Double Layer
II. Quantitative Study of Adsorption of Ions on the Mercury Electrode
Dolores Marln and Francisco Mendicutil
Universidad de Alcala de Henares, Alcala de Henares, Madrid, Spain
As we said in a previous paper ( I ) , the adsorption of ions
constitutes the underlying phenomenology of the double
layer and contributes to the most experiment-consistent
molecular model of the interface.
Two types of adsorption are responsible for most of the
changes in the rate of electrochemical reactions, (i) nonspe-
cific adsorption and (ii) specific adsorption, either of elec-
troactive or electroinactive species.
In theearlier paper ( I ) the&alitativedetectionofadsorp-
tionof ions and neutral molecules wasstudied. In this work a
quantitative study of adsorption of ions is made. A simple
procedure to obtain the surface excesses of cations and an-
ions on mercury from KC1 aqueous solutions by measuring
the interfacial tension of the mercury-solution interface as a
function of concentration and potential is explained. The
Esin-Markov coefficient, which is an indicator of specific
absorption of chloride ions is also calculated. Once specific
or contact absorptions of chloride ions has been detected, it
must be evaluated as function of concentration and charge
density on the metal b y Grahame method (2). Finally, a
comparative study of potential & on the OHP vs. charge
density on the electrode surface, with specific adsorption of
chloride ions or without specific absorption is made.
Theory (5-5)
Applying the Gihhs adsorption isotherm to a cell with an
ideally polarizable mercury electrode, a nonpolarizable indi-
cator electrode of calomel (reversible to chloride ions) and a
KCIaqueous solution, we will be able to ohtain the electroca-
pillary equation:
where qMis the excess charge density on the electrode, E- is
the potential of the working electrode measured with respect
to the reference electrode reversible to the anion.....
r~+rn.o!
~..*-, is
the relative surface excess for the cation (that we approach
to absolute surface excess a t these concentrations) (4), and
WKcl is the chemical potential of KC1 solutions. The Gibbs
surface excesses given as
where a* is mean ionic activity, can he evaluated by means
of graphical differentiation from large y - In af plots.
Smooth curves must he drawn through y - In af coordi-
nates in the interval 0 to -1500 mV of E-.
On the other hand, at constant composition, from eq 1we
obtain the well-known Lippmann equation:
712 Journal of Chemical Education
Values of r- might he obtained as difference between the
charge densitv on the metal and r, (it mav he convenient to
expr& the sirface excess the termsof itskquivalent charge
q*):
where z* is the charge of ions and F the Faraday constant.
One indicator of specific absorption of charged species is
the Esin-Markov effect (3),which is manifested by a shift in
the PZC (potential of zero charge or electrocapillary maxi-
mum) with a change in the electrolyte concentration. The
magnitude of the shift is usually linear with the logarithm of
electrolyte activity, and the slope of the linear plot is the
Esin-Markov coefficient for the condition of qMconstant, as
for the cell mentioned above. This coefficient should he zero
in the absence of specific adsorption of ions, negative when
anions are snecificallv adsorbed and nositive for the case of
specific adsorption of cat ions.
To obtain sneciticallv adsorhed charee from the measured
surface excesses, we need to assume a nonthermodynamic
procedure. The anionic or cationic excess charge can he
expressed hy the sum of the specifically adsorbed charges,
ql-, and the diffuse layer charges, qd-, so that
From diffuse layer theory for 5 2 electrolytes
where all magnitudes are sufficiently known.
Now, an assumption originated from Grahame (2) is made
that the cations are not specifically adsorbed in all range of
potentials so that q+ = qdt and
[ (- 5)
q+ = z+ IT+= t ( 2 ~ ~ e C ) ' "exp- ] - 1
(8)
From the above equation C$Z is calculated. Once +z is
known, qd- can he calculated from eq 7. The anionic specific
adsorbed charge ql- is obtained from eq 6.
Electrocapillary curves of five aqueous solutions of KC1
have been obtained from drop-time measurements as was
'Present address: Department of Polymer Science. University of
Akron, Akron, OH 44325.
explained earlier ( I ) . The drop-time values have been con- quantity (electroneutrality of interface). On the other hand,
verted into interfacial tension values by multiplying with the there is a nositive excess of chloride ions a t small negative
constant factor mq/2rr,. As the interfacial tension of a solu- charge on i h e electrode and potassium ions a t value~more
tionO.l N KC1 a t -700mV (vs. SCE) is known to he 427 dyn/ positive than the PZC. None of these features can he ac-
cm (6),the last factor can he ohtained by measuring the drop counted for hy an electrostatic model such as the hasic
time under that condition at some fixed mercury column Gouy-ChampmanStern theory.
height. Ordinarily, the charge on the electrode is counterbalanced
The flow rate, m, in practice does not depend either on the by an excess of one ion and a deficiency of the other, as we
solution or on the potential of the electrode. However, it is 8 can see in the more negative region of Figure 3. If the elec-
dependent on the height of the mercury column. So, if the trode became even more negative, the excess charge is ac-
mercurv column height is not changed,. the constant factor is
the same for every &lution.
All potentials must he referred to that of a reversihle
ca~omd~ electrode in thesame solution, which is reversihle to
chloride ions. That means that students must build a calo-
mel electrode for each solution in order to support the condi-
tion E- constant in the eq 2 (7).
Caution must he taken in handling mercury.
Results and Discussion
Figure 1 shows the electrocapillary curves for five solu-
tions of KC1 of 0.001 N, 0.01 N, 0.05 N, 0.1 N, and 1 N
concentrations. Once these curves are ohtained, the next
step consists of plotting y vs. In af a t several electrode
potentials, as shown in Figure 2 (activity coefficients were
ohtained from literature or were calculated using the well-
known Dehye-Huckel formula) (8).For a 1:l electrolyte a t
25 OC, eq 2 takes the form
q+ = -1.9479

where q+ is the charge of cations in pC/cm2and S theslope at

each potential and concentration in the units corresponding
to Figure 2. From this equation and eqs 3 and 4 we have
obtained the q+, qM, and q- values, respectively, a t each
potential of electrode and concentration. An example is giv-
en in the table a t 0.01 N KC1 solution. The results are
denicted in Fieure 3 in form of charge components of anions
an'd cations vsy surface charge on the electrode.
We can differentiate. in Fieure 3, two solid curves, the
charge components of cation; q+ (first and second quad-
rants), anions, q- (third, fourth, and first quadrant), and a
dashed line (bisector of first and third quadrants) as charge
component of interface on the solution side. Figure 2. Surface tension versus -In a+ plots at different potentials on the
In the PZC when qM = 0, we should expect the excess of electrode. E L for KC1 solutions at 25 'C.
potassium ions as well as the excess of chloride ions to he
zero; however, Figure 3 shows that both anions and cations
are adsorbed on the surface electrode, logically in the same

Figwe 1. Ele~n~capillary curves of surface tension versus potential E- (re-

ferrsdlo Indicator electrode reversible to chloride ions), for mercury in contact Figure 3. Surface excesses (as components of charge) versus charge densihl
with KC1 solutions at the indicated concentrations at 25 OC. on theelecbode. @for mercury in 0.01 N KC1 solution at 25 OC.

Volume 65 Number 8 August 1988 713

 Figure 7. Schematic representation of ion distribution, considering anions
specifially adsorbed, when the electrode is charged (a, b) or is not charged
Flwe 6 Varmtms 01 the polentoal dla (between the OhP an0 the bu r 01 me (c). Potential profilesthrough the solution side of the double layer in the same
so utlon) dersus charge dens hl on tncelecnode. pfar 0 0 1 N KC so m onat 25
*C 1 0 ) raking lnto account spsc#llcadsorpllon of cnlorlae ons. (01 wnnout
specific adsorption

specific adsorption (column 8) that was calculated as de-
scribed in previous paper ( I ) . All results were plotted vs.
charge on the surface on the electrode in Figure 6.
In this paper we try to explain the results with specific
adsorption like the previous one (I) by means of their poten-
tialprofiles a t t h e three different situations like qM> 0, q M <
0, and qM= 0.
At the left of the PZC, the charge on the electrode is
positive and $2 is negative. In this case, if IqMI is the numeric
value of charge density on the electrode, then a superequiva-
lent quantity of ions required to compensate the wulomhic
forces is specifically adsorbed on the I H P (Inner Helmholtz
Plane), hence lql-I > IqMI.Consideringa rigid I H P the poten-
tial profile should drop linearly to the negative value limited
tive, chloride ions can approach the electrode surface like
specifically adsorbed ions. The potential profile is represent-
ed in Figure 7b. In this case mz
has the same sign as that in
absence of specific absorption and hoth curves are coinci-
dent a t high cathodic potentials even when there is not
specific adsorption.
Finally, when the density of charge is zero, 4 2 is also
negative. The potential profile is represented in Figure 7c.
It is remarkable that all results, as in the previous paper
(I), were obtained hy undergraduate students in their lab-
oratories.
Literature Cited
~~ ~ ~

by the IHP. From this point onward the potential increases
to the asymptotic limit zero in the bulk of solution according
to the Boltzmann distribution of charges. The consequence
is that on the OHP (Outer Helmholtz Plane) the potential $9
is negative (Figure l a ) , while in absence of specific adsorp-
tion is oositive.
At more negative potentials on electrode than the PZC, 4 2
is also negative. When the charge on the electrode is nega-
1. Marin, D.; Mendicuti F. J. C h m , Educ., in press.
2 Gmhsmc,D. C ChemReu. l O l l , I I , 4 4 l .
3. Bard, A. J.;Faulkner,L. R.Electrochemical Methods; Wiley: NerYork, 1980:Chapter
12.
4. Bockria. J. O'M.; Roddy, A. K. N. Modern Elerlrorhemistry; Plenum: New York. 1972:
vo1.2.
5. Bockris, J. O'M. J. Cham. Educ. 1983,60,265.
6. Weissberger, A,; Rassiter, B. W.Ed.Physico1 MethodaofChemistry; Wiley: NewYork.
1971:Vol. I. Part 11. Chapter V.
I . Matthew G. P. Ezperim~nmiPhysical Chernirlry; Clarendon: Oxford, 1985; p 124.
S. Atkim, P. W. Physical Chemistry: Freeman: New York, 1986: p 244.

The 1988 Dexter Award

The Division of the History of Chemistry of the American Chemical Society and the Dexter Chemical Corporation
would like to announce that the 1988Dexter Award for outstanding accomplishment in the history of chemistry has been
awarded to Lutz F. Haber of the University of Surrey. Son of Fritz Haber, winner of the 1919 Nobel Prize in Chemistry,
L. F. Haber was born in Berlin and educated in Germany, Switzerland, and England, receiving degrees in economics from
hoth the London School of Economies and the Universityof London. His career as an economist has included employment
not only in academia, but in the private industrial and governmental sectors as well. His contributions to the history of
chemistry are based on three hooks, all of which have been published by Oxford University Press: The Chemical Industry
During the 19th Century, The Chemical Industry: 1900-1930, and The Poisonous Cloud: Chemical Warfarein the First
World War. The award, which consists of a cash prize of $2000 and an engraved plaque, will hp presented to Haher at the
Fall National Meeting of the American Chemical Society in Los Angeles.

Volume 65 Number 8 August 1988 715