5.

POLAROGRAPHY
5.1. Polarographic methods
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.

Fig.5-1 Schematic presentation of some polarographic methods.

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

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 few milliseconds). The values of Ein and tp are kept
constant throughout the recording of the polarogram and E p is changed from drop to drop (Fig.51a).
The limiting current in NPP is diffusion controlled. The experimental requirements for
diffusion control are the same as those for DC polarography. Since t p 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 t p = 1 ms, the diffusion layer thickness is about
210-4 cm, while the radius of the mercury drop is about 0.05 cm at t = 5 sec and m = 1 mg/sec).
Furthermore, the area of the drop is virtually constant during the application of the pulse (t 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)
For comparison, the current for DC polarography at time t is
(2)
The current under NP conditions is larger than that under DC conditions. The enhancement of the
current is

(3)
For typical conditions, t = 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 by an order of magnitude.
The i/E relationship for Nernstian processes at DCP and NPP is given by
(4)
The detection limit of NPP is about 210-7 M.
Differential pulse polarography (DPP). From 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 are given in Fig.5-1.
The current is sampled twice during a drop life-time: (i) at t 1, just before the pulse, and (ii) at t,
just before the drop fall. The polarogram represents the current difference
as
function of the base potential E b. 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

and Epeak are

(5)

(6)
The peak form of the DP voltammogram is explained below. At sufficiently positive
potentials, Eb - E0 > (120/n) mV, the faradaic currents

and i(t1) are both zero, and thus

also
is zero. At sufficiently negative base potentials, E b - E0 < (120/n) mV, the faradaic
process proceeds at maximum rate and the diffusion-limited current is reached; the current is
independent of potential and
difference

is determined by

s zero. At potentials in the vicinity of

the current

and has a finite value.

For non-Nernstian processes

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
is derived from the variation of the current around
The
derivative di/dE for non-Nernstian processes is smaller than for Nernstian, and results in a
lower

peak.
Although (DiF)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.
Square wave polarography (SWP). High sensitivity and low detection limit are
obtained with this technique. It is similar to DPP, however, the entire potential sequence is
applied during the life-time 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 drop birth, in order 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 nonNernstian ones. Detection limit of the method is about 10-7 M.
5.2. Handling the dropping-mercury electrode (DME)
The mercury capillary may be easily clogged and care must be exercised to prevent
contamination. The DME must never be allowed to stand in solution when mercury is not
flowing. Before allowing any solution to come in contact with the DME, raise the leveling bulb
and check that mercury drops are formed at the end of the capillary. Allow the mercury flow
during the entire laboratory session. After use, the capillary should be washed thoroughly with
distilled water. The mercury reservoir is then lowered to stop the flow.
Note: BE AWARE! Mercury vapors are poisonous!
Notify the instructor in the event of mercury spill. Mercury should be
cleaned up immediately. Do not throw it down the drain.
Reference electrode
An Ag/AgCl/1 M KCl reference electrode is used. Its potential is -19 mV vs SCE.
Chemicals

1.
2.
3.
4.
5.
6.
7.
8.

1 M KNO3
0.1 M KNO3
5.00 mM ZnCl2
0.2 % Triton X-100
0.01 M TlNO3
0.01 M KIO3
0.1 M NaCl
0.1 mM Tl+, 0.1 mM Cd2+, 0.1 mM Zn2+, 0.1 mM Ni2+, 0.002 % Triton X-100
in 0.1 M NH4OH - 0.1 M NH4Cl buffer
9. 0.5 M acetate buffer (pH 4.6)
10. 0.2 % ascorbic acid (freshly prepared)

Exp. 1. Oxygen waves

Fill the polarographic cell with 0.1 M KNO3 without passing the deaeration step. (Ask the
instructor for help). Record the polarogram using a voltage range of 0.2 to 1.8 V and a suitable
current sensitivity (
, tp = 20 ms, pulse amplitude = 20 mV, scan rate = 10 mV/s). Mark on
the polarogram, what are the electrode processes that take place at each wave. Estimate the
concentration of dissolved oxygen, assuming that the mercury flow rate is 1 mg/sec and D =
210-5 cm2/s.
After the first polarogram has been obtained, empty the cell, rinse and fill it with a
deoxygenated solution of 0.1 M KNO3. Run a polarogram of the deaerated solution.
Hereafter, all solutions for analysis should be deaerated.

Exp. 2. Polarographic spectrum

Introduce into the polarographic cell the deoxygenated solution containing 0.1 mM of
+
2+
Tl , Cd , Ni2+ and Zn2+. Record the polarogram in the potential range from -0.2 to -1.6 V, using
several polarographic modes: DC, NP, DP and SW. Compare E 1/2 values with those found in the
literature.
Exp. 3. Capacitance currents
The purposes of the experiments are:
(a) to observe the potential of zero charge, E Z, at a dropping-mercury electrode by recording
i vs E curves in solutions containing supporting electrolyte only;
(b) to measure currents due to charging of the double layer.
Record a polarogram of a deaerated 0.1 M KNO 3 solution at potentials 200 mV around
EZ (EZ = -0.45 V vs SCE, in absence of specific adsorption). Use an expanded potential scale.
Record a current-time plot for a single drop at E = E Z. Repeat for a potential positive and
a potential negative to EZ. Do not forget to mark the zero current. Determine the value of E Z and
compare with data in literature.
Analyze the current/time plots and compare with theory. Estimate from the current/time
plots the double layer capacitance, assuming m = 1 mg/sec.
Exp. 4. Maxima and maxima suppression
Run a polarogram of 1 mM Zn 2+ in 0.1 M NaCl. Repeat the experiment with the same
solution, containing 0.002% Triton X-100. Note the effect of the detergent on both the peak and
the limiting current.
Exp. 5. Migration currents
The purpose of the experiment is to test the effect of the concentration of the supporting
electrolyte on the limiting current. For this purpose run polarograms of 1 mM Tl + solution with
increasing concentrations of KNO3 (0, 1, 2, 5, 10, 50, 100 mM). Use the potential range of 0.1
to 1.0 V (
, tp = 20 ms, pulse amplitude = 20 mV, scan rate = 10 mV/s). Plot the limiting
current vs concentration of supporting electrolyte. Compare with theory, assuming equal
equivalent conductances for all ionic species of interest.
Repeat the experiment by replacing the Tl+ solution with KIO3. In that case 0.002% Triton
X-100 is required to suppress the polarographic maxima. Use the potential range of 0.8 to -1.8
V. The electrode reaction of the reduction of KIO3 is:

Exp. 6. Analysis of the polarographic wave

The purposes of the experiment are:

(a) to verify that the limiting current of the TI+ - reduction polarographic wave is diffusion
controlled;
(b) to determine the half-wave potential and the number of electrons involved in the reduction.
Prepare 0.5 mM solution of TlNO3 in 0.1 M KNO3. (The Tl+ concentration has been
chosen low enough in order to neglect potential drop in the solution). Run a polarogram in order
to choose a potential in the limiting current region. Record a current/time plot at the chosen
potential. Prove, that the current is totally diffusion controlled, and calculate the diffusion
coefficient, assuming that m = 1 mg/sec.
In order to enable an accurate measurement of the currents along the wave, run an
additional polarogram at a slow scan rate (5 mV/s).
Determine E1/2 of the Tl+ reduction wave and compare with literature.
Determine the number of electrons involved in the reduction process from E vs log[(id i)/i] plot.
Exp. 7. Quantitative determination of Zn2+ in drinking water
Fill the cell with the sample of drinking water and record a polarogram. You may prefer
to use one of the more sensitive polarographic methods (normal pulse, differential pulse or
square wave). Make a rough estimation of the concentration of Zn2+.
For the analytical determination use both the standard addition method and the calibration
curve method. Show the instructor your detailed plan of operation, including the composition of
the solutions. Prepare the standard solutions in 50 ml volumetric flasks. For the calibration curve
method use as the supporting electrolyte the solution of 10 mM NaCl. Compare the results of the
two methods of determination.
Exp. 8. Determination of ascorbic acid (Vitamin C) in citrus juice by the standard-addition
method.
Ascorbic acid yields a well-defined polarographic oxidation wave. The determination can
be carried out directly in freshly prepared diluted juice as well as in conserved citrus juice. The
method of standard additions is used for the quantitative determination of the concentration of
the Vitamin C.

Ascorbic acid
Procedure
1.
Calibration curve

Dehydroascorbic acid

Prepare a fresh stock solution of 50 ml 0.2 % ascorbic acid.

Prepare five standard solutions of ascorbic acid in volumetric flasks of 25 ml. To each one
add 0.5 ml 0.5 M acetate buffer and different volumes of 0.2 % ascorbic acid: 0, 200, 400, 600
and 800

. Dilute to the mark with distilled water.

For each solution record a NP (

, tp = 20 ms, pulse amplitude = 20 mV, scan rate = 10

mV/s) and SW (
, tp = 20 ms, pulse amplitude = 20 mV, scan rate = 100 mV/s)
polarograms over the potential range: -150 to +200 mV vs. Ag/AgCl/1 M KCl, with E in = -150
mV. Consult with the instructor about the preferable mode of polarography to be used in further
experiments.
Plot id vs. concentration of ascorbic acid. Is the plot linear and does it pass through the
origin? On the basis of these observations decide if the standard-addition method is applicable.
2.
Determination of ascorbic acid in citrus fruits
Squeeze an orange, grapefruit or lemon until about 10 ml of juice is obtained. Filter the juice
through a porous funnel (pore size about 1 mm).
Prepare four 25 ml volumetric flasks. Add to each, 0.5 ml of 0.5 M acetate buffer, 2.0 ml of
the juice and standard additions of 0, 200, 400 and 600
of 0.2 % ascorbic acid. Dilute to the
mark with distilled water.
Record polarograms under the same conditions as in the calibration step.
Draw the standard additions plot and determine the concentration of the analyte. Report the
concentration of ascorbic acid (Vitamin C) in the original sample (juice) in mol/l and ppm.
3.

Determination of ascorbic acid in conserved citrus juice

Plan an experiment for the determination of ascorbic acid in preserved (commercial) citrus
juice. Use the scheme of the previous experiment. Consult with the instructor as to the
differences in procedure for preserved as opposed to natural juice.
Recommended Literature
1.
H. H. Willard, L. L. Merritt, J. A. Dean and F. A. Settle, Instrumental Methods of Analysis.
2.
D. A. Skoog and D. M. West, Principles of Instrumental Analysis.
3.
D. A. Skoog and J. J. Leary, Instrumental Analysis.
4.
D. C. Harris, Quantitative Chemical Analysis.
5.
A. J. Bard and L. R. Faulkner, Electroanalytical Chemistry.

Go to Main Page

6. STRIPPING VOLTAMMETRY

6a. ANODIC-STRIPPING ANALYSIS

Principles of the method

Anodic-stripping analysis is the most sensitive of all commonly used electroanalytical
techniques. Analyses can be performed at the trace level and are applicable 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):

A short-time electrolysis (30 sec to 5 min) in a stirred solution and at a potential suitable for the
reduction of the ions of interest (E -E1/2 about -200 mV) may result under proper conditions in a
fairly concentrated amalgam. This step is called the electrodeposition step. The concentration of
the metal ion in the film depends on concentration of Mn+ in solution, time of electrolysis and
rate of stirring. Since the electrodeposition is carried out on small electrodes, the amount of
material deposited into it usually does not change significantly the concentration of the metal
ions Mn+ in the solution. Step 1 is only an intermediate step and there is no need to know the
concentration reached in the amalgam. However, it can be estimated.
The enrichment of the metal M in the amalgam in respect to the initial concentration of
M , CMn+, is estimated in stirred solutions, using Nernst simplified model (eq.3 in
section"Coulometric titrations").
n+

For typical laboratory conditions the Nernstian layer thickness in well-stirred solutions is about
20
.
As a result of electrolysis for a time t, the concentration of M in the amalgam, CM(Hg), is

where A and V are the area and the volume of the mercury electrode.
The enrichment of the metal in the amalgam, using D = 10-5 cm2/s, is

The enrichment factor at HMDE

For a hanging mercury-drop electrode A/V = 3/r, and for r ~0.03 cm it is 100 cm-1, thus

For a 100 s deposition time, the enrichment factor is 50.

The enrichment factor at TFME
The TFME consists of a thin mercury film coated on glassy carbon. A/V for this electrode
depends solely on the thickness of the film. Typical dimensions for a thin-film mercury electrode
are: A = 0.2 cm2 and film thickness about 10-5 cm. The value of A/V for TFME is 10 5, which is
1000 times that of HMDE.

As a result of a 100 sec electrolysis, the concentration of the metal in the amalgam will be
~5104 times larger than that of the metal in the solution.
The enrichment factor for a hanging mercury-drop electrode is 1000 times smaller than
that for a thin mercury film. Nevertheless, substantial increase in concentration is achieved also
with this type of electrode for electrolysis time t larger than 100 sec.
The degree of decrease of concentration in solution as result of the electrodeposition step
is calculated for a mercury film electrode for the following conditions: the area of the film, A =
0.2 cm2; the initial concentration of the metal ions in the solution, C Mn+ = 10-8 M; the volume of
the tested solution is 20 ml; the time of deposition is 100 s; the Nernstian layer thickness during
the deposition step is 20
. At the end of the electrolysis step the number of moles of the metal
electrolyzed in the film, CM(Hg) = 10-12 mole (verify this value!). Thus, the decrease of
concentration of Mn+ in solution after the electrolysis is negligible (0.5 %).
Step 2. Rest period
After a predetermined time, the stirring of the solution is turned off. The solution is
allowed to become quiescent and the concentration of the metal in the amalgam - to reach
uniformity. The rest period extends for about 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 time of electrolysis, stirring rate and concentration of Mn+ in solution.

Cleanliness requirement for glassware

The glassware you will use is especially cleaned for this highly sensitive determination.
Use only glassware on which the type of chemical and its concentration are marked. Do not
interchange glassware. In order to minimize contamination, the amount of glassware should be
reduced as much as possible. For example, the sample will be introduced into the cell not with a
pipette, but directly from the sample bottle by weighing.

Sample preservation
Drinking water samples should be preserved by adding 10 ml of 1 M HNO 3 to each liter
of sample immediately after collection. Acidification to a pH between 1 and 2 is an essential first
step in water sampling: a) it arrests biological growth; b) it affects the release of trace metals
from organic components (humic and fulvic acids) and c) it reduces metal loss caused by
adsorption on the container wall.

Sample pretreatment
The presence of surface-active compounds in the samples consists a major problem in the
use of solid electrodes. Surfactants compete with the analyte on the electrode surface for active
adsorption sites, causing distortion, lower sensitivity and instability of the signal of the analyte.
The hanging mercury-drop electrode, owing to its renewable surface, is inherently less sensitive
than solid electrodes to surfactants.
Severe peak distortions are overcome with different methods: UV irradiation 2 of the
sample, coating the electrode with permselective film or membrane that prevents the surfactant
from reaching the electrode surface3, addition of fumed silica to the analyte 4, wet digestion and
others.

Exp.1. Determination of Pb2+ and Cd2+ in drinking water, using hanging mercury-drop
electrode

Chemicals

1. 1.0010-4 M Pb(NO3)2 in 10 mM HCl

2. 1.0010-4 M CdCl2 in 10 mM HCl
3. 10 mM HCl supporting electrolyte
4. 1 M HNO3

Electrodes:

working - HMDE
reference - Silver wire (1.5 mm diameter)

Basic procedure for the anodic-stripping analysis

Prepare fresh solutions of Pb2+ and Cd2+, 10-6 M each, in 10 mM HCl. For drinking water
samples: collect tap water into a clean plastic vessel, add 10 ml of 1 M HNO 3 to each liter of
water, as needed for sample preservation.
Pipet into the cell 5.00 ml of the supporting electrolyte and 0.05 ml of one of the 10 -6 M fresh
prepared solutions of the metal. Perform an anodic-stripping analysis under the following
conditions:
Method Voltammetric analysis: SW
Deaeration step (bubbling N2)
Preconcentration step (Deposition):
Rest step (Equilibration):

t = 120 s
E = -900 mV
t = 60 s
t=5s
Potential scan = from -900 to -200 mV

Anodic dissolution step:

step duration = 0.1 s

step amplitude = 5 mV
pulse amplitude = 25 mV

Stirring rate

800 rpm

Test of reproducibility. Repeat several times the basic procedure in the same solution. Report the
average and the standard deviation of the slope.
Effect of electrolysis time. Repeat the stripping procedure with different electrolysis times: from
30 to 120 minutes. Note that the signal is linearly changed with the time.
Calibration curve. A calibration curve for the analyzed metal is constructed for two reasons: (a)
to enable rough estimation of the concentration of the metal in the unknowns by comparing peak
heights, and (b) to test if linearity between analytical signal and concentration is obtained in the
concentration range if interest. This is a basic condition for applying the standard-additions
method, used for the analytical determination in this experiment.

Insert into the cell 5.00 ml of the supporting electrolyte. Record a stripping curve of the blank
following the basic procedure. Repeat the experiment with five subsequent additions of 0.05 ml
of the 10-6 M Pb2+ solution. Plot the calibration curve.

Determination of Cd2+ and Pb2+ in drinking water

Carry out at least three stripping voltammograms of a drinking water sample. On the basis of
your acquired experience make a rough estimation of the concentration of the analyte. Make an
appropriate standard addition. Run a new voltammogram. If your guess was successful, repeat
the voltammogram. If not, make a new guess.
Report the concentration of the analyte in mol/l and ppb. Compare your results with the official
permissible levels.

Exp. 2. Determination of Pb2+ in drinking water, using the silver rotating-disk electrode

The Rotating-Disk Electrode (RDE)

One of the best methods of obtaining efficient mass transport in a highly reproducible
manner is by the use of the rotating-disk electrode. The RDE consists of a cylindrical metal rod
embedded in a larger cylindrical plastic (e.g., Teflon) holder. The electrode is cut and polished
flush with its holder, so that only the bottom end of the metal cylinder is exposed to the solution.
The configuration of a rotating-disk electrode is shown schematically in Fig.6-1. The
most important feature of the RDE is that it acts as a uniformly accessible surface, which
means that the rate of mass transport to the surface is uniform. This is by no means self evident,
considering that the linear velocity of points on the surface increases with their distance from the
center of rotation. The other important property of the RDE is that flow of the solution around it
is laminar up to rather high rotation rates.

Fig.6-1 The rotating-disk electrode. The electrode and the insulated material are marked by
filled and clear areas, respectively.

Since the flow is laminar, it is possible to calculate rigorously the rate of mass transport.
The rotating-disk electrode was developed following the mathematical solution given by Levich
of the hydrodynamic equations describing the rate of transfer of substance in solution to a
rotating disk surface, in terms of the angular velocity of rotation
(
, N in rps), the
0
diffusion coefficient D, the concentration C of the substance and the kinematic viscosity of
the solution. For the case when the reaction is relatively fast and the current is determined by
mass transport, the corresponding equation for the limiting current density
Levich, is:

, developed by

where is in A/cm2, D in cm2/s, in cm2/s , in rad/s and C0 in mol/cm3. In such a case the
limiting current is independent of potential over a wide range. This range of potential is limited
at one end by the reversible potential and a small overpotential needed to drive even a very fast
reaction to mass-transport limitation and at the other end by another reaction which may take
place, usually the evolution or oxygen or hydrogen in aqueous solutions.

Experimental procedure

The silver rotating-disk electrode4 is well suited for the determination of lead in ppb and
sub-ppb concentrations.
A two-electrode cell configuration is used (cf., Fig.6-2). The working electrode is a silver
rotating disk. A silver wire acts as a combined counter/quasi-reference electrode. The potential of
the silver wire is stabilized by the presence of chloride ions in working solution.
Handling of the silver disk electrode. The silver disk electrode can be used over
hundreds of measurements without any pretreatment, provided the surface-active agents in the
samples are destroyed. The proper functioning of the electrode is judged according to two
criteria:
(a) the reproducibility of the anodic stripping voltammograms;
(b) the degree of linearity between the analytical signal and the concentration.
If the criteria are not fulfilled to our satisfaction, the electrode should be polished with
0.05 mm alumina powder, rinsed thoroughly with distilled water, sonicated for 3 min for removal
of alumina particles and rinsed again with distilled water.

Fig.6-2 Electrochemical cell for anodic-stripping voltammetry.

Chemicals

1. 1.0010-4 M Pb(NO3)2 in 10 mM HCl

2. 1 M HNO3
3. Combined 10 mM HNO3 and 10 mM NaCl supporting electrolyte

4. Digestion solution containing 2 M HNO3 and 2 M H2SO4

5. 0.05

Electrodes:

alumina powder

working - Silver disk electrode (area about 0.07 cm2)

reference - Silver wire (1.5 mm diameter)

Basic procedure for anodic-stripping voltammogram

Since the work is performed in trace concentrations of analyte (about 10-8 M), care should
be taken in the use of utensils: for each concentration use only the vessels marked respectively.

1. In a 100 ml volumetric flask prepare solution of 1.0010 -6 M Pb(NO3)2 in 10 mM

HNO3 from the 1.0010-4 M Pb(NO3)2 stock solution.
2. Pipet into the cell 5.00 ml of the combined 10 mM HNO 3 and 10 mM NaCl supporting
electrolyte and 0.200 ml of the 10-6 M solution of Pb2+. Start the stirrer.
3. Perform an anodic-stripping analysis at a rotation rate of 3500 rpm under the
following conditions:
Method Voltammetric analysis: SW
Pretreatment step (Conditioning):

E = -40 mV
t = 10 s

Preconcentration step (Deposition):

E = -700 mV
t = 30 s

Rest step (Equilibration):

t=3s

Anodic dissolution step:

Potential scan = from -700 to -40 mV

Frequency = 25 Hz
Step potential = 25 mV
Amplitude = 5 mV

The analytical signal can be quantified by: a) the stripping peak current, b) the stripping
peak area, and c) the average slope at the two inflection points of the peak. Use the slope for
quantitative evaluation of analyte, since this parameter yields the best linear response vs.
concentration.
3. Precision. The precision of an analytical method is the degree of mutual agreement
among results obtained under identical conditions. Statistically, the precision is expressed as the
relative standard deviation of a set of measurements.
Run five subsequent voltammograms and calculate the average and the relative standard
deviation of the slope.
4. Effect of rotation rate. Repeat the stripping procedure for different rotation rates
(2000 - 8000 rpm). Plot the analytical signal as function of the square root of the rate of rotation.
5. Effect of electrolysis time. Repeat the stripping procedure with different electrolysis
times: from 15 to 120 seconds.
6. Background correction. Traces of impurities in the reagents contribute to the
background and should be taken into account. Pipet into the cell 5.00 ml of the combined 10 mM
HNO3and 10 mM NaCl solution and run a stripping voltammogram in the supporting electrolyte
only. Note the value of the analytical signal of lead in the background (the slope) and use it later
to correct the calibration curves.
7. Calibration curve. A calibration curve in the range of 0 to 810-8 M of Pb2+ is
constructed for two reasons: (a) to enable rough estimation of the concentration of Pb 2+ in the
unknowns by comparing peak heights, and (b) to test if linearity between analytical signal and
concentration is obtained in the concentration range if interest. This is a basic condition for
applying the standard-additions method, used for the analytical determination in this experiment.
Insert into the cell 5.00 ml of the combined supporting electrolyte. Record a stripping
curve of the blank by following the basic procedure, but increase the deposition time to 60 s.
Repeat the experiment with five subsequent additions of 0.1 ml of the 1.0010 -6 M Pb2+ solution.
Plot the calibration curve.

Determination of Pb2+ in drinking water

1. Collect a tap water sample as discussed in Sample preservation. For preservation of

sample and proper functioning of the reference electrode, add 1 ml of the 1 M HNO 3 to 100 ml
of tap water. If the analysis is carried out immediately after the sample collection, the
acidification step can be omitted.
2. Pretreatment of samples. Water samples are pretreated in order to overcome
interferences due to surface-active compounds. The procedure applied consists of digestion with
nitric and sulfuric acids and heating to 650C. Nitric acid destroys organic materials and sulfuric
acid supplies sulfate ions to ensure that the lead ions form a temperature-stable lead sulfate.
The efficiency of the pretreatment is tested by comparing the lead content in pretreated
and unpretreated synthetic solutions.
Digestion of unknowns, blank and control sample
(a) Unknown: 50.00 ml drinking water, acidified for preservation.
(b) Blank: 50.00 ml Type I Reagent Grade Water, acidified as the unknown.
(c) Control sample: 50.00 ml 210-8 M Pb2+, acidified as the unknown.
Perform the digestion of the duplicates of: (a) the unknown drinking water sample, (b)
blank, and (c) the synthetic control sample (the latter is used to test if lead is lost during the
digestion procedure), according the following procedure: insert 5.00 ml of the sample to be
digested into a quartz beaker (quartz is stable at high temperatures, and the leaching of lead from
quartz is considerably less than from Pyrex glass), add 2 ml of the digestion mixture (2 M
HNO3 + 2 M H2SO4) to each beaker.
Transfer the beakers to a muffle furnace and keep at 300C for about an hour to evaporate
gently the solution to dryness. Then heat the furnace to 650C and keep the beakers for
additional 20 minutes. Allow the beakers to cool to room temperature, and add 5.00 ml of the
combined 10 mM HNO3 and 10 mM NaCl supporting electrolyte to each one of them.
3. Analysis of the pretreated samples. Add 4.00 ml of the undigested 210-8 M
Pb2+ control sample (c) to the electrochemical cell. Perform twice the basic stripping procedure
with a deposition time of 60 s. Run another voltammogram with a new 4.00 ml aliquot of the
control solution to exclude a possibility of contamination of the cell. Verify that the
reproducibility of the three measurements is satisfactory. Run a blank stripping voltammogram
using 4.00 ml of the combined supporting electrolyte.
Repeat the above step using the digested 210-8 M Pb2+ solution sample (c). Run the
voltammogram of the digested blank sample (b). Calculate the relative difference of the signals
of the treated and the untreated solutions each one corrected for the respective blanks.

For the unknown samples (a) and the blank (b) perform a quantitative determination
based on standard-additions method. Run stripping voltammogram of the sample. Make a rough
estimation of the lead concentration by comparing the analytical signal of the unknown with
those of the calibration curve. If the agreement between the duplicates is satisfactory, perform the
standard-additions procedure on one of the duplicates only. Keep the following rules in respect
with the standard additions: (a) the volume of a single standard addition should be smaller than
5% of the volume of the solution in the cell; (b) the increase in concentration with each addition
should be lower than 40% of the concentration of lead, roughly estimated by consulting the
calibration curve, recorded under identical conditions. Calculate the concentration of lead in the
digested unknown sample and in the digested blank.
Calculate the concentration of lead in the drinking water sample. Report the
concentration of the analyte in mol/l and ppb. Compare your results with the official permissible
levels.

Exp. 3. Measurement of contamination of water by Pb2+ as a result of contact with ceramic

glazes and crystal glasses,
using the silver rotating-disk electrode

Lead compounds have been and are still used in the manufacture of ceramic glazes and crystal
glasses.
Certain compounds of lead, particularly brightly colored lead oxides, have been used for leaded
glasses and leaded glazes on ceramics for thousands of years. The addition of lead improves the
appearance and cutting properties of crystal glass. Small amounts of lead are also present in
optical glass. The major application of leaded glass is in television screens and computer
monitors, and serves to protect viewers from the harmful X-rays generated by these appliances.
Lead-containing glazes are used in some pottery, tiles and tableware.
Crystal glasses contain up to 30 % lead oxide, PbO. The European definition of lead crystal as
glass that contains a minimum of 24% lead oxide is a feature that once contributed to its
reputation for quality. The purpose of lead oxide is to increase the density of glass, which in turn,
increases the refractive properties. When it is cut and polished, it creates more colors and sparkle
than regular glass. On contact with water or other solutions, the lead is slowly released in trace
amounts, especially in acidic solutions.

To read more about the properties of lead Go to

http://www.ldaint.org/factbook/factbookch1.htm
http://ianrpubs.unl.edu/water/g1333.htm

Electrodes:

working - Silver disk electrode (area about 0.07 cm2)

reference - Silver wire (1.5 mm diameter)

Chemicals

1. 1.0010-4 M Pb(NO3)2 in 10 mM HCl

2. 1 M HNO3
3. Combined 10 mM HNO3 and 10 mM NaCl supporting electrolyte
4. 0.05

alumina powder

Experimental procedure
The same configuration of the electrochemical cell is used (see Exp. 2).
For the preparation of the sample, heat about 100 ml of deionized water in a glass beaker until
the water boils, add 1 ml of 10 mM HCl (pH 4). Transfer the hot water to a glazed ceramic vessel
or to a crystal glass, wait for about 20 min. Use this solution for determination of the degree of
contamination by Pb2+.
Follow the basic procedure of the anodic stripping (see Exp. 2) for recording voltammograms for
blank and analyte solutions.
Perform a quantitative determination using the standard-addition method. Consult with the
instructor about the details, concerning the volume of the sample and the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metal in the cell. Report the concentration of
the metal in the sample in mol/l and ppm.

References
1. C. M. G. Van den Berg, Anal. Chim. Acta, 1991, 250, 265.

2. J Jarbini, and W. R Heineman, Anal. Chim. Acta, 1986, 186, 11.

3. A. Economou and P. R. Fielden, Analyst, 1993, 118, 1399.
4. M. Brand, I. Eshkenazi and E. Kirowa-Eisner, Anal. Chem., 66, 4660(1997).
5. E. Kirowa-Eisner, M. Brand and D. Tzur, Anal. Chim. Acta, 385, 325(1999).

Recommended Literature
1.

D. A. Skoog, Principles of Instrumental Analysis.

2.

D. A. Skoog and D. M. West, Principles of Instrumental Analysis.

3.

D. A. Skoog and J. J. Leary, Instrumental Analysis.

4.

A. J. Bard and L. R. Faulkner, Electroanalytical Chemistry.

6b. ADSORPTIVE STRIPPING VOLTAMMETRY

Adsorptive stripping voltammetry (AdSV) is similar to anodic-stripping

voltammetry (ASV). The method consists of two main steps, in analogy to ASV:

(a)
Accumulation step, in which the metal ion is accumulated on the electrode as an
adsorbed metal complex.
A surface-active complexing agent is added in 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 (at nanomolar
or sub-nanomolar concentration) reacts with the adsorbed ligand to form an adsorbed complex.

This process is carried out in stirred solution and under potential control. The analyte reaches the
electrode by convection (as in the preconcentration step of anodic-stripping voltammetry).
(b)
Stripping the adsorbed metal ion, which is realized by electroreduction of the
adsorbed complex.
Square-wave voltammetry is used in this step. The amount of adsorbed metal is determined from
the value of the peak current or from the sum of the slopes at the inflection points of the peak.

The ligands used in AdSV are surface-active compounds or are able to interact
chemically with mercury (the presence of -electrons benefit the adsorption process and the
presence of S donors helps the chemisorption process). The kinetics of the complex formation
must be fast.
In this experiment the ligands are dimethylglyoxime (DMG) and 8-hydroxyquinoline
(oxine). In some applications the use of mixture of ligands enables simultaneous determination
of up to six trace metals.

The detection limit of AdSV depends on the chemistry of the system and can be as low as
10 M.
-12

Adsorptive stripping suffers from interferences resulting from competitive adsorption of

surface-active substances present in the analyte. The most common methods for destroying

organic matter in the samples are: addition of fumed silica (adsorbs the surface-active
substances), ultraviolet irradiation, wet and dry ashing.

Cleanliness of glassware
The glassware used is especially cleaned for this highly sensitive analysis. Prior to use
the glassware is immersed for a few hours in a liquid cleaner, followed by immersion in 1:1
aqueous HNO3 and then rinsed with copious amounts of deionized water.
It is recommended to use dedicated vessels for the various analytes and for different
concentrations.
In order to minimize contamination, the amount of glassware and plastic ware should be
reduced as much as possible.

Exp. 1. Simultaneous determination of traces of heavy metals

released from domestic utensils.

This experiment follows the work of C. M. G. van den Berg et al 1. Van den Berg
demonstrated the advantages of using mixture of ligands in AdSV. With DMG
(dimethylglioxime) as ligand only Ni and Co are determined by adsorptive stripping
voltammetry 2,3. Addition of oxine (8-hydroxyquinoline) enables simultaneous determination of
several metals: Cu, Pb, Cd, Ni, Co and Zn. The concentration range depends on the species
present and is roughly from sub-nanomolar up to about 50 nM. At higher concentrations of the
metals deviation from linearity may be observed. Thus, an excess of one of the analytes may
interfere with the analysis. For this reason, drinking tap water, which normally contains
micromolar concentration of Zn, cannot be analyzed by using mixture of ligands, the content of
Ni and Co in tap water can be determined using DMG only.
(In this experiment the HEPES buffer has been replaced with an ammonia buffer).
The method of standard additions is used for the quantitative determination of the metal
concentrations.

Chemicals

1. 0.5 M ammonia buffer pH 9.24

2. 0.01 M DMG in 96% ethanol

3. 0.1 M oxine in 0.15 M HCl (stock solution, stored in refrigerator)
4. 1 mM oxine (freshly prepared monthly)
5. 10 mM HCl
6. 0.1 M NaCl
7. 0.1 mM Cu2+ in 10 mM HCl
8. 0.1 mM Pb2+ in 10 mM HCl
9. 0.1 mM Cd2+ in 10 mM HCl
10. 1.7 mM (100 ppm) Ni2+ in 10 mM HCl
11. 1.7 mM (100 ppm) Co2+ in 10 mM HCl
12. 0.05 mM Zn2+ in 10 mM HCl

Electrodes:

working - Hanging mercury-drop electrode (HMDE)

reference - Ag/AgCl/1 M KCl
counter - Pt wire

Basic conditions for adsorptive stripping voltammetry

Deaeration step (bubbling N2)

t = 120 s

Accumulation (adsorption ) step

E = -200 mV
t = 30 s

Rest step

t = 10 s

Reduction (stripping) step

technique SWV
E = from -200 to -1400 mV

step duration = 0.1 s

step amplitude = 5 mV
pulse amplitude = 25 mV
Stirring rate

800 rpm

Fig.6-3 Simultaneous determination of 15 nM Cu 2+, 15 nM Pb2+, 15 nM Cd2+, 11 nM Ni2+, 11

nM Co2+ and 15 nM Zn2+
in 82 mM ammonia buffer pH 9.24, 0.16 mM DMG and 8.2
Experimental conditions: see above table.

oxine.

Experimental procedure

1. Demonstration of the use of mixture of ligands

a) Blank solution containing DMG only as ligand
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG
solution. Record a stripping voltammogram of the background according to the conditions for
adsorptive stripping voltammetry, summarized in the table above.
b) Adding Ni2+ and Co2+ to the blank
Prepare by stepwise dilution 5 ml of diluted separate solutions of Ni 2+ and Co2+ from the
respective 1.7 mM (100 ppm) stock solutions: 1 ppm (17
) in 10 mM HCl, and 0.02 ppm (0.34

) in 10 mM HCl, 0.2 ppm (3.4

) in 10 mM HCl.

Add 100
of each 0.02 ppm solution to the cell containing the blank. Run a stripping
voltammogram. Well defined peaks of Ni and Co should appear.
c) Adding Cu2+, Pb2+, Cd2+ and Zn2+
Following section 1b, add to the cell 100
of a freshly prepared solution containing 1
of
2+
2+
2+
2+
each of Cu , Pb , Cd and Zn in 10 mM HCl. Record a stripping voltammogram. Do you
observe any change as result of the presence of the added metals?
d) Adding oxine
Add to the above cell 50
of 1 mM oxine solution. Record a stripping voltammogram. Note
that the peaks of all the species appear only in the solution containing the mixture of ligands.

2. Test for linearity of analytical signal vs. accumulation time

It is important to verify the range of accumulation time over which linearity is achieved. Perform
the test for linearity for the metal to be analyzed in the following experiments.
Rinse the cell. Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of
0.01 M DMG. Record a stripping voltammogram of the background.

Add to the cell 100

of 0.02 ppm Ni2+ prepared in the previous experiment. Run a series of
voltammograms for different values of the accumulation time over the range of 20 to 80 sec.
Plot the analytical signal (sum of the slopes at the inflection points) vs. accumulation time.

3. Test for linearity of analytical signal vs. concentration (calibration curve)

In order to validate the use of the standard addition method, it must be shown that the peak
current of the stripping voltammogram depends linearly on the concentration of the element. For
this purpose run a series of voltammograms with increasing concentrations of the analyte, and
plot the calibration line over the concentration range of 8 40 nM of the metal.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG.
Record a stripping voltammogram of the background for an accumulation time of 40 sec.
Add to the cell 100
of 0.02 ppm Ni2+ prepared in the previous experiment and run a
voltammogram. Repeat this step with four more additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
(corrected for background) vs. concentration of the metals in the cell.

3.1. Quantification of species

(a) The quantification is carried out by the standard addition method, which should be
performed in the concentration range, where linearity of the calibration curve has been verified.
In the analysis of samples with unknown concentration of analyte, the first step is to estimate the
concentration level of the unknown by measuring the analytical signal and comparing it to the
calibration curve constructed early.
_

If the signal is in the range of the calibration curve, proceed by the standard addition
method.

If the signal of the unknown is larger, there are several possibilities:

(a) decrease the time of accumulation (not lower than 20 s);
(b) use a smaller volume of the sample for introduce into the cell;
(c) dilute the sample;

(d) check the linearity at higher concentrations by building a calibration

curve in a higher concentration range.

If the signal is lower, the possibilities are:

(a) increase the time of accumulation;
(b) increase the volume of the sample introduced into the cell;
(c) if the detection limit permits, construct a calibration curve in a lower
concentration range.

(b) Always perform first a measurement of the analytical signal in the background. For
obtaining results with reasonable accuracy the signal of the unknown should be at least twice the
value of the background.

4. Applications

4.1. Determination of contamination of water by Ni2+ as a result of contact with stainless steel
Stainless steel being in contact with hot water release traces of Ni. The contamination of Ni is
higher in presence of acids.
This experiment can be performed with any stainless steel equipment: any kind of vessels,
heating elements for preparing water for hot drinks, kettles and pots with stainless steel parts,
etc.

To prepare the samples, heat 100-200 ml of deonized water containing 10 mM NaCl (the
addition of the salt is to simulate drinking water). Leave the hot water in contact with the
stainless steel for about 20-40 min. Use this solution to determine the amount of Ni 2+ leached
from the stainless steel.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG.
Record the stripping voltammogram of the background.
Add to the cell 0.05 2.0 ml of the analyte solution and record a voltammogram. The aliquot of
the unknown is determined by the concentration of the analyte: the larger the concentration the

smaller the portion of added sample (cf., note 3.1.). Make at least two standard additions, using
the proper diluted solution of Ni2+ (0.02 ppm or 0.2 ppm) and run the voltammograms again.
Consult with the instructor about the volume of the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metal in the cell. Report the concentration of
the metal in the sample in mol/l and ppb. What is the pH of the analyte sample?

4.2. Determination of contamination of water by Ni2+ as a result of contact with a nickel strip
Prepare a sample by inserting a Ni strip (total area about 60 cm2) into a 100 ml glass beaker filled
with deionized water. Wait for about 20-30 min. It is possible to use hot water for shortening the
waiting time. Use this solution to determine the amount of Ni2+ leached from the strip.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG.
Record the stripping voltammogram of the background.
Add to the cell 0.050-0.100 ml of the analyte solution and record a voltammogram. Make at least
two standard additions, using the 0.2 ppm solution of Ni2+ and run the voltammograms again.
Consult with the instructor about the volume of the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metal in the cell. Report the concentration of
the metal in the sample in mol/l and ppm.

4.3. Direct determination of Ni2+ in drinking (tap) water

Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG.
Record the stripping voltammogram of the background.
Rinse the cell and run another voltammogram for the solution containing 3 ml tap water, 2 ml
deionized water and the same amounts of ammonia buffer and DMG. Use the method of standard
additions, as in the previous applications, for quantitative determination of Ni 2+ in the sample of
tap water. Report the concentration of the metal in tap water in mol/l and ppb. Compare your
results with the official permissible levels.

4.4. Contamination of water by Pb2+ as a result of contact with glazed ceramic vessel

Lead compounds have been and are still used in the manufacture of ceramic glazes and crystal
glasses. Certain compounds of lead, particularly brightly colored lead oxides, have been used for
leaded glasses and leaded glazes on ceramics for thousands of years. The addition of lead
improves the appearance and cutting properties of crystal glass. Small amounts of lead are also
present in optical glass. The major application of leaded glass is in television screens and
computer monitors, and serves to protect viewers from the harmful X-rays generated by these
appliances. Lead-containing glazes are used in some pottery, tiles and tableware. On contact with
water or other solutions, the lead is slowly released in trace amounts, especially in acidic
solutions.

To read more about the properties of lead Go to

http://www.ldaint.org/factbook/factbookch1.htm
http://ianrpubs.unl.edu/water/g1333.htm

On a hot plate, heat about 100 ml of deionized water in a glass beaker until the water boils, add 1
ml of 10 mM HCl (pH 4). Transfer the hot water to a glazed ceramic vessel, wait for about 20
min. Determine the degree of contamination by Pb2+ in this solution.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG
and 50

of 1 mM oxine solution. Record the stripping voltammogram of the background.

Add to the cell 0.1 0.2 ml of the analyte solution and record a voltammogram. Make at least
two standard additions, using the 1
solution of Pb2+ and run the voltammograms again.
Consult with the instructor about the volume of the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metal in the cell. Report the concentration of
the metal in the sample in mol/l and ppm.

4.5. Contamination of water by Pb2+ as a result of contact with crystal glass

Crystal glasses contain up to 30 % lead oxide, PbO. The European definition of lead crystal as
glass that contains a minimum of 24% lead oxide is a feature that once contributed to its
reputation for quality. The purpose of lead oxide is to increase the density of glass, which in turn,
increases the refractive properties. When it is cut and polished, it creates more colors and sparkle
than regular glass.

On a hot plate, heat about 100 ml of deionized water in a glass beaker until the water boils, add 1
ml of 10 mM HCl (pH 4). Transfer the hot water to a crystal glass, wait for about 20 min. Use
this solution as analyte for the determination of Pb2+.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG
and 50

of 1 mM oxine solution. Record the stripping voltammogram of the background.

Add to the cell 0.1 0.2 ml of the analyte solution and record a voltammogram. Make at least
two standard additions, using the 1
solution of Pb2+ and run the voltammograms again.
Consult with the instructor about the volume of the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metals in the cell. Report the concentration of
the metal in the sample in mol/l and ppm.

4.6. Determination of traces of Pb2+ released in water as a result of contact with brass parts
used in water-delivery lines
Brass is an alloy of copper, containing mainly copper and zinc. It is used in connecting parts of
water-delivery lines. Small amounts of lead are sometimes added to improve the mechanical
characteristics of the alloy.
Lead rarely occurs naturally in water. Most lead contamination takes place at some point in the
water delivery system. This occurs as a result of corrosion, the reaction between the water and
lead in parts of the water-delivery system. Components of water-delivery systems which may
contain lead include service connections, pipes, solder and brass fixtures. Lead in drinking water
from plumbing is most often a problem in either very old or very new houses. Many household
faucets, plumbing fittings, check valves and well pumps are manufactured with brass parts.
While brass contains some lead to make casting easier and the machining process more efficient,
the lead content of brass plumbing components is now restricted to a maximum of 8 %. Even at
this low level, however, lead can be leached from new brass faucets and fittings. Eventually, if
the water is not corrosive, hard-water minerals deposit on the interior of the plumbing. These
deposits form a calcium carbonate lining inside pipes and fittings, which protects against lead
contamination. It may take up to five years for an effective calcium carbonate lining to form.
Softening naturally hard water with an ion-exchange water softening unit can either prevent or
dissolve the calcium carbonate scale, eliminating its possible protective effect.

To read more about the properties of copper Go to

http://ianrpubs.unl.edu/water/g1360.htm

Place in a beaker a brass connector from a water-delivery line and fill with deionized water at
room temperature. Leave over night. Use this solution as analyte for the determination of traces
of Pb2+.
Add to the cell 5 ml of deionized water, 1 ml of 0.5 M ammonia buffer, 0.1 ml of 0.01 M DMG
and 50

of 1 mM oxine solution. Record the stripping voltammogram of the background.

Add to the cell 0.1 0.2 ml of the analyte solution and record a voltammogram. Make at least
two standard additions, using the 1
solution of Pb2+ and run the voltammograms again.
Consult with the instructor about the volume of the standard additions.
Estimate the values of the analytical signal from the voltammograms. Plot the analytical signal
corrected for background vs. concentration of the metals in the cell. Report the concentration of
the metal in the sample in mol/l and ppm.

References
1. Carlo Colombo, Constant M. G. van den Berg, Anal. Chim. Acta, 1997, 337, 29-40.
2. Miropi G. Paneli and Anastasios Voulgaropoulos, Electroanalysis, 1993, 5, 355-373.
3. S. B. Adeloju, A. M. Bond and M. H. Briggs, Anal. Chim. Acta, 1984, 164, 181.