Electrochemistry cannot be understood unless one understands the locations at

which important events occur. Electrode reactions can only take place at the
interface between the electrode and the solution of electrolyte. 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. The adsorption of
ions and neutral molecules constitutes the underlying phenomenology of the
double layer and contributes to the most experiment-consistent molecular
model of the interface. The rate of electrochemical reactions is influenced by
the double layer structure, that is, by the presence of adsorbed species on the
electrode.

Theory
Electrocapillary curves are a primary tool in adsorption studies in
electrochemistry. They are simply plots of surface tension versus Potential.
Since good measurements of surface tension are-made far more conveniently
at 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(MAX) where
m is the mass flow rate of mercury issuing from the capillary, g is the
gravitational acceleration and t(MAX) is the lifetime of the drop. This force is
counterbalanced by the surface tension acting around the circumference of the
capillary, whose radius is rc; thus,
ECN
One can easily see that the drop time t(max) is directly proportional to surface
tension y; hence a plot oft,,, versus potential 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 at constant temperature and pressure takes the form,
ECN
where qM is the excess charge density on the electrode, E+ is the potential of
the working electrode measured with respect 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
electrocapillary equation (eq 2), it is clear that
ECN

hence the excess of electric charge on the electrode is the slope of the
electrocapillary curve at any potential. According to the Gouy-Chapman diffuselayer theory for a z-z electrolyte
ECN

where r is the dielectric constant, c is the concentration of the electrolyte in the

bulk of solution, and 4o is 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-Chapman limit x = 0, the metallic surface, as the inner limit of the diffuse
layer and suggests an equipotential plane at an unspecified distance xz from
the electrode surface. This plane is now commonly 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
ECN
where $2 is the potential at the OHP defined by 42 = @(xz) - ds). It must he
pointed out that this model does not take into account the specific adsorption.
Equation 5 can he transformed into the relationship
ECNS
which permits evaluation of 42 from qM at any potential.

Experimental
The simplest measuring apparatus that will give time-potential curves with a
dropping mercury electrode is shown schematically in Figure 1. The electrolyte
solution is placed in a beaker, and a saturated calomel electrode serves as a no
polarizable electrode, while the mercury drops flowing from the glass capillary
form the polarizable electrode. The capillary is connected by rubber tubing to
the mercury reservoir, which is placed approximately 50 cm above the capillary
orifice. Both electrodes the mercury electrode (through a platinum contact and
the calomel electrode are connected directly to simple potentiometer fed with a
2-V battery.

Procedure
Solutions of 0.1 N KC1,O.l N KI.0.1 N N IC4H,)4CI, and saturated amyl alcohol in
0.1 KC1 must be prepared. Each solution is a placed in the vessel, and the
potential applied is gradually raised from O a 1500mV in steps of 100 mV,
except for the vicinity of electrocapillary maximum (ECM), for which the steps
are 50 mV. In order to determine the drop time tmax that is, the period
between the beginning 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
electrocapillary curves 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 height of the mercury column h, so this must be
kept constant during the measurement.

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 significant
variations as the electrolyte is changed. A feature common to all the curves is
the existence of a electrocapillary maximum (ECM). Since the slope of the
curve is zero at this point, the potential at which it occurs is the potential of
zero charge (PZC) for the system. Thus qM = qs = 0 at the PZC (qM is the
excess charge on the electrode and qS on the solution). At more neeative
~otentials the dro~s became negatively charged, while the; acquire a positive
charge at more uositive potentials. The units of electronic charge composing
any excess repel each other; hence they counteract the usual tendency of the
surface to contract, and they weaken the surface tension.
As can be seen in Figure 2 the electrocapillary maximum, which lies at -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. Since
the electrode is more polarizable than the solution, the

5 GRFICAS

counterchange is induced there. To regain the condition qM = 0, the potential

must be shifted to a more negative value, so that the excess of specifically
adsorbed anions is exactly counterbalanced by an opposing excess charge in
the diffuse laver. Similar conduct occurs in 0.1 N (CdHdaCI. . . . the
electrocapillary maximum lies in -300 mV, but in this case the specific cation
adsorption shifts the ECM in the positive direction.
The flattening of the electrocapillary curve, observed in the case of amyl
alcohol in 0.1 N KC1 (Fig. 4), is characteristic of the adsorption of neutral
molecules. As can be seen, the adsorption is more effective near the potential
of zero charge. As the electrode 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 of t(max)
against E of the solution 0.1 N KC1 can be converted in y-E plots (taking into
account that the interface tension of this solution at -700 mV (vs. SCE) is 427
(Dyn/cm)

GRAFICA
TABLA
by multiplying by the factor 42718.4. From the y-E curve obtained (Fig. 5), the
charge density, qM, can be evaluated by the slope of the curve at 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 to a
symmetrical parabola and determines the tangent at its middle point. The
results obtained are given 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
ECN
Where 42 is in millivolts and qM in rC/cm2. The values obtained 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
negative, and therefore 42 is positive (Fig. :a). On the contrary, at more
negative potentials than the EMC, m2 is negative (Fig. 7h). In the ECM, the
electrode is not charged, there is not excess charge on solution and 42 is zero
(Fig. 7c).
It must be taken into account that the specific adsorption has been ignored.
That means, no charge is presented between 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 information from time measures?