J. Electroanal. Chem.

, 165 (1984) 167-180 167

Elsevier Sequoia S.A., Lausanne - Printed in The Netherlands

UNDERPOTENTIAL DEPOSITION OF LEAD ON SINGLE CRYSTAL FACES

OF GOLD

P A R T I. T H E I N F L U E N C E O F C R Y S T A L L O G R A P H I C ORIENTATION OF
THE SUBSTRATE

A. HAMELIN
Laboratoire d'Electrochimte lnterfaciale du C.N.R.S., 1 place A. Briand, 92195 Meudon Cedex (France)
(Received 9th August 1983; in revised form 7th November 1983)

ABSTRACT

The influence of the crystallographic orientation of the gold substrate surface on lead deposition and
removal in the underpotential region is studied in detail. In order to observe systematic changes in the
cyclic voltammograms, the faces of the three main zones of the unit projected stereographic triangle are
grouped into five sections following bond order notation or a notation based on the TLK model of the
surfaces. Correlations with the potential of zero charge are discussed. A comparison with ionic adsorption
is made.

(I) INTRODUCTION

U n d e r p o t e n t i a l d e p o s i t i o n ( U P D ) is the electrochemical a d s o r p t i o n of a sub-

m o n o l a y e r or a m o n o l a y e r of cations on a foreign metal s u b s t r a t e at p o t e n t i a l s m o r e
positive than the reversible p o t e n t i a l of the d e p o s i t e d metal. This p h e n o m e n o n has
a l r e a d y been extensively studied on p o l y c r y s t a l l i n e substrates a n d on crystal faces
[1]. I m p o r t a n t changes in the cyclic v o l t a m m o g r a m s (CV) were o b s e r v e d for differ-
ent a d s o r b a t e s on the same substrate, even of the same c r y s t a l l o g r a p h i c o r i e n t a t i o n
(c.o.).
In o r d e r to gain further u n d e r s t a n d i n g of the influence of the physical state of the
substrate, the c.o. of gold was c h a n g e d systematically [2], especially close to the (100)
face [3]. Consequently, systematic variations in the c u r r e n t peaks of the CVs were
observed.
The structure of the a d s o r b a t e on gold was tentatively explained b y c o m p a r i s o n
o f the U P D on ( l l l ) - o r i e n t e d thin films a n d c o n v e n t i o n a l gold faces [4].
F o r metals crystallizing in the face-centred cubic system, following either the
b o n d o r d e r n o t a t i o n [5] or a n o t a t i o n b a s e d on the T L K m o d e l [6], it is clear that the
c.o.s, d i s t r i b u t e d on the three m a i n zones of the unit p r o j e c t e d stereographic triangle
c a n be g r o u p e d into five sections, the (311) a n d (210) faces a p p e a r i n g as " t u r n i n g

0022-0728/84/$03.00 © 1984 Elsevier Sequoia S.A.

168

(b)
10 (111(-(100(= (11,9,9
7(111( (~00)=(433} ,
s(ttl( (=0o)=(755},,/"

3(111)-{100)=(211
4

2(111)-(100) 3'
( 3 3 1 = 3(n1(-(1~1)
z O)-( )

31to0}-(111)=(511

10(]~0)-{111)=(1!

(100) f (110}
(210) (10,1,0) = (]10)= (210)= (32o) =
10(1~0) (110) 3(100)-(11D) 2(110) (10o) 3(110)-(100)
2(I00) -(110)

Fig. 1. Unit projected stereographic triangle for face-centred cubic structure, with the (100) face at the
centre of the projection. (a) Regions which correspond to different bond orders [5]: region (1) bond order,
abcdef; (2) abcedf; (3) abcefd: (4) abecdf; (5) abecfd. (b) Accepting the notation of Lang et al. [6]:
n(htktlt)-(h~ksls), where (htktlt) represents the terraces, n is the width of the terrace in number of
atoms and (h~ksl~) represents the steps.

points" on the (111)-(100) and (100)-(110) zones, respectively (see Fig. 1 and its
caption). Therefore the (111), (100), (110), (311) and (210) faces should have extreme
electrochemical behaviour. For the faces of gold this was observed for the pzc's (see
Fig. 10 of ref. 7).
The purpose of this paper is to show that our experimental results for the U P D of
lead on gold faces are in agreement with the above proposition, although some
secondary p h e n o m e n a are observed.

(II) EXPERIMENTAL

The experimental conditions have already been described previously [2,3]. The
CVs were observed at the equilibrium of adsorption, i.e. the potential imposed on
the electrode was varied with time sufficiently slowly so that diffusion of the active
species and the kinetics of deposition and removal did not affect the curves (20
m V / s ) . They were recorded during continuous cycling of the electrode; each cycle
included oxidation of the gold surface and subsequent reduction. Measurements
were carried out at r o o m temperature.
The base electrolyte was 10 m M HC104; for U P D studies 1 m M P b F 2 was added.
All solutions were deaerated with nitrogen.
All c.o.s are distributed on the three main zones of the unit projected stereo-
graphic triangle (Fig. 1); most of the faces were those used in refs. 2 and 3. All faces
were subjected to cycling in pure H C I O 4 before U P D study. In pure deaerated acid
observation of the current peaks for oxidation of gold and reduction of the
monolayer of oxide was used to check the physical and chemical states of the
surfaces. Systematic changes in the peaks with c.o. were observed for oxidation as
 169

well as for reduction; extreme situations were observed for the (111), (110), (100),
(311) and (210) faces.

(Ill) RESULTS

For all faces hydrogen evolution was strongly inhibited by the adsorbed lead.
"Chelation" of the gold oxide noted in ref. 2 was visible on all faces. For all faces,
stopping (20 s) the potential at the negative end of the potential range explored (ie.
just before the reversible potential of lead) did not modify the CV, therefore
deposition of the monolayer of lead seems to be completed at the surface of gold at
this potential.
Both deposition and removal of lead occurred at potentials far from the oxidation
(and reduction) of the gold surface, as can be seen in Fig. 1 of ref. 2.
For all faces, deposition and removal of lead were nearly reversible, except for the
(111) face and its neighbouring faces for which an irreversibility has already been
described [2]. Therefore for all faces we give the CV corresponding to the removal of
lead. The results are given in five groups which correspond to the five sections
observed on the three main zones of the unit projected stereographic triangle (Fig.
1).
The five faces of gold which present extreme behaviour will be discussed in more
detail. CVs for deposition and removal will be given and reversibility will be
analysed.

(III.1) The (111)-(110) zone (Fig. 2)

A general understanding of these results is easy if we accept the hypothesis that

the surface of the gold substrate can be described by the T L K model (terrace, ledge,
kink). From the (111) face, which is a terrace, to the (110) face, which can be written
according to the descriptive notation of ref. 6: 2(111)-(111), a systematic change
should be and is observed. According to the T L K model, the width of the terraces
diminishes and the density of the monoatomic steps increases; in parallel, in the CVs
the high narrow peak disappears and the peak at ca, 0 V vs. SCE increases. The T L K
model seems to be valid,
Examining the CVs more carefully, we can see a wealth of detail. The small peak
observed at the most positive potentials for the (111), (554) and (332) faces is highly
irreversible, as can be easily understood from Fig. 3 which gives the deposition and
removal for the (111) face; this irreversibility seems to be linked to terraces which
are at least six atoms wide (see Fig. 1).
The small negative peak appeared only for terraces less than four atoms wide.
With decreasing width from four to two atoms it increased. For the (110) face this
peak was clearly observed, its maximum being at - 0 . 3 6 V, and was slightly
irreversible as can be seen from Fig. 4.
We studied two samples, the c.o.s of both being (554). One gave a high double
peak (see Fig. 2 of ref. 2) comparable to that observed for the (111) face, and the
170

@A c rn ~
-100

50

71:1 :71
[~'ti I
;7,!1
• ,,"

/ ,.-,/" (332)
,'/ ~'(~s~)
,l.o/
• ,,'/(55£
,(331)

)"{I /I. ,A(111 )

- 03 0 E seE/V
Fig. 2. Voltammograms for the stripping of lead from faces of gold, the c.o.s of which are on the
(111)-(110) zone.

'i/H A cm-Z~~[ F:
'i

5[

; i
o ..... ""-:' °.:3 . . . .
-O.A • i 0 z--.O 3

...... :....... i I --!:'--E/V

~bc,
' .i j /
\_; ' '~.i

50

Fig. 3. Cyclic voltammograms for the gold (111) face showing the effect of different ranges of potential
scan [2].
 171

20

• f ..... .~,

- 0.1

50

Fig. 4. Cyclic voltammogramsfor the gold (110) face showing the effect of different ranges of potential
scan.

other showed a single high peak (Fig. 2), although high irreversibility existed for
both samples. This shows the extreme sensitivity of the CVs to the c.o. of the
substrate; there was probably a slight difference in the c.o.s of the two samples and
consequently the CVs are different.
All the CVs were integrated for removal (stripping); the results for this zone are
summarized in Table 1. In the second column, the charges due to total removal are
given (charging of the double layer was assumed to be constant in the U P D region
and equal to the value observed in the potential range where there was no faradaic
reaction). In the third column, the charges due to the peak corresponding to lead
removal from the monoatomic steps are given. In the fourth column, the charges due
to the small peak observed at the most negative potentials are given. In the fifth
column, the charges corresponding to the highly irreversible peak observed at
positive potentials are given. Lead was assumed to be adsorbed as a neutral
substance [8].
Examining the data of Table 1 (as for the subsequent tables), one should keep in
mind that several difficulties are encountered when determining extensive parame-
ters on single crystal faces. There is an error in the geometric area because of the
positioning of the isolating material on the walls of the crystal. The working area
could be different from the geometric area; here the roughness factor was assumed
to be unity. To measure the charge due to the faradaic process, the charge due to the
172

TABLE 1
Charges associated with removal of lead from faces in the (111)-(110) zone
c.o. Experimental charges, o/#C cm- 2
Total charges Charges for Charges for the Charges for
from - 0.45 V the peak from peak from - 0.45 the highly
+ 10% + 0.10 to - 0.10 V to - 0.30 V irreversible peak
(111) 272 15 (0) - 39
(554) 273 36 (38.9) - 38
(332) 274 57 (67.6) 14
(221) 275 100 (105.8)
(331) 276 124(128.2) 28 -
(551) 265 161 (162.2) 37 -
(110) 233 182(224) 36

d o u b l e layer was e s t i m a t e d as m e n t i o n e d above, but this could also entail errors.

A n d last b u t not least, when m e a s u r i n g the charge c o r r e s p o n d i n g to a p e a k which is
close to another, there is some d o u b t at which p o t e n t i a l s one should begin a n d finish
integration.
However, the influence of the increasing d e n s i t y of the m o n o a t o m i c steps at the
surface of these gold faces is clearly u n d e r s t o o d from T a b l e 1 if we c o m p a r e the
e x p e r i m e n t a l charges due to these steps with the calculated values, given in p a r e n t h e -
ses in the third column. The latter were calculated in a very crude way, assuming
that lead a t o m s could sit side b y side along a m o n o a t o m i c step, although m o r e
f a v o r a b l e sites certainly could exist on these faces, as was discussed in ref. 4.

(111.2) The (111)-(100) zone

As the (311) face a p p e a r s as a turning p o i n t in this zone (Fig. 1), we d i v i d e d the

results into two groups.

(III.2.a) From the (111)face to the (311)face (Fig. 5)

The general c o m m e n t s given a b o v e for the (111)-(110) zone are still valid, i.e. the
high p e a k c o r r e s p o n d s to leaa r e m o v a l f r o m the terraces, the o t h e r large p e a k
c o r r e s p o n d s to r e m o v a l from the m o n o a t o m i c steps; the small p e a k at positive
p o t e n t i a l s is highly irreversible.
However, two p o i n t s must be m a d e : first, the m a x i m u m of the p e a k due to the
r e m o v a l of lead f r o m the steps is ca. 0.025 V m o r e positive than that for the
(111)-(110) zone; this is not surprising since the steps in this section have a (100)
c.o. whereas they h a d a (111) c.o. in the first zone studied; secondly, this p e a k for the
(311) face seems to consist of two peaks, each being reversible (Fig. 6). This last fact
implies that there are two possibilities, c o r r e s p o n d i n g to slightly different energies,
of placing lead on the (311) face; this is not surprising if we c o n s i d e r its a t o m i c
constitution.
 173

i//p A cm-2 14

11

-100 It

'111
jill
IIII

I.

I,iI
50 i!~l
1

ill (311)
I iII : .././(211)
"'~ / 'il ,." 7~(5331
•/ ,, h, ./ / ...~"~,-4755)
/r ,.!1 ~,_. .,,',~" ~.i11.9.9)
~:."~ ./-4-.--::' ,.~ "~ " ~ :-2t ~ - '~-...~-. -'" ":

- 0.2 0 EscE/V
Fig, 5. V o h a m m o g r a m s for the stripping of lead from gold faces, the c.o.s of which are on the (111)-(311)
section of the (111)-(100} zone.

For the (211) c.o., two different samples were studied; both gave the same CV.
The small peak at the most negative potentials decreased from (311) to (755) and
appeared to consist of two peaks for this last c.o. The small peak at the most positive
potentials observed for (11, 9, 9) and (755), as for (111), was highly irreversible (Fig.

•20 A /.''!"":.

.: i -.+0.1
i"~
:
:: x
' "-
I '- -}
#

i -0 9_;i ;0 i i. ,K

.i.
i

:/" . . . . "<
•i ~
\'~ \ i
.I ..:
'\ / "

Fig. 6. Cyclic v o l t a m m o g r a m s for the gold (311) face showing the effect of different ranges o1 potential
scan.
174

TABLE 2
Charges from faces in the (111)-(100) zone
c.o. Experimental charges, o/ff C cm- 2
Total charges Charges for Charges for the Charges for
from - 0.45 V the peak from peak from - 0.45 the highly
_+10% +0.10 to -0.10 V to -0.25 V irreversible peak
(111) 275 15 (0) - 39
(11, 9, 9) 214 37 (37.7) 27
(755) 296 74 (63.8) 36 20
(533) 294 84 (96.8) 38 -
(211) 287 110 (129.5) 56
(311) 294 165 (191.4) 109 -

3), and was connected to terraces oriented (111) and wider than six atoms as for the
(111)-(110) zone.
Charges were obtained by integration of the CVs for removal of lead from the
gold surfaces. The results are summarized in Table 2. The comments made for Table
1 hold, except for the small peak at the negative potentials of (311) and (2!1) for
which we assumed the shape of the peak for integration to be symmetrical.

(III.2.b) From the (311)face to the (100)face (Fig. 7)

F o r this section, the terraces are ( 1 0 0 ) - o r i e n t e d a n d the m o n o a t o m i c steps are
( 1 1 1 ) - o r i e n t e d (Fig. 1).
T h i s section has a l r e a d y b e e n s t u d i e d in d e t a i l [3]. W e still b e l i e v e that the large
p e a k o b s e r v e d f r o m - 0 . 1 0 to + 0.10 V is r e l a t e d to r e m o v a l f r o m b o t h steps a n d
terraces, as d e m o n s t r a t e d b y i n t e g r a t i o n (Fig. 8 of ref. 3).
T h e h i g h l y i r r e v e r s i b l e peak, o b s e r v e d in t h e ( 1 1 1 ) - ( 1 1 0 ) z o n e a n d the p r e c e d i n g
section, d o e s n o t a p p e a r ; it is a c t u a l l y c o n n e c t e d to the ( 1 1 1 ) - o r i e n t e d terraces.
T h e a m p l i t u d e o f the p e a k at the m o s t n e g a t i v e p o t e n t i a l s d e c r e a s e d f r o m (100) to

' i ~ A cm 2
.40
/(311)
/. /
/.-..I->-
l20 /.. _:--~...-(19,1,1)
//l[~, l) /,, / ~ //- ~(100)

0.2 6 E scr.,/V
Fig. 7. Voltammograms for the stripping of lead from gold faces, the c.o.s of which are on the (100)-(311)
section of the (100)-(111) zone.
 175

(511) and at the same time the peak shifted negatively; this is due to the addition of
the (111) steps on the (100) face.
The total experimental charges for removal of lead were respectively (in f f C / c m 2):
294 for (311), 293 for (511), 300 for (19, 1, 1) and 265 for (100).

(111.3) The (110)-(100) zone

As the (210) face appears as a turning point in this zone (Fig. 1), we divided the
results into two groups.

(llL3.a) From the (100)face to the (210)face (Fig. 8)

This section has already been studied in detail [3]. By changing the c.o. from (100)
to (210), kinked steps are added to a (100) terrace; the (210) face is mostly made up
of kinks [5]. Kinks do not exist for faces in the other zones. The general comments
given in section III.2.b are still valid for this section.
Three differrent samples were studied for the (210) face. They gave the same CV,
reversibility was observed all along the potential range of UPD, and further
exploration of the range of potential increased the peak observed at - 0 . 3 8 V
removal (Fig. 9).
For the (100) face, reversibility of the CV was observed all along the UPD region
[3] (Fig. 10). Therefore reversibility seems to exist for all faces of this section.
However, for the (310) face the most negative peak observed for removal corre-
sponds to two small peaks for deposition.
The three main peaks of the complicated CV observed for the (100) face were still
visible for the (610) face which is 6(100)-(110)); the maximum of the peak at the
most negative potentials was still at - 0 . 3 0 V (see Fig. 2a of ref. 3). This peak was
not visible for faces further from (100) but another peak existed at negative
potentials, the maximum of which was at ca. - 0 . 3 8 V; therefore the negative peak
of (100) corresponds to a process which requires a width of terraces of more than
three atoms.
The peak at the most positive potentials along this section of the (100)-(110) zone

i • A ¢m~

~310)
.(1 o,to)
20 / /, ,(loo)

,\\ ~.. /f)...._ ~ ~.~ ~,,,\

' ' - 012 ' 0 EscE / V

Fig. 8. Voltammograms for the stripping of lead from gold faces, the c.o.s of which are on the (100)-(210)
section of the (100)-(110) zone.
176

/~IA.C m -i' .".

30 ,/ '

20 / !i"~
/ ii ~
- ... .~ \ ,,~
-0 5 ," .I: \ ~..- -/" \ .....
, .: - I, ,~- , , , ,

~o,i.......",i.,.,." \ i~;/~

k$
Fig. 9. Cyclic voltammograms for the gold (210) face showing the effect of different ranges of potential
scan.

increased and simultaneously its peak potentials shifted positively. This corresponds
to an increase in the density of kinked steps. This density reached a maximum,
among the faces studied here, at the (210) face, hence the peak potential is the most
negative for this face. Obviously it is easier to put lead on kinks that are on densely

401 ilpA'cm-z
f

20
il.
,j "" f f ",
,I ,I ,i , ,~..,............
,.. • .....- ~ "
} o.2, i 0.4,.
............oG~
..............
i$J[i 04 '
::.e.q/t~. ]I ~. j.i" " ~..............
.I J [i HE/V
," .I' ' !

20 it v ......
I ilj,,
!1"

40 a) i b)

Fig. I0. Cyclic voltammograms for the (100) face of gold showing the effect of different ranges of
potential scan [3].
 177

TABLE 3
Charges from faces in the (110) (100) zone
c.o. Experimental charges o/~ C cm- 2
Total charges Charges for the Charges for the peak
from -0.45 V peak (max at -0.30 V) (max at ca. -0.38 V)
± 10% from -0.45 to -0.27 V from -0.47 to -0.30 V
(100) 274 60 -
(10,1,0) 250 45
(610) 270 30
(310) 300 - 70
(210) 250 - 74
(210) 250 - 74
(320) 288 70
(110) 233 - 40

packed steps a n d terraces, and it is more difficult to remove it.

We integrated the CVs as above for stripping of lead; the observed charges are
given in the first part of Table 3. We included the experimental charges observed for
the (610) face. We separated the charges observed for the peak at the most negative
potentials into two groups. In the third c o l u m n are the charges for (100), (10, 1, 0)
a n d (610), the peak m a x i m u m of which is at - 0 . 3 0 V; in the fourth c o l u m n are the
charges for (310) a n d (210), the peak m a x i m u m of which is at ca. - 0 . 3 8 V.

(ll13.b) From the (210)face to the (110)face (Fig. 11)

The (210) face is mostly made up of kinks; the (110) face consists of densely
packed lines of atoms. F o r the (320) face an i n t e r m e d i a t e situation exists if we accept
the T L K model.
For these faces the CV presented m a i n l y two peaks: the peak at the most positive
potentials shifted negatively in potential with a decreasing n u m b e r of kinks at the
surface; the a m p l i t u d e of the peak at the most negative potentials increased with this
parameter. N o irreversibility was observed for this group of faces.

I~Acm2
40
/~-(210)
,/1 -(320)
2 ~ / //~',\(110)

' -0'2 ' 0 EscE/V

Fig. 11. Voltammograms for the stripping of lead from gold faces, the c.o.s of which are on the
(210)-(110) section of the (100)-(110) zone.
178

The charges determined by integration are given in the second part of Table 3.

(IV) D I S C U S S I O N

Obviously the changes observed for the CVs with c.o., obtained at equilibrium of
lead adsorption on the gold faces, are systematic as long as the faces are grouped
into five sections (Figs. 2, 5, 7, 8 and 11). These sections of the three main zones of
the unit projected stereographic triangle correspond to systematic changes in the
atomic arrangement of these faces (Fig. 1). The influence of the monoatomic steps
on the CVs is clearly visible; it is also indicated by the charges due to stripping of
lead, obtaining by integration of the peaks (Tables 1 and 2).
The peak at the most negative potentials is probably due to a change in structure
of the adsorbed atoms allowing the accomodation of more lead on the gold surface.
The stability and the reconstruction of the faces will be discussed in Part II of this
series.

(IV.l) Correlations between underpotential shifts, electronic work-function differences,

pzc differences and c.o.

A relation between the underpotential shift, AEp (between the potential for bulk
and monolayer stripping), and the difference of the electronic work functions of the
two metals (adsorbate and substrate) has been proposed [9]: Agp = 0.5 Adp. For lead
on gold faces this relation does not apply clearly [10].
The work function, as the potential of zero charge (pzc) (they are linearly related),
even for crystal faces, is a global parameter which includes in a single value of
energy (or potential) the effects of steps, terraces, kinks a n d . . , defects; conversely,
the UPD CV of a face gives the energy spectrum of the surface of the face (as long
as no other phenomenon interferes). Therefore only for faces which have one type of
adsorption site (and no secondary phenomenon) would one peak be observed for
UPD, and consequently the relation could be applied. But we have seen that for
most of the gold faces several UPD peaks are observed.
However, if we modify the relation proposed by Gerischer et al. [9], so that only
the electrochemical parameters observed on gold faces are used, between the two
extreme cases
A?2o, , A Ep = O. 5A72o', ep,.
The (111) and (210) faces were chosen because in a first approximation they give
mainly one peak for deposition and thus they are assumed to have only one type of
adsorption site on their surfaces. For deposition
A (~210)
l l l ) A ~ ~p
- = 0.28 and AOll)AE =0.46
"~'~(210)~ pzc

which is not far from what was expected.

In fact, any parameter which reflects, by atomic data, the specificity of the
different faces: the calculated surface energy (see Fig. 10 of ref. 7), the density of
 179

dangling bonds at the surface, will vary in parallel with the pzc or the charge due to
stripping of lead from the gold steps (see Tables 1 and 2) as a function of c.o.

(IV.2) Comparison of UPD of lead and ionic specific adsorption on gold faces

Ionic specific adsorption is understood from the variations of the differential

capacity vs. potential curves (C(E)). But for this type of adsorption the situation is
more complex than for UPD because besides the capacity peak due to ionic
adsorption (which correspond to the inflexion point of the isotherm for half-cover-
age), reorientation of the solvent dipoles also gives a capacity peak. Furthermore,
another capacity peak could be observed for partial charge transfer [7]. On the
contrary, for UPD of P b / A u charge transfer is complete all along the range of
potential explored [8] and reorientation of the solvent does not appear.
The influence of the monoatomic steps has been observed for chloride adsorption
on gold faces of the (111)-(110) zone [11]. The results for iodide adsorption, for
faces distributed on the three main zones of the unit projected stereographic triangle
[12] could, in the same way as our results for UPD, be divided into five sections for
easier interpretation. This was done for bromide adsorption on gold faces [13]. The
fact that sometimes one of the capacity peaks is just a shoulder on the other one (or
merges with the other) makes analysis of the results more difficult than for UPD.
However, the systematic decrease in the high double peak observed for the (111)
face, as well for the UPD spectrum and the C(E) curves, as the terraces diminishes,
is observed for both cases. A systematic increase in the peak corresponding to the
steps is simultaneously observed when the c.o. is changed from (111) to (110), from
(111) to (311), from (100) to (311), and from (100) to (210), for both types of
adsorption.
The reconstruction of the first layer of gold atoms observed or suggested to
explain the secondary features of the C(E) curves [14] should appear on the UPD
spectra; this will be discussed in Part II.

(IV.3) Comparison with other UPD data

(IV.3.a) On gold faces

For gold faces, mainly the three faces of the simplest indices, results for the UPD
of lead and other foreign metals have already been published and compared [1,8,10].
The results obtained for the deposition of lead on a thin layer of (111)-oriented
gold and simultaneous conductance measurements of the thin layer of gold [4] are in
agreement with our results: the five breaks observed on the charge-potential curve
correspond to the peaks that we observed on the UPD curve.

(IV.3.b) On other substrate faces

For no other substrate has the influence of the c.o. been analysed in such detail as
for gold.
Anyway, the difference in the bonded strength of each pair (adsorbate-substrate),
180

the reconstruction of some substrates and not of others, the complete charge transfer
o n l y f o r s o m e p a i r s , a n d a l l o y i n g in s o m e c a s e s w o u l d m a k e c o m p a r i s o n d i f f i c u l t .

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