Experiment #8:

ELECTROCHEMICAL BEHAVIOR OF LEAD

In this experiment, you will examine the electrochemical technique called cyclic voltammetry and study
its application to kinetic problems.

Required Readings (S indicates Skoog, et al.; K indicates Kellner on the Reserve List.)
1. Kissenger and Heineman, “Cyclic Voltammetry”, J. Chem. Educ. 1983, 60, 702.
2. Larry R. Faulkner, J. Chem. Edu. 1983, 60, 262.
3. Appendix II - Electrochemistry, this manual.
4S. Chapter 22, “An Introduction to Electroanalytical Chemistry”, Skoog, et. al.
5S. Chapter 25D, “Cyclic Voltammetry”, Skoog, et. al.
or
4K. Section 7.3.2, “Voltammetry”, pp. 297-312 (ignore passages on polarography),
Kellner, et. al.
5K. Section 4.4, “Redox Systems”, pp. 115-123, Kellner, et. al.

In this experiment, the Pb2+/Pb0 couple is used as an example of an electrochemically reversible redox
system to introduce some of the basic concepts of cyclic voltammetry. By experimenting, students will
know the electrochemical of lead ion by voltammetry and understand the signals in voltammetry
techniques (CV, DC, NP, DP, SqW).

THEORETICAL BACKGROUND
1. Cyclic Voltammetry. One of the most useful features of cyclic voltammetry is the ability to generate
a potentially reactive species and then examine this species immediately by reversal. Scan rate is the
important time-related variable in cyclic voltammetry. It can extend from ~10 mV/sec to 2000 V/sec
with fast potentiostatic and recording apparatus, but with x-y recorders, the fastest scan is about 1 V/sec.
The observed voltammetric response depends strongly on the mechanism of the electrode process, and
this aspect gives cyclic voltammetry its diagnostic utility. One limiting case is the "reversible" case, in
which the kinetics of electron transfer to and from the electrode is very fast and the oxidized and reduced
forms are both stable. In this instance, the average of Epc and Epa is essentially E0', and Epc and4Epa
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are separated by 60/n mV. Both peak potentials are independent of scan rate and concentration. The
forward peak current adheres to the Randles-Sevcik relation,

if = (2.69 x 105) n3/2 A D1/2 v1/2 C*

where the current is in amperes, n is the number of electrons transferred per molecule electrolyzed, A is
the electrode area in cm2, D is the diffusion coefficient of the electroactive species in units of cm2/sec,
v is the scan rate in V/sec, and C* is the concentration of the electroactive species in moles/cm3. The
constant 2.69 x 105 is only true at T = 298 K. The important points are the linear dependence on n3/2, C*,
and v1/2. The inverse square root of time dependence embodied in the v1/2 term reflects control of the
current by diffusion of reactants to the electrode.
If electron transfer to the electrode is lower than or comparable with the rate at which the potential
changes due, for example, to high resistance (low ion mobility) in the solution, then there will be a
potential difference (called an internal resistance or iR drop) between the working electrode and the
reference electrode that will 'delay' the apparent peak potential during the scan in a given direction. This
will lead to values of Ep significantly larger than 60/n mV. However, a plot of Ep vs scan rate should
extrapolate to nearly the theoretical value.

The experiment outlined below demonstrates the determination of the following: the formal reduction
potential (E 0 ); the number of electrons transferred in the redox proc-ess (n); the diffusion coefficient
(D); electrochemical reversibility; and the effects of varying concentration (C) and scan rate (v).
The electrode reaction during the scan from -1000 mV to 0.0 mV is
Pb2+ + 2e = Pb, Eo = -0.126 V vs. NHE at 25°C
The electrode potential, E, is thermodynamically determined by the Nernst relationship
E = Eo + (0.0591/n) log (aox/aR)
where aox is the activity of the oxidized species, Pb(II) in the present case and aR is the activity of the
reduced species, Pb0. Experimentally, the activity is affected by the presence of other ions. For
practicality, we, therefore, define a “formal potential” that uses concentration in mole/L rather than
activity, which we do not know. The Nernst becomes E = Eo’ + (0.0591/n) log [COX/CR]
The potential, E, at any point along the I-E wave should reflect the concentration of the Pb(Hg) at the
electrode surface in the presence of whatever background electrolyte you are using.
Irreversibility is when the rate of electron transfer is sufficiently slow so that the potential no longer
reflects the equilibrium activity of the redox couple at the electrode surface. In such a case, the Ep values
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will change as a function of the scan rate. The computer-controlled potentiostat has algorithms 9 to
evaluate the Ip and EP values, calculate the area under the I-E curves (the integrated charge), and compute
an estimated electron transfer rate constant. A unique feature of an electrochemical reaction is that a
"reversible" electrode reaction at low scan rates can become "irreversible" at high scan rates. Why is
this?
2. Direct current polarography (DCP)
In direct current polarography (DCP) a constant potential is applied during the entire drop-life
time. A current-voltage curve is constructed by applying a series of potential steps, each step being
synchronized with the drop fall. In most instruments, however, linearly changing potential is applied,
with a rate slow enough that the change of potential throughout the drop-life time is about a few
millivolts. The current is measured at the end of the drop life.

a b

E E τ c
0.5-5s
tp 10.0
1-50ms 7.5 DC
~
~

DC t
1
5.0
2-5mV
~
~

2.5
0.0
~
~
~~

150 NP
2-5mV
NP 100
50
E in
0
~
~

~
~

~
~

~
~

i, µA
40
DP
30
DP
Ebase ΔE = 10 - 100mV 20
E base
E base 10
~
~

2-5mV
~
~
~
~

0
~
~

30
SW
20
SW
10
2-5mV
10-100mV
0
~
~

~
~

10-200Hz
t -0.7 -0.8 -0.9 -1.0 -1.1 -1.2 -1.3
t
E, V vs SCE
drop drop drop drop
fall fall fall fall

Fig.8-1 Schematic presentation of some polarographic methods.

(a) Potential sequence of a polarogram.
(b) Potential sequence on a single drop (n current sampling).
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(c) Current-potential curves for 1 mM Zn2+ in 1 M KNO3. 0
DC: τ = 2 s; NP: τ = 2 s, tp = 5 ms; DP: τ = 2 s, tp = 5 ms; ΔEp = 20 mV;
SW: delay time = 4 s, ΔEp = 20 mV, f = 100 Hz.

3. Normal pulse polarography

In normal pulse polarography (NPP) the mercury-drop electrode is held for most of its duration
at a constant potential Ein, at which no electrochemical reaction takes place under given experimental
conditions. The potential of interest Ep is applied in the last stage of the drop life, for a length of time tp
(of the order of a few milliseconds). The values of Ein and tp are kept constant throughout the recording
of the polarogram and Ep is changed from drop to drop (Fig.7-1a).
The limiting current in NPP is diffusion controlled. The experimental requirements for diffusion
control are the same as those for DC polarography. Since tp is of the order of milliseconds, the diffusion
layer thickness is very small compared to the radius of the mercury drop reached at the end of its life.
The equations for planar diffusion can be applied with much better agreement than for DC polarography
(for tp = 1 ms, the diffusion layer thickness is about 2·10-4 cm, while the radius of the mercury drop is
about 0.05 cm at τ = 5 sec and m = 1 mg/sec). Furthermore, the area of the drop is virtually constant
during the application of the pulse (τ is much larger than tp). The constancy of the area implies also that
no correction factor for the expansion of the diffusion layer is required (the (7/3)1/2 factor). Thus,
1/ 2
⎛ D⎞
*⎜
i d ( NP) = nFA τ C ⎜ ⎟
⎟
πt
⎝ p⎠ (1)

For comparison, the current for DC polarography at time τ is

1/ 2
1/ 2 *⎛D⎞
id ( DC) = (7 / 3) nFA τC ⎜ ⎟
⎝ πτ ⎠ (2)

The current under NP conditions is larger than that under DC conditions. The enhancement of the current
is
1/ 2
⎛ τ⎞
id ( NP) / id ( DC) = (3 / 7)1/ 2 ⎜⎜ ⎟⎟
⎝ tp ⎠ (3)

For typical conditions, τ = 5 s and tp = 5 ms, this ratio is about 20. The contribution of the charging
current is identical for both NPP and DCP, and thus the detection limit of NPP is lower than that of DCP
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by an order of magnitude.
1
The i/E relationship for Nernstian processes at DCP and NPP is given by
 RT id − i
E = E1/ 2 + ln
nF i (4)

The detection limit of NPP is about 2·10-7 M.

4. Differential pulse polarography (DPP)
From an analytical point of view, the sensitivity of DPP is even better than that of NPP. The potential
sequence on a single mercury drop and the potential sequence used for recording an entire differential
pulse polarogram is given in Fig.6-1. The current is sampled twice during a drop lifetime: (i) at t1, just
before the pulse, and (ii) at t, just before the drop fall. The polarogram represents the current difference
Δi = i(τ) − i(t 1 ) as a function of the base potential Eb. The curve is peaked-shaped. The height of the peak
is proportional to the concentration of the electroactive species.
For Nernstian processes Ox + ne = Red and C*red = 0, the faradaic component of the current at
the peak (Δi F ) peak and Epeak are

nF ΔE
1/ 2 1 − exp
⎛D ⎞ RT 2
( Δi F ) peak = nFA τ C*ox ⎜ πtox ⎟
⎝ p ⎠ nF ΔE
1 + exp
RT 2 (5)

ΔE
E peak = E1/ 2 −
2 (6)

The peak form of the DP voltammogram is explained below. At sufficiently positive potentials,
0
Eb - E > (120/n) mV, the faradaic currents i(τ) and i(t1) are both zero, and thus also (Δi F ) peak is zero.
At sufficiently negative base potentials, Eb - E0 < (120/n) mV, the faradaic process proceeds at a
maximum rate, and the diffusion-limited current is reached; the current is independent of potential and
(Δi F ) peak s zero. At potentials in the vicinity of E 1 / 2 the current difference Δi F is determined by ∂i F / ∂E b
and has a finite value.
For non-Nernstian processes (Δi F ) peak is smaller than for Nernstian ones. The sensitivity and the
detection limit of DPP are better for Nernstian processes, while for DC and NP polarography, they are
independent of the type of the processes. The reason for this can be understood by noting that the
equations for the limiting current in DC and NP polarography (eqs.1 and 2) do not contain assumptions
about Nernstian processes. For the case of DPP, however, the value of (Δi F ) peak is derived from the
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variation of the current around E 1 / 2 The derivative di/dE for non-Nernstian processes is smaller than for
Nernstian, and results in a lower Δi F peak.

Although (ΔiF)peak is smaller than the limiting current at NPP, the detection limit at DPP is lower
(about 10-7 M) due to the efficient compensation for the charging current.
5. Square wave polarography (SWP).
High sensitivity and low detection limits are obtained with this technique. It is similar to DPP, however,
the entire potential sequence is applied during the lifetime of a single drop. The voltammogram is
obtained in a few seconds, compared to much longer times with the other techniques.
The potential sequence is applied several seconds after the dropping birth, to take advantage of a
larger surface area of the mercury drop.
As in the case of DPP, the difference of the current before and after the application of the pulse
is measured. The performance of the method is better for Nernstian processes than for non-Nernstian
ones. The detection limit of the method is about n.10-7 M.
6. Anodic stripping voltammetry method
Principles of the method
The anodic-stripping analysis is the most sensitive of all commonly used electroanalytical
techniques. Analyses can be performed at the trace level and apply to solutions containing metal ions in
the concentration range of 10-6 - 10-12 M. Other advantageous features of stripping voltammetry include
the capability for simultaneous multielement determination and relatively inexpensive instrumentation
compared to that required for the spectroscopic techniques.
Three types of working electrodes can be used:
(a) the classical hanging mercury-drop electrode (HMDE),
(b) the thin-film mercury electrode (TFME),
(c) solid electrodes (gold, silver, surface-modified carbon).
The sequence of steps of the anodic stripping analysis is described below.
Step 1. The electrodeposition step
The metal ions Mn+ of interest are deposited (preconcentrated) electrochemically into or onto
the surface of an electrode (usually a mercury film electrode or a hanging mercury-drop
electrode), in the form of amalgam, M(Hg):

Step 2. Rest period 5

After a predetermined time, the stirring of the solution is turned off. The solution is allowed 3
 to become quiescent and the concentration of the metal in the amalgam - to reach
uniformity. The rest period extends for about 5 - 30 sec, during which the applied potential
remains unchanged, thus ensuring that no reoxidation of the metal by traces of oxygen takes
place. During the rest period the electrodeposition current decreases (Explain why).
Step 3. Stripping
After the preconcentration step, the deposited metal M is oxidized ("stripped") from the
mercury electrode back into the solution by oxidation to the ionic form under conditions of
diffusion control, using one of the voltammetric methods:

The anodic diffusion current is used to determine the concentration of the metal in the
amalgam, which is proportional to the time of electrolysis, stirring rate, and concentration of
Mn+ in the solution.
7. Adsorptive stripping voltammetry (AdSV)

Adsorptive stripping voltammetry is similar to anodic stripping voltammetry and cathodic stripping
voltammetry except that the preconcentration step is not controlled by electrolysis. The preconcentration
step in adsorptive stripping voltammetry is accomplished by adsorption on the working electrode surface,
or by reactions with chemically modified electrodes.
Accumulation step, in which the metal ion is accumulated on the electrode as an adsorbed metal complex.
A surface-active complexing agent is added to the solution (at a concentration not greater than 1 mM).
The ligand forms an adsorbed layer on the electrode surface (usually on a hanging mercury-drop
electrode) as soon as it is introduced into the solution. The analyte reacts with the adsorbed ligand to
form an adsorbed complex.

This process is carried out in stirred solution and under potential control.
Stripping the adsorbed metal ion, which is realized by electroreduction of the adsorbed complex.
PROCEDURE
Materials and equipment
Reagents
- Standard solution lead: 100 ppm Pb2+, 1.0 ppm
- Electrolyte solutions: 5
+ HCl 2 M 4
 + A 3 M acetate buffer (pH 5.0) was prepared from acetic acid and sodium acetate solution.
+ Xylenol orange was dissolved in high purity water give a 0.01 M stock solution, and further
diluted to give a 0.001 M working solution
- All other chemicals were analytical reagent grade.
Equipment
- All measurements were performed with an µAutolab type III (Netherlands), interfaced with the
electrode assembly 663 -VA Metrohm, Switzerland), and controlled by software 757 VA computrace.
The three-electrode system consists of a hanging mercury drop electrode (HMDE) as a working
electrode, an Ag/AgCl/KCl reference electrode, and a glassy carbon rod auxiliary electrode.
- Volumetric flasks and volumetric pipets
EXPERIMENTAL PROCEDURE

Checking the electrodes in the cell. Note that the Ag/AgCl reference electrode is stored in a KCl
solution. Remove it and rinse with doubly distilled H2O. The Ag/AgCl electrode must not be allowed
to dry out. When you complete your experiment, rinse with water and return to the vial containing the
storage buffer.
Fix appropriate nitrogen flow and stirring rate.

1. Running cyclic voltammetry

- The preparation of the measurement solution: Take 5.00 mL of the 1.0 ppm Pb2+ standard solution
into a 50 mL volumetric flask, added 2.5 ml of the 2M HCl solution and filled up to the mark with
doubly distilled water. Pour that solution into the cell and start measuring with the following steps:
- Open the software 757 computrace and switch on the potentiostat.

- Use select Mode in the Method menu to select cyclic voltammetry (CV) as the technique.

- Choose conditions: Initial nitrogen purge time 300s, start potential -1.2 V; End potential 0V; scan rate
20 mV/s, nuber cycle 1 (see Fig.6.2).
- Click OK.

- Save signals and peak search to record peak current (Ip) and peak potential (Ep)

- Change the scan rate from 20 mV/s to 500 mV/s, other conditions the same experiment 1.

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Fig.8.2. Exploratory specification and exploratory curve of cyclic voltammetry

2. Polarographic spectrum

- The preparation of the measurement solution: Take 2.50 mL of the standard 1.0 ppm Pb2+
solution into a 50 mL volumetric flask, added 2.5 ml of the 2M HCl solution and filled up to the mark
with doubly distilled water. Pour that solution into the cell and start measuring with the following
steps:
- Open the software 757 computrace and switch on the potentiostat.

- Use select Mode in the Method menu to select Differential Pulse (DP) as the technique.

- Choose conditions: Initial nitrogen purge time 300s, deposition potential -1.0V; deposition time 0s;
start potencial -1.0 V; End potential -0.1V; pulse amplitude 0.05 V; pulse time 0.04 s; voltage step 0.01V;
voltage step time 0.4s. sweep rate 0.025 V/s (see Fig.6.3).

5
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 Fig 8.3. Fig. : Exploratory specification and exploratory curve of differential pulse
- Click start.

- Change the polarographic modes such as Direct Current (DC), Normal Pulse (NP), Square wave
(SqW), and other conditions the same DP technique ( conditions in Fig.6.4; 6.5; 6.6).

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Fig.8.4. Exploratory specification and exploratory curve of Sampled direct Current

Fig.8.5. Exploratory specification and exploratory curve of Normal Pulse

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 Fig.8.6. Exploratory specification and exploratory curve of Square Wave

Save signals and peak search to record peak current (Ip) and peak potential (Ep). Compare peak current
(Ip) and peak potential (Ep) between different techniques.
3. Anodic Stripping Voltammetry method
- The preparation of the measurement solution: Take 5.00 mL of the standard 100 ppb Pb2+ solution
into a 50 mL volumetric flask, added 2.5 ml of the 2M HCl solution, and filled up to the mark with
doubly distilled water. Pour that solution into the cell and start measuring with conditions:
Initial nitrogen purge time 300s, deposition potential -1.0V; deposition time 30s; equilibration time 5 s;
start potential -1.0 V; End potential -0.1V; pulse amplitude 0.05 V; pulse time 0.04 s; voltage step 0.01V;
voltage step time 0.4s. sweep rate 0.025 V/s. Note that using deposition time, the solution was kept under
stirring. After the deposition time had elapsed, the stirring rod was stopped and 5 s was allowed for the
solution to become quiescent and the working electrode surface was evenly distributed. Then the
voltammogram was recorded by scanning the potential towards the positive direction applying the
differential pulse (DP).

5
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 Fig. 8.7. Exploratory specification and exploratory curve of Differential Pulse Anodic Stripping
Voltammetry

Save signals and peak search to record peak current (Ip) and peak potential (Ep). Compare the result of
peak current with differential pulse polarography.
4. Adsorptive stripping voltammetry method (AdSV)
- The preparation of the measurement solution: Take 5.00 mL the standard 100 ppb Pb2+ solution into
50 mL volumetric flask, added 2.5 mL the 10-4 mol.L-1 xylenol orange solution and 10 mL acetate
buffer solution (pH = 5), and filled up to the mark by doubly distilled water. Pour that solution into
the cell and start measuring with conditions:
Initial nitrogen purge time 300s, deposition potential -1.0V; deposition time 30s; equilibration time 3 s;
start potential -0.3 V; End potential -1.0V; pulse amplitude 0.05 V; pulse time 0.04 s; voltage step 0.01V;
voltage step time 0.4s. sweep rate 0.025 V/s. Note that using deposition time, the solution was kept under
stirring. After a 3 s quiescent time, scan the potential from -0.3 V to -1.0 V using differential pulse
cathodic stripping voltammetry.
Save signals and peak search to record peak current (Ip) and peak potential (Ep).

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 Fig.8.8. Exploratory specification and exploratory curve of Cathodic Differential Pulse Adsorptive
Stripping Voltammetry
Pre-Lab Assignment

Results and discussion

- Report the experimental results. Summarize the results about peak current and peak potential for each
voltammogram. Currents should be recorded in nA and potentials should be measured in V.
- Calculate the absolute value of the ratio of the reverse current and the forward current, ipc/ipa, for all the
voltammograms obtained. Comment results and electrochemical reaction?
- Comparision results (Ep, IP) from DC, NP, DP, SqW method, advantages and disadvantages of each
method.
- Compare the result of peak current with differential pulse polarography, anodic stripping voltammetry
and adsorptive stripping voltammetry.

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