Elecmckimica Ada, Vol. 37, No. 12, pp. 2137-2144, 1992 00134686/92 55.00 + 0.

00
F’rinted in Great Britain. 0 1992. Pngamon Press Ltd.

ADSORPTION OF ORGANIC SUBSTANCES AT

ELECTRODES: RECENT ADVANCES

SERGIO
TRASATTI
Department of Physical Chemistry and Electrochemistry, University of Milan, Via Venezian 21,
20133 Milan, Italy

(Received 30 January 1992)

Abstract-Recent developments concerning four areas in the field of adsorption of organic compounds
at electrodes are critically examined and discussed. The topics are: (1) possibility of experimental
determination of the molecular size factor, n; (2) effect of the nature of the metal on the Gibbs energy
of adsorption; (3) effect of the crystallographic orientation of the metal surface; (4) effect of functional
groups in the adsorption of aromatic compounds from non-aqueous solvents. Results show: (1) the value
of n appears to be * 1 for all substances irrespective of the molecular size; (2) the nature of the metal
is mainly seen through the desorption of the preadsorbed water molecules; (3) the effect of the atomic
density of the metal surface cannot be assessed unambiguously from the few data available; (4) functional
groups can change the adsorbate-solvent interactions as well as the aromaticity of the benzene ring. The
combined effects can turn a physical interaction with the metal surface into a strong, specific chemical
interaction via the x-electron system, as a consequence of changes in the interfacial orientation.

Key worak: adsorption isotherm, single crystal face, metal-water interaction molecular size factor,
functional group.

INTRODUCTION that adsorption at solid/liquid interfaces is in fact a

The study of the adsorption of organic substances at
electrodes, although it dates back to the early days
of interfacial electrochemistry with the pioneering
work of Gouy[l], still attracts wide interest because
of its impact on our understanding of the structure of
the electrical double layer[2,3], the kinetics of elec-
tron transfer[rl], the general field of corrosion (inhi-
bition)[S], and the mechanism of electrode processes
(role of intermediates)[6,7]. Recent reviews have
dealt with the adsorption of aliphatic[8] and aromatic
compounds[9] at the Hg electrode, and with a
comparison of different molecular models of the
adsorption layer[ lo].
Although information on the molecular structure
of the adsorbate can be obtained in situ by means
of non-electrochemical techniques[ 111, the thermo-
dynamic analysis of surface concentrations (or sur-
face excesses) is still the most used route to gain
insight into the mode of adsorption of organic com-
pounds[ 121. This entails the description of the exper-
imental data by means of an adsorption isotherm,
and the construction of an adsorption model based
on the derived adsorption parameters.
In this context, how to proceed in the thermo-
dynamic analysis and how to interpret the resulting
adsorption parameters are still matters of discus-
sion[l315]. The aim of this paper is to analyse a few
aspects which have recently emerged, and which can
contribute to gaining more insight into the molecular
details of adsorption at electrodes.
solvent-replacement reaction[ 161 described by the
generalized equation:
B(sln) + nS(ads) c-) B(ads) + nS(sln), (1)
where B stands for adsorbing substance (adsorbate)
and S for solvent.
Figure 1 provides a pictorial view of equation (1)
to emphasize the fact that under similar circum-
stances adsorption parameters are not representative
of B only, but of both B and S. Therefore, they give
information about the mode of adsorption of B and
at the same time they can be used to derive infor-
mation about the state of the solvent at the interface.
In general, for a generic parameter Y, it is possible to
write:
A Y(ads) = [ Ya(ads) + Y,(sln)] - [ Yi,(sln) + Ys(ads)]
(2)
or, in another form:
AY(ads) = [Ys(ads) - Ya(sln)] - [ Y,(ads) - Y,(sln)]
(3)
Equation (3) emphasizes that the change of
parameter Y upon adsorption also contains the
change of Y for the solvent upon desorption. Typi-
cal examples of parameters including contributions
from the replaced solvent are the adsorption poten-
tial shift and the adsorption Gibbs energy. Rel-
evant discussions have been presented recently
[14, 15, 17-201.

MODEL OF THE ADSORPTION LAYER SIZE FACTOR

There exists general consensus about the concept of The term n in equation (1) is the so-called size
the adsorption equilibrium: it is universally accepted factor. Physically, it is defined as the number of

2137
2138 S. TRASATTI
solvent molecules replaced by one molecule of adsor-
bate. Its quantitative value depends on the model of
the adsorption layer.
A generalized definition of n is[21]:
n= k&lb&, (4)
where A, and A, are the area of interface occupied by
one molecule of B and S, respectively, and 1s and 1,
are the thicknesses of the adsorption layer expressed
in terms of unit of molecular thickness. Therefore, for
an adsorption layer whose thickness is the same as the
thickness of the molecules of B, 1, = 1 and Is is equal
to the number of monomolecular layers of S in the
adsorption layer.
The way n is expressed varies among different
authors. Some authors adopt a monomolecular layer
for the adsorption region[22,23]. Under similar cir-
cumstances la = Is = 1 in equation (4) and n turns out
to coincide with the ratio of the projected areas of B
and S, respectively. Therefore, n is a model-dependent
parameter whose value has been as a rule calculated,
since no direct experimental determination has been
envisaged for long.
A point of debate is whether or not n must
explicitly enter the adsorption equilibrium. Two pos-
itions have been taken. In Frumkin’s approach n is
not introduced, which is tantamount to assuming
n = 1. The corresponding adsorption isotherm has
the form[24]:
KJa/(l- Wlev(-24d = I%, (3
where t& is the fractional coverage of the interface
with B, xa is the mole fraction of B in solution, u the
particle-particle interaction parameter at the inter-
face, and /I the adsorption constant. On the other
hand, if n is introduced explicitly, the same mode1 on
which the Frumkin isotherm is based leads to the
isotherm bettem known as the Flory-Huggins
isotherm[25]:
[e,/(i
-8,)“e”-i]exp(-2a’B,)=fl’x,. (6)
Proof that n must appear in the equations (ie that
n # 1), might be obtained indirectly by analysing the
fitting of experimental data to adsorption isotherms.
Figure 2 simulates adsorption data conforming
either to a Frumkin isotherm or to a Flory-Huggins
isotherm. A linear test of the Frumkin isotherm
(t?,/( 1 - t&)x, us 0,) clearly produces a non-linear
0 0
+ C = exp{ln xa - @AJRT + K}.
a 0
Fig. I. Model of adsorption as a solvent replacement
reaction.
6 - .
t (4
.,,ll:::::::...*.............,..
1’ -..
-.
e
Fig. 2. Simulation of isotherm tests. (a) Data conforming to
a Frumkin isotherm (1) plotted in terms of a Flory-Huggins
isotherm (2) with n = 3; (b) data conforming to a
Flory-Huggins isotherm (2’) with n = 3 plotted in terms of
a Frumkin isotherm (1’).
test in terms of the Flory-Huggins isotherm
(0,/(1 - 8,)“xs us 6,). However, since experimental
data, however accurate, are somewhat scattered, it
is in practice hard to discriminate between the two
models graphically. The only discriminating criterion
which can be adopted is a linear regression analysis
of the experimental tests, which does not provide any
physical certainty.
There have only been two specific attempts to
determine the value of n. In one case, Damaskin[26]
concluded that the experimental data were better
represented by an equation with n = 1. Conversely,
Lawrence and Parsons[22] reached the opposite con-
clusion by fitting the data, for instance of sulpholane
adsorption, to a Flory-Huggins isotherm with
n = 2.27. On the other hand, the present author
observed[27] that if adsorption data are available
only in a limited range of Be, it is impossible to reach
any conclusive evidence.
In the above context, a recent paper by Nikitas[28]
has apparently provided a clue to the solution of the
problem. Nikitas has claimed that n can be obtained
thermodynamically from the raw experimental data.
While the full derivation can be found in the original
paper, the fundamental equations are the following:
w1 - 0
n = lim (7)
*d-1 c(iix, - e,)- X,/X,
where x is the mole fraction in solution, x0“ the mole
fraction at the interface, and C is given by the
expression:
(8)
In equation (8) @ is the experimental surface pressure
due to adsorption (@ = y0 - y), and K is a constant
for a given system:
K = (YO- Y;)ABIRT. (9)
In equation (9) y,, is the interfacial tension of the pure
solvent and 7; is that of the pure solute. Since the
 Adsorption of organic substances at electrodes 2139

t b)

Fig. 4. Adsorption of dimethoxyethane at the free surface of

--.._._
8- -.-w-L
----____
I
0 02 0.4 0.6 0.8
e shown in Fig. 3b. Also in this case the extrapolation
Fig. 3. Adsorption of dimethoxyethane at the free surface of
water: raw experimental data[29]. (a) Plot of equation (8) to
determine the constant term; (b) plot of equation (7) to
determine the value of n.
value of 76 may not be available, K can be obtained
from equation (8) by extrapolation:
K = -iby, (In xs - @A,/RT).
Thus, by means of two extrapolations it is poss-
ible, according to Nikitas, to determine the value
of n.
Nikitas has pointed out that the extrapolated value
of K is sensitive to the accuracy of the experimental
data, and that the value of n is extremely sensitive to
the value of K. A smoothing procedure of the raw
data is thus advisable. Unlike Nikitas, it is suggested
here that a very effective smoothing is obtained if the
raw data are fitted by an isotherm and the isotherm
parameters are then used to recalculate the data.
While a more detailed discussion of this point will be
given in a forthcoming paper, an example of data
processing is provided here.
Figure 3a shows a plot of equation (8) using raw
experimental data[29]. Since the highest value of 0s
water: smoothed experimental data. Plot of equation (7) to
determine the value of n.
1 is 0.8, the extrapolated K cannot be very accurate.
Once K is introduced into equation (8), and conse-
1 quently into equation (7), the resulting plot is as
is not very accurate but a linear regression analysis in
the range 0.3 c 0s < 0.8 provides a value close to 1
for n.
The same raw experimental data have then been
fitted by a Frumkin adsorption isotherm and the
adsorption parameters obtained. By means of the
corresponding state equation, smoothed e-0, and
I&,-xs pairs of data have been recalculated. If the
smoothed data are introduced into equation (8), and
(10) then into equation (7), the resulting plot is as shown
in Fig. 4. Now the extrapolation turns out straight-
forward, and the resulting value of n is very close to 1.
It can be questioned that the use of an isotherm
to fit the experimental data will produce smoothed
data reminiscent of the isotherm used. This is not the
case. Smoothing consists in fact in describing the
@-log xs raw data by means of an analytical func-
tion. It will be shown in a forthcoming paper that the
choice of the function to describe the experimental
data is without any substantial effect on the derived
value of n, provided the fitting is sound.
Data for other four organic compounds[29-311
have been processed in the same way. The results
are summarized in Table 1. While the calculated value
of n ranges from 4.5 to 7.8 in terms of molar
volume ratio (or from 2.8 to 3.5 in terms of ratio of
projected area), the values of n derived by extrapol-

Table 1. Theoretical and “experimental” sixe factor

n

Theoretical*
Adsorbate V A “Experimental”
1,4-Dioxane 4.7 2.9 Hg/sln 1.0*0.1
1,2-Dimethoxyethane 5.8 3.3 air/sin 1.0*0.1
Hg/sln 1.0*0.1
1,2_Diethoxyethane 7.8 3.5 air/sin 0.9 f 0.2
Hg/sln 1.2*0.2
Succinonitrile 4.5 2.8 air/sin 1.0 f 0.2
Hg/sln 0.8 f 0.2
Glutaronitrile 5.3 2.8 air/& 0.8 f 0.3
Hgjsln 0.8 f 0.3
2-Butanolt 5.0 2.8 air/& 1.6 f 0.3
Hg/sln 0.6 f 0.3
Trioctylposohine oxide? 10.9 8.7 Hg/MeGH 0.8 f 0.3
lV = Molar volume ratio; A = projected aa ratio.
tFrom Ref. [28].
2140 S. T~rri
ation are in the range 0.8-1.2, ie always approxi-
mately 1. In Table 1 the previous data of Nikitas[28]
are also reported. Again, the value of n for two
organic compounds is not far from 1, despite the fact
that in one case the area ratio is close to 9.
The obtained results can suggest contrasting
conclusions.
(1) The unit value of n indicates that the n
water molecules displaced by one molecule of adsor-
bate count (or behave) as a cluster from a statistical
point of view. Therefore, n = 1 in equation (1). This
would support the earlier analysis of Damaskin[26]
and would corroborate the approach on which the
Frumkin isotherm is based. However, n = 1 does not
mean that solvent molecules desorb as clusters or that
clusters of exactly the same size as the adsorbate
pre-exist. More simply, from a statistical point of
view the n solvent molecules must not be counted
separately. If this is the case, all existing analyses in
which the value of n has been postulated as # 1
should be reconsidered.
(2) The derivation of n as suggested by Nikitas[ZS]
is not a fully thermodynamic operation. In fact, in
order to define n the size of the solvent must necess-
arily be introduced. The experimental data depend on
the presence of the solvent but they do not contain its
parameters explicitly. Thus, in order to define n,
extra-thermodynamic assumptions or positions must
be adopted. The situation is that, contrary to the
possibility of thermodynamics, more information is
looked for than the raw data can give. In other words,
the raw experimental data do not contain any infor-
mation on n, therefore they cannot provide any value
of n other than 1.
No firmer conclusions can be reached for the time
being. Further analysis is needed and will be reported
in a forthcoming paper. However, one may wonder
why the surface pressure, which is determined by the
surface concentration and depends on the bulk con-
centration, should be different depending on whether
or not solvent molecules are desorbed as monomers.
NATURE OF THE ELECTRODE METAL
Equation (1) and Fig. 1 suggest that the Gibbs
energy of adsorption at electrodes must contain, in
particular, a contribution from the desorbed solvent.
More specifically, it can be written as:
A,,G” = A,Go - nA,G”. (11)
AsG” includes B-S and B-M(meta1) interactions at
the interface. Thus, to a first approximation, equation
(11) can be. rewritten as[32]:
AadGo = AG”(B-S) + AG”(B-M) - nAG”(S-M).
(12)
The first term on the right-hand side of equation (12)
allows for the different state of B in the bulk and on
the surface in the absence of specific interactions with
the metal, which is in turn accounted for by the
second term. Thus, AGo accounts for any
squeezing out effect of B molecules from the solution.
For a given organic compound AG”(B-S) is (to a
first approximation) the same at different electrodes.
If the organic compound is adsorbed in an orien-
tation allowing only weak, non-specific interactions
with the metal surface, AGO can also be con-
sidered independent of the nature of the electrode
surface. Under similar circumstances, equation (12)
becomes:
A(A_,GO) = -A[AG”(S-M)], (13)
ie the variation in Gibbs energy of adsorption be-
tween two metals equals approximately the difference
in the work to desorb solvent molecules (n is the same
for different orientations of B in case the molar
volume ratio is used).
The validity of equation (13) has been tested in
particular for sp metals[33,34]. As a measure of AC”
(S-M), the enthalpy of formation of the oxide MO
has been used. This is shown in the inset of Fig. 5
for the adsorption of n-pentanol. AadGo is seen to
decrease as ArHo increases, ie as the work to
displace solvent molecules increases. In the plot the
position of Ag looks reasonable: with a low value of
ArHo( ie with a weak affinity for water mol-
ecules, the AadGo is high. However, more recent
results[35] give a much lower value of dadGo for Ag,
as indicated by the arrow in the inset. This has been
justified by the authors of Ref.[34] in terms of ion
co-adsorption (sulphates) in the case of their earlier
results[36]. Thus, Ag turns out not to fit the plot in
the inset. The same is the case for Au, if recent results
are considered[37,38]. A,H”(MO) of Au is in fact not
very different from that of Ag, and AB,Go is also
small. Therefore, the plot in the inset of Fig. 5 does
not seem appropriate to include sd metals together
with sp metals.
This author has recently shown[39] that a more
universal parameter than ArH”(M0) is obtained from
the plot of the potential of zero charge vs. the electron
work function. This new parameter X, called the
“interfacial parameter”, encompasses the various
contributions to the interfacial potential drop:
XM = 6~~ + g’(dip). (14)
In equation (14) 6~~ is the modification of the surface
potential of the metal due to the contact with the
solution, and gs (dip) is the surface potential brought
in by the liquid phase.
r 21-
E ..“Q
3 #- -5.
P
$ ,,_
* 15-
0 -a1 -02 -0.3
Ax/V
Fig. 5. Plot of the standard Gibbs energy change at zero
coverage for the adsorption of n-pentanol on various
metals, against the “interfacial parameter” AX derived from
the work function-potential of zero charge relationship.
Inset: the same data plotted against the standard enthalpy
of formation of the oxide M0[33,34].
 Adsorption of organic substances at electrodes
Since gs (dip) is related to any specific interactions
between the metal and solvent molecules[40], ArHo
(MO), as used in the inset of Fig. 5, is likely to include
only part of the factors governing AadGo. In fact,
the modification of the electron distribution at the
surface of the metal (which determines the surface
potential of the metal) is also a consequence of
specific M-S interactions, although these may not
contribute to the orientation of solvent molecules.
Therefore, XM is thought to measure the interaction
between the metal and the solvent more globally.
Figure 5 shows a plot of A,,G“ vs. AX, a relative
value of XM taken with respect to Hg (absolute values
cannot be obtained; on the other hand, they are not
needed in this correlation). The data points gather
around a straight line more closely than in the inset
of the same Fig. 5. Moreover, the point for Ag now
falls quite nicely on the common straight line. The
point of Au is low, but the interfacial parameters of
polycrystalhne surfaces (as it is the case for this
result) are not perfectly defined: the data for Ag on
the contrary refer to the (110) face.
It can be concluded from Fig. 5 that the interfacial
parameter X simulates the strength of the interaction
between the solvent and the metal surface better than
ArH”(MO), and that the Gibbs energy of adsorption
of organic substances, provided no specific adsor-
bate-metal interaction takes place, varies with the
nature of the metal in a way which can be closely
predicted by the value of X”: the larger the contri-
butions (electronic and solvential) to the interfacial
potential drop in the absence of foreign adsorbates,
the weaker the tendency of organic substances to be
adsorbed.
It is interesting that Ag and Au are poor adsor-
bents despite the weak affinity for water (ie low value
of A,HO). This confirms that, as stated earlier by this
author[33,41], in the case of sd metals electronic
contributions to the interfacial properties are more
important than solvential contributions.
CRYSTAL FACE SPECIFICITY
Work on adsorption of organic substances at metal
single crystal faces has been reviewed by this author
in a previous paper[42]. If adsorption at single crystal
faces is assumed to be governed by the same factors
as at heterogeneous (polycrystalline) metal surfaces,
Fig. 5 can be used to predict the order of crystal face
sequence. It has been shown previously[42] that the
more compact the crystal face, the more positive the
potential of zero charge. At the same time, XM
increases (linearly) as the potential of zero charge
becomes less positive[41] (ie XM is higher for open
faces than for close-packed structures). In this con-
text, it can be expected from Fig. 5 that AadG” should
decrease as the potential of zero charge becomes less
positive, ie on going from the more compact to the
more open faces.
The above prediction was confirmed in the pre-
vious review[42] on the basis of the very few data
available at that time. In particular, a linear corre-
lation between AadGo and E,,, was found (with the
expected trend) for Pb, Zn and Au. In the case of
Bi, there appeared to be a non-monotonic variation
2141
although AadGo varied in the expected way from the
more open face (111) to the more compact face (2TT).
The data existing for Ag at the time of the review also
showed that this metal conformed to the same rule,
ie the A,d G” for the (111) face was higher than for the
(100) face. However, those data were later shown[35]
to be vitiated by ion co-adsorption. Therefore, the
agreement of the data for Ag with the predictions
above now appears rather fortuitous.
Recently, work on single crystals of Au[43,44] and
Ag[35] revealed an inversion in the expected order of
crystal face specificity. This is shown in Fig. 6 where
the earlier data for Au and Ag are confronted with
the more recent data on the same metals. In the case
of Ag the authors have interpreted the new observed
sequence as indicating that the (111) face is more
“hydrophilic” than the (100) face, a conclusion which
contrasts with other evidence[41]. Also, for Au the
authors have reached the conviction that the ob-
served behaviour is related to specific interaction of
the OH group of alcohols with the metal surface.
It is clear that the explanations provided by the
different authors for the same pattern observed with
Au and Ag do not agree. In fact, the strong inter-
action of RaH postulated for the (110) face of Au
implies that this face interacts strongly with water as
well, ie the (110) plane can be defined as more
“hydrophilic”. Opposite conclusions are in the end
reached for Ag and Au, two metals crystallizing in the
same system and with almost the same atomic size.
On the other hand, the data for Ag are taken in KF
solutions. Fluoride ions have been shown[45] to
adsorb on Ag, especially at defects[46]. Thus, the
effect of ion co-adsorption cannot be ruled out for Ag
even in fluoride solution, although this is excluded
by the authors themselves on the basis of their
observation of constancy in E, =o with varying KF
concentration[47].
The above data indicate that some additional,
not yet identified factors, should probably be taken
into account with single crystal faces of sd metals.
Other available data concern the adsorption on Ag
and Au[4&50] of pyridine, an aromatic compound
I l./'
/- //
Fig. 6. Plot of the standard Gibbs energy for the adsorption
of various substances vs. the potential of zero charge of
different crystallographic faces of metals (1,l’) Ag; (2,2’)
Au. (1) n-Pentanol from KF solutions[35]; (1’) n-hexanol
from Na$O, solutions[36]; (2) tqxntanol[43,44]; (2’) di-
ethylether[S9].
2142 S. Trww-r~
whose ascertained specific interaction with the metal
surface[Sl, 521 prevents discussion of the data in the
context of the above approach. Further studies are
thus needed to gain decisive insight into these factors.
ADSORPTION FROM NON-AQUEOUS
SOLVENTS
Equation (12) clearly shows that the energetics of
adsorption can be understood in terms of a number
of pairwise interactions: adsorbate-solvent, adsor-
bate-metal, metal-solvent, and also solvent-solvent
and adsorbate+adsorbate which are included but not
explicitly expressed. In order to single out (to a first
approximation) one contribution at a time, some of
the factors must be made constant and the others
varied. Thus, metal-water interactions can be seen (as
shown above) by working “at constant solvent and
adsorbate” and varying the metal. Further, metal-
adsorbate interactions can be detected by working “at
constant adsorbate and solvent” and by confronting
the situation at the air/solution interface[29,30]. Ac-
cordingly, adsorbate-solvent interactions can be in-
vestigated by working “at constant metal and
adsorbate” and by varying the solvent.
Although the above reasoning is only a simplifica-
tion, it illustrates the general strategy which can be
adopted depending on the aim of the research work.
A topic which falls in the above context is the effect
of substituents and functional groups on the inter-
facial behaviour of organic substances. Investigations
of the adsorption of classes of homologous com-
pounds have been usually carried out from aqueous
solution[8]. Due to the hydrophobic interactions in
aqueous solution, organic substances are as a rule
adsorbed by squeezing out effects so that they nor-
mally interact with the electrode surface through the
inert hydrocarbon tail. This leads to A,,G” being
correlated with the solubility of the adsorbing sub-
stance, and varying approximately quadratically with
the electric field at the interface[53].
In non-aqueous solvents the nature of the adsor-
bate-solvent interaction changes substantially and
this may lead to interfacial orientations quite differ-
ent from those in aqueous solution, and therefore to
new and unexplored interfacial situations. In this
context, research work on the interfacial properties of
differently substituted aromatic compounds has been
carried out in ethylene glycol solutions, a solvent in
Table 2. Organic compounds
Benzene
C,HrH
Toluene C,H+H,
Phenol C,H&H
Aniline C,HrNH,
Benzoic acid C,HdOOH
Dimethylaniline C,H+(CH,),
NH,
o -Toluidine C,H/
\CH,
,N(CH,),
Dimethyl-o-toluidine C,H,
\CH,
Solvent: ethylene glycol.
Fig. 7. Plot of the relative variation of the standard Gibbs
energy of adsorption for various substituted benzene com-
pounds on Hg from ethylene glycol solutions us the elec-
trode potential in the rational male. (1) Benzene; (2) benzoic
acid, (3) dimethyl-o-toluidine; (4) dimethylaniline; (5) phe-
nol; (6) aniline.
which fundamental interfacial studies have already
been performed[54].
Table 2 summarizes the substances investigated.
The basic molecular unit is the aromatic nucleus to
which the following substituents have been attached:
-CH3, -OH, -NH2, -COOH, alternatively further
substituted with CH, groups. The aim was to change
the aromaticity of the ring and at the same time
the adsorbat-olvent interaction. Some of these
substances were studied in aqueous solution by
Blomgren and Bockris[55] long ago with a different
aim. While detailed results are reported in another
paper[56], Fig. 7 shows that the electric field depen-
dence of Asd G” (among other parameters) splits these
substances into two groups. For some of them a
quadratic dependence of AndGo on the electric field
is observed, while for the others the dependence is
linear and AndGo increases as the field becomes more
positive.
The picture in Fig. 7 suggests that competition
exists between the effect of the substituents on the
solubility and their effect on the aromaticity of the
ring. It is clear that a quadratic dependence of AadGO
entails strong adsorbate-solvent interaction so that
only squeezing out effects operate. This is the usual
pattern obtained in the adsorption of these substance
from aqueous solution. A linear dependence of AadG”
on the electric field simulates the adsorption of
anions, ie increasing interaction with positive charges.
Similar behaviour has been observed with thiourea,
known to interact chemically with Hg via the sulphur
atom[57]. Therefore, the linear dependence of Asd G”
suggests that a chemical interaction takes place via
the n-electron system of the aromatic ring with
partial charge transfer to the metal. This model is
supported by the observed shift of the potential of
zero charge towards more negative values[S 581.
Table 3 summarizes the above conclusions.
 Adsorption of organic substances at electrodes
Table 3. Subdivision of substituted benzene
compounds adsorbed on Hg from EG
Group A Group B
(non-interacting) (interacting)
Benzene Phenol
Toluene Aniline
Benzoic acid DM-aniline
DM-o-toluidine o-Toluidine
The interfacial behaviour of organic compounds
can thus be modulated by modifying substituents
and functional groups. Although this is a well-known
strategy, it is essential to modulate at the same
time the adsorbat+solvent interaction for the
adsorption behaviour to be modified completely.
Thus, molecules which are otherwise only physically
held at the metal surface can be changed into chemi-
cally adsorbed entities. This is especially important
in the field of corrosion inhibitors, and the results
illustrated here provide an example of the strategy
which can be adopted to obtain the desired effects.
CONCLUSIONS
Four recently developed topics in the field of
adsorption of organic substances have been examined
and discussed. The following conclusions can be
drawn.
(1) Nikitas’ approach to the determination of the
size factor gives n N 1 for all substances examined.
This outcome warns against introducing a calculated
size factor as a postulate, but at the same time hints
of the possibility that the true value of n, if different
from 1, cannot in fact be obtained thermodynami-
cally from the experimental data. Further studies are
needed to assess the situation.
(2) The adsorption Gibbs energy of organic com-
pounds varies with the nature of the electrode metal
essentially as a result of different metal-solvent inter-
action strengths. Data for different metals turn out
to be in a closely linear correlation with the “inter-
facial parameter” X obtained from work func-
tion-potential of zero charge plots. This result
confirms the strict consistency of different parameters
and of their analysis as carried out by this author in
previous papers.
(3) Consistently with the logic of point (2), the
adsorption Gibbs energy is found to vary linearly
with the potential of zero charge of the different
crystallographic faces of a given metal. However,
recent results for Ag and Au have shown an inversion
in the expected sequence of crystal faces. While
possible reasons of experimental interference have
been suggested, the results point to the possible
existence of still unidentified factors in the adsorption
of organic substances on well-defined metal crystal
faces. Further studies with different adsorbates are
necessary.
(4) Dramatic changes in adsorbat+metal inter-
action are seen as aromatic compounds with various
substituents and functional groups are adsorbed on
Hg from non-aqueous solvents. Different substituents
can modulate the adsorbate-solvent interaction as
2143
well as the aromaticity of the benzene ring in such a
way that it is possible to obtain either physical or
strong chemical adsorption. Working in non-aqueous
solvents is essential to observe these effects, since
squeezing out effects as a rule prevail in aqueous
solution thus smoothing down any further details.
Acknowledgements-This work was supported by the
MURST (40% funds) and the CNR.
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