Double Layer
I. Qualitative Detection of Adsorption of Ions and Neutral Molecules on the Mercury
Electrode and Excess Charge on the Electrode
Dolores ~ a r and
h Francisco Memlicuti
Universidad de Alcala de Henares, Alcala de Henares, Spain
Electrochemistry cannot be understood unless one under-
stands the locations a t which important events occur. Elec-
trode reactions can only take place at the interface between
the electrode and the solution of electrolvte. Interfacial
zones on the two sides of the interface have dimensions of a
few tens of angstroms and the whole structure is called the
double layer. '['he adsorption of ions and neutral molerules
constitutrs the underlying phenumenolopy of the double
layer and contributes t o t h e most experiment-consistent
molecular model of the interface. The rate of electrochemi-
cal reactions is influenced by the double layer structure, that
is, by the presence of adsorbed species on the electrode.
The~ry~-~
Electrocapillary curves are a primary tool in adsorption
studies in electrochemistry. They are simply plots of surface
tension versus votential. Since good measurements of sur-
face tension are-made far more conveniently a t liquid-metal
electrodes, work with mercury has dominated in this area.
The simplest device to produce electrocapillary curves is the
dropping mercury electrode (DME). The weight of the drop
at the end of its life is gmt,.,, where m is the mass flow rate
of mercury issuing from the capillary, g is the gravitational
acceleration. and t-...-"-is the lifetime of the droo. This force is
counterbalanced hy the surface tension acting around the
circumference of the capillary, whose radius is r,; thus,
One can easily see that the drop time t,. is directly propor-
tional to surface tension y; hence a plot oft,,, versus poten-
tial has the same shape as the true electrocapillary curve.
The ordinate is simply multiplied by a constant factor,
which can be separately taken into account. Sometimes
these plots of drop time are also called electrocapillary
curves.
The Gibbs adsorption isotherm for a ionic system a t con-
stant temperature and pressure takes the form,
-dy = q"dE, + r,dp
where qM is the excess charge density on the electrode, E+is
the votential of the workine electrode measured with resnect
to the reference electrode reversible to cation (E+) or anion
(E-), r+is the relative surface excess for the cations (r+) or
anions ( L ) , and fi is the chemical potential. From the elec-
trocapillary equation (eq 2), it is clear that
' Author to whom correspondence should be addressed.
Bard, A. J.; Faulkner, L. R. Electrochemical Methods; Wiley: New
York, 1980; Chapter 12.
Bockris, J. O'M.; Reddy. A. K. N. Modern Electrochemistry; Ple-
num: New York. 1973; Vol. 2.
4Bockris. J. O'M. J. Chem. Edoc. 1983, 60,265.
hence the excess of electric charee on the electrode is the
slope of the electrocapillary curve at any potential.
According to the Gouy-Chapman diffuse-layer iheory for
qM= (8RTec)'" sinh (zF+&RT) (4)
where r is the dielectric constant, c is the concentration of
the electrolyte in the bulk of solution, and 4ois the potential
difference between the surface and the bulk of solution; that
is, 60 = 6 (X= 0) - $4~). The other quantities in eq 4 are the
gas constant R, the absolute temperature T, the Faraday
constant F, and the electronic charge on ions z.
The model proposed by Stern abandons.the Gouy-Chap-
man limit x = 0, the metallic surface, as the inner limit of the
diffuse layer and suggests an equipotential plane at an un-
specified distance xz from the electrode surface. This plane
is now commonlv called the "outer Helmholtz plane"
(OHP), and it is the plane of closest approach for the ions to
the electrode surface. So eq 4 takes the form
qM= ( ~ R T c c )sinh
~ ' ~(zF$~IZRT) (5)
where $2 is the potential at the OHP defined by 4 2 = @(xz)-
d s ) . I t must he pointed out that this model does not take
into account the specific adsorption. Equation 5 can he
transformed into the relationship
4%= (2RTIzF) aresinh qM
(~RTcc)''~
which permits evaluation of 4 2 from qMat any potential.
(2)
Experlrnental
The simplest measuring apparatus that will give time-potential
curves with a dropping mercury electrode is shown schematicallyin
Figure 1. The electrolyte solution is placed in a beaker, and a satu-
rated calomel electrode serves as a nonpolarizable electrode, while
the mercury drops flowing from the glass capillary form the polariz-
able electrode. The capillary is connected by rubber tubing to the
mercury reservoir, which is placed approximately 50 cm above the
eaoillarv
. . orifice. Both electrodes. the mereurv electrode (throueh a
platinum contartl and the calomel elrotr<,dr,are connected directly
m a simple potrntiomcrrr fed u i t h a ? - \ ' I,atttry.
Procedure
Solutionsof0.1N KC1,O.l N KI.0.1 N N IC4H,)4CI,nnd~at!!rnrrd
amyl alcohol in 0.1 KC1 must lw prepared. Ench solution ir. placed in
the \,essel,and the potenrial applied is gradually raised frum O 18,
Volume 65 Number 7 July 1988 649
 _.; ----
'Potentiometer ":..:::

T ~ e s Capillary
e r v o i ? .
... A

" . . " sahlrat-

F l o w 2. EleCiroca~illarvcurves of d r m time aoalnst ~otentialItakin0
e&slomal elecnode GCE) as referencela1dropping mercury eleclrade (DMEI
m 0 1 N KC ( 0 1 and 0.1 N KI ( A l a t 25 OC.

~efere'nce S\olution
electrode studied
Figure 1. A simple apparatus for measuring sumce tension.

1500 mV in steps of 100 mV, except for the vicinity of electrocapil-

lary maximum (ECM), for which the steps are 50 mV. In order to
determine the drop time t,.., that is, the period between the begin-
ning of drop formation and falling off of the drop, the time taken by
a large number (10-30) of drops is measured with a stopwatch and
divided by the number of drops. Plots of drop time versus potential
yield the electrocapillarycurves for each solution. Caution must be
taken in handling mercury since its vapors are poisonous and it is
very easy to spill.
As we want to compare the different electrocapillary curves, we
must use caution when preparing all the solutions that must have
the same concentrations. Besides, drop time is dependent of the Figure 3. Electrocapillary cuwes in 0.1 N KC1 (.)and 0.1 N N(C&Is)&l (A)(%%
height of the mercury column h, so this must be kept constant legend of Fig. 2).
during the measurements.
Results and Discussion
Figures 2 to 4 show the electrocapillary curves of 0.1 N KI,
0.1 N N(C4H9)&l, and saturated amyl alcohol in 0.1 N KCI,
respectively, together with the electrocapillary curve or 0.1
N KC1 used as a reference. The shape of electrocapillary
curves is approximately parabolic although there are signifi-
cant variations as the electrolyte is changed. A feature com-
mon to all the curves is the existence of a electrocapillary
maximum (ECM). Since the slope of the curve is zero a t this
point, the potential a t which it occurs is the potential of zero
charge (PZC) for the system. Thus qM = qs = 0 a t the PZC
( q M is the excess charge on the electrode and qS on the
solution). At more neeative ~ o t e n t i a l sthe d r o ~ sbecame
negatively charged, while the; acquire a positive charge a t
more uositive potentials. The units of electronic charge com-
posing any excess repel each other; hence they counteract
the usual tendency of the surface to contract, and they weak-
en the surface tension.
As can be seen in Figure 2 the electrocapillary maximum,
which lies a t -400 mV in 0.1 N KCI, shifted toward more
negative potentials, -700 mV, in 0.1 N KI. This is indicative
of the more pronounced specific adsorption of iodide anion. F gum 4 Elsnroeapl lary cwves in 0 1 N KC1( 0 1and saturated amyl alcaho m
Since the electrode is more polarizable than the solution, the 0 1 N r(CI ( A ) (see legend a1 F g 21

650 Journal of Chemical Education


Figwe 5. Electrocaplllary curve for the mercury-aqueous 0.1 N KC1 lnteriace
at 25 'C. E- vs. SCE.
Figure 6. Variation of me potential 6. between the outer Helrnholh plane
(OHP) and the bulk of the solution against potential E- vs. SCE in 0.1 N KC1 at
25 'C.
counterchange is induced there. T o regain the condition q M
= 0, the potential must be shifted to a more negative value,
so that the excess of snecificallv adsorbed anions is exactlv
counterbalanced by an'opposing excess charge in the diffusk
laver. Similar conduct occurs in 0.1 N (CdHdaCI.
. . .the electro-
capillary maximum lies in -300 mV, but in this case the
soecific cation adsor~tionshifts the ECM in the ~ o s i t i v e
-..- - -.-...
The flattening of the electrocapillary curve, observed in
the case of amyl alcohol in 0.1 N KC1 (Fig. 4). is characteris-
ticof the adsorption of neutral molrcules. As ran be seen, the
adsorption is inore effective near the porential of zero
charge. As theelectrode charge increases, the electric field in
the double layer starts to draw in strongly polarized water
molecules, which leads to displacement of the less polar
organic molecules. Adsorption can take place only near the
PZC, where the water can he removed easily.
Plots oft,, against E of the solution 0.1 N KC1 can be
converted in y-E plots (taking into account that the inter-
face tension of this solution at -700 mV (vs. SCE) is 427
Welssberger. A,: Ross~ter.6. W . . Eds. PhysicalMemodsofChem
istw W ley: N e w York.1971: Vol. I. Pan 11. Chapter V.
Fngure 7 Schematic representauan of #on$d strlbdlon when the electrode s
charged(s, bl or Is "oncharged (cl Potential profl es thr0.g" the SolAon slae
of the double layer in the same cases.
Charge Density q for the Ditferent Potentials
Valves cdcvlated graphic8lly.
aVaI~es obtained by numericalprocedure
d ~ n l c mby) ~multiplying by the factor 42718.4. From the y-E
curve obtained (Fig. 5), the charge density, q M , can be evalu-
ated by the slope of the curve a t any potential. The slope can
be calculated, or graphically as it is shown in the same figure
or by a numerical procedure that fits three consecutive
points t o a symmetrical parabola and determines the tan-
gent a t its middle point. The results obtainedaregiven in the
table.
The $2 potential can be calculated by using eq 6. For a
solution 0.1 N KCI at 25 "C, that equation can be written
where 42 is in millivolts and q M in rC/cm2. The values oh-
tained are given in Figure 6. These values can be explained in
the following form. At the left of the ECM, the charge on the
electrode is positive, the excess charge on solution is nega-
tive,and therefore mz is positive (Fig. :a). On the nmtrary,at
more negative potentials than the EMC,m2 is negative (Fig.
7h). In the ECM,thr electrode is not chareed. - . there is not
excess charge on solution and 4 2 is zero (Fig. 7c).
It must be taken into account that the specific adsorption
has been ignored. That means, no charge is presented be-
tween electrode surface and OHP.
It is remarkable that all the results presented have been
obtained by undergraduate students. Is it not wonderful to
obtain excess charge on the electrode and structural infor-
mation from time measures?
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