu. N. Shekter, D. N. Levchenko, and V. S. Luneva, Zashch. Me!.
1982. 18,933.
O'' S. M. Reshetinikov, T. G. Krutkina, L. L. Makarova, and L. B. Ionov, Zashch. Met., 1981, 17, 343.
Is' V. I. Ponomarenko. Yu. V. Fedorov, Z . V. Panfilova, V. A. Sazouora, and V. N. Postuov, Zashch
M e t . , 1980, 16,456.
''' T. N. Dzhalilov, V. R . Vezirova, T, A. Gasanov, R. F. Sharifora, and R. G. Gadzhieva. Gazm
Promst., 1980, No. 6, 37.
A . I. Trufanova, T. A. Lazareva, S . F. Khlebrikova, M. G. Kosareva, and V. V. Ermoshina, Zashch
Met., 1981,17,56.
Adsorption at Solid Electrodes 23
cathodic polarization measurements. These compounds were found to be efficien!
inhibitors, their protective action increasing in the order nitrophenolates
c nitrosalicylates < dinitrosalicylates < nitroterephthalates < dinitrophenolates.
Nowosz-Arkuszewska’ has reported on the performance of oil films,
547155

obtained by nitration of a paraffin-free low sulphur crude oil, as inhibitors for steel
in aqueous K,SO, solution. It is p r ~ p o s e d ”that
~ the active fraction of the com-
plex mixture of inhibitors is adsorbed on the metal via the -NO2 groups, affecting
the passive film and suppressing the anodic reaction. The observation that the
additional presence of saturated fatty acids’ 5 5 could improve protection was
explained in terms of the fatty acids stabilizing the chemisorbed layer formed by
the nitrated crude oil.
Avaca et al.’ ’6 correlated specific adsorption and corrosion inhibition, using
1-butylpyridinium bromide (BPB) at mercury as a model system. Study of this
inhibitor on mild steel in H,S04 solutions indicated that the compound adsorbs
strongly on the metal, forming a complete monolayer of BP’ ions at 0.1 mol dm-
concentrations and multilayers for higher concentrations, inhibiting the anodic
corrosion reaction.
Several research groups have addressed the corrosion problems associated with
stainless steels. Normally these alloys (based on iron-nickel-chromium) are pro-
tected by a self-created film of oxide, but under certain conditions, notably in the
presence of the chloride ion, this passive film can break down and corrosion can
occur, often in a localized pitting fashion. In some circumstances the stainless steel
can cycle between the active and passive conditions producing current oscillations.
Podesta et al.”’ have identified the conditions under which this phenomenon
occurs for an austentitic stainless steel (AISI type 303) in 1 M H2S0, containing
C1- ions. The occurrence requires a heterogeneous distribution of inclusions
and carbides at the metal surface, and a concentration range of C1- such that
active and passive areas co-exist, so that C1- ion adsorption competes with the
accumulation of corrosion products.
Schmid and Huangi5* studied the properties of the compound 4,7-diphenyl-
1,lO-phenanthroline (DPP) as an inhibitor of the corrosion of a 304 stainless steel
(based on the 18-Cr, 8-Ni alloy) in 0.1 M HCl solution. For a surface coverage of
8 < 0.5 the experimental data fitted five adsorption isotherms: Frumkin, Virial
coefficients, Hill-de-Boer, Blomgren-Bockris, and Conway-Barradas. At higher
surface coverages deviations were found. Polarization curves at constant
e ( 0 . 1 0~x 0.5) all had cathodic Tafel slopes of 116 mv decade- identical to the
DPP-free system, the current decreasing with increasing 0 at constant potential.
The inhibiting effect of DPP was ascribed mainly to a surface blocking effect at
both anodic and cathodic sites.
Abd El Wahab et ~ 1 . ” studied
~ the polarization behaviour and pitting corro-
sion of iron-chrome (7-24 w% Cr) alloys in the absence and presence of C1-. As
the chrome content increased, the active dissolution current decreased while the
lS4 I. Nowosz-Arkuszewska, Corros. Sci., 1981,21,41.
155 1. Nowosz-Arkuszewska, Corros. Sci., 1983,23,75.
156 L. A. Avaca, E. R. Gonzalez, and A, Ruvolo Filho, J . Appl. Electrochem., 1982,12,405.
15’ J. J. Podesta, R. C. V. Piatti, and A. J. Arvia, Corros. Sci., 1982,22, 193.
15* G . M. Schmid and H. J. Huang, Corros. Sci.,1980,20,104l.
159 F. M. Abd El Wahab, M . G. A . Khedr, and H. A. El Shayab, J . Mater. Sci.,1982,17,3401.
passive and transpassive currents increased. An increase in C1- concentration
first affected the oxygen evolution reaction, then progressively eliminated the
passive region, and finally caused pitting corrosion, revealed by potential oscil-
lations in the galvanostatic polarization curves. The results are discussed in terms
of competitive adsorption between the aggressive and inhibiting anions for the
active sites o n the alloy surface. Abd-El-Nabey et investigated the pitting
corrosion of stainless steel in 0.1 M KC1 in various mixtures of water with organic
solvents (methanol, isopropanol, 2-ethoxyethanol, ethyleneglycol, and aceto-
nitrile), finding that the organic component inhibited the corrosion process. This
was attributed to increases in the viscosity, so that the corrosion products diffused
more slowly out of the pit.
The combination of mechanical stress and corrosive environment is a very real-
istic one and can rapidly lead to failure, where the mechanical stress alone would
easily be sustained by the component. It is a phenomenon of localized corrosion,
like pitting corrosion, assisted by the release of the energy of mechanical strain.
MacDonald et evaluated a range of compounds (Na,SiO,, Na,PO,,
Na,CrO,, Na2S03, NaCN, octadecylamine, cyclohexylamine, hexylamine. and
morpholine) as inhibitors of stress corrosion cracking of type 403 stainless steel in
10 mM Na2S0, solutions at 100 "C. The only effective inorganic inhibitor was
Na,SiO,, and the efficiencies of the organic inhibitors decreased in the order given
above.

Nickel.-Casanova et al. 1 6 2 studied the corrosion behaviour of nickel in acidic

media in the presence of various anions, either stable or reducible. The reactive
anions were readily reduced and led to negligible dissolution. The stable anions
had differing influences; OH -, for example, produced an adsorbed passive Ni2 +

species, while HSO,- led to dissolution with formation of Ni2 ions. +

Ekilik et found that long-lived radical surfactants of the type

RC=ON--O- efficiently suppressed anodic dissolution and pitting corrosion of
nickel in 0.05M LiC10, solutions in acetone, AN, DMSO, formamide, and
butyrolactone. These radical compounds, which were much more effective than
the corresponding non-radical forms, did not affect the potentials of activation
and passivation but decreased the current.
R e ~ h e t n i k o v 'has
~ ~ shown that 10-3-10-' M DMSO in H,SO,+K,SO,
solutions (pH &2) is effective in inhibiting the electrode reactions of nickel. Tht
adsorption of DMSO, which was described by the Temkin isotherm, blocked tht
electrode reactions leaving the mechanism unchanged.

Tin and Cadmium.-Abdel Aal et a1.1657'66investigated the inhibition of corrosior

of tin and cadmium in 0.1 M H,SO, by DMSO, phenylsulphone, (PhCH,),SO,
and their sulphides and sulphoxides. The compounds (PhCH,),SO, an(
IhO B. A. Abd-El-Nabey, N. Khalil, M. M. Eisa, and 11. Sadek, Surf Technol., 1983, 20,209.
B. Bavarian, A. Moccari. and D. D. MacDonald, Cnrrmion ( N A C E ) , 1982,38, 104.
I h2
A. Casanova. A. Jouannean, and M. C . Petit, Ann. Univ. Ferrura, Sez. 5 Suppl., 1980, No. 7, 55.
'" V. V . Ekilik, V. P. Grigor'ev, and G. N. Ekilik, Zushch. M e f . . 1982, 18, 114.
l b 4 S. M. Reshetnikov,Zushch. Met., 1981,17,341.

I h S M. S. Abdel Aal, A. A. Abdel Wahab, and F. H . Assaf, Metalloher-uche. 1980,M. 323.

Ihh
M . S. Abdel Aal and F. H . Assaf, Tmns. SAEST, 1980, 15, 107.
A dsorp t ion at So lid Electrodes 25
(PhCH,),SO stimulated corrosion because of their reduction on the electrode
surface. The inhibiting efficiency of the other compounds decreased in the order:
Me,S> DMSO > Me,SO, > Ph,S > Ph,SO, > Ph,SO.

Titanium.-Petit et al.167have made a critical survey of inhibitors for the corro-

sion of titanium and zirconium and their alloys in acid media. The corrosion rate
of titanium can be reduced by introducing multivalent ions, and inorganic and
organic oxidants, though the concentrations of these additives should be main-
tained above some critical value, below which corrosion is enhanced. Complexing
organic compounds are also effective inhibitors and do not show such critical
behaviour. The susceptibility of titanium and zirconium to fluoride media can be
reduced by complexing the F - ions. Some compounds that inhibit corrosion of
titanium may enhance it on zirconium.
Skuratnik et al.' 68 investigated the cathodic polarization behaviour of titanium
in 1 g dm- NaCl solutions (pH 1.8-2) containing variable amounts of dissolved
chlorine, in connection with the electrolytic production of chlorine. Titanium
corrosion under these conditions produces TiH, which inhibits the adsorption of
H,. The presence of chlorine decreases the corrosion rate but causes the formation
of hypochlorite.
Gerasyutina et al.' 6 9 * 1 7 0 have investigated two approaches to corrosion protec-
tion of titanium in HCl, H,SO,, and (Cl- + SO,, -) mixtures at temperatures up
to 80 "C. Additions of polyethylene-polyamine (0.1-0.5 g dm- 3, or alizarin
derivatives (0.5-2 mM)169 had a strong protective effect due to specific adsorp-
tion. In another approach,'70 industrial waste materials, from the production of
Ti-Mg alloys, and containing mainly Ti, C1, Fe, C, Al, and Mg, were also effective
corrosion inhibitors.

Zinc.-Troquet et al. 1 7 1 investigated the mechanism of inhibition of zinc

corrosion in 1 M HC1 by tetraphenylphosphonium bromide. The reduction of this
compound occurred in two ways, first by fracture of the P-C bond with sub-
sequent formation of Ph,PO, and second by aromatic ring reduction. These two
modes of reduction have opposite effects on the inhibition process; Ph,P and its
oxide are strong inhibitors, but the reduction of aromatic rings favours the desorp-
tion of adsorbed compounds and limits their inhibiting efficiency. Troquet et aZ.172
extended this work to consider a range of phosphonium salts of the type
Ph4-,,P+nBu,,X- (OGyG4). When y > 1 the reduction products of these salts do
not appear, and in these cases the electrostatic adsorption and chemisorption are
important for inhibition.
Abdel Aal et a1.17, have reported the effect of benzenethiol and its methyl,
amino, and carboxylic ring substituted derivatives, benzylthiol and thioglycollic

J. A. Petit, G. Chataihier, and F. Dabosi, Corros. Sci., 1981,21, 279.

Ya. B. Skuratnik, V. B. Torshin, I. V. Riskin, and M. A. Dernbrovskii, Elektrokhimiya, 1980,16,906.
169 L. I. Gerasyutina, L. G. Karyaka, F. M. Tulyupa, and I. N. Tovkes, Zashch. Met., 1981,17,728.
170 L. I. Gerasyutina, L. G. Karyaka, F. M . Tulyupa, V. I. Ivanisenko, and V. I. Cherkashin, Zashch.
Met., 1981, 17,211.
171 M . Troquet, J . P. Labbe, and J. Pagetti, Corros. Sci., 1981,21, 101.
172 M. Troquet and J. Pagetti, Electrochim. Acta, 1982,27, 197.
173 M . S. Abdel Aal, A. A. Abdel Wahab, and A. El Saied, Corrosion (NACE), 1981,37, 557.
26 Electrochemistry

acid, on the corrosion of zinc in HOAc, H,SO,, and HCI solutions. In acetic acid,
compounds which function by an adsorption mechanism were effective inhibitors,
while those forming surface chelates were not. In H,SO, and HCI most
compounds, except o-methylbenzenethiol (H,SO, and HCl) and benzenethiol
(H,SO,), accelerated zinc dissolution. Inhibitor adsorption followed the
Langmuir isotherm and the mechanisms of the hydrogen evolution reaction and
zinc dissolution were unaffected by inhibition. The same authors’ 74 also examined
the compounds triphenylbenzyl- and tetrabenzyl-phosphonium chloride and
Bu,NClO, ( 1 V 6 to l o p 3M) as corrosion inhibitors for zinc in 0.1 M HClO,
(pH 1-3). These compounds behaved as mixed inhibitors, with predominantly
anodic effects at higher concentrations. Adsorption followed the Langmuir
isotherm, and left the reaction mechanisms for the hydrogen evolution reaction
and dissolution unchanged.
Keily and Sinclair’ 7 5 used measurements of polarization resistance and
hydrogen evolution rates to evaluate mixtures of ZnO with various quaternary
compounds as corrosion inhibitors for zinc in KOH solutions. Popescu et a1.’76
give the corrosion reaction of zinc in 1-6 M NaOH solutions as comprising the
oxidation of zinc,
Zn+H20-*ZnO+2H’ f 3 e - (7)
balanced by the reduction of water,
2H,O + 2e - +H, +2 0 H -
The addition of urea and aniline increase the cathodic overpotential for the second
reaction, due to a change in the concentration of water in the double layer.

4 Aluminium
Draiic et al. showed that the nature of the anion present in the electrolyte can
significantly affect the ease of anodic dissolution of aluminium, and proposed a
model based on anion adsorption to account for this. In the absence of any
adsorption the electric field across the oxide layer opposes the movement of both
aluminium and oxygen-containing ions. The field stimulates the transport of
electrons evolving hydrogen at the oxide surface. With the adsorption of
negatively charged ions (e.g. Cl-), the field is reversed and now assists film growth.
The model also explains variations in the effect of different anions in terms of
variations in energies of adsorption.

5 Bismuth
Pal’m and Pyarnoya’78 determined the free energy of adsorption of 1- from
(KI + K F ) solutions on polycrystalline and single crystal bismuth. They found that
the integral capacitance of the space between thc electrode surface and the outer
Helmholtz layer was unaffected by the identity of the exposed crystal face, despite
large variations in hydrophilic behaviour.
lq4 M . S. Abdel Aal and A. El. Saied, Trans. S A E S T (India). 1981. 16. 197.
T. Keily and T. J. Sinclair, J . Power Sources, 1980, 6,47.
B. Popescu, V. Brinzoi, and 0. Radovici, Rev. Chim. (Buchnresr), 1980,31,69.
I” D. M . Draiic. S. K. Zecevic, R. T. Atanasoski, and A. R. Despic, Electrochirn. Actu, 1983,28. 751.
”’ U. V. Pal’m and M . P. Pyarnoya, Elekfrokhimi.l;a, 1980. 16, 1599.
Adsorption at Solid Electrodes 27
Pal'm and co-workers have also made several studies of the adsorption of ionic
species (I-, SCN-, K + ) and organic molecules at bismuth-alcohol interfaces,
using differential capacitance-potential measurements. Pal'm et al. have investi-
gated the adsorption of a series of n-alkanes (from heptane to n o n a d e ~ a n e ) ' ~ ~ , ' ~ ~
on to bismuth in aqueous 0.1 M LiC10, containing ethanol, and of various hydro-
carbons (benzene, naphthalene, anthracene) on bismuth in the presence of both
ethanolI8 and methanol.' 8 2 The differential capacitance curves indicated that in
the presence of both alcohols, the hydrocarbons could adsorb in the flat or inclined
configurations. In addition to the well-known adsorption in the vicinity of the
P.z.c., a second adsorption region occurred at high positive potentials associated
with n-electron interaction between the hydrocarbon and bismuth electrode.
Vyaertnyu and Pal'mis3 considered the adsorption of the ions I - and SCN- for
0.1 M solutions of LiI, LiSCN, and LiC10, in propan-2-01. The adsorption
parameters of I - and SCN- were similar. Branching of the hydrocarbon chain
influenced the structure of the bismuth-solution interface more than the chain
length. In a similar study using butan-1-01 these authors'84 found that while
adsorption of I - and SCN- altered little with increase in alkyl chain length, the
adsorption of K markedly increased. The activation energy of adsorption
+

decreased in the order I - > S C N - > K + . Pal'm et ~ 1 . have l ~ ~described a

procedure, based on differential capacitance measurements, for calculating the
adsorption parameters of tetra-alkylammonium ions on bismuth in alcoholic
media.

6 Cadmium
Vijh'" has interpreted the observations of Abd-El-Halim et ~ 1 . " ~on cadmium
electrodeposition in terms of anions adsorbing on the cadmium surface. These
adsorbed anions form a surface compound on the cadmium, leading to demetal-
lization and to changes in its P.Z.C.Vijh argues that specific adsorption of anions
can provide a theoretical framework for understanding the r81e of anions in
cadmium electrodeposition.
Two reports on the photoelectrochemistry of cadmium compounds have been
found in the review period. Gorodiskii et al.lss found that adsorption peaks and
photocurrent spectra for monocrystalline CdS were shifted towards the red region
in the presence of various dyes, crystal violet, methylene blue and rhodamine C in
the presence of formaldehyde. Spectral relationships of photocurrents measured
through the phase boundary were explained in terms of an electron-transport

179 A . R. Alumaa, N. A . Paltusova, and U. V. Pal'm, Elektrokhimiya, 1981,17, 144.

A . R. Alumaa, N. A. Paltusova, and U. V. Pal'm, Elektrokhimiya, 1981,17,311.
A . R . Alumaaand U. V. Pal'm, Elektrokhimiya, 1981,17, 1413.
A. R. Alumaa, E. K. Yuriado, and U. V. Pal'm, Elektrokhimiya, 1983,19, 126.
M. G. Vyaertnyu and U. V. Pal'm, Elektrokhimiya, 1981,17,1567.
l E 4 M. G. Vyaertnyu and U. V. Pal'm, Elektrokhimiya, 1980,16, 1603.
lE5 U. Pal'm, M. Vaartnon, and M . Salve, Coll. Czech. Chem. Commun., 1981,46,2158.
A . K . Vijh, Surf. Technol., 1983,20, 193.
"' A. M. Abd. El-Halim, M. I. Sobahi, and A. 0. Baghlaf, S u q . Technol., 1983,18,225.
"' A . V. Gorodiskii, G . Ya. Kolbasov, and N. I. Taramenko, Ukr. Khim. Zh., 1982,48,735.
28 Elect ro chem istrj

model with the participation of surface electron states. Bockris et al.ls9 have
applied i.r. spectroscopic methods to the study of the photo-assisted reduction of
CO, at p-CdTe electrodes.

7 Carbon
Because of its combination of chemical inertness with electrical conductivity,
carbon has been used in one form or another, in a wide variety of electrochemical
investigations in the fields of inorganic, organic, and biological electrochemistry.
Murata and Matsuda' 90 have investigated the relation between zeta potential
and various physico-chemical properties, e.g. particle diameter, specific surface
area, and adsorption of iodine and diphenylguanidine, for a number of carbon
blacks used in rubbers and printing inks. The same authors191 also investigated
the adsorption of Cu2+, Ni2+, and SO4,- ions from the respective sulphate
solutions on to the Stern layer of carbon black particles, and found a contribution
to the zeta potential at the particle-solution interphase. The amounts of specifi-
cally adsorbed SO,,- at the Stern layer and the surface excess charge were
calculated. The slipping plane was found to be located within the diffuse part of
the electrical double layer. Shteinberg et found the adsorption of H,, O,,
K', and SO4,+ from H,SO, or KOH solutions to be 2-3 times greater on
isotropic than on anisotropic pyrolitic carbons. In terms of adsorption rate, the
former was comparable with active graphite, and the latter with ordinary graphite.
'
Janssen et al. 9 3 have calculated the effect of molecular chlorine diffusion upon
the theoretical current-potential relation for chlorine evolution occurring by the
Volmer-Tafel and Volmer-Heyrovsky mechanisms. A minimum Tafel slope of
29.6 mV at 298 K was calculated for both mechanisms. For the former mcchanism
this occurred with the Tafel reaction or chlorine diffusion as the r.d.s.; for the
latter mechanism this occurred when it was the chlorine diffusion from the
electrode into the bulk solution that was the r.d.s.
Bishop and Cofre19, also studied the generation of chlorine, using RDE
voltammetry on a glassy carbon electrode (GCE) in 1 M H,SO,. The equilibrium
potentials were determined and the overall reaction in the generation of chlorine
was found to be:
2 Cl-eCl, +2e- (9)
without the participation of C1, - . A two-step reaction mechanism was proposed:

(r.d.s.)
Pletcher et ~ 1 . used
l ~ ~vitreous carbon as the cathode substrate for the deposi-
tion of molybdenum from an aqueous citrate bath. Thin films of the metal could

Is') B. Aurian-Blajeni, M. Ahsan Habb. I . Taniguchi, and J. O'M. Bockris. J. Electroanal. C'hem., 1983,
157, 399.
'')(' T. Murata and Y. Matsuda, Electrochim. Acta, 1982,27, 795.

19' T. Murata and Y. Matsuda, Denki Kagaku, 1980,48,564.

'91 N. M. Zagudaeva, V. S. Vilinskaya, M. R. Tarasevich, and G . V. Shteinberg, Elrktrokhimiya, 1981,
17,461.
lY3 L. J. J. Janssen, G. J. Visser, and E. Barendrecht, Elccrrochim. Actn, 1983,28, 15s.
E. Bishop and P. Cofre, An. Quim., 1981,77B, 1 19.
'" S. Daolio. M. Fleischmann, and D. Pletcher, J . Elrctroanal. Chew., 1981, 130, 269.
A dsorp tion at Solid Electrodes 29

be electroplated, but the process was accompanied by hydrogen evolution,

catalysed by the metal itself and other molybdenum species. Potential sweep and
step experiments showed crystal growth to comprise processes of continuous
nucleation and three-dimensional growth, mediated by a chain of adsorbed
intermediates formed in electrochemical pre-equilibria.
LovreEek et al. 196 used RDE voltammetry and galvanostatic techniques to
study the reduction of oxygen at a graphite electrode in alkaline solution. Residual
currents were observed and ascribed to the reduction of oxidized carbon species
and to the formation of atomic hydrogen absorbed on the graphite. Pure oxygen
reduction was found to occur in two waves of equal height, each corresponding
exactly to a 2-electron reaction. The first wave was interpreted as the reduction of
oxygen to the peroxide species via the steps:
O,-+O,(ads) (12)
+
O,(ads) e -P 0, - (ads) (13)

HO,(ads) f e - +HO, -(ads) (16)

The RDS was suggested to depend on rotation speed; at slow speeds, the migra-
tion of the 0, - ion to active sites on the partially blocked electrode, and at high
speeds, the first electron-transfer step. In the second wave the peroxide species was
reduced, without intervening desorption, to water, with simultaneous formation of
adsorbed atomic hydrogen. Experimental results also suggested that the atomic
hydrogen participated in the oxygen reduction.
Kolomoets and Pleshakov' 97 have made a chronopotentiometric study of the
cathodic reduction of SOC1, on graphite. The reduction of SOC1, involved
adsorption at the electrode and diffusion, which could be preceded by a chemical
step at low current densities.
Brainina et al."* studied the reactions occurring at a graphite electrode in an
aqueous solution containing 1.5 M HC1+ 0.4 M KI 0.2 mM Hg(NO,),. The +
adsorption of the Hg1,- complex was shown to be responsible for inhibiting the
discharge of Hg2+ at the electrode. The discharge of the HgI,- complex was
influenced by the presence of AS'", which was itself adsorbed on the graphite
surface.
Two groups of workers have looked at electrode reactions at graphite in molten
electrolytes. Bansal and Anand'" used a.c. and d.c. voltammetric techniques to
study graphite, platinum, and stainless steel electrodes, in molten acetanilide at
135 "C with different supporting electrolytes. Oscillopolarograms of Fe"', Co" and
Ni" were interpreted in conjunction with d.c. polarograms in terms of reaction
mechanisms involving adsorbed intermediate species. Damianacos et ~ 1 . ~ ' ' used
transient techniques (chronopotentiometry and cyclic voltammetry) in the study of
the discharge of 0,- at graphite electrodes in a LiCl-NaC1 bath at 700 "C. The
experimental results indicated a strong adsorption of the electroactive species on
B. LovreEek, M. Batinic, and J. Caja, Electrochim. Acta, 1983,28,685.
19' A. M. Kolomoets and M. S. Pleshakov, Elektrokhimiya, 1981, 17,390.
19' Kh. Z. Brainina, A. V. Chernysheva, and N. Yu. Stozhko, Zh. Anal. Khim., 1982,37, 1790.
'99 K. K. Bansal and M. L. Anand, J . Zndian Chem. SOC.,198 1,58,770.
2oo D . Damianacos, F. Lantelme, and M. Chemla, Electrochim, Acta, 1983,28,217.
30 Electrochemistry

the graphite, associated with a rapid kinetic mechanism. The diffusion coefficient
of 02-was calculated to be 0 = 3 . 5 x lo-' cm2 s - l at 700 "C.Assuming a linear
adsorption isotherm gave an equilibrium superficial density of 0.12 pmol cm-,
for 0 2 -corresponding
, to a bulk concentration of 84.5 pmol cmP3.
A number of research groups have used carbon, in one form or another, as an
inert substrate upon which is adsorbed the electrochemically active material. For
example, Mayer and Jiittner," investigated the electrocatalytic influence of
underpotential lead adsorbates on a glassy carbon electrode upon the reduction of
0, and H,O, in 0.5 M HClO,. An overall 2-electron reduction of 0, to H,O, was
found on glassy carbon, which was positively catalysed by Pb2+,at a limited num-
ber of active sites on the glassy carbon surface. However, the further reduction of
H,O, was nearly completely inhibited by the presence of Pb2+.
There has been considerable interest in thc electrochemistry of various deriva-
tives of porphyrin and phthalocyanine adsorbed on graphite. Bettelheim et al.2 0 2
found that iron(Ir1) tetra(N,N,N-trimethylani1inium)porphyrin on glassy carbon-
catalysed oxygen electroreduction, reducing the overpotential by 400 mV and
approximately doubling the H,02 yield to -50%. Zaga1203has shown that iron
-
and cobalt phthalocyanines adsorbed on graphite act as electrocatalysts for N2H,
oxidation, with the former being more efficient than the latter. The same author204
has also investigated the electro-oxidation of NH,OH at iron tetrasulphophthalo-
cyanine adsorbed on graphite. Some catalytic effects were found, but the NH,OH
adsorbed strongly at the iron sites of the phthalocyanine modifying its redox
properties and probably inhibiting its catalytic activity. In a separate communica-
tion, Zagal et al.,05 report that in the presence of NH,OH the phthalocyanine-
modified graphite electrode did not show the expected Fe'/Fe" and Fe"/Fe"'
voltammetric peaks, but instead showed a new peak corresponding to the
reversible oxidation of the NH,OH-phthalocyanine complex.
Carbon electrodes have been utilized in studies of the electrochemistry of
organic and biological compounds. Two groups of workers have looked at the
adsorption of naphthols on carbon electrodes. Theodoridou et observed an
adsorption peak in the electrochemical reduction of 1-nitro-2-naphthol at carbon
fibre electrodes, that was cathodic of the diffusion-controlled reduction peak. The
adsorption peak appeared when the electrode was held at positive potentials in
acidic solutions of the nitro-naphthol, and its identity was confirmed by its
dependence on voltage sweep rate and concentration. Eisinger and AlkireZo7
determined isotherms for the adsorption of P-naphthol from a buffered aqueous
solution of 0.5 M K2S0, on to graphite powder over a potential range of 1.27 V.
The powder surface area was sufficient to enable the degree of adsorption to be
determined from spectrophotometric analysis of bulk concentration. At all poten-
tials, a Langmuir adsorption isotherm modified for the displacement of solvent
molecules, was followed up to 60-65 YOof monolayer coverage. Experimental
0. Mayer and K. Juttner, Electrochim. A C E U1982,27,
, 1609.
'O' A. Bettelheim, R. Parash, and D. Ozer, J . EZectrochem. Soc., 1982, 129,2247.
"' J. H. Zagal, J. Electrounal. Chem., 1980, 109, 389.
'04 J. H. Zagal. E. Villar, and M. S. Ureta-Zanartu, J . Electroanal. Chem., 1982, 135,343.
'05 E. Villar, M. S. Ureta-Zanartu, and J. H . Zagal, Bull. SOC.Chil. Quim., 1982,27,218.
'06 E. Theodoridou, P. Karabinds, and D. Jannakoudakis, Z . Nuturjbrsch., 1982,37B, 112.
'07 R. S. Eisinger and R. C. Alkire, J . Efectroanal. Chern., 1980,112,327
Adsorption at Solid Electrodes 31

data suggested that each naphthol molecule displaced six water molecules, in
agreement with calculations of projected areas. The greatest adsorption observed,
2.5 x lo-'' mol cm-2, agreed with the calculated monolayer coverage by p-
naphthol molecules laid flat on the graphite surface. Over the potential range
explored the adsorbability constant increased six-fold, with adsorption increased
at more positive potentials. Desorption was only partially reversible.
Ueda et a1.208studied the stability of catechol-modified carbon electrodes in the
electrocatalysis of the oxidation of dihydronicotinamide adenine dinucleotide
(NADH) and ascorbic acid. The stability of the catechols (amide-linked 3,4-
dihydroxybenzylamine and vinyl-polymerized eugenol) immobilized on the car-
bon electrode surface was examined as a function of electrode potential and
solution pH. The loss of electroactivity was first order and correlated with the
catechol being in the oxidized quinone state. In this form the catechols catalysed
the oxidation of NADH and ascorbic acid, although NADH accelerated the
catechol deactivation rate. The electrode could be reactivated by extractive treat-
ment with an organic solvent, suggesting that adsorption by an oxidative product
of NADH was responsible for the deactivation. In contrast, Huck209 found that
phenoxazines and related compounds, adsorbed on graphite electrodes, could be
good catalysts for the oxidation of NADH to NAD', providing their redox poten-
tial was more anodic than - 0.3 V (SCE). It is suggested that the reaction involves
a charge-transfer complex without releasing unbound electrons and H ions. +

Two groups of researchers have investigated the electrochemistry of glucose at

modified graphite electrodes. Kulis and Cenas2' found the electrochemical
oxidation of glucose to be catalysed in the presence of glucose oxidase (FAD)
immobilized on a glassy carbon electrode modified by adsorption of mediators,
such as 9,lO-phenanthroquinone and tetracyano-p-quinodimethane. The relation
between the biocatalytic current and the nature of the electrode itself is discussed.
''
Ianniello et aL2 used differential pulse voltammetry to follow the direct electron
transfer between covalently immobilized glucose oxidase and a graphite electrode
modified by cyanuric chloride. A well-defined peak, resulting from the reduction
of the FAD, was observed at -0.51 V (Ag/AgCl), which is 0.1 V more positive
than for the free enzyme. Observations suggested that the peak for the covalently
attached enzyme was due to the reduction of the prosthetic group as part of the
enzyme molecule, rather than the FAD adsorbed on the electrode surface.
Oren and S ~ f f e r ~ ' have
~ , ~ investigated
'~ an interesting and potentially useful
application of ion adsorption to water desalination. Desalting is effected by syn-
chronized cycles of electric charge and solution flow between high specific area
carbon electrodes, a process termed electrochemical parametric pumping (ECPP).
The electrically induced processes of adsorption and desorption build up an axial
concentration gradient along the cell. The overall performance of the two-
electrode cell is determined solely by the characteristics of each single electrode,
that is the degree of adsorption4esorption as a function of potential and solution
'08 C. Ueda, D. C. S. Tse, and T. Kuwa, Anal. Chem., 1982,54,850.
'09 H . Huck, Fresenius' Z . Anal. Chem., 1982,313,545.
'lo J. Kulis and N. Cenas, Biokhimiya (Moscow), 1981,46, 1780.
'I1 R. M . Ianniello, T. J. Lindsay, and A. M. Yacynych, Anal. Chem., 1982,54, 1098.
'I2 Y. Oren and A. Soffer, J . Appl. Electrochem., 1983,13,473.
'I3 Y. Oren and A. Soffer, J . Appl. Electrochem., 1983,13,489.
32 Elect r ochenz is try

concentration. However, the two electrodes are harnessed together such that the
electric charge given up to one electrode is delivered to the other. In the first
article,2 Oren and Soffer derive and analyse desalting efficiencies, isopotentio-
grams (analogous to adsorption isotherms) and other optimization factors for the
basic two-electrode ECPP cell, in terms of the properties of the single electrodes.
This study was extended to consider the performance of a multi-stage pump,
where steady-state concentration ratios of 150 could be developed between top
and bottom of the column. Two models for the working multistage column were
considered. The first is a continuum model based on a solution of the two-phase
mass transport equation using proper boundary and initial conditions; the second
treats the column as an array of ideally mixed cells. In both models interphase
equilibrium was assumed using the isopotentiograms as the specific equilibrium
curves. Both models agreed well with experiments, especially in the cases where
initial concentration was high, and the interphase equilibrium was maintained.
Koresh and Soffer2l4took a more general approach to electroadsorption in the
micropores of molecular sieve carbon electrodes, proposing stereoselectivity to
occur in three modes. First, cations are accommodated in preference to anions in
pores which comprise C-0 dipoles, with the negative end facing the pore; second,
anions are the preferred species in pores with C-H dipoles; third, a general
favouring of smaller ions, equal for both cations and anions, corresponding to a
non-specific adsorption of point charges. All three effects disappear after extensive
activation of the carbon, which generally enlarges the pore system.

8 Chromium
Shcherbakova et a1.215made a voltammetric study of the anodic dissolution of
chromium and its alloys with 0.5% of lanthanum and tantalum in 0.05 M H 2 S 0 4
at 17-60 “C and with voltage scan rates of 0 . 1 4 . 5 mV s - I . A cathodic peak was
observed in the anodic polarization curves at low temperatures and scan rates.
This was explained in terms of chemical interactions of the surface metal atoms
with OH- ions from solution, followed by adsol.ption of the reaction products on
the electrode to produce passivation.

9 Cobalt
Tsygankova and Vigdorovichz16 have studied the dissolution of a polycrystalline
cobalt electrode in aqueous and ethylene glycol solutions containing C1- and
C104- ions. The reaction order of the dissolution was determined and a mechan-
ism involving the formation of adsorbed intermediates proposed.
However, cobalt has aroused more interest in its role of catalyst in oxygen elec-
trodes. Trunov and Verenikir~a”~studied mixtures of Ni-Co-0 system oxides,
and found reproducible behaviour for repeated potential scanning in the region to
-0.45 V(SHE). The behaviour in the potential range -0.45 to -0.65 V was not
reproducible, and this was attributed to the presence of chemisorbed oxygen and
2‘4 J. Koresh and A. Soffer, J . Electroanal. Chem., 1983, 147,223.
’15 L. G. Shcherbakova, L. N . Yagupol’skaya, A. N. Rakitskii, and I. N. Frantsevich, Dokl. Akad. Nauk
S S S R , 1981,258,957.
216 L. E. Tsygankova and V. I. Vigdorovich, Zh. Prikl. Khim. (Leningrad), 1981,54,2761.
A. M. Trunov and N . M. Verenikina, Elektrokhimiyn, 1981.17, 135.
Adsorption at Solid Electrodes 33
to changes in the valence state of cobalt. In the related work of Durand and
Anson,,I8 Co" porphyrin was adsorbed on graphite in order to catalyse oxygen
reduction. The electroreduction of this adsorbed catalyst occurs at potentials well
separated from those where oxygen is reduced, showing that more than a simple
redox catalysis is involved. The porphyrin also catalyses the electro-oxidation of
hydrogen peroxide.
Kobussen and Broers2l 9 proposed a mechanism for the oxygen evolution reac-
tion on La,,,Ba,~,CoO, in 1-6 M KOH solution, involving two adsorbed inter-
mediates. The d.c. and a.c. behaviour of the system is derived by a simple, and by a
rigorous, method. The former method applied to the more general Frumkin-type
adsorption; the latter considered only Langmuir-type adsorption. A mechanism
involving peroxide with two adsorbed intermediates fitted the experimental results
for oxygen evolution.
Yasuda et -
observed an oxidation peak at -0.75 V (Hg/HgO) in the
cyclic voltammetry of Co(OH), in 5.8 M KOH. This peak was ascribed to the
oxidation of adsorbed hydrogen produced during the preceding cathodic sweep.
No such peak was observed for Ni(OH),.

10 Copper
Recent studies on adsorption at copper electrode systems have centred on the
application of modern analytical techniques for characterizing the features
involved in commercially pertinent processes.
Fleischmann et aLZ2l have used the Surface Enhanced Raman Scattering
(SERS) technique to study the adsorption properties of the common electroplating
and refining additive, thiourea. They report that the SERS spectra were generally
of poor quality and suggest that better interpretations can be derived from the sil-
ver electrode. Nevertheless, compiled results indicate that thiourea is adsorbed via
sulphur, and at low pH the adsorbed thiourea remains unprotonated.
The same authors have also studied the adsorption of quinoline and
isoquinoline in 0.2 M K 2 S 0 4 and 2 M H,SO, using SERS,,,, showing that the
adsorption of quinolines in K2S04 solution depends on the potential with respect
to the pzc of the metal. The effects are more pronounced in the case of
isoquinoline. It was shown that in 2 M H,SO, quinoline ions form ion pairs at the
electrode surface. When C1- was added to the electrolyte the spectra indicated a
displacement of SO,, - to leave a quinoliniumshloride surface complex.
Benner et al.223used SERS to monitor the redox reaction of adsorbed cyanide
complexes. The growth and decay of the SERS spectra were correlated with the
reactions indicated by cyclic voltammetry.
Horanyi et used radiotracer techniques, with the isotopes 36Cland 14C,to

'I8 R. R . Durand jun. and F. C. Anson, J. Electroanal. Chem., 1982,134,273.

219 A. G. C. Kobussen and G. H. J. Broers, J. Eleclroanal. Chem., 1981,126,221.
220 H . Yasuda, K. Iwai, and G. Takeshima, G. S. News, Tech. Rep., 1980,39,82.
221 M. Fleischmann, I . R. Hill, and G. Sundholm, J. Electroanal. Chem., 1983,157,359.
222 M . Fleischmann, I. R. Hill, and G. Sundholm, J. Electroanal. Chem., 1983,158, 153.
223 R. E. Benner, K. U. Von Raben, R. Dornhaus, R. K. Chang, B. L. Laube, F. A. Otter, Surf. Sci.,
1980, 102, No. 1,7.
224 C. Horanyi, E. M. Rizmayer, and P. Joo, J. Electroanal. Chem., 1983,149,221.
34 Electmchemistrj>

examine the adsorption of C1- and thiourea on electrodeposited porous copper

layers. The potential dependence for thiourea was studied over a wide range
( - 400 to 300 mV on SHE scale) where it is strongly adsorbed.
Correlation of radiotracer and polarization measurements showed a relation-
ship between coverage with thiourea and reaction rate. In the case of C1- ions a
significant coverage with respect to the adsorbed species was found at low con-
centrations ( l o p 4mol drn-,) and at low potentials ( - 300 mV). A further com-
munication by the same authors225 indicates that the specific adsorption of
HSO,- ions in 1 mol dm- HClO, supporting electrolyte is significant even at low
H,SO, concentrations, and that the surface of the electrode is partly covered with
adsorbed HSO,- ions in the anodic dissolution process.
Oxygen adsorption has been studied by Droog and Schlenter226on single
crystal surfaces by the use of cyclic voltammetry in 1 M NaOH solution. Clear
evidence was found to illustrate that the electrosorption of oxygen is plane specific.
Polycrystalline copper produces considerably different results.
Investigations involving oxyanions of phospho-acids by Bakirov et has
produced an order of adsorbability showing an increase through the series
H,P04-, H,PO,-, and H,PO,-. The adsorption rates at -0.25V (SHE) are
0.058,0.085, and 0.096 s - respectively.
Dissolution studies in non-aqueous acetic acid solutions containing perchlorate
by Kiss et show that the reaction is controlled either by diffusion or mixed
dilTusion/charge transfer kinetics, depending on the composition of the medium.
This shift in kinetics is attributed to the adsorption/desorption of OAc- ions.
Dissolution in HNO, is strongly dependent on intermediates as is shown by
El-Cheikh et al.229The r6les of HNO, and NO in the dissolution were investi-
gated by cathodic and anodic polarization, I-t and E-t responses. Mechanisms are
suggested for the different stages of dissolution.
Wu and Nobe,,' have shown that substituted benzotriazoles (BTA) have a
direct inhibitive effect on the rate of copper dissolution in H 2 S 0 4 by surface
adsorption and blockage. BTA-NH,, BTA-CO,H, and BTA-Cl stop the pro-
duction of Cu". Other benzotriazoles, namely BTA-NO,, BTA-CH,, and
unsubstituted BTA allow the production o f slightly soluble organo-Cu' complexes,
as the oxidation product. In the presence of Cl- ions the production of Cu'
chloride complexes was evident with all benzotriazoles.
Chloride was also investigated, by Al-Kharafi and E l - T a n t a ~ y , , ~in' alkaline
phosphate solutions, where a mechanism of Cl- attack involving adsorption,
interaction with a soluble intermediate, and precipitation of the passivating
products is presented. Observations were made, by Lakshmana Sarma and
N a g e ~ w a r , ~of~ , the morphological changes which occur during the electro-
deposition of Cu on the Cu(100) plane, from an acid sulphate bath and in the pres-

"' C. Horanyi, E. M. Rizmayer, and P. Joo, J. El~ctrounul.Cheni., 1983, 154, 281.

lZh M. Droog and B. Schlenter, J. Electmunal. Chem., 1980,112,387.
22' M. N. Bakirov, R. S. Vakhidor, and N. V. Ioslovich, Elektrokhimiya, 1980,16, 1012.
228 L. Kiss, M. L. Varsanyi, and A. Bosquez, Acta Chim. Acad. Sci.Hung., 1981,107, 11.
229 F. M. El-Cheikh, S. A. Khalil, M. A. El-Manguch, and A. 0. Hadi, Ann. Chim. ( R o m e ) . 1983.73. 75.
230 J. S. Wu and K . Nobe, Corrosion I N A C E ) , 1981, 37, 223.
21' F. M. Al-Kharafi and Y . A. El-Tanlawy, J . Electrochem. Soc.. 1981, 128,2073.
232 R. Lakshmana Sarma and S. Nageswar, J. A p p . Electrochem., 1982.12,329.
Adsorption at Solid Electrodes 35
ence of known concentrations of 2-mercaptoethanol at various current densities.
The deposit structure varied considerably with both c.d. and 2-mercaptoethanol
concentration. Electrokinetic parameters were correlated with the morphological
changes and mechanisms proposed. The same authors have also examined the
{ 1 lo] face,233noting similar growth processes and presenting transport mechan-
isms. Chromopotentiometric and potentiodynamic studies of copper coated
platinum sheet in H,SO,-Na,P,O, solutions containing CuSO, by Pikel'nyi and
L~shkarev,,~,have shown that the reduction of Cu2+ is preceded by a surface
chemical reaction involving adsorbed species. The rate constant of interaction
between adsorbed Cu and pyrophosphate was calculated. Thiourea and certain
inorganic anions were found to accelerate the reduction mechanism.
Kuznetsov et al.235have investigated the effect of the structure of furfuralde-
hyde derivatives on the kinetics of electro-deposition of Cu in an aqueous-DMF
electrolyte. A diffusion coefficient for the Cu ions in the mixed electrolyte was
derived (0.67 x cm2 SK and
) a mechanism for the reduction process and the
I

adsorption of complexes was proposed.

Passivation of Cu and the r6le of some anions in the mechanism of film forma-
tion and breakdown in alkaline phosphate solution has been observed by
Al-Kharafi and E l - T a n t a ~ y A. ~mechanism
~~ involving C1- adsorption or its
exchange with OH- attached to the soluble metal ion is discussed.
The influence of dipole moment on the adsorbability and hence reducibility of
acetaldehyde, benzaldehyde, and furfural in ethanol-water mixture (1 :1) contain-
ing 0 . 5 M H 2 S 0 , has been reported, by Noubi et al.,237for both bulk and
electrodeposited copper electrodes. The potentials at which the reduction takes
place are highly dependent on dipole moment. It was found that increasing
aldehyde concentration, lower current density, increasing temperature, and the
addition of some salts caused an increase in reduction current efficiency. Increase
in ethanol concentration also results in increased reducibility; however a critical
concentration is reached after which the reducibility decreases.

11 Gallium
A number of workers have taken advantage of the low melting point (30 "C) of
gallium to use it as an alternative to mercury, and we have excluded these studies
from our consideration in this review. However, there have also been a few studies
of the electrochemistry of gallium semiconductor materials. Dare-Edwards et
al.238studied p-GaP and other p-type III/V semiconductors to try to determine
the reasons for the very low efficiency of photogeneration of hydrogen at poten-
tials just positive of the flatband potential. The efficiency only rises to reasonable
levels at potentials >0.6 V positive of the flatband, which renders the materials
unsuitable for solar photoelectrolysis cells. The poor performance was caused by

233 R. Lakshrnana Sarma and S. Nageswar, J . Electrochem. SOC.(India), 1982,31,33.

234 A. Ya. Pikel'ny and Yu. M . Loshkarev, Elektrokhimiya, 1981, 17,441.
235 V. V.Kuznetsov, V. P. Grigor'ev, and 0. V. Fadeeva, Elektrokhimiya, 1981,17,1895.
236 F. M. Al-Kharafi and Y. A. El-Tantawy, Corros. Sci., 1982,22, I .
237 G. A . Noubi, M. F. El-Shahed, F. El-Cheikh, and H. Mansour, Indian J . Chem., 1980,17A,564.
238 M.P. Dare-Edwards, A. Hammett, and J. B. Goodenough, J . Electroanal. Chem., 1981,119, 109.
36 Electrochemistry
surface hydrogen atoms formed in the first step of the photo-assisted hydrogen
evolution reaction. In addition to their subsequent conversion into hydrogen,
these atoms may be reoxidized by holes tunnelling to the surface from the valence
bond, this process only being suppressed at very negative potentials. The perform-
ance of p-GaP could be much improved by the adsorption of a layer of Ru"'
chloride, which appeared to reduce the tunnelling effect. In contrast, Gerischer
and Muller239examined hydrogen evolution on n- and p-GaAs. It was found that,
as with metal electrodes, it could occur in two ways: (a) at -0.5 V (SCE) by the
reduction of H 3 0 + and (b) at - 1.25 V by the reduction of H,O. In both cases
conduction band electrons are responsible for the two reduction steps, forming
adsorbed H atoms in the first step, and H, molecules in the second. Hole injection
occurs only to a negligible extent, although appearing energetically feasible.
Thapar and R a j e ~ h w a r ~examined
~' the photoelectrochemical oxidation of a
variety of aromatic hydrocarbons on n-GaAs electrodes immersed in AlC1,-
n-butyl pyridinium chloride molten salt electrolyte. Changes in current-voltage
characteristics of illuminated n-GaAs electrodes due to slight changes in electro-
lyte composition enabled mapping of the bandgap energy levels responsible for

-
mediating charge transfer. One set of such states seemed to be located at an energy
0.6 eV below the conduction band edge in n-GaAs. These states were considered
to arise from specific adsorption of C1- ions from the electrolyte. The positions of
the reduction waves on n-GaAs in cyclic voltammograms indicated a second set of
surface states situated very close to the valence band edge.

12 Gold
As a noble metal, gold has, over the years, been used extensively to provide an
inert surface for study of the effects of crystallographic orientation on double layer
and adsorption phenomena. Indeed, some of the earliest work on double layer and
adsorption at single crystals was done on g ~ l d . ~ ~ 'More
. * ~ recent
* work, however,
has centred on its use as a relatively stable 'workbench' on which novel systems
can be investigated. Bioelectrochemical reactions are particularly interesting and
varied. Aldaz and V a ~ q u e studied
z ~ ~ ~the oxidation of pyruvic acid in acid media
on gold Oxidation was noted to begin at +400 mV(SCE) and take place on both
the clean gold surface and on oxidized gold, the process continued by adsorption
of the acid on to the surface, following a Temkin isotherm, until such a potential is
reached where surface gold oxidation was complete.
Taniguchi et ~ 1 . have
' ~ ~used gold to study whether or not electron transfer can
occur between an electrode and a biological molecule, cytochrome c via an interac-
tion of n-electrons provided by sulphur-bridged bipyridines. It was found that
bis(4-pyridyl) sulphide and bis(4-pyridyl) disulphide are both effective as pro-
moters of rapid electron transfer. Furthermore, at the disulphide irreversibly
234 H. Gerischer, N. Miiller, and G . Haas, J . Electroanal. C'hem., 1981, 119,41.
240 R. Thapar and K. Rajeshwar, J . Electrochem. SOC.,1982,129,560.
24' G. M. Schmid and N. Hackerman, J . Electrochem. SOC.,1962,109.243.
242 G. M. Schmid and N. Hackerman, J . Electrochem. Soc., 1963, 110,440.
243 A. Aldaz and J. L. Vazquez. J . Electroanal. Chem., 1981,130,209.
244
1. Taniguchi, K. Toyosawa, H. Yamaguchi, and K. Yasukouchi, J . Electroanal. Chern.. 1982. 140.
187.
Adsorption at Solid Electrodes 37
adsorbed gold electrode, a reversible redox wave of cytochrome c was observed
for the first time. Other work by Haladjian et al.24s has studied the competi-
tion between cytochrome c and 4,4'-bipyridyl, 1,2-bis(4-pyridyI)ethylene, and
aldrithiol-4 for the adsorption at gold electrodes.
Vosaki and Hill246have examined the adsorption behaviour of 4,4'-bipyridyl at
the gold water interface. From capacitance measurements and the observation of
gold oxide formation inhibition reorientation (flat to perpendicular) is proposed at
about - 0.1 V (SCE). The importance of this phenomenon in relation to promot-
ing electron transfer between cytochrome c and gold is discussed. The mechanism
and kinetics for the two-electron oxidation of NADH to NAD at gold electrodes
+

at various pHs and NADH concentrations have been studied by Samec and
E l ~ i n g . They
~ ~ ' postulate that analogues for the system can be provided by sul-
phide species adsorbed on a gold surface. NADH is strongly adsorbed on gold.
However, since the oxidation of adsorbed NADH starts at more positive poten-
tials than oxidation of bulk NADH, the latter occurs at gold surfaces covered
by adsorbed NADH. Recent publications by Russian workers, in particular
Tarasevich et a1.,248,249 show a particular interest in the dissolution and complex
formation of gold with amino-acids and peptides. They provide information on
the composition and structure of the bioinorganic compounds formed and present
mechanisms for their formation. Glycylglycine, cysteine, and histidine were
studied and it was established that glycylgycine is irreversibly adsorbed and that
the degree of adsorption is very sensitive to pH. Adsorption from alkali phosphate
buffer (pH 3.0-12.0) was studied and deprotonation of the carboxyl groups in
alkaline media resulted in the greatest adsorption. It is interesting to note that they
suggest that the study of these bioinorganic systems may well open the way to
microbial methods of processing gold-containing ores. The apparent standard rate
constants for the couples quinone/hydroquinone and Fe"'/Fe" in the presence of
adsorbed benzoquinolone in 1 M H2S04 on gold have been determined from low
overpotential impedance studies (2W800 Hz) of the system by Schmidt and
Holme~.~ ~ ' degree of adsorption between 0.0 and +0.7 V(SHE) was found to
The
be nearly independent of electrode potential.
Underpotential deposition (UPD) is now a well-established topic of study due,
in large measure, to studies at gold electrodes. Swathirajan et al.25' have investi-
gated the thermodynamic properties of monolayers of silver and lead deposited on
polycrystalline gold in the underpotential region. The ring disc method was
adopted and provided details on free energies and equilibrium potentials. The
dependence of the underpotential shift on the UPD monolayer coverage and the
effect of solution complexation to produce anionic metal species indicate that no
partial charge exists on the UPD species. Anomalous adsorption isotherm
parameters are explained by the gradual variation of the electron work function
2*5 J. Haladjian, P. Bianco, and R. Pilard, Electrochim. Acta, 1983,28, 1823.
246 K. Vosaki and H. A. 0.Hill, J . Electroanal. Chem., 1981,122,321.
247 Z . Samec and P. J. Elving, J . Elecfroanal. Chem., 1983,144,217.
248 M. R. Tarasevich, A. Yu. Safronov, V. A. Bogdanovskaya, and A. S. Chernyak, Elektrokhimiya,
1983, 19, 167.
2*9 A. Yu. Safronov, M. R. Tarasevich, V. A. Boydanovskaya, and A, S. Chernyak, Elektrokhimiya,
1983, 19,421.
250 G . M. Schmidt and T. A. Holmes, J . Electrochem. SOC.,1981,128,2582.
251 S. Swathirajan, H. Mizota, and S. Bruckenstein, J . Phys. Chem., 1982,86,2480.
38 E k c tr ochem istry
of the substrate with UPD coverage. Further work of Swathirajan and
B r ~ c k e n s t e i n ,extends
~~ to an interpretation of the potentiodynamic response
during the underpotential deposition of silver on polycrystalline gold. Again the
rotating ring disc was employed, giving a relationship between the negative shift in
the pzc, UPD coverage, and underpotential shift. Under equilibrium conditions
the changing current during the potential scan can be related quantitatively to the
pzc shift. Kinetic models that involve the coupling of mass-transport, adsorption,
and charge transfer are analysed. A mixed control model involving the above is
presented, which agrees with experimental results.
A radiotracer study of the adsorption of C1- and HSO,- ions in 1 M HClO, on
porous gold and underpotential deposited metals on gold was carried out by
Horanyi et This revealed a continuous increase in C1- adsorption between 0
and 1.3 V (SHE) at the porous gold electrode. However the HSO,- ions were
adsorbed to a measurable degree only above 300 mV. In both cases a decrease in
adsorption occurs at potentials where oxide formation begins (above 1200 mV).
When Cd2+,Cu2+,and Ag are underpotentially deposited a significant increase
+

in C1- adsorption is noticed.

Cyclic voltammetry on gold single crystal faces ({lOO} and its vicinal faces) of
lead UPD, carried out by Hamelin and KatayamaZ5, has yielded a discussion of
the processes which make up the complex i-E curves. Explanations involving
adsorption, reconstruction, and nucleation processes are presented.
Sayed and Juttner2 have investigated the electrocatalytic effect of under-
potential bismuth deposits on the cathodic reduction of oxygen and hydrogen
peroxide at polycrystalline and single-crystal { 1 11} and { 100) gold surfaces in
0.5 M HClO,. On bare gold an incomplete two-electron reduction of 0, to H,O,
was found to predominate which in the presence of Bi3+ is positively catalysed.
The catalytic activity was correlated with the degree of bismuth adsorbate
coverage and the arrangement of ad-atoms depending on the crystallographic
orientation of the gold. The effect of mixed C1- and Bi3+ adsorption on the
reduction process was also studied.
The adsorption of oxygen, its evolution and reduction at any electrode is always
of particular interest and gold is no exception. As well as the previously mentioned
UPD of bismuth there are other recent observations of oxygen-gold interaction.
Work by Adzic et indicates that if a gold surface is modified by bismuth
ad-atoms the reduction of oxygen leads to H0,- via a 2e- process and to OH- via
a 4e- process. The rate determining step for this process changes over a very small
potential range from the chemical reaction to charge transfer. Shifting the poten-
tial to more negative values results in the reaction becoming diffusion controlled.
The charge transfer r.d.s. is
O,+e--N- (ads)
The investigations of Alvarez-Rizatti and Juttner257link lead UPD on gold and
the electrocatalysis of 0, reduction. Rotating disc electrodes of { I 1 I}, {loo}, and
252 S. Swathirajan and S. Bruckenstein, J . Eleclroanal. Chem., 1983, 146, 137.
253 G. Horanyi, E. M. Rizmayer, and P. Joo, J. Electroanal. Chem., 1983, 152,211.
254 A. Hamelin and A. Katayama, J . Electroanal. Chem., 1981,117,221.
*” S . M. Sayed and K . Jiittner, Electrochim. Acta, 1983,28, 1635.
2sh R . R. Adzic, N. M. Markovic, and A. V. Tripkovic, Glas. Hem. Drus. Beograd, 1980,45,399.
”’ M. Alvarez-Rizatti and K. Juttner, J. Electroanal. Chem., 1983,144,351.
Adsorption at Solid Electrodes 39
(1 lo} single crystal gold were used in 0.5 M HClO, solutions. As with bismuth, a
positive catalytic effect was observed which was dependent on the degree of adsor-
bate coverage and the crystallographic orientation of the gold. The results
obtained are discussed in terms of different oxygen adsorption models and are
compared with those for lead on silver. Adzic et ~ 1 . have ~ ' ~also examined lead
ad-atom effects on oxygen reduction, again reaching the same conclusion of posi-
tive catalytic activity but present more detail in the form of a mechanism for the
process. They suggest a change from 2e- to a 4e- reduction process when lead
modifies the gold surface. In the potential region where AuOH makes up the sur-
face, the Pb-AuOH interaction is said to cause the catalytic effects. At more
negative potentials on bare gold the UPD of lead atoms provides the catalytic
properties. The same authors259 support the findings of Alvarez-Rizatti and
Juttner257with their investigations on the reduction of oxygen in alkaline solu-
tion. The OH chemisorption on gold is strongly dependent on crystallographic
orientation and hence oxygen reduction is structurally dependent. Thallium adsor-
bates at small overpotentials were found to inhibit oxygen reduction on the {loo}
plane but catalyse it at the { 11l} and the { 1lo} faces. At higher overpotentials a
4e- reduction takes place at all three planes covered with thallium ad-atoms.
Investigations of oxygen electrosorption on polycrystalline gold in acid con-
ditions, by Florit et u I . , ~ ~ '
revealed an anodic prepeak preceding the electrosorp-
tion which occurs when performing cyclic voltammetry. The origin of the small
amounts of oxygen formed during the potential cycling is suggested to be the
formation and heterogeneous chemical decomposition of a peroxide-type struc-
ture on the metal surface when most of the surface is covered by oxygen atoms. A
pathway for oxygen electroreduction on gold is presented. Lorenzola et ~ 1 . also ~ ~ '
provide evidence, from rotating disc electrodes, for the existence of a superoxide
ion participating in the oxygen electroreduction. The process was interpreted as
a reversible le- transfer to give 02-,followed by the disproportionation of
the superoxide ion which in the presence of water could account for hydrogen
peroxide formation. A disproportionation constant of the order lo5 mol S- was '
evaluated.
Electroformation of the 0-containing layer on gold in alkaline solutions has
been examined by Martins et It is said to initiate through the formation of
an OH,,, monolayer. This then undergoes further electro-oxidation and
simultaneous chemical transformations yielding an Au(OH),-type layer. The
oxygen electroadsorption mechanism is noted by Florit et uE.263to be very sensi-
tive to electrolyte composition. The current/voltage profiles are interpreted in
terms of specific adsorption of the anions. Two groups of anion are distinguished:
Group I containing those anions which contribute to the electrolyte solution struc-
ture by hydrogen bonding, and Group I1 comprising the anion whose hydrogen
bonding is less significant. A general electrochemical adsorption isotherm and
adsorption kinetic equation for the anions on polycrystalline gold are discussed.
258 R. R. Adzic, A. V. Tripkovic, and N. M. Markovic, J . Electroanal. Chem., 1980, 114, 37.
259 R. R. Adzic, A. V. Tripkovic, and N. M. Markovic, J . Electroanal. Chem., 1983,150,79.
260 M. I. Florit, M. E. Martins, and A. J. Arvia, J . Elecfroanul.Chem., 1981, 126,255.
261 T. A. Lorenzola, B. A. Lopez, and M. C. Giordano, J . Electrochem. SOC.,1983,130, 1359.
262 M. E. Martins, R. 0.Cordova, and A. J. Arvia, Electrochim. Acfa, 1981,26, 1547.
263 M. I. Florit, M . E. Martins, and A. J. Arvia, J. Electroanal. Chem., 1983,151,209.
40 Electrochemistry

The hydrogen evolution reaction (HER) is a perpetual topic and adsorption/

desorption is an integral part of the process. Andricacos and Cheh264have investi-
gated the system recently on electrodeposited gold rotating disc electrodes. Levich
plots are presented for hydrogen evolution in 0.25 M Na,SO, (pH 3.2). The reac-
tion was seen to proceed at high coverages of H + with electrochemical desorption
as the rate determining step. Chao et aZ.265have employed secondary ion mass
spectrometry (SIMS) as a tool for the study of the distribution of hydrogen on
gold whilst undergoing hydrogen evolution. Both surface and in depth studies
were carried out by etching with an ion beam. With electrodes composed of a small
number of crystals, the absence of abnormal hydrogen concentration at the grain
boundaries was taken to indicate that diffusion did not follow this path. The
profiles observed were consistent with a model based on simple uniform bulk
diffusion.
Visible adsorption spectroscopy was used by Bowden and Hawkridge266to fol-
low the kinetics of viologen cation radicals reacting at hydrogen-evolving gold
electrodes in pH 6-8 electrolytes. A thin layer, optically transparent, electro-
chemical cell was employed under quasi-steady-state conditions. Zero-order
behaviour with respect to the viologen cation radical was determined. Increasing
pH shifted the hydrogen evolution reaction and the viologen cation radical
reaction 60--70 mV/pH unit negative. A mechanism is proposed involving a fast,
non-rate-limiting, chemical reaction between the viologen cation radical and
adsorbed H atoms. This investigation shows the increasing r6le of spectroscopic
techniques in helping to evaluate electrochemical phenomena. A study using
ESCA (Electron Spectroscopy for Chemical analysis) on emersed gold electrodes
has been carried out by Hansen et aZ.267Gold films evaporated on to glass were
compared using cyclic voltammetry and ESCA with aqueous solutions of CsSO,
and Cs halides in order to demonstrate the differences in the cation surface con-
centration for weakly and strongly adsorbing anions. A short note by Neff and
KotzZh8points out the advantages of electron spectroscopic techniques as applied
to electrodes, and presents a preliminary study of the surface properties of gold
electrodes, which have been emersed from acidic aqueous electrolytes, under ultra
high vacuum conditions. The fact that the complete double layer apparently stays
intact under these conditions is highly surprising. The work function of the
electrode and the presence of water were determined simultaneously.
SERS is becoming a widely used additional technique and Busby and
C r e i g h t ~ have
n ~ ~ developed
~ a method of producing a gold electrode particularly
suitable to the application of SERS. The process of manufacture involves elcctro-
plating at low current densities from dilute (< 10- M) solutions of a salt or com-
plex in the absence of supporting electrolyte. SEM observation shows the surface
to consist of small spherical particles of fairly constant diameter (typically 70 nm).
These electrodes exhibit intense SERS scattering. To show their utility, data are

264 P. C. Andricacos and H . Y. Cheh, J . Electrochem, Soc., 1981,128,838.

265 F. Chao, M. Costa, R. Parsons, and C. Grattepair, J. Electroanal. Chem., 1980, 115, 31.
2 6 6 E. F. Bowden and F. M. Hawkridge, J . Electroanal. Chem., 1981,125.367.
"' W. N. Hansen, D. M. Kolb, D. L. Rath, and R. Wille, J . Etecrroanal. Chem., 1980. 110, 369
W. Neff and R. Kotz, J . Electroanal. Chem., 1983,151,305.
269 C . C . Busby and J. A. Creighton, J . Electroanal. Chem., 1982,140,379.
Adsorption at Solid Electrodes 41
presented on the behaviour of pyridine and naphthalene adsorbed on to these
electrodes.
Modulated electroreflectance has been applied to the study of the adsorption of
ethyl ether on polycrystalline and (110) single crystals of gold. Nguyen Van
Huong et al.2 7 0 supplemented results from admittance measurements with electro-
reflectance spectra for ether in aqueous solutions of 0.02 M NaF. Comparison of
the results with those for mercury show that gold adsorbs ether less strongly. The
electroreflectance measurements show anisotropic characteristics in the adsorp-
tiondesorption region, probably due to the sudden change in layer structure. Fur-
ther, there is evidence for the absence of any chemical interaction between gold
and ether molecules. Electroreflectance measurements have also been used by the
same research to observe the adsorption of bromide ions on single crys-
tals of gold. It was noted that the adsorption parameters did not differ as a func-
tion of the atomic structure of the gold surface, in contrast with the behaviour of a
neutral substance. Modifications of the spectra and of the azimuthal anisotropy of
the { 1lo} and { 31 I } planes by adsorbed Br- provide evidence to suggest there is
an influence of the grooved structure of the gold substrate on the mechanism of
reorganization of the superficial atomic structure induced by the adsorption pro-
cess. This study reinforces the work by Bellier’” where it was shown that surfaces
with the same type of superficial atomic configuration exhibit similar behaviour
of halide adsorption phenomena. This reaction was found to be related to the
presence of atomic ‘rails’ on the gold surface.
The reactions of gold in aqueous cyanide as investigated by Thurgood et ~ 1 . ’ ~ ~
were found to follow a three-species series process as the potential was shifted
through the range - 0.8 1 to 0.64 V. All steps involved an adsorbed species.
The dependence of the adsorption of chlorobenzene at the gold-0.5 M H2S0,
interface on electrode potential, bulk concentration, and temperature has been
investigated by Czerwinski and S o b k o ~ s k i using
’ ~ ~ a 14C labelling technique. At
higher bulk concentrations of chlorobenzene, multilayer adsorption was observed.
It is suggested that the chlorobenzene is oriented perpendicular to the electrode
with the chlorine atom in contact with the gold. Quantitative studies on the
adsorption of diethyl ether on the three low-index faces { 11I}, { 1lo}, and { 100) of
gold were carried out by Lipkowski et ~ 1 . The ’ ~ ~adsorption parameters such as
free energy of adsorption (AG,) and limiting Gibbs excess free energy (rmaX) were
calculated and compared with earlier results on mercury. H a r n e l h ~ ’ ~ has
~
examined the co-adsorption of sulphate ions and pyridine on the { 1 I 1}, { 1 lo}, and
(100) faces of gold. The adsorption4esorption of pyridine can be clearly
observed. For all three faces co-adsorption is described. Surface reconstruction is
seen to interfere with pyridine adsorption at the {loo} face. The (210) face of gold

270
C. Nguyen Van Huong, C. Hinnen, J. P. Dalbera, and R. Parsons, J. Electroanal. Chem., 1981, 125,
177.
271
C. Nguyen Van Huong, C. Hinnen, and A. Rousseau, J. Electroanal. Chem., 1983,151, 149.
272
J. P. Bellier, J. Electroanal. Chem., 1982, 140,391.
273
C. P. Thurgood, D. W. Kirk, F. R. Foulkes, and W. F. Graydon, J. Electrochem. SOC.,1981, 128,
1680.
274
A. Czerwinski and J. Sobkowski, Electrochim. Acta, 1980,25, 13 13.
215
J. Lipkowski, C. N. Van Huong, C. Hinnen, and R. Parsons, J. Elecrroanal. Chem., 1983, 143,375.
216
A. Hamelin, J. Electroanal. Chem., 1983, 144,365.
42 EIec t rochenzist ry
has been investigated by the same researcher.’” The sodium fluoride solution
interface was found to be ideally polarizable over only a short range of potential.
Fluoride is adsorbed on the (210) face. By means of a.c. polarography the adsorp-
tion isotherms of hydroquinone, some N-substituted p-phenylenediamines,
1-phenyl-pyrazolidin-3-one sulphite and iodide were measured at pH 10.5 on gold
by Jaenicke and K~bayashi.’~’The results are represented by Langmuir iso-
therms. Whilst adsorbed hydroquinone is displaced by sulphite, all the other sub-
stances are able to displace sulphite from the electrode. The displacement was
found to be irreversible with the exception of iodide. The results are in agreement
with observations of catalytic effects of some additives in photographic develop-
ment. In an extension of this the rates of adsorption of iodide and of
adsorption displacement of sulphite by iodide were measured at a rotating gold
disc in solutions containing hydroquinone.
Lacoeur et ~ 1 . ~have
” carried out pzc determinations for gold single crystals of
different orientations. Using these data and values for the gold work function, they
show that a very limited perturbation is induced by the adsorbed water layer in the
atomic rearrangement of the metallic surface, compared with the structure in a
vacuum.
Differential capacitance data and voltammetric curves are presented by
Lipkowski ct ~ 1 . for ~ ~electrodes
’ which were made from Au-SiO, amorphous
eutectic (glass), comprising 69% Au and 31% Si, and are compared with
polycrystalline gold. The glass electrode was found to be much more hydrophilic.
The reduction peak of the oxide on the glass is significantly different, suggesting
that some chemical steps may occur following the adsorption and charge transfer.
The underpotential deposition of lead shows that the adsorption sites on the
glass are much more dispersed and strongly inhibit most of the two-dimensional
association of lead.

13 Indium
Zhuchkova ct ~ 1 . have
’ ~ ~used ellipsometric and electrochemical methods to study
the surface condition of electropolished indium in 0.1 M KOH. The oxidized
forms of indium, In(OH),, and InOOH were detected in relative proportions
dependent on electrode potential. Oxidation was preceded by oxygen adsorption
at -0.2 V(NHE).
Kapusta and H a ~ k e r m a n ~found
~ , the electrochemical behaviour of formal-
dehyde on indium to be similar to that reported for mercury cathodes. Tafel slopes
of 65-80 mV decade- indicated the protonation of a reaction intermediate to be
the rate-determining step of the reaction. The value of the slope depended slightly
on concentration and pH, due to adsorption under Temkin conditions. The reac-
tion order with respect to formaldehyde was close to unity in the limiting current
2’7 A . Hamelin, J. Electroanal. Chem., 1982, 38, 395.
W. Jaenicke and H . Kobayashi, Electrochim. Actu, 1983,28,245.
27y W. Jaenicke and H . Kobayashi, Electrochim. Acta, 1983,28,249.
’’’ J. Lacoeur, J. Andro, and R. Parsons, Surf: Sci.,1982,114,320.
J. Lipkowski, R. M . Reeves, and M . R. Krishnan, J . Electroanal. Chem., 1982, 140, 195.
2n2 N. A. Zhuchkova, Z . I. Kudryartseva, and N. A. Shumilova, Elektrokhimiya, 1981,17,955

2 R 3 S . Kapusta and N. Hackerman. J. Electroanal. Chem., 1982,138.295.

Adsorption at Solid Electrodes 43
region, but smaller in the Tafel region. For other work on indium, see the section
on tin.

14 Iron
A good deal of the work carried out during the review period has concerned
adsorption phenomena on iron and iron alloys. The majority of this work has con-
sidered corrosion processes and their mitigation by an adsorbed inhibitor. The dis-
tinction between corrosion studies of iron and studies of the separate anodic and
cathodic processes is a fine one, and the work reviewed here should be considered
in conjunction with the iron corrosion studies reviewed in Section 3.
Kuznetsov and F e d ~ r o vstudied~ ~ ~ the cathodic polarization behaviour of
Armco iron in H2S04 solutions in the presence of cryptocyanine. At inhibitor con-
centrations that produce 75% blocking of the iron surface the mechanism of
hydrogen evolution was altered. The H atom recombination was inhibited while
H reduction remained a rapid process. The same authors,285using differential
+

capacitance measurements, also found the presence of 1% sodium naphthalene

sulphonate markedly to affect hydrogen evolution on Armco iron. Krishtalik et
aLZs6observed the presence of I - (as 0.4 M KI in 0.5 M H2S0,) to change the rate
of hydrogen evolution on iron, shifting the polarization curve in the cathodic
direction by 80-100 mV. R e ~ h e t n i k o v studied
~'~ the hydrogen evolution reaction
on iron in 1 M HC1 and KC1 solutions in the presence of butynediol and also
trimethylbenzylammonium perchlorate and iodide. Butynediol reduced the rate by
adsorption, decreasing the active electrode surface area. The perchlorate and
iodide compounds, however, affected the potential of adsorption and decreased
the rate of the discharge step of the H + ion.
Zamanzadeh et al.z88 have presented the results of a preliminary study of the
effects of implanted helium, iron, and platinum upon the absorption of hydrogen
by iron. The location of implanted platinum, modified by the selective dissolution
of iron from the surface, affected the kinetics of the hydrogen absorption process.
The rate of hydrogen absorption decreased with increasing surface platinum con-
centration in both NaOH and H2S04 (both at 0.1 M). The implantation of helium
or iron produced no significant changes in permeation behaviour. Surface analysis
by Rutherford backscattering suggested the interdiffusion of iron and platinum to
occur during dissolution.
Nobe et aLZS9also studied the hydrogen penetration reaction on iron during
cathodic polarization in the presence of halide ions, H,S, and the acetylenic alco-
hol hexynol. In the presence of halides the rates of hydrogen evolution and pene-
tration, and the corrosion current all decreased in the order C1> Br > I. Hydrogen
evolution and penetration were both catalysed by H2S, but its effect was con-
centration-dependent only in the latter case. The penetration was enhanced during
284 A. A. Kuznetsov and Yu. V. Fedorov, Zashch. Met., 1981, 17,445.
285 A. A. Kuznetsov and Yu. V. Fedorov, Elektrokhimiya, 198 1,17,634.
286 T. Sh. Korkashvili, V. M . Tsionskii, and L. I. Krishtalik, Elektrokhimiyu, 1980,16,886.
287 S. M. Resnetnikov, Zh. Prikl. Khim., 1981,54, 590.
288 M. Zamanzadeh, A. Alloun, H. W. Pickering, and G. K. Hubler, J . Electrochem. Soc., 1980, 127,
1688.
289 I. M. Pearson and Y. Saito, Werkst. Korros., 1980,31,763.
44 Elect rocIieinist r j -
corrosion, when a new surface was formed, rather than during cathodic polariza-
tion. The addition of hexynol inhibited hydrogen evolution and penetration rates
in the presence of H2S and halide ions.
Zakro~zyniski~ has
~ "described a sensitive method for determining the amount
of absorbed hydrogen in steel. The method is based on the electrochemical
measurement of the hydrogen desorption rate. The equations governing the diffu-
sion-con trolled desorption process are analysed, and applications of the method
are suggested.
Various research workers have encountered adsorption phenomena in studies of
the anodic dissolution of iron. These studies have often been quite specific, e.g. on
single crystal electrodes of highly pure iron, and in non-aqueous electrolyte solu-
tions. Naumova and B a t r a k ~ v ~found~ ' that the crystallographic parameters
influenced the mechanism of anodic dissolution of iron in aqueous H,SO, solu-
tions. The { 100) crystal face dissolved via the Bockris mechanism, while the { 1 1 I }
face followed the mechanism of Hurlen. Anisotropic adsorption was observed in
solutions containing I - . Draiic and Hao292studied the dissolution of high purity
iron in KOH solutions (concentration range 5 x 10-2-5 M). Cathodic pretreat-
mcnts gave reproducible anodic Tafel plots, which were explained by a reaction
mechanism in which FeOH,,, and Fe(oH),,,,,, were the intermediate species,
adsorbed under Temkin conditions. The primary stable product of the electrode
rcaction was HFeO, ~,with the final product being precipitated Fe(OH),.
Lazorenko-Manevich and S o k ~ l o v -a2 9~6 ~have
~ discussed the anomalous dis-
solution behaviour of the iron-group metals in terms of the formation of easily
polarized surface complexes of adsorbed water so that the metal is electrostatically
screened by the adsorbed layer. Consequently the rate of anodic dissolution is
much less dependent upon electrode potential. This effect is observed with iron
and cobalt but not with These authors investigated the nature of water
adsorption using electroflectance spectroscopy of iron in aqueous294 and
anhydrous acetonitrile solutions,295and of Fe,04 in aqueous solutions.296
Draiic and V ~ r k a p i c ,have
~ ~ proposed a single reaction mechanism for the
anodic dissolution of iron in acid solutions. According to this mechanism, a
change in the properties of the system, such as internal stress, can raise the rate
constant of the slowest reaction step, and this can then change. In the proposed
mechanism the precursor of the passivating species is tentatively assumed to be
adsorbed Fe(OH),, bascd upon an adsorption free energy of 80 kJ mol-'.
~ ~ ' proposed a general model for the active to passive
Vilche and A r ~ i a have
transition of the iron-group metals, based on the adsorption processes attendant
upon electrode reactions and the structure and stability of the passivating films.
The model is founded upon four key considerations: ( u )the non-equilibrium struc-
ture of the electrochemical interface, (b) competition between different adsorption
290 T. Zakroc7yniski, Corrosion ( N A C E ) , 1982, 38, 218.
'" N. I. Naumova and V. V. Ratrakov, Elektrokhimiya, 1981, 17, 1290.
*'* ' D . M. Draiic and C . S. Hao, Electrochim. Acta, 1982,27, 1409.
293 R. M. Lazorenko-Manevich and L. A. Sokolova, Elektrokhimiyu, 1981, 17, 39.
2y4 R. M. Lazorenko-Manevich and L. A. Sokolova, Elektrokhimiya, 1981,17,45.
295 R . M. Lazorenko-Manevich, L. A. Sokolova, and Ya. M. Kolotyrkin, Elektrokhimiya, 1983, 19,411.
296 R. M. Lazorenko-Manevich, L. A. Sokolova, and Ya. M. Kolotyrkin, Elektrokhimiya, 1981. 17, 858.
207 D. M . Draiic and L. Z. Vorkapic, Glas. Item. Drus. Beograd, 1981,46,595.
298 J. R. Vilche and A. J. Arvia, An. Acad. Nuc. Cirnc. Exactus Fis. 'Vat. Buenos Aires, 1981. No. 33. 33.
Adsorption at Solid Electrodes 45

processes with intervention of ions and polar species, ( c ) progressive deprotona-

tion and dehydration of the species present in the anodic film, and (6) the influence
of both short- and long-term ageing processes upon the characteristics of the
passive layer.
Bernhardsson and M e l l ~ t r o e m have
, ~ ~ derived the form of the anodic polariza-
tion curves of stainless steel in H,S04 on the assumption that the passivation
process follows the Langmuir adsorption isotherm.
Bowen and Hurlen300 have reported the effects of illumination on the reactions
of the Fe(CN)64-/Fe(CN),3- couple at passive iron electrodes in a borate buffer
of pH 8.1. The rate of oxidation of the former species is markedly increased by
illumination, whereas the reduction of the latter species was unaffected. The results
were explained in terms of a photogalvanic mechanism involving excitation and
reaction of the Fe(CN)64- species adsorbed on the electrode surface.
One way of ensuring that the electrochemistry is representative of an active
metal surface is continuously to renew that surface by scratching or machining
during the experiment. Burstein has exploited this interesting technique for a num-
ber of metals ( e g . silver, see Section 20) and in ref. 301 the effect of reactive anions
(bicarbonate, chloride, phosphate) on the behaviour of scratched iron in aqueous
alkaline solutions is reported. Chloride and phosphate both accelerate the first
oxidation step by direct formation of surface complexes with Fe'. Bicarbonate
does not behave this way but does enter the second oxidative step to react with
adsorbed FeOH, giving an Fe" complex. In all cases the Fe' intermediate forms a
complete monolayer at potentials below the Fe/Fe'* reversible potential.
There has been some interest in the electrochemistry of haematite (a-Fe,O,) in a
variety of situations. Shinar and Kennedy3', investigated the photoanodic oxi-
dation of I - and Br- in competition with the oxygen evolution reaction at doped
haematite electrodes in aqueous solutions in the pH range 0-13. Secondary reac-
tions involving electrogenerated species were found to occur in highly alkaline
solutions. The electro-oxidation of iodide involved the adsorption of I - .
Ardizzone et al. 303 used acid-base potentiometric titration methods to investi-
gate the specific adsorption of the ions Ca2+,Cd2+,and Pb2+ on to particles of
haematite in suspension in KNO, solutions. They found that the cross-over point
of the titration curves could be interpreted as the pzc only in the case of no or
negligible specific adsorption. The authors conclude that this method of determin-
ing pzc by titration must be reconsidered in the case of specific adsorption.
Ardizzone and for mar^^'^ went on to apply the approach to the adsorption of
Co2 on to haematite. A significant amount of radioactive 6oCocan be lost in this
+

way, by association with corrosion products, from boiling water nuclear reactors.
These authors found that Co2 adsorption was directly, but not wholly reversibly,
+

dependent upon solution pH. The adsorption of Co2+also appeared to modify the
primary H +-OH - adsorption equilibria of the iron oxide surface.

299 S. 0. Bernhardsson and R. Mellstroem, ASTM STP, No. 727, 1981, p. 352.
300 W. R. Bowen and T. Hurlen, Acta Chem. Scand. Ser. A , 1981,35,359.
301 G. T. Burstein and D. H . Davies, Corros. Sci., 1980,20, 1143.
302 R. Shinar and J. H. Kennedy, J . Eleclrochem. Soc., 1983,130,860.
303 S . Ardizzone, L. Formaro, and J. Lykleino, J . ElectroanaL Chem., 1981,133, 147.
304 S. Ardizzone and L. Formaro, Surf Technol., 1983,19,283.
46 Electrochemistry

Melendres and Feng305 examined the electrochemical behaviour of iron

phthalocyanine (FePc) in the reduction of oxygen in 0.05 M H,SO, using cyclic
voltammetry and RRDE techniques. Oxygen reduction was found to be
accompanied by the formation of H,O,, and peroxide intermediates were impli-
cated in the 'deactivation' of FePc upon repeated cycling. Multiple redox waves
observed in cycling were attributed to hydrogen adsorbed on different surface
sites.
Warren et al. 3 0 6 have studied the electrochemical behaviour of chalcopyrite
(CuFeS,) from various sources. All samples showed a passive-like response in
anodic polarization, though currents in the passive region varied widely, this being
ascribed mainly to impurities. At higher anodic potentials, in the transpassive
region, the observed increases in current were explained in terms of the decompo-
sition of water with the formation of chemisorbed oxygen, which in turn released
copper and formed SO,' - ions.

15 Lead
Adsorption on lead electrodes has been studied in a wide variety of conditions.
Radhakrishnan and Nageswar307 have examined the effect of 2-mercaptoethanol
on lead electrocrystallization from aqueous fluoborate electrolyte solutions.
Growth habit modifications and changes in kinetic parameters were related to
additive concentrations and current density. Deposit grain-size decreased, notably
at low additive concentrations. Suitable transport mechanisms were proposed with
the help of i.r. and X-ray data.
Micka et ~ 7 1 . ~have
' ~ made in situ conductance measurements on lead accumu-
lator negative plates, and found the conductance of the active ions to be lower in
freshly charged plates, and to increase with time. This was attributed to hydrogen
adsorption. Shaldaev and Rybalka309 used the discharge of CdSO, on to a
smooth lead electrode in 5.2 M sulphuric acid at -40 to +20 "C to study the
adsorption of various accumulator expander materials. Dense and hard adsorbed
films could form on the lead, reaching a thickness of 4 pm.
Damaskin et d 3 1 0 have studied the adsorption of tetrapropyl- and
tetrabutylammonium cations on to polycrystalline lead from KI and Na,SO,
solutions, using capacitance measurements. Ershler et a1.31 have obtained
electroreflectance spectra for lead and for indium electrodes in polarized light in a
solution containing aniline, benzene, and 2-acetyl-5-bromothiophene. A new mini-
mum was observed in plane-polarized light, unaffected by the electrode potential,
which corresponded to the charge-transfer band in the absorption spectra for
adsorbateeelectrode complexes.
Chartier et have shown that the underpotential deposition of a cadmium
ad-atom layer on lead increases the rate of electroreduction of oxygen in H,SO,.
305 C. A Melendres and X. Feng, J. Electrochem. Soc., 1983,130,811.
306 G. W. Warren, M . E. Wadsworth, and S. M. El-Ragly, Metull. Trans., 1982, 13B, 571
307 C. Radhakrishnan and S. Nageswar, J . Appl. Electrochem., 1983,13, 1 I t .
30* M. Calabek, K. Micka, and J. Sandera, J. Power Sources, 1983,10,271.
309 V. S. Shaldaev and K. V. Rybalka, Elektrokhim., 1981,17, 1656.
310 L. P. Khmelevaya, B. B. Damaskin, and A. I. Sidnin, Elektrokhim., 1981, 17,436.
'" A . B. Ershler, A. M. Foontikov, and I. M. Levison, J. Electroanal. Chem., 1982,136,83.
312 P. Chartier, A. Sehili, and H. Nguyen Cong, Electrochim. Acta, 1983,28,853.
Adsorption at So lid Electrodes 47
Rotating disc experiments revealed a non-diffusional component of the total
current which was increased in the presence of adsorbed cadmium.
Kokarev et d 3 1 3 used radioisotope methods to investigate the effect of anodic
polarization on the adsorption of sulphate and phosphate ions on to both a- and
P-PbO,. The two versions of this method that were used, determining the radio-
activity of the electrode either immersed or withdrawn from solution, could give
different results.

16 Manganese
Tari and Hirai3l 4 investigated the potential-pH relationship for synthetic
P-MnO, in various electrolytes, obtaining - 0.060 V/pH for concentrated ZnC1,
and tetraethylammonium perchlorate solutions, but -0.100 V/pH for I M NH4C1.
The behaviour in the presence of Mn2+ was close to the theoretical value of
-O.l18V/pH. The observed behaviour was ascribed to inhibition of the dis-
proportionation reaction of Mn"' in MnO,, so that the Mn2+ ions largely respon-
sible for determining potential response to pH, were not formed. The effect of
ZnC1, appeared to be based on ion-exchange adsorption of Zn2+ ions on to the
oxide surface, to inhibit the disproportionation reaction.

17 Molybdenum
Turner and Parkinson3' have applied chronocoulometric techniques to the deter-
mination of adsorbed tri-iodide on the Van der Waals surfaces of single crystal
n-MoSe, electrodes. The adsorption isotherm was measured and correlated to the
observed shifts in flat band potential of the semiconducting electrode. A possible
surface packing structure of the adsorbed species was proposed.
Bard et ~ 7 1 . ~ "used impedance techniques to study the electrode-solution inter-
face for n-MoTe, in acetonitrile containing various redox couples spanning a wide
range of redox potentials. The benefits of using the in-phase component for
(OO)

determining properties of surface states are discussed. The adsorption from the
1-/13- system on to n-MoTe,, is compared for aqueous and acetonitrile solvents.
Magner et aL3' used X-ray photoelectron spectroscopy (XPS) and electro-
chemical techniques to characterize mixed Fe-Mo and Mo naphthalocyanines as
catalysts for oxygen reduction and evolution. The incorporation of molybdenum
resulted in higher activities for both anodic and cathodic polarizations. The data
are interpreted in terms of reversible adsorption and electron transfer steps.

18 Nickel
The work on nickel can conveniently be classified in three categories: cathodic pro-
cesses, anodic processes, and electrochemistry of nickel-related electrodes (e.g.
oxide, sulphide).
313 G. A. Kokarev, V. A. Koleskinov, and M. Ya. Fioshin, Elektrokhim., 1983, 19, 196.
314 I. Tari and T. Hirai, Electrochim. Acra, 1982,27, 149.
315 J. A. Turner and B. A. Parkinson, J. Electroanal. Chem., 1983,150,611.
316 G. Nagasubramanian, R. L. Wheeler, G. A. Hope, and A. J. Bard, J. Electrochem. Soc., 1983, 130,
385.
317 G. Magner, M. Sary, G. Scarbeck, J. Riga, and J. J. Verbist, J. Electrochem. SOC.,1981, 128, 1674.
48 Elertrochemistrj~
The cathodic processes investigated include electrodeposition and electro-
reduction reactions, though interest has focused more on the hydrogen evolution
reaction. In an impedance study of nickel electrodeposition from sulphate and
chloride electrolytes, Epelboin el ~ 2 1 . ~showed
'~ the kinetics to be dependent on the
type of anion present. In the presence of chloride, a slow electrode activation with
cathodic polarization predominated. In sulphate electrolyte solutions a low
frequency capacitive feature, enhanced by decreasing pH, was ascribed to an inter-
action between the nickel and hydrogen discharges. These authors proposed a
mechanism where the ad-ion Ni+.ds acts both as a reaction intermediate and also
as a catalyst associated with a propagating link site. The adsorbed hydrogen, Hads,
generated by the presence of Ni+ads,was considered to inhibit hydrogen evolution.
Chassaing et ~ 1 . also~ ' ~used impedance measurements to investigate the
kinetics of nickel electrocrystallization from acidified chloride electrolytes with
and without but-2-yne- 1,4-diol and sodium benzenesulphonate. A reaction
mechanism was proposed to account for the observed specific effects of the anions.
In sulphate electrolytes it involves the interaction between adsorbed hydrogen
strongly bonded to the surface and the intermediate adsorbed species Ni+ads. In
chloride electrolytes the model envisages the slow desorption of an adsorbed
anionic species. The specific effects of the inhibitors are also considered.
Maksimov et ~ 2 1 . ~have
~ ' considered the adsorption of capric acid on nickel and
on copper electrodes during the electrodeposition of highly dispersed cobalt. A
layer of capric acid forms on the copper electrode (faster in the case of nickel) and
interacts with surface oxides there to increase its polarization.
Conway et al.321describe observations on nickel and on Raney-type leached
Ni-A1 alloys that suggest a three-dimensional hydride layer is formed during
cathodic polarization with hydrogen evolution in alkaline solution, which then
decomposes at low cathodic overpotentials. For example, after polarization at
high cathodic overpotential, hydrogen evolution continues at an appreciable rate
after interruption of the current; alternatively, an anodic current is observed as the
cathodic overpotential is reduced. The kinetics of decomposition of this thin sur-
face layer of hydride were evaluated using open-circuit potential decay measure-
ments. A mixed corrosion-type mechanism was proposed with the anodic
decomposition of hydrides:
M H + O H - - + M +H,O+e (17)
being coupled with cathodic hydrogen evolution by
M + H,O+e ---+MH,,,+OH-
and
MH,,,tH,O + e - + M+ H, +OH
A number of research groups have investigated the hydrogen evolution reaction
at nickel electrodes in various situations. Korovin ct u f . 3 2 modified
2 Raney nickel
electrodes by solutions of copper and lead salts to adsorb the respective metal
jl* I. Epelboin, M . Jousselin, and R. Wiart, J . Elwtroanul. Chem., 1981, 119, 61.
31') E. Chassaing, M. Jousselin, and R. Wiart, J. Electround. Chem.. 1983, 157, 75.
320 1. A. Maksimov, E. P. Zhelibo, and T. M. Shveli, Ukr. Khim. Zh., 1981,47, 1014.
32' B. E. Conway. H . Angierstein-Kozlowska. M. A . Sattar, and B. V. Tilak, J . Electrochem. Soc., 1983.
130, 1825.
322
N . V. Korovin. 0. N. Savel'eva, and N. I. Kozlova, Elrktrokhimi~~u, 1980, 16, 585.
Adsorption at Solid Electrodes 49

atoms. Potentiodynamic measurements in 0.1 M KOH showed that the rate of

hydrogen evolution was significantly increased in the presence of these adsorbates.
The same treated nickel electrodes with a wider range of metal adsor-
bates (cadmium, lead, bismuth, thallium, and mercury). The hydrogen overpoten-
tial decreased as a result, especially in the case of cadmium and thallium. Korovin
et al.324also pretreated nickel black with nitrate solutions of cadmium and lead,
and found a decrease in the hydrogen evolution overpotential, again attributed to
the adsorption of divalent ions of the respective metal. The maximum rate of
hydrogen evolution on nickel black was attained with 60 minutes treatment in
3 1 M Cd (NO,),.
Various authors have considered the effect of adsorbed organic species on the
cathodic behaviour of nickel. Re~hetnikov,,~’using double layer capacitance
measurements, found dimethylformamide (DMF) to adsorb on nickel at pH
values of &2 and to follow a modified Temkin isotherm. The formation of D M F
hydrates containing a proton more easily discharged than H,O thus accelerated+

the rate of hydrogen evolution. Binkauskiene et al.326studied the hydrogenation

of the unsaturated glycols, but-2-ene- 1,4-diol and but-2-yne- 1,4-diol on a rotating
nickel cathode during hydrogen evolution, as a function of the diffusion and
adsorption of these additives, the rate of hydrogen evolution, and the state of the
nickel surface. Maitra and Bhatta~haryya,,~ used galvanostatic methods to inves-
tigate the effect of C1-, Br-, and I - ions (at 0.1 mM) on the cathodic polarization
of nickel in de-aerated 0.5 M H,SO, solutions containing dicyandiamide and
related compounds (at 1 mM). The halide ions and the organic compounds
exhibited a synergistic relationship, attributed to their co-adsorption on the nickel
electrode.
The anodic dissolution and passivation of nickel has also been considered.
Maitra et al.328extended their study of the cathodic behaviour of to con-
sider anodic processes. The effects of the organic compounds on the passivation
parameters (primary passivation potential, critical and passive current densities)
depends upon their ability to form complexes with the surface metal oxides and
hydroxides. Synergistic interactions between the organic compounds and halide
ions were determined mainly by the specific adsorption of the latter species.
Reshetnikov, 29 proposed the following reaction scheme for nickel dissolution
in acid media at pH < 2:
+
Ni SOi-=[NiSO,] e- ads+ (20)
[NiSO,]-,d,+NiSO, e- + (21)
NiS04=Ni2+ SO,2 -+ (22)
For pH > 2 the mechanism became:
+
Ni H,OS[NiOH],,, e- + (23)
[NiOH],,,+[NiOH] fads+e- (24)
[NiOH]fad,sNi2+ + OH - (25)
323 I. V. Korovin, 0.N. Savel’eva, N. I. Kozlova, T. V. Lapshina, and M . V. Kumenko, Dnkl. Akad.
Nauk SSSR, 1981,257,149.
324 G . S. Koustantiourd, A. G. Kicheev, and N. V. Korovin, Elektrokhimiyu, 1981,17,1335.
325 S.M . Reshetnikov, Zh. Prikl. Khim., 1981,54,2619.
326 E.Binkauskiene, J. Viagyl, A. Bodnevas, Liet. TSR Mokslu Akad. Darb., Ser. B, 1981.No. 1.3.
327 A. N. Maitra, K. Bhattacharyya, and G. Singh, J . Indian Chem. SOC.,1980,57,854.
328 A.N.Maitra, K. Bhattacharyya, and G. Singh, Indian J . Chem., 1981,20A,1209.
329 S.M.Reshetnikov, Zh. Prikl. Khim., 1981,54,2618.
 50 Elect r ochenzis t r j -
The presence of DMF325inhibited the anodic dissolution of nickel in acid media.
El-Tantawy and A l - K h a ~ - a f i studied
~~' the role of C1- ions in the breakdown of
nickel passivity in NaOH solutions. In the absence of C1-, the anodic peak
heights (Z,,,) due to the formation of a- and S-Ni(OH), and NiO(OH), as well as
the parameter I,,,t,,, (where t,,, is the time at I,,,) from the current-time curves,
showed negligible dependence on NaOH concentration in the range 0.01-1 M.
For voltage sweep rates ( V ) of 1-200 mV/s- the relationship I m a x V~ held true.
The presence of CI- resulted in significant increases in both I,,, and I,,,t,,,
and a new ZmaX-Vrelationship where I m a xV1I2. ~ The attainment of passivity
was inhibited by C1-, but could still be achieved. With increasing C1- concentra-
tion passivity showed signs of breaking down (beyond [Cl-]/[OH-] 3) and
the passivation current also increased.
-
The authors propose a mechanism of C1.- attack involving surface adsorption,
increasing solubility of an intermediate nickel hydroxide species that nucleates into
the passive film, and peptization of the deposited oxide by C1-. Fischer and
H ~ r n u n g e r also-studied
~~' the effect of adsorbed C1- on nickel passivation. The
layer of a-Ni(OH), deposited from Ni(NO,), solution passivates a nickel elec-
trode, but in NiCl, solutions C1- is adsorbed on the electrode followed by
precipitation of a black nickel oxide that does not show passivating properties.
Kovtun et al.332 identified a region of secondary passivation of nickel in
0.5-2.5 M H,SO, in the voltage range 1.2-1.9 V (NHE), attributed to the
formation of H,02 adsorbed on the nickel.
Several studies have been made of electrode systems in which nickcl is the major
but not the sole component. Palanisamy et a1.333have studied some electrochemi-
cal aspects of the process of cathodic deposition of Cd(OH), on to a nickel
substrate. Two distinctly different deposition products can be formed, both of
which readily convert into crystalline hexagonal Cd(OH),. The best conditions for
cadmium impregnation of the nickel plaque material are low current density
(31 mA ern-,) so that the nickel electrode potential stays positive of -0.65 V
(SCE). This produces a high loading, and uniform distribution, of cadmium
that needs no further formation process to achieve maximum capacity. Some
voltammetric data are also presented that indicates a somewhat reversible hydro-
gen adsorption on the negative cadmium-impregnated nickel electrode during
overcharge.
Maximovitch and B r 0 n O e 1 ~ investigated
~~ the activity of nickelkzinc catalysts in
the electro-oxidation of methanol in (1 M KOH + 1 M MeOH) at 60 "C. On
smooth nickel the oxidation of methanol is strongly inhibited by superficial oxides,
whereas the oxides on Ni-Zn alloys are easier to reduce. The presence of adsorbed
hydrogen was noted and is discussed.
Sadakov et a1.33sstudied the formation of nickel-boron alloys from electrolyte
solutions containing nickel sulphamate and the carborane ion (C,B,H derived
from trimethylaminododecahydrodicarbaundecaborate. The carborane ion was

330 Y . A. El-Tantawy and F. M . Al-Kharafi. Electrochim. Acto. 19112, 27.691.

331 W. Fischcr and I. Horunger, Korrosion (Dresden), 1981, 12, 19.
332 V. N . Kovtun, A. M. Greshchik, and V. P. Zhuravel, Elektrokhimiya, 1981,17, 1695.
333 T. Palanisany, Y . K . Yao, D. Fritts, and J. T. Maloy, J . Elertrochem. Soc., 1980, 127,2535
334 S. Maximovitch and G. Bronoel, Electrochim.Acta, 1981,26, 1331.
335 G. A. Sadakov, A. Ya. Ezikyan, and F. I. Kukoi. Elektrokhimiyu, 1980, 16, 1837.
Adsorption at Solid Electrodes 51

adsorbed on the cathode surface, where it decomposed by an autocatalytic

mechanism to provide boron which was then included as an interstitial solid
solution in the nickel.
In a study of the electrochemical behaviour of NiS, Hanada et ~ 1 found
. that
~ ~ ~
the cathodic polarization of a- and P-NiS was accompanied by the reaction steps:
02+4H++4e-+2H20 (26)
NiS+2H+ + 2 e - + N i + H , S (27)
2H + 2e- +H2
+
(28)
The hydrogen with the H f was adsorbed on the a-phase sulphide, upon which a
sulphur-rich layer formed more easily than on the P-phase. However, provided
that the conditions were such as to create a sulphur-rich layer, hydrogen also
adsorbed on the P-phase sulphide.

19 Platinum
Platinum is by far the most thoroughly investigated and characterized solid elec-
trode metal, and has to a large extent been the material upon which fundamental
studies of adsorption have been based (see Section 2). The understanding of the
platinum surface that has been achieved has provided a sound basis for extending
the scope of adsorption studies not only to consider a very wide range of organic
adsorbates, but also to develop new instrumental techniques for studying the 'in
situ' electrode.
The last four years have provided a substantial amount of diverse information.
This section starts with (i) a short introduction comprising publications which
contribute to the fundamental knowledge of the platinum surface structure and its
modes of action and considers the use of new instrumental techniques of obser-
vation and analysis. The section continues to consider (ii) oxygen, hydrogen, and
water, (iii) organic adsorbates, and finally (iv) inorganic adsorbates.

Fundamental Studies.-Scortichini and Reilly have produced a series of

papers337- 339 which describe the in situ surface characterization of platinum elec-
trodes using underpotential deposition of hydrogen and copper. The surface of a
platinum (100) electrode pretreated by flame annealing and quenching in sul-
phuric acid is shown to contain a high concentration of structural defects such as
vacancies and self-adsorbed platinum atoms. Adsorbed hydrogen is more strongly
bound at these defects than on a uniform platinum {loo} surface. Potential cycling
in 1 M HCl produced further defects whilst oxide formation and reduction in
0.5 M H,SO, was shown to have the opposite effect. Similar effects on polycrystal-
line platinum are also discussed. The annealing/quenching process on a (100)
surface yielded the reconstructed { I 1O}-( I x 2) surface, which gave two distinct
hydrogen adsorptiondesorption waves in dilute HClO,. The { 1 I I} surface when
pretreated was found to be either highly defective or to possess a high degree of
surface lattice strain which resulted in an unusually strong binding of adsorbed
336 N . Hanada, T. Kishi, and T. Negai, Denki Kagaku, 1981,49,348.
337 C . L. Scortichini and C. N. Reilly, J . Elecfroanal. Chern., 1982,139,233.
338 C. L. Scortichini and C. N . Reilly, J. Efectroanal. Chem., 1982, 139,247.
339 C. L. Scortichini and C. N . Reilly, J . Electroanal. Chem., 1982, 139,265.
 52 Elf c t rochem ist r j
hydrogen. Potential cycling of the (100) and (111) surfaces in sulphuric or
perchloric acid removed most of the defect sites. Some loss of surface order as a
result of cycling was indicated by an increase in the width at half-height of the
monolayer copper stripping peaks. In a further short communication340the same
authors identify single crystal surfaces, in addition to platinum (1 lo), which
exhibit the non-equilibrium state of hydrogen adsorption that is commonly
referred to as the 'third anodic peak' since it appears only on the positive scan
between the major hydrogen waves observed in sulphuric acid electrolyte.
Woodward, Scortichini, and Reilly have, in a further publication341 used
time-resolved staircase voltammetry to show the absence of a cathodic counterpart
to the 'third anodic peak'. The results are presented for platinum (110) in
sulphuric acid.
Electrolyte purity affects all electrochemical measurements, and a study at
platinum electrodes has been carried out by McNicol et al.342Potential step and
cyclic voltammetry methods were used on low surface area electrodes. Pre-purifi-
cation of the electrolyte was found to have no significant influence on the metal
surface area available for hydrogen adsorption determined immediately after an
electrochemical cleaning step. However, maintaining the electrode potential at
0.5 V (SHE) for 1 to 30 minutes results in the progressive suppression of hydrogen
adsorption. owing to the adsorption of impurities which block active sites. All
electrolyte samples, irrespective of degree of pre-purification, exhibited this effect.
Impurities were found to contribute to measured anodic currents at platinum elec-
trodes working between 0.4 and 0.6 V. These effects could largely be eliminated by
pre-electrolysis of the electrolyte (H,SO,) for several days using platinum gauze
electrodes at 2.1 V.
Bewick and have employed infra-red spectroscopy to the study of
hydrogen adsorption on platinum. A correlation between a number of i.r. absorp-
tion bands, in the range 1 . 6 7 . 5 pm, and the formation of weakly bound hydro-
gen on polycrystalline platinum was established. Spectra from aqueous acid
electrolytes, fully deuterated systems, and mixed H,O-D,O systems were
analysed. A model for weakly bound hydrogen in which it is bonded to a parti-
cular water structure is proposed. Fourier transform infra-red spectroscopy has
also been applied by Bewick and others344v345to observe the interface between
platinum and acetonitrile. A mechanism for the adsorption of the solvent is pro-
posed, which illustrates the sensitivity of the technique in observing the difference
between adsorbed and bulk acetonitrile. Absorbance changes due to water
molecules associated with acetonitrile were also noted.
Soriaga and H ~ b b a r dhave ~ ~ made
~ accurate measurements of the limiting
coverages of forty different adsorbed aromatic compounds on platinum elec-
trodes. Experimental data were obtained by linear potential sweep voltammetry
and potential-step chronocoulometry using thin-layer electrodes. Calculations

340 C. L. Scortichini and C. N. Reilly, J . Elecrroanal. Chem., 1983, 152, 255.

341
F. E. Woodward, C. L. Scortichini, and C. N. Reilly, J . Elecrroanal. Chem., 1983, 151, 109.
312 B. D. McNicol, R. Miles, and R. T. Short, Electrochim. Acta, 1983,28, 1285.
343 A . Bewick and J. W. Russell, J . Electroanal. Chem., 1982, 132, 329.
'" T. Davidson, B. S. Pons, A. Bewick, and P. P. Schmidt, J. Electroanal. Chem., 1981, 125,237
345 B. S. Pons, T. Davidson, and A. Bewick, J. Electroanul. C'hem., 1982,140,211.
346 M . P. Soriaga and A. T. Hubbard, J . Am. Chem. Soc., 1982,104,2735.
A dsorp tion at Solid Electrodes 53
were based on covalent and Van der Waals radii, as tabulated by Pauling, and
were tested against the results of classical adsorption experiments. The most
probable molecular orientation at the electrode was determined for each
adsorbed compound. The changes in orientation which occur as a result of the
co-adsorption of iodide are presented in a subsequent paper.347
K ~ n i m a t s u ~describes
~' a method of determining the infra-red reflection
absorption spectrum of the adsorbed CO produced by the chemisorption of
methanol at platinum. Linear sweep voltammetry was applied at fixed wavenum-
ber, through a series of wavenumbers in order to establish a reflection adsorption
spectrum between 0.1 and 0.7 V (SHE). Quantitative data were obtained on the
dependence on potential of the integrated band intensity and the wave number for
maximum absorption. Methanol adsorption in 1 M H 2 S 0 4 has also been studied
by Beden et al.349 by infra-red spectroscopy. Their conclusions from preliminary
measurements are that the dominant adsorbed species existing at high coverage is
linear C r O . Some bridge-bonded C=O species is also present, particularly at
more negative potentials, but no spectroscopic evidence for COH species under
these experimental conditions was found. Beden and c o - ~ o r k e r salso ~ ~ ~ ~ ~ ~
explored the possibility of employing electrochemically modulated infra-red
reflectance spectroscopy (EMIRS) to the study of the C=O species which is
present at platinum electrodes through the electrosorption of formic acid. The
possibility of obtaining quantitative date from EMIRS was also examined.

Adsorption of Oxygen, Hydrogen, and Water.-A voltammetric study of oxygen

chemisorption on platinized platinum electrodes in acid solutions has been carried
out by Druz and N o ~ i k o v a They.~~~observed that both oxygen chemisorption
and electrode surface oxidation occurred simultaneously irrespective of the elec-
trode pretreatment. Specific adsorption of oxygen decreased with decreasing
temperature but the amount of charge required for the reduction of surface oxides
was temperature independent. An extension of this study to alkaline (NaOH)
media353 showed a similar decrease in adsorption with lowering of temperature
and also an increased affinity for oxygen in this solution.
A novel approach to the study of oxygen adsorption was adopted by Okamoto
et a1.354who observed the exchange current due to oxygen on platinum in a solid
electrolyte concentration cell. Oxygen partial pressures po2 ranged from 6 x 10' to
2 x lo4 Pa, at temperatures between 600 and 1000 K. It was found that i, is a
function of po2 with a maximum at a specific po2 which is dependent on
temperature. The slope of log i, versus log po2 plot for the high po2 region is
approximately 0.2, and for the low po2 region 0.2 to 0.6. The results are explained
in terms of an electrochemical reaction of oxygen dissociatively adsorbed on
platinum via a two-electron mechanism. On the basis of Langmuirs isotherm, the
heat of adsorption of oxygen on platinum is 180 kJ mol. -
347 M . P. Soriaga and A. T. Hubbard, J . Am. Chem. Soc., 1982, 104,2742.
K. Kunimatsu, J. Electroanal. Chem., 1982, 140,205.
349 B. Beden, C. Lamy, A. Bewick, and K. Kunimatsu, J . Electroanal. Chem., 1981, 121,343
350 B. Beden, A. Bewick, and C. Lamy, J. Electroanal. Chem., 1983,148, 147.
351 B. Beden, A. Bewick, and C. Lamy, J . Electroanal. Chem., 1983,150,505.
352 V. A. Druz and Z . N. Novikova, Zh. Fiz. Khim., 1980,54, 1818.
353 Z. N. Novikova and V. A. Druz, Zh. Fiz. Khim., 1980,542293.
354 M. Okamoto, G. Kawamura, and T. Kudo, Electrochim Acta, 1983,28,379.
 54 Elect rnchem i s q

The rotating ring-disc technique was used by Hsueh et to make a com-

parative study of the electrode kinetics of oxygen reduction at platinum in
perchloric, phosphoric, sulphuric, trifluoromethanesulphonic acids (all at pH 0)
and in potassium hydroxide (pH 14). Cyclic voltammetry showed that in the
potential region 0.8 to 0.6 V (SHE), the rate of oxygen reduction decreased in the
-
order KOH > H,SO, CF,SO,H > H,PO, > HCIO,. This order of reactivity is
related to the specific adsorption of anions from the different electrolytes, and their
effects on the platinum oxidation reaction. The higher rate of oxygen reduction in
KOH is due to minimal adsorption of the OH- ion.
A cyclic voltammetric study of oxygen electroreduction in 1 M NaOH solution
by Amadelli et al.3s6has shown that lead and thallium underpotential deposition
will enhance oxygen reduction. Both these ions have also been shown to offset the
inhibitive properties of cadmium and barium on oxygen reduction. A mechanism
for these processes is discussed.
~ ~ ~examined the effect of the adsorption of
Mateeva and c o - ~ o r k e r shave
H2S03 on the reduction of oxygen at platinum. H,SO, was found to inhibit
oxygen reduction at all potentials. However, the degree of inhibition, which is
dependent on the degree of H,SO, adsorption, is potential dependent with a maxi-
mum at 0.3 to 0.4 V. A kinetic model of the processes of potentiostatic reduction
of different forms of oxygen chemisorbed on a platinum electrode is presented by
Tyurin et together with I-Ecurves for three forms of chemisorbed oxygen.
A study of the adsorption behaviour of the platinum (100) surface in H,SO,
solutions has been presented by Clavilier and co-workers. 5 9 They employed
both low energy electron diffraction and atomic emission spectroscopy to charac-
terize electrodes which had been subjected to cyclic voltammetry in 0.5 M H,SO,.
Adsorption-desorption processes are discussed for both oxygen and hydrogen at
platinum.
Hydrogen evolutions on platinum is controlled by the combination reaction

Thus the rate of hydrogen evolution is greatly influenced by the surface coverage
of atomic hydrogen. Motoo and Okada360have carried out a systematic study of
the effects of metal deposition (Cu, Sn, Bi, and As) on the anodic and cathodic
polarization currents of the platinum-hydrogen system. The significance of the
geometrical relationship between the foreign ad-atoms and the platinum surface
was stressed in the interpretation. The effect of chemisorbed CO on hydrogen
evolution at platinum in 0.5 M H2S04 has been measured by B~eiter.,~'Cover-
ages by CO between 0 and 60% had little effect on the cathodic current density,
and mass transport processes were largely rate controlling. A rapid drop in current
occurs > 60% coverage with a transition from mass-transport to interfacial kinetic
control. This decrease was followcd by a slower decrease at coverages > 85%, due
to hydrogen evolution on top of the CO chemisorbed layer.
3ss K. L. Hsueh, E. R. Gonzalez, and S. Srinivasan, Electrochim. Actu, 1983,28,691.
35h K.Amadelli, J. A. Molla, and E. Yeager, J . Electroonol. Chem., 1981, 126, 265.
357 E. S. Mateeva, V . A. Shepelin, and E. V. Kasatkin, Elektrokhimiyu, 1981, 17,617.
3sR Y. M . Tyurin. G. F. Volodin, and Y. V. Battalova, Elektrokhirniyn, 1981,17,241.
35') J. Clavilier, R. Durand, G. Guinet, and R. Faure, J . Electroanul. Chrm., 1981, 127, 281
"" S. Moloo and T. Okada, J . Elwtroanal. Chem., 1983, 157. 139.
361 M. W. Breiter, J . Electrounal. Chem., 1980, 115,45.
Adsorption at Solid Electrodes 55
The effect on hydrogen adsorption at platinum electrodeposited onto different
substrates has been investigated by Lin-Cai and P l e t ~ h e r . ~They
~ ’ electro-
deposited platinum onto both vitreous carbon and gold from a K2PtC1,-H,S0,
bath. It was observed that deposits on carbon did not show characteristic hydro-
gen adsorption until quite thick layers of platinum were formed, while on gold
even thin deposits exhibited ‘normal’ behaviour. In addition, small platinum
centres on gold were found to be unusually active for the oxidation of formic acid
but those on carbon showed no activity. These results illustrate the necessity to
investigate fully the effects of the support matrix on precious metal catalytic
activity. Another comparative study on the electrolytic behaviour of thin platinum
films on glassy carbon was carried out by Rivera Garsias et a1.363Adsorption and
evolution of oxygen and hydrogen and the oxidation of formic acid on platinum at
glassy carbon electrodes in 0.5 M H,SO, were investigated. The results are
compared with those obtained on solid platinum.
The adsorption of water on platinum from DMSO solution has been investi-
gated by Wieckowski et ~ 1Tritium
. ~ ~ ~ was employed (so that the
radiolabelling
adsorbing species became HTO) and it was found that a maximum surface
concentration of 1.1 x 10’ mol cm-’ was achieved. This value was attributed
to a monolayer of the adsorbate. The adsorption was found to correspond to a
Temkin isotherm. No potential dependence of HTO adsorption was observed.
Chankashvili et ~ studied the kinetics and mechanism of water reduction
1 . ~ ~ ~ 9 ~ ~ ~

at a platinum electrode in DMSO solutions. The rate limiting step of the process
was shown to be the removal of adsorbed atomic hydrogen from the platinum sur-
face. A heterogeneous chemical step in which the adsorbed hydrogen reacts with
solvent molecules regenerating water complicates the overall process.

Me,SO+ 2H,,,-+Me2S+H20 (30)

An estimate of the heat of adsorption of the hydroperoxyl radical produced in
the two-electron reduction of oxygen is presented by H ~ a r eThis
. ~ is
~ given
~ as
- 69 kJ mol- for AGads.

Organic Adsorbates.-The adsorption processes occurring on the platinum elec-

trode (taken as an example of a transition metal displaying strong electrocatalytic
properties) have been classified, by W i e c k ~ w s k i into
, ~ ~ three
~ groups: (i) the sur-
face complexing processes with the participation of the adsorbate n-electrons and
the hybrid d-orbitals of the metal; (ii) the adsorption in the second ad-layer of the
platinum interfacial region, and (iii) the electrochemical reactions of the organic
molecules with the water molecules chemisorbed onto the platinum electrode. The
nature of the binding forces operating within each group has been qualitatively
described.
362 J. Lin-Cai and D. Pletcher, J . Electroanal. Chem., 1983, 149,237.
A. E. Rivera Garsias, V. M. Gryaznov, V. S. Kondrasheva, and A. M. Skundin, Elektrokhimiya,
1981, 17, 1069.
364 A. Wieckowski, M . Szklarczyk, and J. Soblowski, J . Electroanal. Chem., 1980, 113,79.
365 M . V. Chankashvili, 0. 0. Denisova, and T. R. Agladze, Soobshch. Akad. Nauk. Gruz. SSR., 1981,
102, 365.
366 M . V. Chankashvili, 0.0.Denisova, and T. R. Agladze, Elektrokhimiya, 1982,18,318.
367 J. P. Hoare,J. Electrochem. SOC.,1982,129, 1438.
368 A. Wieckowski, Electrochim. Acta, 1981, 26, 1121.
56 Elrctrochemistrj

Carbon monoxide is often considered as a model molecule for electrosorption

studies from electrolytic solutions. It is also often involved in electrochemical
systems as an intermediate in the electro-oxidation of higher organics as is
demonstrated in the i.r. and EMIRS studies by Beden et u1.349-351A preliminary
note outlines further investigation by Beden and c o - ~ o r k e ron s ~the
~ ~electrosorp-
tion of carbon monoxide from a saturated 0.5 M HClO, solution onto the (100)
{ 1 10) ( 1 1 1 faces and polycrystalline platinum electrodes. K ~ n i m a t s u ~has ~'
extended his study of the behaviour of the adsorbed CO species as a product of
methanol c h e m i ~ o r p t i o n ~over
~ ' a wider potential range between 0.3 and
1.3 V (SHE) by determining its i.r. spectra by in situ i.r. combined with fast linear
sweep voltammetry. The evolution of carbon dioxide was also observed as a func-
tion of potential by monitoring the intensity of the i.r. adsorption bonds due to
CO,.
The possible existence of different types of CO-adsorbed species on platinum
was demonstrated by Bilmes et who obtained current-potential profiles in
1 M HClO, CO (1 atm) saturated solution and N, (1 atm) saturated solution. The
experiments furnished clear evidence that CO can be oxidized in acid electrolyte on
polycrystalline platinum by different reactions which can be associated with the
multiplicity of the corresponding electrochemical spectra. The electrocatalytic
oxidation of CO, HCO,H, and MeOH on platinum (IOO}, (1 lo}, and { 11 1) single
crystals was compared by Lamy and c o - ~ o r k e r sThe . ~ ~similarity
~ of the behav-
iour of CO and MeOH on all three crystal planes led them to the conclusion that
the oxidation of both compounds involves CO-like intermediates. Formic acid
however was found to behave quite differently, particularly on the { 100) and { 11 1 )
faces, suggesting the involvement of different adsorbed intermediates.
The r61e of the surface and the bulk of the electrode in CO oxidation at platinum
has been investigated by Motoo et ~ 1A monolayer
. ~ ~ submonolayer
or ~ amount
of platinum was deposited on a gold substrate and then tin ad-atoms deposited on
the platinum-gold electrodes. The tin ad-atoms were found to enhance the kinetics
of CO oxidation on electrodes which had a complete monolayer of platinum in the
same way as they do on a bulk platinum electrode. Thus it was concluded that it is
the surface layer which is important in the electrocatalysis of CO oxidation. In an
extension of this study by the same authors374 arsenic was deposited on a
platinum clectrodc, and rather than the expected catalyst poisoning effect, CO
oxidation was found to be greatly enhanced. The 0 atoms adsorbed by arsenic
ad-atoms facilitate the oxidation by combining with CO molecules adsorbed by
platinum sites. It was also found that CO is the excess reactant and the number of
0 atoms is the limiting factor.
It has been noted by B r e i t e ~that
- ~ ~the
~ coverage of CO on platinized platinum
decreases only slightly during the reduction of oxygen in 0.5 M H,SO,. However
CO disappears within 500 seconds on smooth platinum at room temperature. The
,'"' B. Beden, S. Bilmes. C. Lamy, and J. M. Leger, J . Electroannl. C'hem.. 1983, 149, 295.
."(' K . Kunimatsu, J. Electroanal. Chem., 1983, 145,219.
."' S. A. Bilmes, N. R. de Tucconi, and A. J. Arvia, J . Electrochem. SOC.,1980, 127,2184.
372 C. Lamy, J. M . Leger, J . Clavilier, and R. Parsons, J . Electroanal. Chem., 1983, 150, 71
373 S. Motoo. M. Shibata, and M. Watanabe, J . Electroanal. Chem., 1980,110, 103.
374 S. Motoo and M . Watanabe, J . Electroanal. Chem., 1980, 111,261.
375 M. W. Breiter, J. Electroanal. Chem., 1981, 127, 157.
Adsorption at Solid Electrodes 57
removal rate differs so much because the total formation of H,O,, referred to the
real surface area, is considerably larger on the smooth electrode.
The adsorption of carbon dioxide on platinized platinum in solutions of
different pH has been investigated by Andreev et al.376using I4C labelled Na,CO,
providing CO, solution concentrations from lo-, to 2 x molar. Results are
presented as CO, coverage as a function of potential.
Methane adsorption and its oxidation on platinized platinum in 0.5 M H,SO,
was studied at 60 “C by Sustersic and c o - ~ o r k e r sTwo
. ~ ~ electrosorbed
~ species
were distinguished from I-E data. These species were assigned to be the COH-type
and CO-type. The latter could be transformed into the former by electrochemical
reduction at potentials where H ad-atoms are present. Horanyi and T o k k o ~ ~ ~ *
have examined the reduction of some halogenated derivatives of methane at
platinized platinum electrodes in acidic media. CH,Cl,, CHCl,, CCl,, and CHJ
were employed and the formation of methane was observed in the course of their
reduction. The shape of polarization curves was strongly dependent on the nature
of the carbon-halogen bond. A general scheme involving loosely and strongly
adsorbed species was proposed to explain the observed phenomena.
The electrosorption and the potentiodynamic oxidation of ethylene on platinum
in 0.5 M H,SO, in the range 20-80 “C has been studied by Solis et a1.379The
ethylene was allowed to adsorb potentiostatically and then an I-E profile recorded
immediately. These profiles show that three different species participated in the
electro-oxidation process. The total process is discussed with reference to a
complex reaction pathway involving electrosorption, interconversion, and
electro-oxidation.
Hubbard and c o - w ~ r k e r have
s ~ ~ examined
~ the electrocatalytic hydrogenation
of ethylene at the { 100){111) faces and polycrystalline platinum in both conven-
tional and thin-layer cells in aqueous solution. It was noted that a strongly
adsorbed hydrocarbon layer formed spontaneously when clean platinum was
exposed to the solution. Reduction of the adsorbed material as well as of ethylene
from solution was found to be independent of crystallographic orientation. Two
pathways for reduction are suggested and discussed. The electrocatalysis of
ethylene reduction by ad-atoms is discussed by Motoo and F ~ r m y a , ~ *they l
introduce the concepts of ‘catalytic domains’ and ‘reaction unit mesh’ in order to
present a complete understanding of the function of a mixed surface (adsorbate
and ad-atom) in electrocatalysis.
Propylene adsorption at a smooth platinum electrode between 0 and 3 V in
0.5 M H,SO, was studied by Sargisyan et ~ 1 . ~through ~ ’ the application of fast
potential pulses. Propylene was found to be adsorbed on the surface of the
oxidized platinum at about 2.2V, and could be used as an acceptor of
electrogenerated radicals.
The kinetic parameters and the mechanism of the hydrogenation of
376 V. N. Andreev, Yu. B. Vasil’ev, N. V. Osetrova, and T. N. Yastrebova, Ekktrokhimiya, 1983,19,381.
377 M. G. Sustersic, R. Cordova, W. E. Triaca, and A. J. Arvia, J . Electrochem. Soc., 1980,127, 1242.
378 G. Horanyi and K. Tokkos, J . Electroanal. Chem., 1982,140,329.
379 V. Solis, A. C. Luna, W. E. Triaca, and A. J. Arvia, J . Electrochem. Soc., 1981, 128, 21 15.
A. T. Hubbard, M. A. Young, and J. A. Schoeffel, J . Electroanal. Chem., 1980,114,273.
381 S. Motoo and N. Furmya, J . Electroanal. Chem., 1982,139, 105.
382 S. A. Sargisyan, 0. A. Khazova, and Yu. V. Vasil’ev, Elektrokhimiya, 1981,17,443.
58 Electrochemistrji

buta-1,3-diene on platinum in aqueous acid are presented by Kita and

S h i m a ~ uTwo
. ~ ~intermediates
~ are postulated to be involved in the reduction,
producing but- 1-ene + cis-but-2-ene and trans-but-2-ene respectively; butane was
produced mainly via a but-1-ene intermediate. Platinum on carbon produced a
reaction rate 10-fold higher that on platinum alone, whilst the rate on Pt-TiO, was

-
one-tenth as f a t as that on platinum. Kubota and Kita384 have found that
platinized platinum in EDTA is extremely selective ( 93%) for the partial hydro-
genation of buta-l,3-diene, giving the same thrcc isomeric butenes as found by
Kita and S h i m u z ~ the
~ * ratios
~ being 13.2:2.5:1 respectively. This high selectivity
is suggested to be due to a specific adsorption of EDTA onto the electrode giving
rise to the replacement of the adsorbed butenes formed from buta-l,3-diene. The
same authors385 have examined the partial hydrogenation of buta- 1,3-diene in
aqueous alkaline solutions. Deuterium exchange has revealed the predominant
successive additions of hydrogen atoms. In addition, n.m.r. spectra show the form-
ation of but-1-ene and trans-but-2-ene and hence exclusive 1,2 and 1,4 addition.
These results are compared with those obtained in 0.5 M H 2 S 0 4 and a mechanism
is discussed.
The adsorption and oxidation of acetylene on platinized platinum in
0.5 M H,S04 between 16 and 80 "C has been studied by Delgado et ~71.~"The
kinetic parameters obtained under potentiodynamic conditions suggest that the
electro-oxidation of adsorbed acetylene proceeds through a reaction pathway
involving a slow initial monoelectronic transfer step.
The oxidation of aliphatic alcohols on platinum was noted, by Kokkinidis and
Jannakovdakis,38 to be markedly catalysed by foreign metal ad-atoms deposited
in the underpotential range. In the case of methanol, the catalytic effect was more
pronounced in basic media. In acidic media the catalytic activity was dependent on
the length of the carbon chain and the number of hydroxy-groups. On bare
platinum the formation and strong adsorption of organic intermediates resulted in
the blocking of the surface active sites. This enhancement of the oxidation process
by underpotential submonolayers has been interpreted in terms of the prevention
of electrode poisoning by products. Raicheva et d . 3 8have
8 investigated the effects
of temperature on the electrochemical behaviour of aliphatic alcohols by potential
sweep methods in the temperature range 15-60 "C. No changes in the mechanism
of electro-oxidation of primary alcohols were observed. In the 1-E curves for
secondary alcohols a new maximum was observed at -0.9V at higher
temperatures. This is probably connected with the oxidation of products of the
destructive chemisorption in the double layer region. The mechanism of electro-
oxidation of tertiary alcohols was found to differ considerably from that of thc two
other types of alcohols; this is attributed to the lack of hydrogen atoms at the
a-carbon atom.
The effect of the method of surface preparation of a platinized platinum

JR3 H. Kita and K . Shimazu, Sfud.Sucp Sci. Cutal., 1981,7, 1480.

3x4 N . Kubota a n d H. Kita, Electrochim. Acta, 1982,28, 861.
"' N. Kuboca. T. Masui, and H. Kita, Electrochim. Acta, 1983.28. 1663.
3Xh A. R. Delgado, A. M. Castro Luna, W. E. Triaca, and A. J. Arvia, J . Electrochem. Sor., 1982. 129,
1493.
3H1 G. Kokkinidis and D. Jannakoudakis, J . Electround. Chern., 1983, 153, 185.
38H S. N . Raicheva. M . V. Christov, a n d E. I. Sokolova, Electrochint. Acta, 1981,26, 1669.
Adsorption at Solid Electrodes 59
electrode on the composition of methanol adsorption products has been studied
by Ventskovskii and c o - w o r k e r ~ .A~ ~chronovoltammetric
~ investigation in
0.5 M H,SO, containing 10 mM methanol led to the conclusions that adsorption
was mainly dependent on the roughness factor. The concentration of chemisorbed
oxidation products was found to increase with ageing of the electrodes. Petrii
et ~ 2 1 . ~ examined
~' the effect of heat treatment at 100-450"C in a hydrogen
atmosphere on the adsorptive characteristics of platinized platinum. The electro-
oxidation of methanol, in 0.5 M H 2 S 0 , 4 . 5 M methanol solutions, was found to
decrease for thermal treatments above 300 "C.
Lamy and others391have carried out a cyclo-voltammetric study on the electro-
catalytic oxidation of methanol in 0.1 M NaOH on the platinum single planes
{ loo){ 1 lo> and { 11 1>.The formation and redissolution of hydrogen and oxygen
layers at the electrode surface are also considered.
Methanol electrosorption and residue electro-oxidation was studied by Leiva
and G i ~ r d a n on o ~platinum
~~ electrodes by means of potentiodynamic profiles.
The results obtained point to CO adsorbed on two sites as the main stable inter-
mediate after methanol adsorption. Current peaks for both electrosorption and
oxidation processes show the splitting into two components that strongly depend
on electrode pretreatment and ionic composition of the base electrolyte. An
explanation of this behaviour is attempted in terms of two different surface states
for the same intermediate. The effect of chemisorbed methanol on the reduction of
ally1 (prop-2-enol) and crotyl (but-2-en- 1-01) alcohols and alloxan was studied in
acidic media on platinized platinum electrodes by Horanyi and T ~ r k o s . The ,~~
composition of the reduction products was found to change significantly due to
the blocking effect of methanol.
The effect of adsorbed chloride ions on the electro-oxidation of ethanol at a
platinum electrode in 0.5MH,S04 at 25°C has been observed by Snell and
K e e n a ~ ~ ' Cyclic
, voltammograms exhibited three anodic waves, one of which
was unusual in that it occurred during the cathodic going potential sweep. The
data indicated that adsorbed species are involved in all three waves. The cathodic
going potential sweep wave is accounted for by the electro-oxidation of ethanol,,,
on a surface free of oxide and chemisorbed species. The same have
extended this study to electrolytes containing HNO,, HCIO,, NaNO,, NaClO,,
NaN0,-Na2S0,, and NaClO,-Na,SO, at 25 "C. The results show that the
anions and pH influence the peak current and potential for all three anodic waves.
The anion effect being more pronounced in acid than neutral solutions.
Ethylene glycol electro-oxidation at platinized platinum electrodes has been
investigated by S i d h e ~ w a r a using
n ~ ~ ~the charging curves technique. The nature of
the chemisorbed layer formed, its electrochemical behaviour, its desorption

jS9 A. Ventskovskii, V. N. Andreev, R. Zelenai, E. Sobkovskii, and V. E. Kazarinov, Elektrokhimiya,

1980, 16, 668.
3y0 0.A. Petrii, A. V. Ushmaev, and I. L. Golichadze, Elektrokhimiya, 1980,16,891.
391 C . Lamy, J. M. Leger, and J. Clavilier, J. Electroonal. Chem., 1982, 135, 321.
392 E. P. M. Leiva and M. C . Giordano. J. Electroanal. Chem., 1983,158, 1 1 5.
393 G . Horanyi and K . Torkos, .I. Electroonal. Chem., 1980, 111, 279.
3y4 K . D. Snell and A. G . Keenan, Electrochim. Acta, 1981,26, 1339.
39s K. D. Snell and A. G Keenan, Elertrochim. Arta, 1982,27, 1683.
396 P. Sidheswaran, Indian J . Chem., 1981, 20A, 570.
60 Elect rochem istrj
pattern and the plausible reaction mechanisms are discussed. The data or
methanol and ethanol films are compared.
Kazarinov et ~ 7 1 have . ~ discussed
~ ~ the adsorption behaviour of ethylene glyco
and its derivatives. Results obtained by different methods (electrochemical and
radiotracer) are compared. Factors influencing the nature and composition 01
adsorbed species are analysed. The behaviour of ethane, ethanol, and ethylene
glycol are compared and general schemes for the processes occurring with the
adsorbed species formed from these compounds are proposed. A further publica-
tion398 presents a reaction sequence leading to different intermediates in
the course of the oxidation of ethylene glycol. Results from adsorption and
steady-state electrocatalytic studies are compared in an attempt to explain
the action of different types of adsorbed species in the electrocatalytic
transformations.
The influence of metal ad-atoms deposited at underpotentials on the oxidation
of ethylene glycol on platinum in acid solution has been studied by Kokkinidis and
J a n n a k ~ u d a k i sPronounced
.~~~ catalytic enhancement by submonolayers of Pb,
T1, and Bi was observed. This was interpreted in terms of decreasing electrode
poisoning by strongly adsorbed intermediates. Similar studies have been carried
out by Kardirgan et af.400,401 where the effect of Cd, Re, Pb, Cu, Bi, TI, and Ru
ad-atoms on the oxidation of ethylene glycol on platinum was observed in both
acid and alkaline media. A qualitative explanation is suggested, based on the
modification (due to ad-atoms) of the coverage of the electrode surface by both
organic adsorption residue and adsorbed hydroxyl.
Sidheswaran402 has noted the existence of an elevated potential plateau for the
oxidation of ethylene glycol films on sintered platinum electrodes. This oxidation
potential was found to be a linear function of the roughness factor of the electrode.
A mechanism of electrochemical oxidation of formaldehyde is presented by
Kuliev et af.403along with a discussion of the possibility of its catalytic decompo-
sition on platinum electrodes. Surface oxides of platinum were noted to take part
in the slow stage of oxidation occurring at anodic overpotentials. Andreev er
n1.404,405 ha ve noted the existence of two types of chemisorbed particles on
platinized platinum during formaldehyde decomposition. The particle types are
dependent on adsorption potential; COH at 0.1-0.2 V and CO, further converted
to COH and COOH at 0 . 4 V (SCE). Further investigations on the influence of
adsorption potential by the same authors406have utilized radioisotopic methods
in conjunction with electrochemical studies.

'" V. E. Kamrinov, Yu. B. Vassiliev, V. N. Andreev. and G. Horanyi, J . Electroanal. Chrm., 1983. 147.
247.
-'" G. Horanyi. V. E. Kazarinov, Yu. B. Vassiliev. and V . N . Andreev. J . Electroanul. Chem., 1983, 147,
263.
.''' G. Kokkinidis a n d D. Jannakoudakis, J. Elec.troanu1.Chrm., 1982, 133, 307.
boo
F. Kardirgan, B. Beden, and C . Lamy, J . Elertroanul. Chem., 1982,136, 1 19.
'O'
F. Kardirgan, B. Beden, and C . Lamy, J . Elrr,troannl. Chem., 1983, 143, 135.
402 P. Sidheswaran, Indian J . Chem., 1981, 20A, 1075.
4"3 S. A. Kuliev, N. V. Osetrova, V. S . Bagotskii, and Yu. B. Vasil'ev, Elektrokhimija, 1980, 16, 1091.
'04 V. N. Andreev and S. A. Kuliev, Elektrokhimiya, 1980, 16, 1451.
'n5 V. N. Andreev, S. A. Kuliev, Yu. B. Vasil'ev, and V. E. Kazarinov, Elektrokhimiya, 1981, 17,205.
"' V. E. Kazarinov, Yu. B. Vassiliev, V. N. Andreev, a n d S. A. Kuliev, J. Electroanal. Ctzem.. 1981, 123.
345.
 Adsorption at Solid Electrodes 61
The use of underpotentially deposited metal atoms as catalytic agents is becom-
ing increasingly investigated because of their promise of enhancement of the rate
for the oxidation of organic fuels. The catalysis of the oxidation of formaldehyde
on platinum by ad-atoms of Pb, Bi, and T1 deposited in the underpotential region
has been examined by Spasojevic et The effect of these ad-atoms was
explained by a prevention of the formation of strongly bound intermediate COH,
through a suppression of hydrogen adsorption on platinum. The smaller effects of
copper ad-atoms were ascribed to their lower adsorbability. A similar study by
Motoo and Shibata,,'* on formaldehyde oxidation, has led to the classification of
ad-atoms into two groups according to their way of affecting the electrode reac-
tion: one consists of Cu, Ag, T1, Hg, Pb, As, Bi, Te, and Se, the other of Ge, Sn,
and Sb. The enhancing effect of the former group was found to depend on the
number of platinum sites occupied by an ad-atom of each species, which suggests
that geometrical control of platinum site arrangement plays an important r61e in
the enhancement. The latter group adsorb oxygen atoms which have some indirect
effect on enhancement. The enhancement of reaction by the latter group is far
greater than the former and is suggested to be via a new rapid parallel path that has
not yet been identified. Adzic and c o - ~ o r k e r s ~have
' ~ studied both formic acid
and methanol oxidation enhancement by ad-atom modified platinum electrodes in
85% H3P04. The rates of reaction were found to be greatly increased. Due to the
adsorption of phosphate ions, formic acid oxidation rates were much lower than
those obtained in HClO,. The order of electrocatalytic activity for methanol was
found to be Pb > Bi > T1. It is proposed that the enhancement reaction rates are
due to the inhibition of hydrogen adsorption and hence of the formation of
poisoning intermediates such as COH.
Potential step experiments on the oxidation of formic acid in aqueous HClO, at
a platinum electrode covered with submonolayer amounts of lead have been car-
ried out by Pletcher and S01is.~'' They confirm the activity of lead as an effective
catalyst, allowing high rates of oxidation over a long period of time. It was noted
that at low formic acid concentrations ( < 1 mM) the rate of oxidation could be dif-
fusion controlled. At higher concentrations (10-500 mM) the rate was found to
be kinetically controlled at short times but at longer times diffusion predominated.
The rate determining step at short times is suggested to be dissociative adsorption
of formic acid at two platinum atoms adjacent to a lead ad-atom. The catalytic
mechanism is discussed. Potential step techniques were again used in a similar
study of platinum surfaces partially covered by Bi, Cd, Pb, and T1 in 1 M HClO,
and in 1 M ClO, of pH 0, 1, and 2 at platinum-lead electrodes, by Fonseca et
~ 2 1 . ~It~ was
' found to be possible to define two time regimes for all these systems.
At short times the current was partly kinetically limited; the rate determining step
being a chemical reaction, probably the cleavage of the C--H bond to give an
adsorbed hydrogen atom and adsorbed organic fragment. At long times, the cur-
rent was almost diffusion controlled. The duration of each time regime was found
to vary with the ad-atom and the solution pH. It is suggested that these parameters
'O' M . D. Spasojevic, R. R. Adzic, and A. R. Despic, J . Electroanal. Chem., 1980, 109,261.
31'' S. Motoo and M . Shibata, J . Electroanal. Chem., 1982,139, 119.
409 R. R. Adzic, W. E. O'Grady, and S. Srinivasan, J . Electrochem. SOC., 198 1,128, 191 3.
410 D . Pletcher and V. Solis, J . Electroanal. Chem., 1982,131,309.
'"I. Fonseca, J. Lin-Cai, and D. Pletcher, J. Electrochem. SOC.,1983, 130,2187.
 62 Elec tr ochem ist r j

determine the rate constant for the chemical step and that in potential sweep
experiments they, in conjunction with the variation of ad-atom coverages, with
potential, lead to apparently different ‘catalytic activities’ and interpretive
discrepancies.
Studies of the adsorption of acetic acid on to platinum from aqueous electro-
lytes by Wieckowski et al.,12 show that in the polarizable potential range the
undissociated acetic acid molecule is adsorbed, and that the process is reversible,
occurring in the second ad-layer of the interfacial region. In the hydrogen region,
the reductive chemisorption of acetic acid was observed. Stenin413has also investi-
gated acetic acid adsorption on platinum by both electrochemical and radio-
isotopic methods. He proposes that the main product of adsorption is either an
anionic type of particle CH3C0, or the acetic acid molecule itself.
The adsorption of propionic acid on a platinized platinum electrode in
1 M HClO, solution was studied, by Horanyi and Rizmayer414 using 14Cand 34Cl
radiolabelling. From their data they conclude that the process of propionic acid
adsorption is reversible.
The adsorption of oxalic acid on a platinum electrode in 0.5 M H,SO, over the
potential range 0 - 3 V was studied by Sargisyan and V a ~ i l ’ e v The .~~~ species
which were adsorbed at different potentials were noticed to behave differently. The
oxalic acid reacted with adsorbed oxygen, and was completely oxidized to CO,.
Inzelt and Szetey416 have also examined oxalic acid oxidation as a function of
potential, temperature, oxalic acid concentration, and pH. Oxalic acid was
observed to be reversibly adsorbed under Temkin isotherm conditions. An
equilibrium between the surface and solution was noted with respect to the OH
radical. The rate determining step was established as the reaction of adsorbed
oxalic acid with adsorbed OH radical.
A cyclic voltammetric study has been used by Lamy et for the charac-
terization of platinized platinum catalysts poisoned by copper. The technique
yielded information which established the degree of coverage by copper and its
corresponding toxicity. Toxicity results obtained for the catalytic hydrogenation
of maleic acid are presented and discussed in relation to the structure of the active
centres. A further publication by the same authors418establishes the fact that each
copper atom deactivates five accessible atoms of platinum.
The adsorption of 14C labelled malonic acid was followed in HC10,-supporting
electrolyte on platinized platinum by HorAnyi and Rizmayer.,19 No strong
chemisorption of malonic acid was observed.
Pctrii et used conductivity measurements and steady-state polarization to
study the adsorption of trifluoroacetic and trifluoromethanesulphonic acids and
their effect on the adsorption of hydrogen and oxygen. Methanesulphonic acid,
ethanesulphonic acid, and sulphoacetic acid have been investigated as fuel cell
412 A. Wieckowski, J. Sobkowski, P. Zelenay, and K. Franaszczuk, Elrctrochim. Arta, 1981.26, 1 1 1 1
413 V . F. Stenin, Ekktrokhimiyu, 1981, 19, 120.
414 G . Horanyi and E. M. Rizmayer, J. Eleclrounal. Chem., 1980. 112,373.
415 S. A. Sargisyan and Yu. B. Vasil’ev, Elektrokhimiya, 1981, 17, 1495.
4Lb G. Inzelt and E. Szetey, Acta Chim. Acad. Sci. Hung., 1981, 107, 269.
417 E. Lamy, J. Rarbier, and C. Lamy, J. Chim. Phys. Phys. Chim. Biol., 1980,77,967.
‘18 E. Lamy and J. Barbier, Electrochim. Acta, 1982,27,7 13.
419 G. Horlinyi and E. M . Rizmayer, J. Electroanal. Chem., 1981,125,219.
42” 0 .A. Petrii. S. Yu. Vasina, and L. Yu. Luk’yanycheva, Elektrokhimiya, 1981. 17, 1383.
Adsorption at Solid Electrodes 63
electrolytes by Ahmad et and rates of electro-oxidation of hydrogen and
propane were evaluated in their presence. It was noted that sulphonic acids con-
taining unprotected C-H bonds are adsorbed onto platinum and decomposed
during electrolysis.
The adsorption of acetone on a platinum electrode from aqueous acidic solu-
tions was investigated by a radiotracer technique and cyclic voltammetry by
Wieckowski et al.422A n-electron complex between platinum and acetone was
followed by a surface polymerization, the length of the chain being dependent on
the bulk concentration of the acetone. The exchange of hydrogen between the
adsorbed acetone and the acidic electrolyte was observed.
Horanyi and R i ~ m a y e rhave ~ ~ ~studied the adsorption and reactivity of
acetonitrile in 1 M H,SO, on a platinized platinum electrode by radiotracer and
polarization methods. Acetonitrile was found to be reduced primarily to acetalde-
hyde through acetimine in the potential range 0-200 mV (SHE). Under certain
conditions ethane was seen to be produced from acetaldehyde. The adsorption of
acetonitrile was measured indirectly by investigating the adsorption of labelled
C1- ions. The acetonitrile was found to undergo two types of adsorptive process
leading to some reversibility and desorption and some total irreversibility.
Szklarczyk and S o b o ~ s kare i ~ in
~ agreement
~ with this work and note that both
ethane and ammonia can be the final reduction products on platinum.
Dimethylformamide (DMF) adsorption at platinum from 0.5 M H,SO, was
observed by the same It was noted that adsorption of D M F was
accompanied by decomposition and that these decomposition products were
desorbed at < 0.1 5 V. A Langmuir adsorption isotherm describes the processes.
The adsorption of glucose on a platinum electrode in 0 . 5 M H 2 S 0 , was
observed, by Nikolaeva’et al.,426to exhibit a maximum at 0.2 V. At more anodic
potentials, adsorption decreased due to the oxidation of the chemisorbed particles.
At more cathodic potentials there occurred competition between hydrogen and
glucose. In 1 M KOH the adsorption maximum was noted to be at 0.5 V.
De Mele and c o - ~ o r k e r have
s ~ ~ observed
~ that the I-E response of glucose on
platinum in the range 0.6-1.0 V (SCE) depends on the perturbation conditions,
the electrolyte composition and the presence of carbon dioxide. Further, from
potentiostatic current transients they suggest that due to interaction between
electroadsorbed species and hydrogen ad-atoms, a far more complex pattern of
reaction exists than has previously been suggested.
Catalysis of oxidation at platinum by adsorbed metals has been applied to glu-
cose in 1 M HClO, by Sakamoto and T a k a m ~ r a . , ~They
* found that adsorbed
metals, bismuth and lead (Mads),formed in the underpotential region led to an
increase in the oxidation current of glucose by about an order of magnitude. The
catalytic activity is dependent on the surface coverage by (Mads).The effects of
Mads were discussed in terms of its removal of adsorbed hydrogen from the
421 J. Ahmad, T. H. Nguyen, and R. T. Foley, J . Electrochem. Soc., 1981,128,2257.
*” A. Wieckowski, P. Zelenay, M . Szlarczyk, and J. Sobkowski, J. Electroanal. Chem., 1982,135,285.
423 G . Horanyi and E. M. Rizmayer, Acta Chim. Acad. Sci. Hung., 1981,106,335.
424 M. Szklarczyk and J. Sobowski, Electrochim. Acta, 1980,25, 1597.
425 M. Szklarczyk and J. Sobowski, Electrochim. Acta, 1981,26, 345.
426 N. N. Nikolaeva, 0.A. Khazova, and Yu. B. Vasil’ev, Elektrokhimiya, 1980,16, 1227.
427 M,F. L. de Mele, H. A. Videla, and A. J. Arvia, J . Electrochem. Soc., 1982, 129,2207.
428 M. Sakamoto and K. Takamura, Bioelectrochem. Bioenerg., 1982,9,571.
64 Electrochem ist rJ1

platinum surface, thus suppressing the production of poisoning lactone-type

species.
The behaviour of physiological amino-acids at platinum electrodes in glucose-
containing Krebs-Ringer solution was studied by Giner et The degree of
amino-acid electro-oxidation and the inhibition of glucose oxidation were found
to be closely related to a parameter representing the strength of adsorption of the
amino-acid. This parameter, in turn, is a function of the intrinsic adsorbability of
the amino-acid and its concentration. Basic and sulphur-containing amino-acids
were found to be the most inhibiting. Certain mixtures of amino-acids were found
totally to inhibit glucose oxidation.
Horanyi et a/.430 have shown that it is possible to obtain the adsorption
parameters of organic species by an indirect method of adsorption of radiolabelled
chloride (3hCl).Maleic, benzoic, and rn-nitrobenzoic acids have been studied and
their adsorption behaviour and electroreduction properties detected.
The electrochemical oxidation of adsorbed aromatic molecules as a function of
orientation on the platinum surface has been studied by Soriaga and co-
w o r k e r ~ . Twenty-nine
~~ compounds, with a variety of structures and chemical
properties have been studied. The number of electrons per molecule transferred in
oxidation was found to be strongly dependent on initial orientation, being smaller
for edgewise than for flat orientations.
The reaction mechanism for the hydrogenation of phenols to produce cyclohex-
anols in aqueous acid was investigated by Sasaki et al.432and was concluded to be
the surface reaction between adsorbed phenols and hydrogen.. Studies on the sub-
stituent effect showed that the hydrogenation is most favoured for unsubstituted
phenol.
The electrodeposition and anodic dissolution of electrochromic films of
heptylviologen perchlorate and the redox system of methylviologen decation-
cation radical in aqueous solutions have been studied by Ushakov et The
adsorbed species were products of simple irreversible chemisorption.
The adsorption of 8.5 to 500mM dimethylamineborane and its oxidation on
platinum electrodes has been investigated by Sazonova et al.434In the hydrogen
evolution potential range neither oxidation nor reduction of adsorbed
dimethylamineborane occurred. Adsorption was noted to involve Pt-C bonding,
and maximum adsorption was observed with 68 mM solutions.

Inorganic Adsorbates.-The electrode kinetics and the mechanism of the Br - /Br2

couple on platinum electrodes has been investigated, by R ~ b i n s t e i n , ~using
~’ a
coulostatic method. The kinetic parameters were calculated from the overpotential
decay curves taking into account partial mass-transport control for a multistep
process. The results were interpreted in terms of the combined adsorption iso-
therm, which is dependent on the size of the adsorbed intermediate. The r.d.s. was
429 J. Giner, L Marinicic, J. S. Soeldner, and C. K. Colton, J. Electrochern. Soc., 1981, 128, 2106.
430 G. Horanyi, V. E. Kazarinov, and V. N. Andreev, J . Eleclroanal. Chem., 1982,133,333.
431 M. P. Soriaga, J. L. Stickney, and A. T. Hubbard, J . Electrounal. Chem., 1983, 144,207.
432 K. Sasaki, 4.Kunai, J. Harada, and S. Nakabori, Electrochim. Acta, 1983,28,671.
433 0.A . Ushakov, B. I . Podlovchenko, Yu. M . Muksimov, and I. V. Shelepin, Elektrokhimiya, 1981. 17.
225.
4’4 S. V . Sazonova, K. M. Gorbunova, and M. V. Ivanov, Elrktrokhimiyu, 1981.17, 1865.
435 1. Rubinstein, J . Phys. Chem., 1981,85, 1899.
Adsorption at Solid Electrodes 65

found to be charge transfer from a Br- ion to form an adsorbed Br atom. On an

oxide-covered platinum electrode this ion is discharged from solution whilst on an
oxide-free surface the ion is adsorbed on the surface. The adsorption of bromine
onto platinized platinum from 0.1, 1 .O, and 3.0 M HBr solutions was studied by
Matveiko et The concentration of Br- had no effect on the amount of
adsorbed bromine, although this did increase with increasing concentration of Br,
in solution.
The reduction of chlorine at a platinum electrode was studied by a rotating disc
method by Miiller and Kaiser.437A change in mechanism for chlorine reduction
with a decrease in chlorine concentration was observed. If the chlorine pressure is
less than 0.1 atm the fast chemisorption of chlorine
c1, +2Cla,,
is replaced by the slow electrochemical adsorption
+C1-
C1, + e - -+Clads (32)
Flisskii and S h l y a p n i k ~ v ~ ~ ' investigated the oxidation of chloride ions on
have
platinum in H,SO, solutions at high anodic potentials. Oxidation of C1, to HClO,
started above 2.6 V. The Tafel slope of the voltammetric curves above 3.0 V was
near 300mV. At potentials above 2.6V two surface layers were formed on the
electrode, the first being composed of platinum oxides and strongly adsorbed
radical-anions from H2S04, the second being made up on compounds containing
C1 and 0.
Conway and Novak439,440have studied the effects of strongly adsorbed halide
ions on the various stages of surface oxidation of platinum anodes in aqueous
H,SO, and HClO, over a wide concentration range. A micrometer titration pro-
cedure was adopted to obtain data points for the competitive adsorption isotherms
for halide ion blockage of electrodeposition of OH and 0 species at platinum. It is
shown that adsorbed I - and Br- in the oxide film lose most of their charge but
C1- remains ionic and thus has much stronger interactions between itself and
electrodeposited OH and 0 species in the developing oxide layer. A method for
quantitatively treating the competitive adsorption, giving information on lateral
interaction effects in the surface oxide film with co-adsorbed halide ions is given in
terms of a differentiated adsorption isotherm function. An extension of this study
by the same discusses the above effects in terms of the tendency of
adsorbed C1- ion to promote place-exchange reconstruction of the OH/O
monolayer on platinum.
The mechanism of the processes occurring at high anodic potentials on
platinum in HC10, aqueous electrolyte has been studied, by Nikolic et al.,442by
the RRDE method. The evolution of oxygen from water was inhibited by the
adsorption of ClO-, at the inner ring. At high anodic potentials, the reaction of
436 N . P. Matveiko, G. I. Novikov, I. M . Zharskii, and A. U. Karizno, Vestsi Akad. Navuk B. SSR, Ser.
Fiz-Energ. Navuk, 1980,2,48.
'"L. Miiller and B. Kaiser, Z . Phys. Chem. (Leipzig), 1980,261, 1011 .
438 M . M . Flisskii and V. A. Shlyapnikov, Elektrokhimiya, 1980,16, 1851.
*39 B. E. Conway and D. M. Novak, Croat. Chem. Acfa, 1980,53, 183.
440 B. E. Conway and D. M . Novak, J . Chem. SOC., Faraday Trans. I , 1982,77,2341.
441 €3. E. Conway and D. M. Novak, J. Chem. Soc., Faraday Trans. I , 1982,78,1717.
442 B. Z. Nikolic, A. R. Despic, and R. R. Adzic, Glas. Hem. Drus. Beograd, 1980,45,9.
adsorbed ClO, gives Cl,O,, ClO,, and HC10, that are detected at the outer ring
The same workers have again employed the RRDE technique to examine alkaline
NaClO, solutions.443 Adsorption of C10, - resulted in the inhibition of oxygen
evolution greater than that produced by C10,-. Hydrogen peroxide was observed
in solution indicating that it can be desorbed prior to its further reaction to
produce oxygen from water.
The electrochemical characteristics of the Cu"/Cu' and the Cu'/Cuo couples at
platinum have been studied in aqueous acetonitrile mixtures by Macleod et
A slow chemical step precedes the oxidation of Cu' to Cu" in electrolytes of high
acetonitrile content. The slow step may be partial removal of acetonitrile from the
solvated Cu' ion prior to electron transfer. Reduction of Cu' is influenced by the
adsorption of acetonitrile onto the platinum.
A linear sweep voltammetric study of the electrochemisorption of Pb2+ on a
platinized platinum electrode in a 1 M HClO, aqueous solution by Ogura and
N a k a n ~ ,showed
~~ that the equilibrium of the process obeyed Temkins' isotherm.
The surfacc covcragc of Pb2 on platinum was calculated.
+

Elcctroreflectance measurements on platinum electrodes in 1 M HClO, contain-

ing 1 mM Pb2+ enabled Takamura et ~ 1 1 to. observe ~ ~ ~ the formation of a lead
submonolayer subsequent to the adsorption of Pb2 at potentials more positive
+

than the Pb2+/Pbcouple. Other work by the same has used the optical
properties of foreign metal submonolayers formed on platinum and other
substrates as underpotentials to characterize a number of adsorbate-substrate
systems. The results allowed the workers to draw tentative conclusions about the
origin of specular reflectance changes due to the presence of a metal ad-layer on
the electrode surface.
Byallozov and L i ~ a v s k ahave
~ ~ ~proposed a mechanism for the cathodic
reduction of TiCl, in DMF from voltammetric and chronopotentiometric
investigations. The reactions:
(33)
and (34)
are proposed. The rate of reduction increased with decreasing TiC1, content in the
solvent. The authors discuss the inhibiting effect of reaction products which are
strongly adsorbed on the electrode surface.
The adsorption of ammonia on platinum was studied, using voltammetric
techniques, by Chernousova and c o - w o r k e r ~ The .~~~adsorption mechanism is
discussed.
The electrocatalytic reduction of nitric acid has been studied at platinized
platinum electrodes in the presence of different supporting electrolytes by Horanyi
and R i ~ m a y e r . ~At~ 'low nitric acid concentrations the polarization behaviour,
''j R . Z . Nikolic, A. R. Despic, and R. R. Adzic, Glus. Hem. Drus. Beograd, 1980,45, 185.
434 1. D. MacLeod, A. J . Parker, and P. Singh, J . Solution Chrm., 1981, 10,757.
H. Ogura and A. Nakano, Suzuka Kogyo Koto Seminon Gnkko K i j o , 1980,13, I 1 1.
446 K . Takamura, F. Kusu, and T. Takamura, Denki Kagaku, 1981,49,562.
447 K. Takamura, F. Watanabe, and T. Takamura, Electrochiin. Actu, 1981,26,979.
448 S. G. Byallozov and A. Lisovska, Elektrokhimiya, 1981, 17,494.
44L) N. I. Chernousova, G. I. Elfimova, and G. A. Bogdanovskii. Zh. Fiz. Khim., 1980,54.2939
G. Horanyi and E. M. Rizmayer, J . Electroanal. Chem., 1982, 140, 347.
Adsorption at Solid Electrodes 67

the shape of the polarization curves, and the reduction rates were found to depend
significantly on the supporting electrolyte. With increasing nitric acid concen-
trations the differences in the character of the polarization curves gradually disap-
peared. Galvanostatic potential oscillations and potentiostatic current oscillations
were observed by the same during the course of the reduction of nitric
acid at a platinum electrode in the presence of chloride ions. The influence of
concentration, current, and potential on the oscillating behaviour were studied
and an explanation of the phenomena was proposed.
The influence of electrosorption of heavy metals in the underpotential region on
hydrazine oxidation on platinum in acid and alkaline solutions was studied by
Kokkinidis and J a n n a k o u d a k i ~ Pronounced
.~~~ inhibition effects were observed,
which were ascribed to the degree of coverage and the electrosorption valencies of
these adsorbates. In a ~ e t o n i t r i l eone
~ ~ third
~ of the molecules of hydrazine or
methylhydrazine or 1,l -dimethylhydrazine were noted to undergo two-electron
oxidation to the corresponding di-imides, while the remaining two thirds act as the
required proton acceptors in neutral acetonitrile. In alkaline solutions, hydrazine
undergoes a four-electron oxidation process while its methyl derivatives are
oxidized to their corresponding di-imides.
The adsorption of hydrogen sulphide onto platinized platinum was investigated
in 0.5 M H2S04 solutions by Dibrova et An adsorption layer was observed
on the platinum surface with chemisorbed particles formed during dehydro-
genation. Kapusta et have studied the anodic oxidation of sulphide species
on platinum electrodes in alkaline solutions. They observed the formation of a
surface layer, containing platinum(1v) sulphide and sulphur, that passivated the
electrode. Further oxidation was only possible after this layer was removed either
by oxidation or reduction. Oxide formation was inhibited because of the com-
peting adsorption of S2- and OH - . Similarly the oxidation of sulphide to sulphur
on oxide surfaces was practically eliminated.
The electrode reactions of adsorbed sulphur dioxide at a platinized platinum
electrode have been studied, by potentiodynamic and radiometric techniques,
by Szklarczyk et al.456 The surface concentration of adsorbed species were
determined. Sulphur ad-atoms and platinum sulphides are proposed as products
of sulphur dioxide adsorption in the double layer and hydrogen potential regions
respectively
The mechanism of adsorption of sulphur dioxide on platinum has been
studied by means of differential and integrated charging curves by Dibrova and
c o - ~ o r k e r s . The
~ ~ ’ composition of the adsorbed layer was noted.
Spotnitz et al.458have noted that the cycling of platinum electrodes, in sulphuric
acid solutions containing sulphur dioxide, between -0.1 and 1.2 V (SCE) results
in the activation of the electrode so that diffusion-controlled sulphur dioxide oxi-
dation currents can be observed in the double layer region on platinum. Without
451 G. Horanyi and E. M . Rizmayer, J. Electroanal. Chern., 1982,143,323.
452 G . Kokkinidis and P. D . Jannakoudakis, J. Electroanal. Chem., 1981,1.30, 153.
453 A. D. Jannakoudakis and G. Kokkinidis, J. Eleclroanal. Chern., 1982, 184,311.
454 G. Ya. Dibrova, G. I. Elfimova, and G. A. Bogdanovskii, Vestn. Mosk. Univ. Khim., 1981,22,406.
455 S. Kapusta, A. Viehbeck, S. M. Wilhelm, and N. Hackerman, J. Electroanal. Chem., 1983,153, 157.
456 M. Szklarczyk, A. Czerwinski, and J . Sobowski, J. Electroanal. Chem., 1982,132,263.
457 G. Ya. Dibrova, G. I. Elfimova, and G. A. Bogdanovskii, Zh. Fiz. Khim., 1981,55, 1259.
458 R. M . Spotnitz, J. A. Colucci, and S. H. T,anger, Elecfrochim.Acta, 1983,28, 1053.
68 Electrochemistrji
activation, sulphur dioxide oxidation proceeds noticeably only in the potential
region of surface oxide formation. Evidence is presented which indicates that
activation results from formation of a catalytic layer of sulphur species. The
catalytic activity of this layer decays with time in the course of sulphur dioxide
oxidation.
In very strong (98%) sulphuric acid, cyclic voltammetric experiments carried
out by Conway and N o ~ a k revealed
, ~ ~ unusual reduction and oxidation processes
on platinum, that were distinct from those found to occur in dilute solutions.
Holding the potential near the H + / Hhydrogen evolution potential in 98% H,SO,
gave rise to the reduction of the acid producing a species that was immediately
chemisorbed and became oxidized in the adsorbed state in a following anodic
sweep through the 'surface oxide formation' potential region. In the succeeding
cathodic sweep a large cathodic current peak followed surface oxide reduction.
This reduction behaviour was accounted for by proposing the formation of SO, or
MSO 3 at potentials near the hydrogen evolution potential followed by oxidation,
possibly to adsorbed dithionate (S,062 - ) or some other chemisorbed S-0
species, in the following anodic sweep. Additions of small quantities of water
diminished the reduction reaction observed.
The electrochemical reduction of the thick oxide film formed on a platinum elec-
trode by severe pre-anodization has been studied in LiOH, NaOH, and KOH solu-
tions of concentrations (0.001-1.0 M) by Shibata and sum in^.^^' An outermost
monolayer oxide and an inner multilayer bulk oxide exhibit different behaviour
during cathodic reduction. In dilute solution both oxides are completely reduced
in a potential range 0.6-0.4V (SHE) in a single step. As the concentration is
increased, however, the reduction potential of the inner oxide layer shifts into the
hydrogen electrosorption region and consequently the amount of oxide reduced at
this potential decreases. The remaining oxide is slowly reduced only at hydrogen
evolution potentials.
An expression has been derived by K h ~ r a n i which
~ ~ ' relates the concentration
of adsorbed species (e.g. methanol) on platinized platinum to the surface
roughness coefficient
Platinum electrode areas have been determined by standard cyclic voltammetric
techniques in 4 M H,SO, at scan rates between 20 and I00 mV s- by Barna et
trI.462 A linear extrapolation of the measurcd charge in the hydrogen adsorption
region to infinite scan rates eliminates the charge associated with the background
hydrogen evolution reaction. The technique allows the direct determination of the
potential of full H coverage and hence the generation of adsorption isotherms.

20 Less-common Precious Metals

Ruthenium.--The effect of the thermal treatment of ruthenium in an argon
atomsphere at 3O&80O0C on its catalytic properties has been investigated by

45y B. E. Conway and D. M. Novak, J . Electrochem. SOL..,1981,128,2262.

460 S. Shibata and M . P. Sumino, Electrochim. Acta. 1981,26, 1587
D. Khorani, Elektrokhimiya, 1981,17,949.
462 G. G. Barna. S. N. Frank, and T. H . Teherani. J . Electrochem. SOC.,1982,129,146.
Adsorption at Solid Electrodes 69
Pletyushkina et al.463The adsorption ability and catalytic activity of the electrode
was inhibited by the treatment.
It was noted by Vukovic et al.464that ruthenium electrodes which were subject
to an anodic/cathodic potential cycling regime from 0.06 to 1.4 V (SHE) developed
a changed state of surface oxidation in comparison with that observed in the initial
sequence of potentiodynamic sweeps. The kinetics of chlorine and oxygen evolu-
tion on these two types of oxidized surface were studied by steady-state polariza-
tion experiments. Current densities for C1, evolution at the cycled ruthenium oxide
surface were 30-times greater than those at the original oxidized surface. Oxygen
evolution currents were increased 8-fold. The effect was truly electrocatalytic since
the surface area remains constant to within 5%.

Rhodium.-Linear sweep voltammograms taken by Ogura and F ~ j i m o t o ~ ~ ’

showed that H f was adsorbed on a rhodium surface, from 1 M H,SO, aqueous
solution, by a two-step process according to a Freundlich isotherm. An analysis of
anodic current transients indicated that, in the oxygen adsorption region, the
adsorption obeyed Elovich kinetics. The oxidation steps:
RhO+Rh,O,-*Rh,O, (35)
accounted for the formation of oxide layers.
Blimes et ~ 2 1 have. ~ examined
~ ~ the electro-oxidation of chemisorbed carbon
monoxide in 1 M HClO, on polycrystalline rhodium. The electrochemical behav-
iour of the system is explained through the participation of two CO-adsorbed
states and its interaction with electrosorbed oxygen. This adsorption reaction can
be correlated with that on platinum.
In a study of electroadsorption of methanol on rhodium in 1 M H,SO, by
Arancibia and C ~ r d o v aa differential
~~~ charge was observed, and ascribed to the
formation of small amounts of surface oxide and adsorption of HSO, which
blocks the active surface sites. The oxidation of organic residue to carbon dioxide
and water increased the anodic charge.
The basic principles of adsorption and electro-oxidation of formaldehyde on
rhodium were investigated by Kazarinov et al.468using electrochemical and radio-
labelling techniques. The species adsorbed on the electrode at 50 mV (SCE) were
found to be more easily reduced than those adsorbed at 400 mV. It was concluded
that at 400 mV the adsorbed aldehyde was dehydrogenated to CO species, which
in turn were oxidized by active oxygen to COOH species. These latter species were
finally reduced to CO and COH species at more cathodic potentials.
Parajon Costa and c o - ~ o r k e r s have
~ ~ ’ examined the underpotential deposition
of copper on polycrystalline rhodium in 1 M H,SO, containing low concen-
trations of CuSO, in the range 25--80°C. Oxidative dissolution of bulk and

463 A. I. Pletyushkina, K. P. Mushkova, L. A. Nasonova, and G. D. Vovchenko, Zh. Fiz. Khim., 1982,
56, 1410.
464 M. Vukovic, H. Angerstein-Kozlowska, and 9. E. Conway, J . Appl. Electrochem., 1982,12, 193.
465 M. Ogura and T.Fujimoto, Suzuka Kogyo Koto Semmon Gakko Kiyo, 1980,13,297.
466 S . A. Blimes, N. R. de Tacconi, and A. J. Arvia, J . Electroanal. Chem., 1983,143, 179.
467 V. Arancibia and R. Cordova, Bol. Soc. Chil. Quim., 1982,27,97.
468
V. E. Kazarinov, V. S. Bagotskii, Yu. B. Vasil’ev, V. N. Andreev, and S. A. Kuliev, Elektrokhimiya,
1982, 18, 185.
469 9. Parajon Costa, C. D. Pallotta, N . R. de Tacconi, and A. J. Arvia, J . Electroanal. Chem., 1983,145,
189.
70 Elect ro diemist rjv

monolayer copper was indicated by current peaks recorded at 0.28V for bulk
copper and 0.48V and 0.58V for the copper monolayer. The influence of
electroadsorbed copper on the H ad-atom monolayer is discussed.

Palladium.-Bucur, Covaci, and B ~ t a ~ have ~ ' carried

- ~ ~ out~ a thorough study
of the galvanostatic desorption of hydrogen from palladium layers. The diffusion
equations are solved by Laplace transform methods and their solutions in terms of
the concentration of dissolved and weakly adsorbed hydrogen are given. The tran-
sient overpotentials occurring in the electrochemical desorption for a reversible
and irreversible oxidation step are also calculated. Good agreement between the
theory and experimental behaviour was obtained. The transfer of hydrogen
between the interface region and bulk of the (Pd-H) electrode occurs by a fast
dynamic equilibrium. The effects of surface structure and solution concentration
on the transfer equilibrium constant were studied. The spontaneous accumulation
of hydrogen in the interface region is suggested to be due to the trapping effect of
the surface defect structure. The influence of the concentration of electrolyte
(H,SO, and Na,SO,), surface structure, and temperature on the anodic
charge-transfer coefficient and the rate constant are also discussed. Other work by
Bucur and B ~ t involved
a ~ ~an ~investigation of the effect of different quantities of
hydrogen initially dissolved in the electrode on the transfer equilibrium at the
(Pd-H)/electrolyte interface. The enthalpy and entropy values for H held in the
surface layer and H dissolved in the bulk have also been estimated from van't Hoff
isotherms by Bucur and B ~ t aThe . ~dependence
~ ~ of AM', AS', and AG:98 on the
roughness factor of the electrode was noted and explained the tendency of H to
accumulate spontaneously in the surface layer.
B ~ e i t e has
r ~ ~measured
~ the potential range of adsorption of hydrogen onto
palladium and noted its similarity to that of platinum. The adsorption obeys a
Temkin isotherm at medium coverages.
Enyo476has deduced exchange current densities and the activation energies of
the constituent steps of the hydrogen evolution reaction on palladium from
galvanostatic overpotential transients.
The adsorption of oxygen on palladium in both acid and alkaline electrolytes
has been studied by Novikova and D r ~ z .It ~was~noted ~ , that
~ ~the ~adsorption
from 0.1 M KOH decreased with increasing temperature. Adsorption started at
1.23 V and weakly bound oxygen was the main species.
Gossner and M i ~ e r a ~have
~ ' monitored the anodic behaviour of palladium in
1 M H,S04. The adsorption of oxygen is shown to compete with corrosion of the
substrate and with its diffusion into the bulk metal. The work of Bolzan et

"' R. V. Bucur and I. Covaci, Elec.lrochim. Acta, 1979, 24, 1213.

471
R. V. Bucur and F. Bota, Electrochim. Actu, 1982,27, 521.
472 R. V. Bucur and F. Bota, Electrochim. Actu, 1983.28, 1373.
473 R. V. Bucur and F. Bota, Electrochim. Acta, 1981,26, 1653.
474 R. V. Bucur and F. Bota, Electrochim. Actu, 1984,29, 103.
47s M. W. Breiter, Proc. Electrochem. Soc., 1979,410.
4'6 M. Enyo, J . Electrounul. Chem., 1982, 134,75.
4i' Z. N. Novikova and V. A . Druz, Zh. Fiz. Khim., 1982,56, 1287.
478 V. A . Druz and Z. N. Novikova, Zh. Fiz. Khim., 1982,56, 1486.
4'9 K. Gossner and E. Mizera, J . Electroanul. Chem., 1981,125,347.
4x0 A. E. B o h n , M. E. Martins, and A. J. Arvia, J . Electrounul. Chem., 1983, 157, 339.
Adsorption at Solid Electrodes 71

on palladium in 1 M H,S04 shows different electrochemical behaviour in the

whole range of electroadsorption and oxide layer formation, depending on the
characteristics of the electrical perturbation during the initial potentiodynamic
sweep of electrodissolution of palladium. The results indicate the formation of
different electroadsorbed oxygen species, depending on the potential range
covered during the experiments.
The adsorption of carbon monoxide on palladium in 0.5 M H2S04 has been
investigated by Breiter.481,48 The oxidations of chemisorbed carbon monoxide
occurs in the absence of a noticeable coverage of 0 atoms below 0.9V. Above
0.9 V the oxidation of Co,& is accompanied by the formation of an oxygen layer.
In the absence of CO,,, the net rate of hydrogen dissolution at potentials of the
a-phase was diffusion controlled at sweep rates <0.1 V s-'. The dissolution rate
was reduced to about half with increasing coverage of Co,& up to 0.6 V. A further
increase in coverage led to a considerable decrease in the dissolution rate.
A mechanistic model has been proposed by Sakellaropoulos and for
the electrocatalytic hydrogenation of ethylene upon palladium at positive poten-
tials, based on the insertion of ethylene into the surface layer of adsorbed H atoms
followed by slow H addition to the resulting surface ethyl radicals.
The adsorption of silver atoms onto palladium plated platinum was noted by
Kolyadko et ~ 1 . to~ occur
' ~ in two ways, differing in their energy characteristics.
The extent of replacement of adsorbed H by adsorbed silver atoms is approx-
imately unity. In the presence of adsorbed silver atoms the inhibition of the
anodic oxidation of formic acid was observed. In further work, Koliadko and co-
w o r k e r ~ note~ ~ that
~ , ~one
~ type
~ of silver adsorbate is irreversibly adsorbed
whilst the other can be desorbed and exists only in the presence of silver ions in
solution. Both forms of silver atoms are adsorbed with practically full charge
transfer,

Rhenium.--Krasik~v~~has used rhenium electrodeposited onto a copper, nickel,

gold, or graphite substrate from H2S04 solutions containing KReO, to obtain
polarization curves. The hydrogen overpotential was found to be independent of
pH in acid media obeying the Tafel equation with a slope of 30 mV. It is proposed
that the rate determining step is the removal of adsorbed hydrogen following a
recombination mechanism.

Iridium.-Voltammetric methods were employed by Semenova et ~ 1 . to~ investi- ' ~

gate hydrogen adsorption on polycrystalline iridium in 0.5 M Na2S04 or KOH
solutions. Evidence is presented for four forms of adsorbed hydrogen on iridium.
Sutyagina et ~ 1 . have
~ ' examined
~ the effect of poisoning iridium electrodes with

481 M. W. Breiter, J . Electroanal. Chem., 1980, 109,243

482 M . W. Breiter, J . Electroanal. Chem., 1980, 109,253
483 G. P. Sakellaropoulos and S. M. Langer, J. Calal., 1981,67,77.
484 E. A . Kolyadko, R. Vettsel', B. I. Podlovchenko, and L. Muller, Elektrokhimiya, 1980, 16, 1096.
485 E. A . Kolyadko, B. I. Podlovchenko, R. Wetzel, and L. Muller, J . Electroanal. Chem., 1982,137, 117.
486 V. E. Kazarinov, B. I. Podlovchenko, E. A . Kolyadko, and V. N. Andreev, J . Electroanal. Chem.,
1983,148,241.
487 V. L. Krasikov, Elektrokhimiya, 1981,17,1518.
488 A . D . Semenova, V. D. Daniletiuk, and G. D. Vovchenko, Dokl. Akad. Nauk SSSR, 1980,253,185.
OB9 A.A. Sutyagina, T. M . Mateeva, T. E. Umantseva, and A. D. Aliev, Zh. Fiz. Khim., 1981,55,700.
72 Electrochemistry

mercury. A virtually exponential dependence was observed for the amount of

adsorbed hydrogen as a function of mercury concentration on the iridium surface.
Potentiodynamic pulse measurements were taken by Shaidullin et a/.490 to
study tin(r1) cations on iridium in 0.5 M H 2 S 0 4 containing 10 mM S n 2 + .The
hydrogen evolution overpotential is affected by both the extent of surface coverage
and the energetic state of chemisorbed tin.
’
Breiter49 has studied the adsorption of carbon monoxide under steady-state
conditions on smooth iridium wire electrodes in 0.5 M H,SO, at room tempera-
ture. The oxidation of chemisorbed carbon monoxide at constant current is
accompanied by the formation of the oxygen layer above 0.6V. Coverage with
Hads was determined as a function of potential at constant coverage with pre-
adsorbed carbon monoxide from anodic charging curves. The isotherms for
hydrogen adsorption are of the Temkin type at carbon monoxide coverages > 0.4.
The adsorption and electrochemical reduction processes of maleic acid on
iridium in 0.5 M H2S04 were observed by Shaidullin et ~ 1Maximum
. ~ adsorp-
~ ~
tion occurred at 0.2 V. At more negative potentials the adsorption decreased due
to the hydrogenation of the chemisorbed particles; at more positive potentials it
again decreased. due to their oxidation. The same researchers493 have examined
the effect of the adsorption of tin(rr) on the cathodic reduction of maleic acid. Sn2 +

had the effect of decreasing the concentration of both the acid and hydrogen
adsorbcd on the electrode surface consequently hindering the reduction of the
acid.
Potentiodynamic measurements by Sutyagina and ~ o - w o r k e r showed s ~ ~ ~ that
sulphur is the main product formed during the adsorption of thiourea on electro-
deposited iridium electrocatalysts in 50 mM H 2 S 0 4 at - 30mV (SHE). The
poisoning of the electrode suppressed the adsorption of hydrogen but no change
was observed in the Ir-Hads bond energy. Poisoning of 60% of the electrode
surface resulted in total inhibition of hydrogen adsorption.
The adsorption of nitrobenzene on iridium and palladium catalyst surfaces from
0.5 M H,S04 produced maxima at 0.2 and 0.35 V respectively, according to data
obtained by Bogdanovich and V a ~ i l ’ e vThe . ~ ~maximum
~ surface coverage was
-50% for both metals. The hydrogenation rate of the adsorbed particles on
palladium was higher than on iridium.
Arsenic adsorbed onto iridium was seen, by Sutyagina et to be oxidized in
50 mM H,S04 and HCl in a two-step process. Below 0.6--0.7 V (SHE). it is
oxidized by adsorbed oxygen to As,O, and above 0.6-0.7 V to solution AsO, - .
In 1 M KOH the oxidation occurs above 0.85 V.
Mozota and have studied the behaviour and properties of the
490
R . Ya. Shaidullin. A. D. Semenova, G. D. Vovchenko, and Yu. B. Vasil’ev, Ekktrokhimiya, 1982, 18,
75.
4‘) 1
M . W. Rreiier, J . Electroanal. Chem.. 1983, 157, 327.
492
R. Ya. Sahidullin, A. D. Semenova, ti. I>. Vovchenko, and Yu. B. Vasil’ev, Z h . Fiz. Khim., 1981,55,
2567.
493
R. Ya. Sahidullin. A. D. Semenova, G. D. Vovchenko, and Yu. B. Vasil’ev, Elektrokhimiya. 1981,55,
1903.
4v4
A . A . Sutyagina, T. M . Matveeva, and M . N . Semenenko, Z h . Fiz. Khim., 1982,56,2046.
4‘) 5
V . B. Bogdanovich and Yu. B. Vasil’ev, Z h . Fiz. Khim., 1981,55,453.
446
A. A . Sutyagina, T. M . Matueeva, and N. E. Popova, Z h . Fiz. Khim.. 1982,56, 1826.
44-
J. Mozota and B. E. Conway, E k l r o c h i m . Arta, 1983, 28, 1.
49x
J. Mozola and R . E. Conway, Electrochim. Acta, 1983. 28, 9.
Adsorption at Solid Electrodes 73

monolayer surface oxide film and thick oxide films produced on iridium elec-
trodes, together with certain aspects of underpotential deposition of hydrogen at
iridium. The surface oxidation behaviour of iridium is compared with that of other
noble metals. A transition between the monolayer oxide and a thick, reversibly
reducible oxide film takes place under cycling between critical potential limits.
Thick film growth is proposed to be the result of the accumulation of oxide pro-
duced in an underlying monolayer during each anodic sweep and which is left in an
incompletely reduced state on each reverse sweep.
The poisoning of Pt, Rh, Pd, Ru, Os, and 0s-Rh alloys with Hg, S, or Pb is
discussed in terms of the structure and surface morphology of the catalysts by
Sutyagina and V o ~ c h e n k o . ~Electroregeneration
~’ of the poisoned catalysts was
achieved by anodic polarization at given potentials and anodic/cathodic cyclic
polarization in 0.05 M H,SO, solutions, with electrolyte replacement.
A correlation of the catalytic activity for anodic chlorine evolution on platinum-
group metals with the nature of the surface film formed during the reaction in a
sodium chloride solution has been attempted by Hara et ~ 1 . , ’ using ~ ~ X-ray
photoelectron spectroscopy. Replacement of hydroxyl ions in the surface film by
chloride ions became easier in the order rhodium, iridium, palladium. The activity
for chlorine evolution increased in this order also. Chlorine molecules were also
found adsorbed on the surface film. It was suggested that the activity for chlorine
evolution might be low when the metal surface was covered by a large amount of
molecular chlorine, the reaction product.

21 Silver
Since it was established that a surface enhanced Raman scattering (SERS)
spectrum could be obtained from pyridine adsorbed on silver electrodes,501silver
has become re-established as an electrode of particular interest. Many recent
studies have concentrated on this method and attempts to correlate SERS with
electrochemical techniques predominate.
Fleischmann et d S ohave 2 related the characteristics of the double layer
capacitance of smooth and roughened {loo}, {l lo}, and ( 1 1l } single crystal and
polycrystalline silver electrodes in 0.1 M NaF electrolytes containing up to
0.3 M C1- ions to the Raman spectra for the system.
Kotz and YeagerSo3have investigated the frequencies of several vibrational
bands of pyridine, pyrazine, p-nitrosodimethylaniline and CN - adsorbed on a
silver electrode as a function of potential using in situ Raman spectroscopy. The
frequencies of all the bands were found to decrease linearly as the potential was
made negative. Several models to explain this effect are suggested and discussed.
A SERS investigation of the nature of the adsorbed species at a silver electrode
surface in aqueous alkali halide solutions containing pyridine, by Fleischmann
and Hill,s04 has shown that both strongly bound Lewis acid co-ordinated
4L)9 A. A. Sutyagina and G. D. Vovchenko, SurJ: Technol., 1981,13,257.
500 M. Hara, K. Asami, K . Hashimoto, and T. Masumoto, Electrochim. Acta, 1983,28, 1073.
501 M. Fleischmann, P. J. Hendra, and A. J. McQuillan, Chem Phys. L e t f . , 1974, 26, 163.
502 M . Fleischmann, J. Robinson, and R. Waser, J. Electroanal. Chem., 1981,117,257.
503 R. Kotz and E. Yeager, J . Electroanal. Chem., 1981,123,335.
504 M . Fleischmann and I. R. Hill, J . Electroanal. Chem., 1983, 146, 353.
 14 Electrochemistrj3
(chemisorbed) pyridine and weakly bound (physisorbed) pyridine exist at the
interface. The requircd conditions for their formation and destruction have been
defined. In the presence of specifically adsorbed halide the physisorbed pyridine
has been found to bc in cquilibrium with an adsorbed form of water.
Fleischmann et uZ.’05 have also examined the SERS spectra of water molecules
and C1- ions which are co-adsorbed at an electrochemically roughened silver elec-
trode. The spectra obtained are discussed in terms of specifically adsorbed C1-
ions. A further investigation of this system by Fleischmann and 13il150hhas shown
the SERS spectra to be dependent on the nature of the supporting electrolyte
cation. The cation dependence and the potential dependence for any given cation
are interpreted as being due to the progressive desolvation of cations with increas-
ing radius and with increasingly negative potentials, the cations being adsorbed as
solvent-separated ion pairs.
Owen and c o - w ~ r k e r s ’have
~ ~ used an optical multichannel analyser to allow
simultaneous monitoring of the SERS spectra of adsorbed water, halide, and
pyridine species at silver electrodes in 1 M RX (X=C1, Br, I, and F) electrolytes
whilst the electrode potential was continuously cycled through the oxidation-
reduction cycle. Laser-induced changes in SERS intensities, electrode surface
morphologies, and cyclic voltammograms were noted. The results indicated
potential-dependent competition among the adsorbates for sites on the silver
surface.
Voltamograms for the silver electrode -electrolyte system with the correspond-
ing SERS spectra of adsorbed silver cyanide complexes, detected using an optical
multichanncl analyser are presented by Benner et al. ’ 0 8 Correlations between the
current peaks in the voltammograms and the Raman vibration frequencies are
observed as the applied potential is cycled through the first and subsequent
oxidation-reduction cycles.
Measurements of SERS spectra of I2CN- and 13CN- and mixtures adsorbed
on silver electrodes were made by Fleischmann and c o - w ~ r k e r sThe . ~ ~spectra
~
were shown to arise from a complex species whose co-ordination number does not
change with electrode potential. This species is suggested to be a [Ag(CN),]-
entity having C2,, symmetry; at very negative potentials a reduced form of this
complex [Ag(CN),]’- co-exists with the Ag’ species at the surface. The shifts in
band position are interpreted in terms of changes in bond character of the
adsorbed C N - species. The spectrum of water co-adsorbed with C N - is also
markedly dependent on the charge density of the adsorbed C N - groups.
Kotz and Yeage? l o have obtained Raman spectra of cobalt tetrasulphonated
phthalocyanine adsorbed on a silver electrode in aqueous electrolytes. They show
that the intensity of the Raman bands is directly related to the amount of charge
transferred during the electrochemical activation of the silver. The strong potential
dependence of the Raman bands is discussed with respect to the resonance

’(” M . Fleischmann. P. J. Hendra. and I. R. Hill, J . Electroanal. Chem., 1981. 117, 243.
5”b M. Fleischmann and I. K.Hill, J . Electroanal. Chon., 1983. 146, 367.
5(17 J. F. Owen, T. T. Chen, R. K. Chang, a n d B. L. Laube, J . Electroanal. Client., 1983, 150, 389
5ox R . E. Benner. R. Dornhaus, R. K. Chang, and B. L. Laube, Surf: Sci., 1980,101,341.
M . Fleischmann, I. R . Hill, a n d M . E. Pemble, J . Eleclroanal. Chem., 1982, 136. 361.
5 I (I
R. Kotz and E. Yeager, J . Electroanal. Chwz.. 1980, 113, 1 1 3.
Adsorption at Solid Electrodes 75
properties of the adsorbate taking into account the orientation of the molecule
on the surface. A further study of the phthalocyanine system by Yeager and
’’
co-workers5 has shown that oxygen can produce significant changes in the
Raman spectra of the adsorbed and solution phase species.
Resonance Raman scattering (RRS) enhancement mechanisms have been
exploited in obtaining surface Raman spectra from the adsorbed anion of dithi-
zon (diphenylthiocarbazone) at silver electrode surface at - 0.2 V (Ag/AgCl) in
pH12 buffer solution by Pemberton and The SERS and RRS detected
adsorption isotherm is presented. Calculations on surface population based on the
suggested orientation of dithizone anion at the silver surface allow a minimum
SERS enhancement factor of 2 x lo3 to be estimated for this system. Other investi-
g a t i o n ~ ~by~ the
~ ’same
~ ’ ~authors have shown that the dithizon anion is reduced
at the azo-group on a silver electrode, but the observed voltammetric wave is split
into surface and bulk components due to the adsorption of the anion at the silver
surface. The product of the reaction, the hydrazo-species, is also adsorbed at the
surface but to a lesser extent. The dithizon anion can also be oxidized at silver to
form the corresponding disulphide compound. This disulphide which is insoluble
in aqueous systems adsorbs at the silver surface in multilayer quantities.
’
Busby and Creighton5’ have investigated the factors influencing the enhance-
ment of Raman spectral intensity by examining the adsorption of 2-amino-5-
nitropyridine (ANP) onto silver. ANP adsorbs strongly at silver and gives an
intense SERS spectrum which identifies the adsorbate as the [ANPI- ion.
Coulometric and spectrophotometric methods are used to provide an in situ
measurement of the surface molecular concentration of this adsorbate. This is
shown to be linearly dependent upon the anodic charge during roughening in
0.1 M KCI over the range 0-150 mC cm-’ for double potential step roughening
cycles. A quantitative measure of the surface Raman enhancement factor for this
adsorbate is obtained, and this is shown to reach a maximum of 1.5 x lo4 for
surface roughening involving the passage of 25 pC cm-’. For this amount of
roughening or greater, it is concluded that the surface roughness further increases
the total SER intensity by a factor of 10 or more due to the resulting high effective
surface concentration of the adsorbate.
Campbell and Creighton’ l 6 have also used 2-amino-5-nitropyridine as well as
pyridine-2-azo-p-dimethylaniline adsorbed on silver electrode surfaces to deter-
mine oxidation profiles for dye molecules and their transition wavelengths. The
results show that for each adsorbed dye the strongly allowed electronic transition
lies approximately 40 nm to the low frequency side of the absorption maximum of
the dye in solution.
The electrogeneration of methyl viologen radical cation (MV’) at a silver
electrode in chloride solution has been studied by Melendres and c o - ~ o r k e r s . ” ~
Evidence for the adsorption of MV+ or a related species was obtained by cyclic

R. Simic-Glavaski, S. Zecevic, and E. Yeager, J . Elrclrounul. Chern., 1983, 150,469.

512 J. E. Pemberton and R . P. Buck, Anal. Chern., 1981,53,2263.
J. E. Pemberton and R . P. Buck, J. Electroanal. Chern., 1982, 132,291.
514 J . E. Pembertonand R . P. Buck, J. Phys. Chem., 1981,85,248.
515 C. C. Busby and J. A. Creighton, J. Electroanal. Chem., 1982, 133, 183.
J. R . Campbell and J. A. Creighton, J. Electroanal. Chem., 1983, 143, 353.
C. A. Melendres, P. C. Lee, and D. Meisel, J. Electrochem. SOC.,1983, 130, 1523.
 76 Electrochemistry
voltammetry and in situ laser Raman spectroscopy measurements. It was observed
that electrode cycling, and high chloride ion concentration stabilize the adsorbed
state of MV’ at the electrode. It appeared possible to distinguish between the
Raman signal due to surface species and to species dissolved in the solution. The
Raman technique was also suggested to be capable of detecting submonolayer
quantities of MV+ and to be useful for monitoring concentration changes of the
radical cation.
The behaviour of mercaptobenzothiazole on silver electrodes has been studied
by Ohsawa et ~ 1 . by ~ SERS technique. Mercaptobenzothiazole is adsorbed.
’ ~ the
on silver at the expense of pre-adsorbed pyridine. Adsorbed mercaptobenzothia-
zole contains thione and ionized thiol species, the former being strongly adsorbed
at the surface.
The results of a study on the optical properties of pyridine on { 1 1 1 ) silver
and gold single crystal surfaces in 0.1 M NaCl are presented by Tadjeddine
and Kolb.’19 Again the absorptive properties of pyridine are shown to be quite
different as an electrosorbate to a solution species.
A quantitative determination of pyridine and cyanide adsorption on silver by a
radiochemical technique undertaken by Blondeau et ~ 1 . ~has ~ ’ shown that the two
adsorbate systems are different. After a dissolution-redeposition cycle the quan-
tity of pyridine adsorbed depends on the extent of oxidation-reduction during the
cycle. For low charge transfer (< 50 mC cmP2) the adsorption increases from
three to nine monolayers and depends on the nature of the supporting electrolyte.
This suggests the formation of new bonds between the pyridine, silver, and the
anion of the supporting electrolyte. For large charges the quantity of pyridine
increases, the rate of increase depending on the supporting electrolyte (KI > K-
Cl> KClO,). It is proposed that trapping of pyridine in the salt formed between
the support electrolyte anion and silver occurs. The quantity of pyridine adsorbed
was observed to be as large as the equivalent of 100 monolayers; this explains
in part the enhancement of Raman scattering observed for this system. After
dissolution-redeposition cycles the quantity of cyanide adsorbed remained
constant. The cyanide-silver system is reversible.
Relationships between surface density of cyanide ions, their bulk concentration,
potential, and electrode charge have been studied and presented by Royozhnikov
and Bek.521 From experimental data the potential drops in the diffuse and
compact part of the electrical double layer were calculated. 5 2 2
Larkin and co-workers”3 have studied the specific adsorption of chloride,
bromide, iodide, azide, and thiocyanate at the electropolished polycrystalline
silver-aqueous interface using differential capacitance measurements. For chlor-
ide, bromide, and azide, quantitative estimates of the surface concentrations of
specifically adsorbed anions were obtained from capacitance-potential data in
mixed fluoride electrolytes. Estimates of the specifically adsorbed charge densities
of chloride, bromide, and thiocyanate anions were also obtained from a ‘kinetic
‘IH M . Ohsawa. H . Matsuda, and W . Suetaka, Chem. Phys. Lett., 1981,84. 163.
“’ A . Tadjeddine and D. Kolb, J . Electroanal. Chem.. 1980, 111, 119.
”O C . Blondeau. Z. Zerbino, and N . Jaffrezic-Renault, J . Electroanal. Ckem., 1980. 112, 127.
‘’I N . A . Rogozhnikov a n d R. Yu. Bek, Elektrokhimiya, 1980, 16,662.
522 N. A . Rogoyhnikov and R. Yu. Bek, Elektrokhimiya, 1980, 17,56.
”’ D. Larkin. K. L. Guyer, J . T. Mupp, and M . J . Weaver, J . Electroanal. Cheni., 1982. 138,401,
Adsorption at Solid Electrodes 77

probe’ technique, which entailed the monitoring of the response of the outer-
sphere reduction rate of [Co(NH,),F]’+ and [Co(NH3),I3+ to the addition of the
appropriate adsorbing anion.
At the average potential of zero charge for the polycrystalline silver surface, the

-
standard free energies of adsorption ( -AG:ds) for chloride, bromide, and azide
were found to be within 5 kJ mol- of the corresponding quantities obtained at
mercury electrodes. Electrochemical roughening in chloride media to give a
surface displaying intense Raman scattering produced only minor changes in the
surface concentration of specifically adsorbed chloride ions.
Larkin524has used a complementary method to take this study further. He has
carried out a computer simulation of the interfacial behaviour of a polycrystalline
silver electrode a sodium fluoride electrolyte using Damaskin models,525and the
single crystal interfacial data of Valette and Hamelin.526
Valette527has studied the change in capacitance with potential at the interfaces
between a (100) silver face and the aqueous electrolytes, NaF, NaClO,, KBF,,
and KPF,. The anionic specific adsorption strength was found to decrease in the
=-
order: F- > ClO, BF, = PF; 2 0. The inverse order when compared with
mercury is explained by a local adsorption on surface defects. In a similar investi-
gation on the (100) face5’* the order of specific adsorption follows the sequence
ClO,> F- > P F , b O . This difference in pattern between the { 1lo} and the {loo}
face suggests that the faces have individual adsorption characteristics and are not
only due to surface defects.
Adsorption of the Br- ion on a { 1lo} silver electrode from mixed solutions of
NaBr and NaF has been investigated, by Valette,529by measuring the double
layer capacity as a function of solution composition. The analysis of the total
inner-layer (differential) capacity as a function of the electrode changes shows that
there is competitive specific adsorption of the F- ion when the Br- concentration
is small with respect to the F- concentration.
Droog5,’ has investigated the anodic oxidation of silver { 11l} and silver { 1lo}
electrodes in sodium hydroxide solution by linear sweep voltammetry and ellip-
sometry. It was found that in the potential region studied dissolution of silver
species and electrosorption of oxygen occur. The ( 1lo} face was much more reac-
tive to oxygen than the { 11l } face. On (1 10) Ag, oxygen is reversibly adsorbed via
a process of random deposition. The halfwidth of the adsorption peak indicates
attractive lateral interactions in the chemisorbed layer.
The behaviour of sulphur adsorbed at a silver interface has been studied by
Nguyen Van Huong et al.531Sulphur forms stable monolayers on single-crystal
silver surfaces in aqueous N a F between -0.4 and - 1.O V (versus Hg/Hg,SO,).
The double layer capacity is substantially lowered and the potential of zero charge

524 D. Larkin, J. Electroanal. Chem., 1983, 157, 123.

525 I . A. Bagotskaya, B. B. Damaskin, and M . D. Levi, J . Electroanal. Chem., 1980, 115, 189.
526 G. Valette and A. Hamelin, J . Electroanal. Chem., 1973,45,301.
527 G . Valette, J . Electroanal. Chem., 1981, 122, 286.
528 G. Valette. J. Electroanal. Chem., 1982, 138, 37.
529 G. Valette, J . Electroanal. Chem., 1982, 132, 31 1.
530 J. M. M . Droog, J . Electroanal. Chem., 1980, 115, 225.
531 C . Nguyen Van Houng, R. Parsons, P. Marcus, S. Motes, and J. Oudar, J . Electroanal. Chern., 1981,
119, 137.
78 Elect rochem istrj’

shifted. The sulphur can be removed by cathodic treatment but the silver surface
cannot be returned to its original clean condition by this method.
>.
Bismuth ions have been seen to be adsorbed on ( 11 I {loo), and ( 110) planes
of silver single crystals up to a close-packed monolayer by Schultze and
B r e n ~ k eOn ~ ~ (100) and (110) surfaces, ordered structures are formed at
. ~ the
lower packing densities. All layers are stabilized by lateral attraction. The poten-
tial-independent desorption on { 1 11) is explained by a consecutive desorption
path corresponding to the Kossel-Stranski mechanism of crystallization. In the
presence of Cl - ions the transfer reaction is enhanced. The catalysis is explained
by the formation of a [BiC1I2+complex increasing the rate of direct desorption
mechanism according to the Langmuir model.
The electrocatalytic influence of underpotential lead adsorbates on the reduc-
tion of nitrobenzene and nitrosobenzene on silver single crystal surfaces in
methanolic solutions has been investigated by Kokkinidis and Juttner. 5 3 3 On the
bare silver PhNO, and PhNO were reduced to phenylhydroxylamine (PhNHOH)
in neutral solutions and to aniline in acid solutions. The underpotential deposition
of lead was seen to cause a partial inhibition of the reduction processes in acid
solutions. The reduction of the intermediate PhNHOH to aniline was entirely
inhibited by a complete coverage of the lead adsorbate.
Zwetanova and Jiittner534have noted the influence of underpotential lead and
thallium adsorbates on the electrochemical reduction of oxygen at rotating disc
electrodes of silver ( I 1 I ) , (loo), and (1 10) in 0.5 M HCIO, solutions at various
concentrations of chloride. On bare silver substrates oxygen is reduced completely
to water. Depending on the degree of coverage and the structural arrangements of
lead and thallium adsorbates on the different crystal planes a partial inhibition of
oxygen reduction is obtained predominantly leading to the formation of the stable
intcrmediate t-I,O,. In the presence of chloride in solution the overpotential for
charge-transfer controlled oxygen reduction increases due to a specific adsorption
of C1 on the silver substrate.
The underpotential deposition of lead onto polycrystalline silver as studied by
Jannakoudakis and K o k k i n i d i caused
~ ~ ~ ~ the partial inhibition of the reduction of
dinitrobenzenes in acid solutions. The reduction of the intermediate phenylenedi-
hydroxylamines is completely inhibited when the silver substrate is covered by
underpotential lead adsorbate.
Hupp et ~ 1 1 . ~have
~ ‘ found that lead layers on silver having coverages in the
vicinity of a monolayer exhibited double-layer properties that were very similar to
those for polycrystalline lead electrodes and markedly different from those for
clean silver. This suggests that the surface atomic layer provides the predominant
influence upon double-layer structure.
The impedance behaviour of the system Ag (lOO}/Tlf, Ag (IOO}/Pb*+, Ag
{ I 10)iTlf, and Ag { I 10)/Pb2+at different potentials in the underpotential region
in the frequency range l00mHz to IOKHz has been studied by Klimmeck and

’j2 J. W. Schultzeand K . R. Brenske, J . Elertroanul. Chem., 1982, 137. 331.

53’ C . Kokkinidis and K. Jiittner, Electrochim. Acta, 1981,26,971.
5 3 4 A . Zwetanova and K. Jiittner. J . Elrclrounul. Chrm., 1981, 119, 149.

s 3 5 P. D. Jannakoudakis and G. Kokkinidis, Electrochim. Acta, 1982,27, 1199.

’”’ J. T. H ~ i p p D.
. Larkin, H. Y. Liu, a n d M . J. Weaver, J . Ekrcrroanal. Chem., 1982, 131,299.
Adsorption at Solid Electrodes 79
Juttner.537The impedance spectra showed that the adsorption of Pb2+ could be
interpreted on the basis of a simple Dolin-Ershler model with accompanying dif-
fusion. For T1+ adsorption, a more complicated model is necessary with fast
transfer at crystal inhomogeneities and slow transfer at homogeneous surface
regions.

22 Tin
Kohl538has investigated the characteristics of novel additives in the high speed
electrodeposition of tin-lead alloys from fluoborate electrolytes. Smooth,
semi-bright deposits were produced at current densities > 800 mA crnp2,near the
mass-transfer limited current. Microlevelling was effected by polymeric surfac-
tants, and uniform current distributions were produced by lactones or related
compounds. When the two additive types were simultaneously present their rela-
tive concentration as well as those of the metal ions determined the deposition
parameters. These additives were found to be cheaper and more stable than those
in current use, as well as permitting higher deposition rates.
Khemelevaya and D a m a ~ k i measured
n ~ ~ ~ capacitance as a function of potential
for polycrystalline as well as various single crystal faces of tin in sulphate solutions
containing cyclohexanol, and in halide solutions containing tetrabutylammonium
iodide. Adsorption parameters of cyclohexanol were similar irrespective of elec-
trode structure. Kuprin and G r i p ~ r ' e v ~investigated
~' the adsorption of camphor
on tin in Na2S0,, by differential capacitance measurements. The characteristic
peaks for adsorptiondesorption processes were not found, and at the desorption
potential a sharp capacitance increase was observed, which was ascribed to the
strong interaction between the adsorbed camphor molecules. The degree of
irreversibility of the cathodic deposition of various metals on tin in the presence of
camphor could be changed either by changing the camphor concentration or the
ionic strength of the solution. Lazarova and N i k ~ l o v discussed
~~' the nature of
adsorption properties of tin, nickel, and the 65% Sn-35% Ni alloy on the basis of
the dependences of pzc on solution pH.
Kapusta and Hackermann2 have examined formaldehyde adsorption on
837542

tin in different situations. They542first determined steady-state polarization curves

for tin in buffer solutions of various pH values, containing 0.001 to 0 . 6 M
formaldehyde. The rate of the hydrogen evolution reaction was enhanced by the

-
presence of the aldehyde, and the overpotential measured at constant current was
0.4V less than for bare tin.
However, the rate of reduction of formaldehyde was to be very slow,
ascribed to the adsorption of unknown formaldehyde-related species on the elec-
trode surface. Kapusta and H a ~ k e r m a n ninvestigated
~~~ the electroreduction of
carbon dioxide and formic acid in aqueous solutions on tin and indium electrodes,

537 M. Klimmeck and K. Juttner, Electrochim. Acta, 1982,27, 83.

"* P. A. Kohl. J . Electrochem. Soc., 1982,129, 1196.
539 L. P. Khmelevaya and B. B. Damaskin, Elektrokhim., 1981,17, 1721.
540 V. P. Kuprin and N. B. Grigor'ev, Elektrokhim., 1980,16,383.
541 E. M. Lazarova and Ts. Nikolov, Elektrokhim., 1980,16, 1231.
542 S. Kapusta and N. Hackerman, J . Electroanal. Chem., 1982, 134, 197.
543 S. Kapusta and N. Hackerman, J. Electroanal. Chem., 1983, 130,607.
80 Electrochenzistrj~

using a.c. impedance and photoemission techniques. Carbon dioxide reduction to

formic acid proceeds with high current efficiency ( - 95%) although the overall
power efficiency is low due to the high overpotential of the reaction. The mechan-
ism of reaction on tin and indium is similar to that postulated on mercury. The
reaction is faster than on mercury, though it can be affected by adsorption of inter-
mediates and the occurrence of side reactions. The reduction of formic acid was
only observed on tin cathodes at low current densities, where the poor efficiency
was related to the formation of organometallic complexes that enhanced hydrogen
evolution.
Novinski et a/.544looked at the hydrogen overpotential on ‘self cleaning’ (by
continuous abrasion) tin electrodes in sulphuric acid, in the presence of halogen
ions. The rate of mechanical renewal significantly influenced the hydrogen over-
potential, decreasing it by -0.12V, corresponding to a halving on the effective
energy of activation for the hydrogen evolution reaction. However, halide ion
adsorption did not effect any further change in hydrogen overpotential.

23 Titanium
Several investigations on titanium and TiO, involving adsorption have been
reported during the review period. We first consider the work on titanium.
Sedenkov et a1.545found that the anodic dissolution of titanium in nitric acid con-
taining 0.1 YOF- was inhibited by the addition of small amounts of H,PO,. It was
proposed that the combination of F- ions and adsorbed phosphate ions formed
insoluble compounds that protected the titanium surface. Other studies have con-
cerned the interaction of titanium with electrogenerated hydrogen. Millenbach et
observed an increased hydrogen uptake by titanium from acid solutions in
the presence of arsenic, and a change in Tafel slope from the near theoretical
1 10 mV/decade, to 170 mV/decade. The authors explain this in terms of the Tafel
reaction being a chemical recombination step rather than the normal electrochemi-
cal Heyrovsky recombination. The former reaction is the slower, so that a surplus
of adsorbed hydrogen is created, some of which diffuses into the bulk titanium
resulting in the observed increase in hydrogen uptake.
Okada547,548 has reported studies of hydrogen absorption by titanium both in
the natural state, and modified by superficial alloying with metals of Groups VIII,
IB, and IV. Hydrogen absorption behaviour was changed by the alloying metal.
Metals which inhibited the oxidation of titanium increased the hydrogen absorp-
tion rate. OkadaS4’ suggests that surface coverage by atomic hydrogen is the criti-
cal factor determining the hydrogen absorption rate. OkadaS4*later observed that
the absorption of hydrogen by Ni-modified titanium obeyed a parabolic law, indi-
cating the bulk diffusion to be the rate determining step, in contrast to unmodified
titanium where the absorption rate is determined by the surface reaction step. The
current efficiency for hydrogen absorption was greatest for Ni-modified titanium.

544 C . I . Nouinski, I . P. I\anov, and M. Vassilera-Diluora, J . Electrochern. Soc., 1983, 130, 1836.
A . M . Sedenkov. L.. R. Berezovskii, and A. P. Krashoperova, Zh. Fiz. Khinz., 1982,56. 2893.
51h P. Millenbach, M . Givon. and A. Aladjem. J. Appl. Electrochcnz., 1983. 13. 169.
”’ T. Okada. Electrochim. Actn, 1982,27, 1273.
5Jx T. Okada. E/c~c,trochim. Actcr. 1983, 28. 1 113.
Adsorption at Solid Electrodes 81

Bockris et al.5 4 9 have explored the possibility of using electrochemical methods

to reduce dissolved oxygen to H,O, and OH- and hence to diminish marine
bacterial fouling by adsorption. The application of steady-state potentials could
decrease bacterial concentration on both the anode and cathode 10&-300-fold,
while potential pulsing was less effective.
Other work has been concerned with adsorption on TiO,. has reported
the first observation of the surface enhanced Raman scattering (SERS) effect on a
semiconductor surface, from I,, generated electrochemically from aqueous KI
solution, and adsorbed on polycrystalline TiO,. Hada et ~have been able
1 . ~ ~ ~ 3 ~ ~

to reduce Ag+ adsorbed on single crystal TiO, by irradiation with 365 nm light,
with quantum yield of up to -0.2. It was proposed that some conduction-band
electrons, produced in the TiO, by irradiation, were transferred to the adsorbed
Ag', and also that positive holes reacted with water molecules. It was also
that the photoreduction of Ag+ was optically sensitized by the presence
of uranine.
Kazarinov et al.553have demonstrated the specific adsorption of various acid
anions on TiO,, and correlated the extent of adsorption with electrode potential,
solution pH, and anion concentration. Solution pH was a more influential
parameter than electrode potential. The strengths of anion adsorption increased in
the following sequence: C10 4< C1- < HSO, < H,PO 4.

24 Zinc
There has been interest in both metallic zinc and ZnO during the review period.
We consider first the work on metallic zinc.
Ipatov and B a t r a k o ~ investigated
~'~ the structure of the double layer on the
(0001) basal plane of single crystal zinc, in aqueous thiourea solutions with KCI as
supporting electrolyte. The dependence of the slopes of the 1/C, versus 1/C,
curves ( C , =the minimum capacitance in the differential capacitance versus
potential curve; C, = the capacitance of the diffuse portion of the double layer)
upon KC1 concentration was explained in terms of spherical adsorption of anions
in the region of chemisorption of water on the electrode. The same authors555
showed that the dependence of pzc on log[thiourea] was 58mV decade-' for
the (0001) zinc single crystal plane and 50mV decade-' for the ( 1 1 ~ 0 )plane.
These low values of the Esin-Markov coefficient were explained in terms of
chemisorption of H 2 0 molecules with a consequent loss of the electrical double
layer.
Kabanov et al. 5 6 used impedance and steady-state polarization techniques to
investigate the mechanisms of hydrogen evolution and potassium incorporation

549 H . P. Dhar, D. W. Howell, and J . O'M. Bockris, J . Electrochem. SOC.,1982,129,2178.

B. H. Loo, J. Electroanal. Chem., 1982, 136,209.
H. Hada, Y . Yonezawa, M. Ishino, and H . Tamemura, J . C'hem. SOC.Furaday Trans. I , 1982, 78,
2677.
552 H . Hada, Y . Yonezawa, and M. Saikawa, Bull. Chem. SOC.Jpn., 1982,55,2010.
553 V. E. Kazarinov, N. N. Andreev, and A . P. Mayorov, J . Electroanal. Chem., 1981,130,277.
554 Yu. P. Ipatov and V. V. Batrakov, Elektrokhimiya, 1980,16,630.
555 Yu. P. Ipatov and V. V. Batrakov, Elektrokhimiya, 1980, 16,624.
556 L. A. Reznikova, D. P. Aleksandrova, and B. N. Kabanov, Elektrokhimiya, 1981,17,542.
82 Electrochemistrj-
during cathodic polarization of a zinc electrode in 0.1--3 M KOH solutions. A
weak specific adsorption of K t was observed, the limiting step for potassium
incorporation into the zinc lattice being the solid-state diffusion process.
Other studies of zinc have revealed processes of adsorption occurring during
anodic dissolution. Tsygankova et af. have proposed a reaction scheme involv-
ing adsorbed zinc intermediate species in the anodic dissolution of zinc in ethanol
containing HC1+ LiC1. Hendrikx et 0 1 . have ~ ~ ~investigated the deposition and
dissolution reaction mechanisms for zinc and amalgamated zinc in 1.5-10 M
KOH using the galvanostatic technique. These authors propose a new reaction
mechanism for amalgamated zinc:

Zn[(OH),(H2O)J2 +Zn[(OH),(H,O),]- + O H - +(a-h)H,O (36)

Zn[(OH),(H,O)J + e - +Zn[(OH),(H,O),]- + O H - +(h-c)H,O (37)
Zn[(OH),(lf,O),]- +Zn[(OH)(H,O),]+OH- +(c--d)H,O (38)
+
Zn[(OH)(H,O),] e -+Zn(Hg) +OH dH,O + (39)

Here the reacting species, Zn[(OH),(H20)J2 . contains water and is adsorbed

at the zinc electrode. Variations in Tafel slopes with change in ionic strength of
solution are explained in terms of the relative sizes of (b - r ) and (c - 6). The differ-
ence between plain zinc and amalgamated zinc was ascribed to differences in the
dcgrcc and nature of adsorbed species. Zinc was considcrcd to be covered with
adsorbed O H - , whilst amalgamated zinc was covered only with adsorbed water
molecules.
Cachet and Wiart559.560also studied the zinc dissolution mechanism but for
chloride electrolytes, using d.c. polarization and impedance techniques. Three
relaxation processes were observed at low f r e q ~ e n c i e s , ~and ~ " it was concluded
that the mechanism of zinc dissolution involves two adsorbed intermediates, and
implies a slow electrode activation with increasing anodic polarization. The strong
stimulation of zinc dissolution by C1- ions was attributed to their influence upon
more than one elementary reaction step. Two parallel paths were proposed560for
zinc dissolution, the major path being catalysed by a Zn+ intermediate and the
minor part catalysed by a Zn2+ intermediate. The mino:d6path was found to be
much more dependent on the %lume diffusion of reacting species than the major
one. Both reaction mechanisms were strongly stimulated by chloride anions. These
authors5"' have also investigated the kinetics of zinc in alkaline zincate electro-
lytes, using impedance and steady-state polarization techniques. It was concluded
from the observation of four faradaic relaxation processes in the impedance spec-
tra that both dissolution and deposition of zinc involve at least four adsorbates,
and do not occur simply by series reactions. Some of the adsorbed species are
formed and consumed by slow reactions occurring in parallel with the main reac-
tion path. A much lower charge-transfer resistance was observed for dissolution
than for dcposition, indicating a change in the electrode kinetics on either side of
the equilibrium potential.
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'"' c'. Cachet and R. Wiarl. J . Elecfmarznl. Cheni., 1980, 111, 235.
"'O c'. Cachet and R. Wiart. J . Lkcirciunul. Chenr., 1981, 129, 103.
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Adsorption at Solid Electrodes 83
Trimbos and Stein562have identified three processes occurring at the zinc oxide
(ZnO)/aqueous electrolyte solution interface upon changing the pH of the solu-
tion. First, there is an adsorption of H f or OH-, second a dissolution or precipi-
tation of ZnO, and third, a further slow process consuming H f or O H - . The
capacitance due solely to adsorption of H + or OH- was isolated and calculated. It
was found to be significantly smaller than the value found by titration, and smaller
than that of the diffuse double layer.
M y a s n i k o ~investigated
~~~ the adsorption of oxygen molecules and methyl
radicals on polycrystalline ZnO in various polar liquid media. The chemical reac-
tivity of the adsorbed species increased with increasing dielectric constant of the
liquid medium.

562 H. F. A. Trimbos and H. N. Stein, J . Colloid Inlerjure Sri., 1980,77, 386.

563 I. A. Myasnikov, Zh. Fiz. Khim.,1981,55, 1283.