Monograph Practical Voltammetry PDF

Monograph
Practical Voltammetry
with the 757 VA Computrace
with the 757 VA Computrace
Dr. U. Schröder and Dr. H. Kahlert
Ernst Moritz Arndt University, Greifswald

Institute for Chemistry and Biochemistry
Soldmannstr. 23, 17489 Greifswald
Advised by Prof. Dr. F. Scholz (Ernst Moritz Arndt University, Greifswald,

Institute for Chemistry and Biochemistry) and U. Loyall (Metrohm Ltd., Herisau, Switzerland)
All rights reserved to the publisher, including translation.

Printed in Switzerland by Metrohm Ltd. , CH-9101 Herisau
8.757.5003 – 2002-09
Contents
Experiment 1
Voltammetry at the dropping mercury electrode and at hanging mercury drops.....................7
Results of Experiment 1......................................................................................................16
Experiment 2
Time response and the separation of capacitive and faradaic current...................................20
Experiment 3
Evaluation of a polarogram at different depolarizer concentrations.......................................26
Experiment 4
Polarographic determination of ascorbic acid......................................................................36
Experiment 5
Tensammetric determination of n-pentanol.........................................................................44
Experiment 6
Electrochemical stripping analysis – anodic stripping voltammetry.....................................50
Experiment 7
Determination of nickel by adsorptive stripping voltammetry...............................................65
Experiment 8
Determination of selenium by cathodic stripping voltammetry.............................................70
Experiment 9
Determination of molybdenum in iron by utilizing a catalytic reaction...................................75
Experiment 10
Determination of bismuth in the presence of copper and lead..............................................81
Results of Experiment 10....................................................................................................85
Experiment 11
Determination of thallium in the presence of cadmium and lead..........................................88
Experiment 12
Complexing capacity of a water sample..............................................................................91
Experiment 13
Cyclic voltammetry............................................................................................................96
Results of Experiment 13..................................................................................................102
Practical help . ..............................................................................................................106
Introduction
Polarographic and voltammetric analysis methods have been an important aid for many years,
particularly for trace analysis in the chemical analysis sector. This importance is based on their
high accuracy and sensitivity, the possibility of carrying out multi-element analyses and the
favorable price-performance ratio.
The mercury electrode is to be regarded as being one of the most efficient electrodes used in
electroanalysis. For its use in solving electroanalytical problems the 757 VA Computrace offers
a wide range of different techniques. These range from the classical direct current polarography
– voltammetry at the dropping mercury electrode – up to the most modern stripping analysis
method at a hanging mercury drop.
The following experiments are intended to provide an introduction to the basic principles of
polarography and voltammetry at the mercury electrode and provide examples showing the
use of these methods in analytical chemistry.
Experiment 1
Voltammetry at the dropping mercury electrode and at hanging mercury
drops
Nature of the task

The following experiment works through the basic principles of polarography. In it you will
become familiar with the various operating modes of the Multi-Mode-Electrode and a range of
measuring techniques (Direct Current DC, Differential Pulse DP).
Experiments
1.1. Influence of oxygen on polarographic measurements
1.2. The basic polarographic curve
1.3. Discharging a depolarizer / SMDE – HMDE
1.4. The polarographic spectrum
Reagents
• Potassium nitrate solution: c(KNO3) = 0.1 mol/L
• Copper standard solution: β(Cu2+) = 1 g/L
• Lead standard solution: β(Pb2+) = 1 g/L
• Cadmium standard solution: β(Cd2+) = 1 g/L
• Zinc standard solution: β(Zn2+) = 1 g/L
• Acetate buffer pH 4.6: c(acetic acid) = 0.1 mol/L
+ c(sodium acetate) = 0.1 mol/L
Procedure
All the experiments in this experiment are carried out in the Exploratory mode of the 757 VA
Computrace.
Experiment 1.1.
Influence of oxygen on polarographic measurements

Part-experiment
Use the following measuring parameters (Fig. 1.1.) in the Exploratory specification window to
record the polarographic curve of a potassium nitrate solution [c(KNO3) = 0.1 mol/L] saturated
with air.
Measuring solution
10 mL potassium nitrate solution [c(KNO3) = 0.1 mol/L]
Exercises
Sketch the curve of the applied potential in the DC mode as a function of time!
Why is a supporting electrolyte used?
What can you see?
Which reactions are
taking place?
What are the conse-
quences for a voltam
metric or polarographic
measurement?
Can the observed effect
be used analytically?
Fig. 1.1. Instrument settings for measuring in the DC mode
Part-experiment
Repeat the measurement in the DP mode (Fig. 1.2.):
Measuring solution
Exercises
Sketch the curve of the applied potential in the DP mode as a function of time!
Discuss the course of the limiting diffusion current in the direct current polarogram and in the
differential pulse polarogram!
Fig. 1.2. Instrument settings for measuring in the DP mode
Experiment 1.2.
The basic polarographic curve

Repeat all the measurements made in Experiment 1.1., but in this case after purging the elec-
trolyte solution with nitrogen (purge time 600 s). If you carry out the measurements in quick
succession then the purging time can be reduced for the experiment in the DP mode. However,
we recommend a minimum purging time of 60 s as the oxygen quickly reenters the electrolyte
solution.
Measuring solution
Exercises
Which reactions limit the useful potential window?
10 Practical Voltammetry
Practical Voltammetry 11
Experiment 1.3.
Discharging a depolarizer / SMDE – HMDE

Use the following measuring parameters (Fig. 1.5.) to record the polarogram of a potassium
nitrate solution to which 100 µL lead standard solution has been added. Compare the polarogram
obtained in this way with the voltammogram obtained with the same solution at the hanging
mercury drop (measuring parameters see Fig. 1.6.).
Measuring solution
+ 0.1 mL lead standard solution [β(Pb2+) = 1 g/L]
Exercise
Explain the different curve shapes for the limiting diffusion currents of the two voltammograms!
Fig. 1.5. Instrument settings for measuring at the SMDE
Fig. 1.6. Instrument settings for measuring at the HMDE
Experiment 1.4.
The polarographic spectrum

Depending on the position of the redox potentials, it is possible to use polarography for the
simultaneous determination of various elements or compounds. An example is the determination
of the environmentally important metals copper, lead, cadmium and zinc.
Use the parameters shown in Fig. 1.7. to record the following series of polarograms. In each
case the additional volume of standard solution (next element) is added to the solution used in
the previous experiment.
Measuring solution
1. 10 mL supporting electrolyte (acetate buffer)
2. as 1. + 100 µL Zn2+ standard
3. as 2. + 100 µL Cd2+ standard
4. as 3. + 100 µL Pb2+ standard
5. as 4. + 100 µL Cu2+ standard
6. Repeat measurement 5 in the DP mode using the parameters in Fig. 1.8.
Exercise
Discuss the differences and advantages/disadvantages of measurements in the DC and DP
modes!
References
[1] J. Heyrowsky, P. Zuman, Einführung in die praktische Polarographie, VEB Verlag
Technik, Berlin, 1959.
[2] L. Meites, Polarographic Techniques, Interscience Publishers, New York, 1965.
[3] M. Geißler, Polarographische Analyse, Verlag Chemie, Weinheim, 1981.
[4] R. Bock, Methoden der Analytischen Chemie, Bd. 2, Verlag Chemie, Weinheim, 1984.
[5] G. Henze, R. Neeb, Elektrochemische Analytik, Springer-Verlag, Berlin 1986.
[6] R. Kalvoda, Electroanalytical Methods in Chemical and Environmental Analysis, Plenum
Press, New York, 1987.
[7] D. A. Skoog, J. J. Leary, Instrumentelle Analytik, Springer-Verlag, Berlin, 1996.
Results of Experiment 1
Experiment 1.1.
Influence of oxygen on polarographic measurements

Oxygen (in acidic to neutral solution) is reduced in two stages at mercury drops:
O2 + 2 e- + 2 H+  H2O2
H2O2 + 2 e- + 2 H+  2 H2O
Fig. 1.9. Direct current polarogram and differential pulse polarogram of an electrolyte solution containing oxygen
[c(KNO3) = 0.1 mol/L]
These reactions are usually unwanted side reactions in polarography. The polarographic waves
produced overlay the reduction currents of the analytes to be determined and therefore interfere
greatly with the analysis.
⇒ Help by purging with pure nitrogen before the measurement
Utilization of the reduction of oxygen: polarographic determination of the oxygen concentration
of solutions and gases.
Experiment 1.2.
The basic polarographic curve

Limit of the potential window in the anodic range: Hg  Hg2+ + 2e-
Limit of the potential window in the cathodic range: 2 H+ + 2 e-  H2 or reduction of the
cations of the supporting electrolyte (possible for example by displacing the formal potentials
of the alkali cations in a positive direction by amalgam formation)
Fig. 1.10. Basic polarographic curves (DC and DP) after purging the electrolyte solution with nitrogen
If the electrolyte solution is not purged sufficiently with nitrogen then the peaks formed by the
reduction of oxygen can still appear. In addition, if a chloride solution is used in the salt bridge
of the reference electrode then, if the reference electrode is kept in the analysis solution for a
long time, a peak may occur at a potential of about 0.2 V. This peak can be traced to chloride
ions entering the analysis solution and forming mercury chloride at the mercury electrode at
the corresponding positive potential:
2 Hg + 2 Cl-  Hg2Cl2 + 2e-
Experiment 1.3.
Discharging a depolarizer / SMDE - HMDE
Fig. 1.11. The reduction of lead [c(Pb2+) = 4.8·10–5 mol/L] in potassium nitrate solution [c(KNO3) = 0.1 mol/L] at
various electrodes
The static mercury drop electrode (SMDE) – combines the properties of the dropping mercury
electrode (DME) and the hanging mercury drop electrode (HMDE). As with the DME, the
mercury surface is renewed continuously. However, the drop surface is constant during the
measurement.
HMDE: Hanging Mercury Drop Electrode – a mercury drop of known size is suspended from
the tip of the glass capillary and the whole potential sweep takes place at this single drop.
A disadvantage of the SMDE in comparison to the HMDE is its higher mercury consumption. In
addition, in this mode the Multi-Mode-Electrode is subjected to greater mechanical stress. The
HMDE is used particularly for measurements in the trace range, where a previous enrichment
of the corresponding depolarizer is necessary.
Experiment 1.4.
The polarographic spectrum
Fig. 1.12. Direct current polarogram and differential pulse polarogram of a solution with the following composition:
Pb2+: 10 mg/L (4.8·10-5 mol/L); Cu2+: 10 mg/L (1.57·10-4 mol/L); Cd2+: 10 mg/L (8.9·10-5 mol/L); Zn2+: 10 mg/L
(1.53·10-4 mol/L) in acetate buffer pH = 4.6
Experiment 2
Time response and the separation of capacitive and faradaic current
During a voltammetric or polarographic measurement the current signal is formed from the
sum of the faradaic and capacitive (non-faradaic) currents. The faradaic current iF is formed by
the discharge of redox-active species (depolarizers) at the electrode surface. This process is
combined with an electron migration between the depolarizer and the electrode. In contrast to
this, the capacitive current (charging current) ic is not based upon electron transfer. It is a result
of the loading of the electrochemical double layer at the electrolyte/electrode phase boundary
caused by a change in potential and/or a change in the electrode surface.
Voltammetric and polarographic determinations of inorganic and organic compounds are
based on the evaluation of the faradaic current as the analytical quantity; this is dependent on
the concentration of the depolarizer. The ratio of the faradaic current to the capacitive current
iF/ic determines the sensitivity of the measuring methods. A knowledge of the rate equations
on which this is based and their utilization can be used to obtain a considerable increase in
the sensitivity.
Nature of the task

The aim of the following experiment is to separate the capacitive and faradaic currents from
each other and investigate their time responses.
Experiments
2.1. Measuring the capacitive current
2.2. Measuring the faradaic current
Reagents
• Lead standard solution: c(Pb2+) = 1·10-3 mol/L
Procedure
In order to investigate the time response of the voltammetric currents, the duration of the potential
step (voltage step time) is varied at constant potential steps.
All the measurements in this experiment are carried out in the Exploratory Mode. Because
some of the potential steps are very short, work is carried out at the hanging mercury drop
(HMDE) instead of at a dropping mercury electrode (DME) or stationary mercury drop electrode
(SMDE).
Experiment 2.1.
Measuring the capacitive current

The measurement of the capacitive current is made in the supporting electrolyte (without depo-
larizer) under conditions in which no charge transfer reactions occur. Please observe the following
points when carrying out the experiments and evaluating the voltammograms:
• If the potential is too negative then overlaying with faradaic currents from side reactions (e.g.
the reduction of residual oxygen, proton discharge) will occur.
• At the electro-capillary zero point (approx. -0.5 V vs. Ag/AgCl//KCl 3 mol/L) the capacity of
the double layer is at its lowest point.
• Capacitive and faradaic current must be determined at the same potential point. This means
that the potential must be selected so that, after the depolarizer has been added, the expected
limiting diffusion current can be measured at this point.
Measuring solution
Fig. 2.1. Instrument settings
Vary the voltage step time in the range 0.002 s - 0.01 s at steps of 0.002 s, 0.003 s, 0.004 s,
0.006 s, 0.008 s, 0.01 s.
Purging the electrolyte: before starting the first potential sweep purge the electrolyte solution
for 300 s with nitrogen. If each of the following measurements is to be made within one minute
then this purge time can be reduced to 60 s. If the intervals between the measurements are
longer then the purge time must be extended accordingly as the oxygen concentration in the
electrolyte increases again relatively quickly.
Evaluation: the voltammograms are evaluated by measuring the current at a measuring potential
of E = -0.38 V. (Use the Signal cursor function in the menu item Signal of the Exploratory
mode.)
Exercises
Draw a diagram showing the construction of the electrochemical double layer!
How does the capacitive current depend on the voltage step time?
Experiment 2.2.
Measuring the faradaic current

In this case Pb2+ is selected as the depolarizer; it discharges itself at the mercury electrode
according to:
Pb2+ + 2 e-  Pbamalg
Measuring solution
0.2 mL lead standard solution [c(Pb2+) = 1·10-3 mol/L]
(corresponds to a depolarizer concentration 2·10-5 mol/L)
The polarograms are recorded as described under the measurement of the capacitive currents.
The limiting diffusion currents obtained are made up of the capacitive and the faradaic current
fractions. This means that to obtain the faradaic current alone the current value of the blank
polarogram (measurement from Experiment 2.1.) must be subtracted from the current value of
the Sample curve (measurement from Experiment 2.2.).
Exercises
How does the faradaic current depend on the voltage step time?
What consequences can be derived from the results for carrying out voltammetric or polaro-
graphic experiments at the mercury electrode?
References
[4] R. Kalvoda, Electroanalytical Methods in Chemical and Environmental Analysis, Plenum
Press, New York, 1987.
Evaluation of the current curves
Fig. 2.3. Capacitive current and faradaic current at various potential step times. Notice the different current scales.
(left: faradaic current If, measurements from Experiment 2.2.
right : capacitive current Ic, measurements from Experiment 2.1.)
supporting electrolyte
(capacitive current): i ~ e-At (with A = 6.7.10-4)
supporting electrolyte + depolarizer
(faradaic current) i ~ t-0.501 i.e. i ~ t-1/2
(to calculate the faradaic current the current value of the supporting electrolyte is subtracted
from the current value of the polarogram with added depolarizer)
Experiment 3
Evaluation of a polarogram at different depolarizer concentrations
The value of an analytical measuring method cannot be measured by using the detection limit of
a particular analyte alone. For as versatile a use as possible the method is equally characterized
by its ability to determine quantitatively several analytes present at the same time in different
concentrations (occasionally in the presence of a large excess of one or more components).
These requirements can be demonstrated by using the analysis of alloys as an example. Alloys
usually consist of a major component with sometimes very small amounts of additional elements.
As the content of these additional elements is very important for the properties of the alloy,
analytical methods are required which can determine the content of the individual components,
e.g. during a production process.
Nature of the task

The performance of direct current polarography (DC) and differential pulse polarography (DPP)
with respect to the quantitative determination of the metals at different concentrations of the metal
ions present is to be investigated by using the polarographic determination of the concentration
of the elements copper, lead and zinc in a sample solution. The influence of parameters such as
pulse amplitude and pulse time on the differential pulse polarogram is to be clarified.
Exercises
Inform yourself about the basic principles of differential pulse polarography!
Explain the signal shape of the polarographic measuring curve!
What dependency of the peak height on the pulse amplitude and the pulse time is to be ex-
pected?
How can the 3σ detection limit of an analytical method be determined?
Experiments
3.1. Determination of the 3σ detection limit of Pb2+ and Zn2+ by DC polarography and DP
polarography
3.2. Determination of the 3σ detection limit of Pb2+ and Zn2+ in electrolytes by DC polarog-
raphy and DP polarography in the presence of an excess of Cu2+
3.3. Dependency of the peak height on the pulse amplitude and the pulse time
Reagents
• Copper standard solution: c(Cu2+) = 1·10-3 mol/L
corresponds to: β(Cu2+) = 63.6 mg/L
• Lead standard solution: c(Pb2+) = 1·10-4 mol/L
β(Pb2+) = 20.7 mg/L
• Zinc standard solution: c(Zn2+) = 1·10-4 mol/L
β(Zn2+) = 6.5 mg/L
When preparing the standard solutions (e.g. in 50 mL or 100 mL volumetric flasks) approx.
1 mL/L concentrated nitric acid [w(HNO3) = 65%] should be added to the standard solution
to stabilize it.
Procedure
All the experiments in this experiment are carried out in the Exploratory mode of the 757 VA
Computrace. The following measuring parameters are to be used for the basic settings for direct
current polarography
(Fig. 3.1.) and differen-
tial pulse polarography
(Fig.3.2.).
Experiment 3.1.
Determining the 3σ detection limits of Pb2+ and Zn2+ by DC polarography
and DP polarography
Record the polarograms in a concentration range from 1·10-7 to 1·10-5 mol/L Pb2+ and Zn2+ at
a concentration ratio of 2:1 (Pb2+:Zn2+).
Proceed as follows: start with the lowest metal ion concentration and add higher concentrations
to the electrolyte step by step; record the polarogram after each addition.
Measuring solution
+ 20 µL lead standard solution [c(Pb2+) = 1·10-4 mol/L]
+ 10 µL zinc standard solution [c(Zn2+) = 1·10-4 mol/L]
Add the lead and zinc standard solution step by step until the total volume of the standard solu-
tion is 1 mL in each case.
The evaluation of the limiting diffusion current is carried out using the commands Wave evalu-
ation (for evaluation of the direct current polarograms) and Peak search (for evaluation of the
differential pulse polarograms) under the menu Signal in the Exploratory curves window. The
3σ detection limit is the smallest concentration that can be detected with a certain degree of
probability by a given procedure or, in other words, the smallest concentration that is larger
than the blank value for the measurement with a degree of certainty of 99.865%. The measured
value for the detection limit yD is obtained from the blank or background value yB and its standard
deviation sB:
yD = yB + 3sB
In order to determine the detection limit record ten polarograms of the supporting electrolyte
solution in succession. Calculate the mean value of the background signal and its standard
deviation; use this to determine the measured value for the detection limit. To obtain the small-
est concentration or mass you should determine slope q of the calibration curve and calculate
accordingly:
yD – yB 3sB
xD = =
q q

Exercises
Plot the current values obtained from the evaluation of the peaks or polarographic waves as a
function of the concentration of the zinc and lead ions!
Determine the minimum concentration at which the elements lead and zinc can be determined
with an acceptable statistical reliability!
Experiment 3.2.
Determining the 3σ detection limits of Pb2+ and Zn2+ in electrolytes by

DC polarography and DP polarography in the presence of an excess of
Cu2+
Repeat Experiment 3.1. twice, but with an additional constant concentration of 1·10-6 mol/L and
4·10-5 mol/L Cu2+ respectively. The measuring parameters are shown in Fig. 3.1. and 3.2.. The
evaluation is similar to Experiment 3.1.
Measuring solution 1
+ 10 µL copper standard solution [c(Cu2+) = 1·10-3 mol/L]
Add the lead and zinc standard solution step by step until the total volume of the standard solu-
tion is 1 mL in each case.
+ 400 µL copper standard solution [c(Cu2+) = 1·10-3 mol/L]
Add the lead and zinc standard solution step by step until the total volume of the standard
solution is 1 mL in each case.
Exercises
Compare the results of the DC and DPP measurements in the absence and presence of the
excess of copper ions!
What consequences can be drawn from the comparison of DC and DPP?
Experiment 3.3.
Dependency of the peak height on the pulse amplitude and the pulse
time
In a differential pulse polarogram the peak height of a depolarizer at a given concentration depends
primarily on the pulse amplitude and the pulse time. This dependency is to be clarified using the
lead peak as an example. Record polarograms for a lead concentration of 1·10–5 mol/L in the
supporting electrolyte at pulse amplitudes in the range from –0.1 to 0.1 V. The other measuring
parameters are shown in Fig. 3.2. Repeat the experiment with a pulse amplitude of 0.05 V and
pulse times in the range from 0.01 to 0.1 s.
Measuring solution
+ 1 mL lead standard solution [c(Pb2+) = 1·10-4 mol/L]
Exercises
Discuss the observed dependencies with respect to any optimization of the measuring param-
eters that these may suggest!
References
[4] J. Mocak, A. M. Bond, S. Mitchell, G. Scollary, Pure & Appl. Chem, 69, 1997, 297-328.
[5] D. A. Skoog, J. J. Leary, Instrumentelle Analytik, Springer-Verlag, Berlin, 1996.
Experiments 3.1. and 3.2.
Determining the 3σ detection limits of Pb2+ and Zn2+ by DC polarography

and DP polarography
The peak currents for lead reduction, obtained from the differential pulse polarograms, show no
marked dependency on the copper concentration in the electrolyte. In both cases (without Cu2+
as well as 4·10-5 mol/L Cu2+) a detection limit of 3·10-8 mol/L was obtained:
Fig. 3.3. Polarograms of electrolyte solutions with the following composition:

a) 1·10-6 mol/L Pb2+, 5·10-7 mol/L Zn2+, without added copper in c(KNO3) = 0.1 mol/L
b) 1·10-6 mol/L Pb2+, 5·10-7 mol/L Zn2+, 1·10-6 mol/L Cu2+ in c(KNO3) = 0.1 mol/L
If copper is present at a similar concentration to lead and zinc then lead and zinc can be deter-
mined in the presence of copper by direct current polarography.
Fig. 3.4. Direct current polarogram and differential pulse polarogram of a solution with the following composition:
1·10-6 mol/L Pb2+, 5·10-7 mol/L Zn2+, excess of Cu2+ (c(Cu2+) = 4·10-5 mol/L) in c(KNO3) = 0.1 mol/L
This shows the limitations of direct current polarography. Under these conditions DP polarography
is far superior to DC polarography.
Fig. 3.5. Dependency of the peak height on the lead concentration in the DP mode
In contrast, with DC polarography the determination of Pb2+ is only possible up to 5·10-7 mol/L
(no excess Cu) or 1·10-6 mol/L (in the presence of 4·10-5 mol/L Cu2+):
Fig. 3.6. Dependency of the peak height on the lead concentration in the DC and DP mode
Experiment 3.3.
Dependency of the peak height on the pulse amplitude and the pulse
time
Fig. 3.7. Dependency of the lead reduction peak height in the DP experiment on the pulse amplitude
Fig. 3.8. Dependency of the lead reduction peak height on the pulse time in the DP experiment
Experiment 4
Polarographic determination of ascorbic acid
Polarography is not only suitable for the quantitative determination of inorganic substances,
but also for a large number of organic compounds. Whether or not an organic substance can
be determined in an aqueous medium by polarography depends primarily on the functional
groups that characterize the redox properties. To a large extent they determine whether a redox
reaction in possible in the given potential window of the mercury drop electrode and whether
the quantitative determination is based on the reduction or oxidation of the compound.
Exercise
Which functional groups of organic compounds can be oxidized and which can be reduced?
Nature of the task

The aim of this experiment is to determine the concentration of vitamin C in selected fruit juices
by using polarography.
Experiments
4.1. Basic principles of the determination (Exploratory mode)
• the anodic wave
• experimental conditions
• drawing up the measuring procedure
4.2. Polarographic determination of vitamin C in fruit juices (Determination mode)
• choice of calibration method
• analysis of fruit juices
Reagents
• Ascorbic acid standard solution: β(ascorbic acid) = 1 g/L
(freshly prepared every day)
+ c(sodium acetate) = 0.1 mol/L
Experiment 4.1.
Basic principles of the determination

Procedure
Part-experiment
Experiment 4.1. is carried out in the Exploratory mode. Use the following measuring parameters
(Fig. 4.1.) to record the polarographic basic curve of an acetate buffer solution.
Measuring solution
20 mL acetate buffer pH 4.6
Add 200 µL ascorbic acid standard to the electrolyte and repeat the experiment.
Exercises
What is the structural formula of ascorbic acid and which are the decisive functional groups?
Which reaction is the formation of the anodic wave based upon?
Why is it necessary to buffer the pH?
Part-experiment
Differential pulse polarography (DPP) is used for the quantitative determination of ascorbic
acid. Repeat the last experiment in the DP mode with the following parameters (Fig. 4.2.). This
procedure will form the basis for working in the Determination mode. Determine the potential of
the peak maximum (manually or automatically). This value will be required in the Determination
mode for automatic peak analysis.
Measuring solution
+ 200 µL ascorbic acid standard solution
Experiment 4.2.
Polarographic determination of vitamin C in fruit juices

Procedure
This experiment is carried out in the Determination mode. The 757 VA Computrace offers
comfortable algorithms for the quantitative analysis, starting with the calibration (calibration
curve, standard addition method) up to preparing the result.
The parameters for the measuring procedure can be transferred from the Exploratory mode to
the Determination mode.
Fig. 4.3. Data transfer
In the Determination mode values such as the cell volume, sample volume, automatic purging
time after the individual standard additions, etc. are entered under Edit parameters. It should
also be possible to find the voltammetric parameters from the Exploratory mode here if the
transfer has been carried out properly. The parameters for automatic peak analysis are stored
under Substances. When setting the evaluation parameters care must be taken that conversion
to the correct output format (concentration unit) is carried out correctly (Fig. 4.4.). The peak
evaluation is carried out according to the height of the peak current
Fig. 4.4. Calculation formula
Measuring solution
+ 200 µL sample
After the measuring curve of the sample has been recorded two portions of 100 µL standard
solution are added. However, these are only approximate values which may need to be corrected
if the conditions vary greatly (very low or very high concentrations). The amount of standard
solution to be added should be sufficient for the expected ascorbic acid concentration. Additions
which are too small or too large increase the error of the determination.
Exercises
Inform yourself about the advantages and disadvantages of using calibration curves!
Why is the standard addition method used in this case?
References
[1] J. Heyrowsky, P. Zuman, Einführung in die praktische Polarographie, VEB Verlag
Technik, Berlin, 1959.
[2] M. Brezina, B. Zuman, Die Polarographie in der Medizin, Biochemie und Pharmazie,
^
Akademische
Verlagsgesellschaft Geest & Portig KG, Leipzig, 1956.
[3] K. Schwabe, Polarographie und chemische Konstitution organischer Verbindungen,
Akademie-Verlag,
Berlin, 1957.
[5] Metrohm Application Bulletin 98.
Experiment 4.1.

The determination is based on the oxidation of ascorbic acid to dehydroascorbic acid:
O C O C
HO C O C
– 2H+ –2e–
HO C O O C O
H C H C
HO C H HO C H
CH2OH CH2OH
(C6H8O6 → C6H6O6 + 2 e– + 2 H+)
In this reaction the redox potential depends on the pH:
E½ ~ 0.059 log c2 H O
2
+
3

With inadequate buffering the pH at the electrode surface can be displaced by the oxidation
reaction of the ascorbic acid. This leads to peak broadening. This risk can be countered by the
addition of the acetate buffer.
Fig. 4.5. Anodic wave in DC polarography and DP polarographic signal from 1·10-4 mol/L ascorbic acid in acetate
buffer
Experiment 4.2.
Polarographic determination of vitamin C in fruit juices:

Result of the analysis of a sample of a commercially available orange juice
Given concentration of vitamin C: 38 mg/100mL
Concentration found: 43 mg/100mL
Note! The vitamin C concentration given on the packaging of juices represents the minimum
value that the manufacturer can guarantee (varies with type of fruit, origin, harvesting time,
etc.). This is why it is not surprising that a higher value is usually found.
Fig. 4.6. Determination of ascorbic acid in the Determination mode
Experiment 5
Tensammetric determination of n-pentanol
Surface-active substances are adsorptively enriched at the electrode/electrolyte phase boundary.
This adsorption is potential-dependent. The measurement of the alteration in the electrochemical
double layer capacity associated with it can be used for the determination of surface-active
substances. In this case alternating current polarography is mainly used. The alternating current
polarogram is obtained by plotting the alternating current amplitude against the DC voltage at the
electrode. As faradaic and capacitive alternating current components have different phase shifts
this means that by phase-selective rectification their relationship and therefore the analytical
sensitivity can be considerably improved.
Nature of the task

The concentration of an aqueous solution of n-pentanol (n-amyl alcohol) is to be determined
by using alternating current polarography.
Experiments
5.1. Phase-selective current recording – possibility of eliminating the capacitive current
fraction
5.2. Phase-selective current recording – possibility of isolating the capacitive current fraction
Reagents
• Potassium nitrate supporting electrolyte 1: c(KNO3) = 0.1 mol/L
• Potassium nitrate supporting electrolyte 2: c(KNO3) = 1 mol/L
• Lead/Zinc standard solution c(Pb2+) = 1·10-3 mol/L
+ c(Zn2+) = 1·10-3 mol/L
• n-pentanol standard solution: c(n-pentanol) = 0.1 mol/L
in methanol:water 10:90
(for a better solubility of n-pentanol in water
the addition of approx. 10 % methanol is
necessary)
Procedure
All the part-experiments in this experiment are carried out in the Exploratory mode of the 757
VA Computrace.
Experiment 5.1.
Phase-selective current recording – possibility of eliminating the capaci-

tive current fraction
This part-experiment is intended to demonstrate the basic principles of alternating current
polarography and phase-selective current measurement.
Exercise
Compare the signal formation in differential pulse polarography with that of alternating current
polarography!
Procedure
Measuring solution
10 mL potassium nitrate supporting electrolyte 1 [c(KNO3) = 0.1 mol/L]
+ 100 µL lead/zinc standard solution
Record the alternating current polarogram of the above measuring solution by using the following
measuring parameters (Fig. 5.1.).
The first measurement
should not be phase-
sensitive. After this alter
the phase-sensitivity
between 0 and 360° at
45° intervals.
Exercises
Compare the results of
the measurements! In-
form yourself about the
conformity of capacitive
and faradaic currents
in alternating current
circuits!
What is the conse-
quence for the alternat-
ing current polarogra-
phy method, which is
based on the utilization
of faradayic currents?
Experiment 5.2.
Phase-selective current recording – possibility of isolating the capaci-

Part-experiment
Repeat Experiment 5.1., but this time with a solution of the following composition:
c(KNO3) = 0.1 mol/L + c(n-pentanol) = 2·10-2 mol/L.
Measuring solution
7 mL water
+ 1 mL potassium nitrate supporting electrolyte 2 [c(KNO3) = 1 mol/L]
+ 2 mL n-pentanol standard solution [c(n-pentanol) = 0.1 mol/L]
In this case the first measurement should also not be phase-sensitive. After this again alter the
phase-sensitivity between 0 and 360° at 45° intervals.
Part-experiment
Record the tensammetric curves (measuring at 90° phase-sensitive) of a concentration series
of n-pentanol in c(KNO3) = 0.1 mol/L.
Measuring solutions
c(n-Pentanol) = 0.001 mol/L, 0.01 mol/L, 0.015 mol/L, 0.02 mol/L, 0.05 mol/L, 0.09 mol/L
Exercises
Interpret the different sections of the tensammetric curve! What are the origins of the two peaks?
How can you explain the adsorption peak shift?
Plot the peak height of the more sensitive adsorption peak against the concentration of the amyl
alcohol! Interpret the shape of the curve obtained!
Determine the potential of the adsorption peak maximums (manually or automatically).
References
[1] L. Meites, Polarographic Techniques, Interscience Publishers, New York, 1965.
[2] B. Breyer, H. H. Bauer, Alternating Current Polarography and Tensammetry, Interscience
Publishers, New York, 1963.
[3] H. Jehring, Elektrosorptionsananlyse mit der Wechselstrompolarographie, Akademie-
Verlag, Berlin, 1974.
Experiment 5.1.
Phase-selective current recording – possibility of eliminating the capaci-

Fig. 5.2. Alternating current polarograms of an electrolyte solution with the following composition: c(Zn2+) = 1·10‑5
mol/L, c(Pb2+) = 1·10‑5 mol/L in c(KNO3) = 0.1 mol/L
An alternating current polarogram is obtained by plotting the alternating current amplitude

against the DC voltage at the electrode. The periodic charging and discharging of the double
layer capacity produces a charging current which, in contrast to the alternating potential at the
electrode, has a phase shift of 90°. As the faradaic alternating current components only have
a phase shift of 45° or less this means that in alternating current polarography the relationship
between faradaic and non-faradaic current and therefore the sensitivity can be considerably
improved by phase-selective rectification.
Experiment 5.2.
Phase-selective current recording – possibility of isolating the capaci-

If surface-active substances are adsorbed at the surface of the mercury then there is a par-
ticularly large change in the double layer. This causes a sudden jump in the capacitive current.
Usually two tensammetric peaks are formed at the potentials at which the surfactants displace
the inorganic ions of the supporting electrolyte in the electrochemical double layer. For neutral
surfactants these peaks lie symmetrically about the electrocapillary zero point. The height of
the peaks and the positions of the peak potentials depend on the concentration of the surface-
active substance and can be used for its determination.
Fig. 5.3. Alternating current polarograms in solutions with the following compositions:
a) c(KNO3) = 0.1 mol/L
b) c(KNO3) = 0.1 mol/L + c(n-pentanol) = 0.01 mol/L
c) c(KNO3) = 0.1 mol/L + c(n-pentanol) = 0.02 mol/L
d) c(KNO3) = 0.1 mol/L + c(n-pentanol) = 0.03 mol/L
In this case the dependency of the adsorption peak follows a typical adsorption isotherm:
Fig. 5.4. Dependency of the adsorption peak on the concentration of n-pentanol
Experiment 6
Electrochemical stripping analysis – anodic stripping voltammetry
Electrochemical stripping analysis is one of the most powerful analytical methods and is certainly
the most sensitive electrochemical analytical method for the determination of heavy metals. This
high detection capability is achieved by the use of an enrichment step before the electrochemi-
cal determination itself. The enrichment of heavy metal ions at a stationary mercury electrode
(drop or film) can be carried out according to various principles:
a) By reduction of the metal ions and formation of an amalgam – reoxidation occurs in the
determination step (anodic stripping voltammetry).
b) By adsorption of bound metal ions in the form of complexes on the mercury surface (adsorp-
tive stripping voltammetry). Either oxidation or reduction can take place in the determination
step.
c) By precipitation of a sparingly soluble compound as the result of an oxidation reaction at
the electrode. The measurement is carried out after a cathodic potential sweep (cathodic
stripping voltammetry).
The aim of Experiments 6, 7 and 8 is the electroanalytical determination of traces of heavy
metals by using anodic, adsorptive and cathodic stripping analysis.
In the quantitative determination of trace elements in natural samples the sample matrix plays
an outstanding role: on the one hand the heavy metal to be determined must normally be
present in the form of ions in an aqueous solution. On the other hand, organic compounds
such as humic acids in surface water can complex (mask) metal ions so that they cannot be
determined quantitatively. The hydrophobia of the mercury also leads to the strong adsorption
of organic compounds at the mercury surface (see Experiment 5). This is why, depending on
the sample matrix (type and concentration of organic compounds), a sample preparation step
may be necessary.
Three important digestion methods are described below. Depending on the selected natural
samples such a digestion may need to be carried out for the analyses in Experiments 6 and 7.
The experiments have been chosen as being environmentally relevant examples.
Sample preparation
1. Acid digestion (wet digestion)
In an acidic digestion the organic matrix is destroyed by the addition of mineral acids (H2SO4,
HNO3, HClO4) and high-temperature oxidation. With the exception of mercury, which is very
volatile, this method is suitable for preparing for the determination of all heavy metals.
To keep the blank values as low as possible all the reagents used should be in a highly pure
form (e.g. suprapur grade from Merck).
In the simplest case the digestion can be carried out in an open quartz vessel over a source of
heat (open digestion). In digestions in closed systems the sample is treated with concentrated
acid and digested at increased pressure and increased temperature. An example of an open
digestion and one of a closed wet digestion are given below.
1.1. Wet digestion in an open system with sulfuric acid and hydrogen peroxide
Reagents
• Sulfuric acid: w(H2SO4) = 96%
• Hydrogen peroxide solution: w(H2O2) = 30%
Procedure
10 mL or 2 g of the sample is placed in a Kjeldahl flask made of quartz and treated with 6 mL
sulfuric acid. With solid samples we recommend that the acid is allowed to act on the sample
for some time before heating. The flask is then heated with either a hotplate or a Bunsen burner.
As soon as a brown coloration is seen in the liquid (or when the solid has been liquefied)
hydrogen peroxide is added drop by drop until the digestion solution remains clear and colorless
when sulfuric acid fumes are seen again. Depending on the matrix the digestion time needed
may be 20 to 40 minutes. After the digestion the solution can be made up to e.g. 50 mL in a
volumetric flask.
1.2. Wet digestion in a closed system
Reagents
• Nitric acid: w(HNO3) = 65%
Procedure
The digestion described here can be carried out in a microwave digestion apparatus (e.g. CEM,
USA). Digestions under pressure are particularly suitable for solid samples and volatile sub-
stances (lead and mercury). Approx. 0.5 g sample is treated with 5 mL concentrated HNO3
and 2 mL hydrogen peroxide solution in the digestion vessel, which is then sealed. The digestion
is carried out with a pressure-controlled temperature program. After the digestion the solution
can be made up to e.g. 50 mL in a volumetric flask. The pressure digestion has the disadvan-
tage that the organic matrix is usually not destroyed completely and post-treatment, e.g. with
a UV-digestion, is required.
2. UV-digestion
This digestion is only recommended for slightly polluted samples and as a post-treatment step
for wet digestion solutions. It is particularly suitable for the digestion of water samples (tap water
normally does not require to be digested, but can be electrochemically analyzed directly).
Instruments:
• UV-digestion apparatus, e.g. 705 UV Digester (Metrohm Ltd.)
Reagents
• HCl w(HCl) = 30 %
Procedure
10 mL of the water sample is filled into one of the quartz reaction tubes of the UV-digestion
apparatus. 100 µL hydrogen peroxide solution is added to the sample for the more effective
destruction of the organic compounds. The digestion period should be approx 2 h (this depends
on the degree of sample pollution and the performance of the UV lamp). This period can be
reduced if 10 µL concentrated hydrochloric acid w(HCl) = 30% is added.
Experiment 6:
The use of anodic stripping voltammetry for the determination of heavy

metals in drinking water and samples of wood
Nature of the task
Determine the dependency of the peak height on the deposition time and on the deposition
potential for a depolarizer. Use stripping voltammetry to determine the concentration of Cu2+,
Pb2+, Cd2+ and Zn2+ in a sample of drinking water and in samples of wood after a suitable
digestion.
Experiments
6.1. Basic principles of anodic stripping voltammetry:
influence of the deposition time
(Exploratory mode)
6.2. Basic principles of anodic stripping voltammetry:
influence of the deposition potential
(Exploratory mode)
6.3. Determination of the concentration of zinc, cadmium, lead and copper in samples of
drinking water (Determination mode)
6.4. Determination of the concentration of zinc, cadmium, lead and copper in wood samples
(Determination mode)
Reagents
• Acetate buffer pH 4.6: c(acetic acid) = 0.1 mol/L + c(sodium acetate) = 0.1 mol/L
• Supporting electrolyte: c(NaCl) = 0.25 mol/L
c(sodium acetate) = 0.025 mol/L
c(acetic acid) = 0.025 mol/L
• Standard solutions:
Metal Original concentration 1/100 dilution 1/1000 dilution
Zn2+, Cd2+, Pb2+, Cu2+ 1 g/L = 1000 ppm 10 mg/L = 10 ppm 1 mg/L = 1 ppm
On dilution the standard solutions must be stabilized with 0.1 mL w(HNO3) = 65% before being
made up to 100 mL with bi-distilled water.
We recommend that all glassware is rinsed with dilute nitric acid [w(HNO3) = 10%] after use
in order to remove heavy metal ions from the vessel walls. Smaller pieces of glassware can be
cleaned very effectively above an appropriate steam bath. The voltammetry cell should also be
rinsed with the acidic mixture after use.
Experiment 6.1.
Basic principles of anodic stripping voltammetry: influence of the de-

position time
The basic principles of stripping voltammetry are to be imparted in this part-experiment. En-
richment stands in the forefront of the experiment as the step that determines the sensitivity
of the method.
Use the following measuring parameters (Fig. 6.1.) to record the anodic voltammogram of a mea-
suring solution consisting of 20 mL acetate buffer + 20 µL lead standard [β(Pb2+) = 1 g/L].
Measuring solution
20 mL acetate buffer
+ 20 µL lead standard β(Pb2+) = 1 g/L
Vary the enrichment time (Deposition time) between 30 and 2400 s.
Plot the peak currents obtained as a function of the deposition time.
Exercise
What effect can be observed?
Experiment 6.2.
Basic principles of anodic stripping voltammetry: influence of the deposi-

tion potential
The enrichment effect depends not only on the deposition time, but also on the deposition
potential.
Starting with the experimental conditions in Fig. 6.2. and vary the deposition potential at a
constant deposition time of 180 s and a potential step time (Voltage Step Time) of 0.5 s by the
following values:
-0.2; -0.35; -0.4; -0.425; -0.437; -0.45; -0.462; -0.475; -0.5; -0.55; -0.6; -0.7 V.
Plot the resulting peak heights as a function of the deposition potential.
Exercises
How do you interpret the result?
What consequence has this result for defining the experimental conditions for the quantitative
determination?
Experiment 6.3.
Determining the concentration of zinc, cadmium, lead and copper in

samples of drinking water
In this Experiment the trace concentrations of the above-mentioned metals are to be deter-
mined in samples of drinking water. For example, tap water which has stood for a long time in
the pipeline (over night) and after running for 10 minutes can be investigated. Differences are
observed, particularly with old water pipes made of lead. After standing for a long time the lead
concentration may have increased considerably.
If water samples are to be investigated then they should be filtered and subjected to a UV-diges-
tion before the measurement.
Before the determination a preliminary investigation of the concentrations of the heavy metal ions
should be carried out in the Exploratory mode (zinc and copper are usually present in higher
concentrations) in order to estimate the standard solution dilution to be used.
Then treat 10 mL sample solution with 10 mL acetate buffer and degas the solution (300 s).
Use the following measuring parameters (Fig. 6.2.) to record the anodic voltammogram of the
solution:
Measuring solution
10 mL drinking water
+10 mL acetate buffer
For each element add 50 µL standard solution (e.g. concentration β(Zn2+) = 10 mg/L, β(Cd2+)
= 1 mg/L, β(Pb2+) = 1 mg/L, β(Cu2+) = 1 mg/L) and record a further voltammogram. Use
the peak currents obtained (in relationship to the initial sample) to estimate the necessary
concentration of the added standards. Determine the peak potentials of the four metals. These
are required for the automatic peak evaluation in the Determination mode.
In order to determine the metals in the Determination mode use the measuring parameters
given above (see Experiment 4 for transferring the specifications). During the determination two
standard additions are added in succession to the analyte solution and the voltammograms
are recorded.
Exercise
Why is the standard addition method used in this determination and not a calibration curve?
Experiment 6.4.
Determination of the concentration of cadmium, lead and copper in

wood samples
The heavy metal concentration in biological investigation systems can be used for the detection
of environmental pollution. This detection encounters difficulties if the environmental pollution
has to be assessed retroactively. Such an analysis requires suitable samples which have as
long a life as possible, have yearly or seasonal growth zones and which are tied to a specific
location. In the past dendrochronological studies into the heavy metal concentrations found in
trees have been carried out, as trees which grow in these latitudes have clearly recognizable
yearly growth zones (annual rings). However, the results obtained to date have been assessed
in very different ways by individual authors. A central question is whether all trees are suitable to
the same extent for use as monitors for retrospective analysis, or whether only certain types of
tree can be used. If all types of trees were to be suitable to the same extent then the distribution
patterns of the heavy metals in their annual rings should be similar when trees from a single
location are investigated.
After a suitable sample preparation step the concentrations of cadmium, lead and copper can
be determined by anodic stripping voltammetry. The distribution pattern is obtained by plotting
the concentrations (referred to the dry substance) against time.
Sample preparation
Normally whole cross-sections of fallen trees are taken and growth drills are used to take samples
from a living tree. The age of the trees can be determined by counting the annual rings. Wherever
possible the individual annual rings are separated out by using a chrome-vanadium chisel. If
the annual rings are too thin then several (max. five) annual rings are combined to give a single
sample. The rings are chopped up coarsely and then ground in a mill to give a fine powder. We
recommend that the wood samples are subjected to a wet digestion in a microwave digestion
apparatus as described above by using a mixture of nitric acid and hydrogen peroxide; this is
followed by UV-photolysis.
Procedure
As the concentrations of the above-mentioned heavy metals in samples of trees are normally in
the ppm range and the position of the peak potentials is already known, it is usually not neces-
sary to make a preliminary investigation in the Exploratory mode.
Place the measuring solution in the voltammetry vessel and use the following parameters (Fig.
6.3.):
Measuring solution
9 mL digestion solution
+ 9 mL supporting electrolyte
Make two standard additions to the analyte solution in succession (20 µL β(Cd2+) = 1 mg/L,
β(Pb2+) = 10 mg/L , β(Cu2+) = 10 mg/L) and record the voltammograms. Correlate the
obtained concentrations with the actual weight of dry substance in each case and plot these
as a function of time.
References
[1] R. Neeb, Inverse Polarographie und Voltammetrie, Akademie-Verlag, Berlin, 1969.
[2] R. E. Tout, W. B. Gilboy, in J. Fletcher: Dendrochronologie in Europe, Symposium,
Greenwich, Juli 1977, 343-350.
[4] K. W. Budna, G. Knapp, Fresenius Z. Anal. Chem., 294, 1979, 122.
[5] M. Würfels, E. Jackwerth, M. Stoeppler, Fresenius Z. Anal. Chem., 317, 1984, 458-
461.
[6] B. Neubert, J. Schäfer, G. Weichbrodt, Labor Praxis, 12, 1988, 956-970.
[7] B. Markert, Plants as Biomonitors, Verlag Chemie, Weinheim, 1993.
[8] R. Bargagli, Trace Elements in Terrestrial Plants, Springer-Verlag, Berlin, 1998.
[9] M. Würfels, E. Jackwerth, Fresenius Z. Anal. Chem., 322, 1985, 354-358.
[10] L. Kotz, G. Kaiser, P. Tschöpel, G. Tölg, Z. Anal. Chem. 260, 1972, 207-209.
[11] G. Knapp, B. Sadjadi, H. Spitzy, Z. Anal. Chem., 271, 1975, 275-278.
[12] G. Knapp, Mikrochim. Acta [Wien], II, 1991, 445-455.
Experiment 6.1.
Basic principles of anodic stripping voltammetry: influence of the deposi-

tion time
Dependency of the peak height on the deposition time:
Fig. 6.4. Anodic resolution of lead after various deposition times in DPASV
Fig. 6.5. Dependency of the peak height on the deposition time
With short deposition times and low metal concentrations the peak height shows linear
dependency on the deposition time (left-hand curve); with longer deposition times and high
metal concentrations the increasing amalgam content of the mercury counteracts any further
enrichment.
Experiment 6.2
Basic principles of anodic stripping voltammetry: influence of the de-

position potential
Dependency of the oxidation peak Pb → Pb2+ on the deposition potential:
Fig. 6.6. Dependency of the peak height in the lead oxidation on the deposition potential (pseudopolarogram)
The dependency shown is known as a pseudopolarographic curve. The maximum increase in

peak height characterizes the formal potential of the Pb/Pb2+ redox system in the electrolyte
used.
It is clear that the 100 mV peak heights negative to the peak potential assume a value that does
not grow any further. A further shift in the deposition potential would not improve the sensitivity
of the lead determination.
Experiment 6.3.
Determination of the concentration of zinc, cadmium, lead and copper

in samples of drinking water
Fig. 6.7. Determination of lead, copper, cadmium and zinc in a sample of water
The investigated water sample was taken from a pipeline with a minimal throughput.
The results shown:
zinc (6 mg/L), cadmium (10 µg/L), lead (5 µg/L) and copper (12 µg/L) compare with the
following limits or guide levels given in the German Drinking Water Regulations:
Zinc (5 mg/L*), cadmium (5 µg/L), lead (40 µg/L) and copper (3 mg/L*) (guide levels are
marked with *).
Experiment 6.4.
Determination of the concentration of cadmium, lead and copper in

wood samples
Radial distribution pattern of cadmium, lead and copper in an oak (92 years’ old)
Fig. 6.8. Example of the radial distribution pattern of cadmium, lead and copper in an oak (92 years’ old) (A. Widmann,
thesis, Ernst Moritz Arndt University, Greifswald, 2000)
Experiment 7
Determination of nickel by adsorptive stripping voltammetry
A considerable extension to the potential of electroanalytical methods is made possible by the
adsorptive enrichment of the species to be analyzed. By using a suitable ligand the cations to
be determined are converted into complexes that are adsorbed on the mercury electrode at a
defined potential and can therefore be enriched. The electrochemical determination of nickel and
cobalt in the trace range has only become possible since the introduction of this method, as in
both cases cathodic enrichment is impossible owing to irreversible electrode processes.
Nature of the task

In the following Experiment a sensitive method for the determination of nickel is described.
Exercise
Inform yourself about which other metals can be determined electroanalytically by adsorptive
stripping voltammetry!
Experiments
7.1. Basic principles of adsorptive stripping voltammetry (Exploratory mode)
7.2. Determination of the nickel concentration of a wine sample (Determination mode)
Reagents
• Ammonia buffer: c(NH3) = 2 mol/L
c(NH4Cl) = 1 mol/L
• Ammonia solution w(NH3) = 25%
• DMG solution: c(dimethylglyoxime) = 0.01 mol/L
116 mg dimethylglyoxime is dissolved in
100 mL ethanol, or
c(dimethylglyoxime-disodium salt) = 0.01 mol/L
304 mg dimethylglyoxime-disodium salt is
dissolved in 100 mL water
The solution should be freshly prepared before the experiment.
• Nickel standard solution β(Ni2+) =1 mg/L
Experiment 7.1.
Basic principles of adsorptive stripping voltammetry

As in the case of anodic stripping voltammetry, in adsorptive stripping voltammetry the enrichment
process also plays a decisive role in the sensitivity of the measuring method. That adsorption
processes can often be of a complicated nature is shown in the following experiment.
The measurement is carried out in the Exploratory mode.
Procedure
100 mL of a 1:10 dilution of the ammonia buffer is adjusted to pH 9.3 with ammonia solution.
25 mL of this solution is transferred to the electrochemical cell together with 100 µL DMG
solution. The measurement is made after a degassing time of 600 s (after the addition of the
standard this time can be reduced to 60 s).
Use the following measuring parameters (Fig. 7.1.) to record the cathodic stripping voltam-
mogram of a measuring solution with a nickel concentration of 2 µg/L. Increase the deposition
time from 20 to 600 s.
Measuring solution
25 mL ammonia buffer, diluted 1:10, pH 9.3
+ 100 µL DMG solution
+ 50 µL nickel standard solution β(Ni2+) =1 mg/L
Exercise
What result do you expect?
Experiment 7.2.
Determination of the nickel concentration of a wine sample

Before the electroanalytical determination the sample must be freed from organic compounds
by an acid digestion (see Experiment 6, wet digestion in an open system).
For determination of the concentration in the Determination mode 5 mL sample is pipetted
into 25 mL supporting electrolyte solution. The measuring parameters according to Fig. 7.1.
should be transferred from the Exploratory mode (see Experiment 4, Fig. 4.3.). We recom-
mend an deposition time of 60 s. Carry out two standard additions. The volume of the added
standard is 50 µL.
Measuring solution
25 mL ammonia buffer, diluted 1:10, pH 9.3
+ 5 mL sample
+ 100 µL DMG solution
References
[1] H. Braun, M. Metzger, Fresenius Z. Anal. Chem. 318, 1984, 321-326.
[2] P. Ostapczuk, M. Goedde, M. Stöppler, H. W. Nürnberg, Fresenius Z. Anal. Chem., 316,
1984, 252-256.
[3] A. Meyer, R. Neeb, Fresenius Z. Anal. Chem., 315, 1983, 118-120.
Experiment 7.1.
Basic principles of adsorptive stripping voltammetry

In contrast to the expected adsorption isotherm an increase in the peak current to reach a
maximum value can be seen. If the adsorption time is further increased the peak current de-
creases. This phenomenon is not easy to understand. It is based on the competitive adsorption
of the complexly bound DMG – which is electrochemically active – and the free DMG, which on
longer adsorption displaces the complexly bound compound from the mercury electrode.
Fig. 7.2. Dependency of the peak height on the deposition time for the reduction of nickel
Experiment 7.2.
Determination of the nickel concentration of a wine sample

A red wine has been used as an example. The nickel concentration of 13.3 µg/L found is below
the maximum value permitted for drinking water (50 µg/L).
Fig. 7.3. Determination of the nickel concentration in a red wine by adsorptive stripping voltammetry after acid
digestion in an open system
Experiment 8
Determination of selenium by cathodic stripping voltammetry
Nature of the task
In this Experiment the basic principles of cathodic stripping voltammetry are demonstrated using
the determination of selenium as an example.
Experiments
8.1. Basic principles of the determination
8.2. Influence of lead and zinc on the determination of selenium
Reagents
• Supporting electrolyte solution 1: c(HClO4) = 0.1 mol/L
c(NH4SCN) = 0.02 mol/L
• Supporting electrolyte solution 2: c(HClO4) = 0.1 mol/L
c(NH4SCN) = 0.02 mol/L,
β(Cu2+) = 1 mg/L
• Selenium standard solution β(SeIV) = 2 mg/L
• Lead standard solution β(Pb2+) = 10 mg/L
• Zinc standard solution β(Zn2+) = 10 mg/L
Procedure
All measurements are carried out in the Exploratory mode of the 757 VA Computrace.
Experiment 8.1.

Add 20 mL of supporting electrolyte solution 1 to the voltammetric measuring cell and first
record a voltammogram of the electrolyte solution. Then add five 40 µL portions of the selenium
standard and record the associated voltammograms.
Measuring solution
20 mL supporting electrolyte solution 1
Repeat the Experiment with supporting electrolyte solution 2.
Exercises
Clarify the individual reaction steps yourself!
What differences can be observed on changing from supporting electrolyte solution 1 to sup-
porting electrolyte solution 2? Why is copper added to the solution?
What dependency of the peak height on the concentration of selenium in the solution is to be
expected and what conclusions would you draw for the determination of selenium (calibration
or standard addition?)
Experiment 8.2.
Influence of lead and zinc on the selenium determination

Add 20 mL supporting electrolyte solution 2 and 20 µL selenium standard solution to the cell
and use the parameters given for Experiment 8.1. (Fig. 8.1.) to record a voltammogram. Add
two 40 µL portions of the zinc standard solution and the lead standard solution in succession
and record the individual voltammograms.
Exercises
What do you observe and how would you interpret your observation?
How could the observed effect be suppressed?
References
[1] P. Fechner, F. Scholz, G. Henrion, C. Trapp, L. Müller, Wasserwirtschaft-Wassertechnik,
8, 1986, 191-192.
´ F. Scholz, J. Electroanal. Chem., 418, 1996, 21-28.
[2] B. Lange, M. Lovric,
[3] B. Lange, F. Scholz, Fresenius J. Anal. Chem., 358, 1997, 736-740.
Experiment 8.1.

Selenium is present in solutions as Se(IV). At a mercury electrode Se(IV) is reduced to Se2-,
which forms sparingly soluble selenides with heavy metal ions. If Cu2+ is present in the solution
then at a particular potential Cu2Se can be enriched at the electrode, as Cu2+ ions are reduced
at the Se(IV) reduction potential to Cu+. During the determination step the dissolution of the
Cu2Se by reduction of the Cu+ ions in Cu2Se can be followed.
Fig. 8.2 Dependency of the peak height on the selenium concentration using supporting electrolyte solution 2
Experiment 8.2.
Influence of lead and zinc on the selenium determination
Fig. 8.3. Influence of lead on the selenium determination
The addition of even higher concentrations of zinc has no influence on the determination. If
lead is added then there is a competitive reaction between the formation of copper selenide and
lead selenide. In the voltammogram this can be seen from the fact that the peak height for the
reduction of the copper selenide decreases noticeably. The shoulder at approx. -720 mV in the
voltammogram can be assigned to the reductive dissolution of lead selenide. The influence of
lead on the determination of selenium can be suppressed by the addition of an EDTA electrolyte
solution as a complexing agent.
Experiment 9
Determination of molybdenum in iron by utilizing a catalytic reaction
Nature of the task
The following Experiment demonstrates the utilization of catalytic currents in combination with
adsorptive enrichment for the analysis of molybdenum in the ultratrace range. It is primarily
concerned with the determination of the detection limit; the use of the method is shown by a
practical example.
Experiments
9.1. Basic principles of the determination (Exploratory mode)
9.2. Determination of molybdenum in a steel sample (Determination mode)
Reagents
• Supporting electrolyte solution: c(mandelic acid) = 0.1 mol/L
c(H2SO4) = 0.1 mol/L
• Molybdenum standard solution β(Mo) = 1 mg/L
• NaClO3 solution c(NaClO3) = 1 mol/L
• Hydrochloric acid (for digestion): w(HCl) = 30%
Procedure
Experiment 9.1. is carried out in the Exploratory mode. The parameters are then transferred to
the Determination mode (see Experiment 4); in Experiment 9.2. the determination is carried
out after digestion of the steel sample by using a calibration curve.
Experiment 9.1.

Part-experiment
Add 10 mL of the supporting electrolyte and 10 mL NaClO3 to the cell and record the basic
curve using the following parameters (Fig. 9.1.). The concentration of sodium chlorate in the
measuring cell is 0.5 mol/L.
Measuring solution
10 mL supporting electrolyte +10 mL NaClO3 solution
Instrument settings
Add 20 µL of the molybdenum standard solution and record a further voltammogram.
Exercise
Suggest a reaction mechanism for the catalytic determination of molybdenum under these
conditions!
Part-experiment
Vary the concentration of NaClO3 from 0.01 mol/L to 0.5 mol/L. Add 10 mL of the supporting
electrolyte to the cell, add a corresponding volume of sodium chlorate solution (1 mol/L NaClO3
solution) and make up to 20 mL with bi-distilled water. Add 20 µL molybdenum standard solution
to the solution in the cell. Record each of the voltammograms and determine the peak height.
Then plot the peak height against the concentration of chlorate in the solution.
Exercise
What dependency of the peak height on the chlorate concentration is to be expected?
Experiment 9.2.
Determination of molybdenum in a steel sample

Weigh out approx. 1 g of a steel sample and digest it with 20 mL concentrated hydrochloric
acid under gentle heating. Make the digestion solution up to 50 mL.
Now transfer the measuring parameters from part-experiment 9.1. to the Determination mode
and record a calibration curve by adding five portions of 20 µL molybdenum standard solution
to the electrolyte solution (10 mL supporting electrolyte + 10 mL 1 mol/L NaClO3 solution).
Store the calibration curve. Add 10 mL of the supporting electrolyte and 10 mL NaClO3 solu-
tion to the cell followed by 40 µL of the digestion solution. First record a voltammogram in the
Exploratory mode with the above-mentioned specifications and determine the peak height. It
may be necessary to dilute the digestion solution further or to increase the sample volume in
the electrolysis cell. If the peak height lies within the range of your calibration curve then carry
out the measurement in the Determination mode using the previously stored calibration curve
(Fig.9.2.). Then use the concentration determined in the solution to calculate the concentration
of molybdenum in the steel sample in µg/g with respect to the original sample weight.
In order to determine the detection limit record the voltammogram of the electrolyte solution
(10 mL supporting electrolyte + 10 mL chlorate solution) ten times (Edit working method
parameters → Determinations → No. of replications = 10) in the Determination mode. In the
Results window you will find the peak heights, mean value for the peak heights and its standard
deviation. From the slope of the calibration curve and the intercept with the y-axis (also contained
in the Results windows) determine the detection limit (see also Experiment 3).
Fig.9.2. Instrument settings
References
[1] G. Henrion, F. Scholz, R. Schmidt, I. Fabian, Z. Chem., 21, 1981, 104-105.
[2] J. Pelzer, F. Scholz, G. Henrion, P. Heininger, Fresenius Z. Anal. Chem., 334, 1989, 331-
334.
Experiment 9.1.
Fig. 9.3. Dependency of the peak height on the chlorate concentration
The following reaction mechanism forms the basis for the determination of molybdenum utiliz-
ing catalytic currents:
At the electrode there is an initial conversion corresponding to
MoVIO2Lig2(H2O)2 + e–  MoVO2Lig2(H2O)2
This molybdenum complex reacts with chlorate according to:
MoVO2Lig2(H2O)2 + ClO3–  MoVO2Lig2(H2O)(ClO3–) + H2O
MoVO2Lig2(H2O)(ClO3–) + e– +2H+  MoVO2Lig2(H2O)2 + ClO2–
In this case the unusually high rate constant (2.2·108 L·mol-1s-1) of the reaction of the
molybdenum(V)-mandelic acid complex with chlorate is responsible for the intensity of the
molybdenum signal.
Experiment 9.2.
Determination of molybdenum in a steel sample
Fig. 9.4. Determination of molybdenum in a steel sample
Sample weight: 3.3 g (steel screws)

The sample contained 18.6 µg/g molybdenum.
Detection limit: 0.103 µg/L
Experiment 10
Determination of bismuth in the presence of copper and lead
Interference can occur in voltammetric and polarographic measurements, for example when the
signals of two of the elements to be determined lie too close to each other. This experiment is
intended to show that the overlapping of analysis signals can be avoided by choosing suitable
experimental conditions.
Nature of the task

In the following Experiment suitable experimental conditions for the determination of bismuth in
the presence of copper and lead are to be found. A focal point is the influence of the electrolyte
solution on the position of the formal potential of bismuth.
Experiments
10.1. Influence of various electrolyte solutions on the position of the formal potential of bis-
muth
10.2. Influence of the concentration of hydrochloric acid on the peak separation of copper
and bismuth
10.3. Detection of bismuth in the presence of copper and lead
Reagents
• Hydrochloric acid: w(HCl) = 30%
• Lead standard solution: β(Pb2+) = 10 mg/L
• Copper standard solution: β(Cu2+) = 10 mg/L
• Bismuth standard solution: β(Bi3+) = 2 mg/L
• Citric acid solution: c(citric acid) = 0.1 mol/L
• Dilute hydrochloric acid: c(HCl) = 0.1 mol/L
• Sodium fluoride solution: c(NaF) = 0.1 mol/L
Procedure
Experiments 10.1. and 10.2. of this Experiment are carried out in the Exploratory mode of the
757 VA Computrace, Experiment 10.3. in the Determination mode.
Experiment 10.1.
Influence of various electrolyte solutions on the position of the formal

potential of bismuth
Place 20 mL of the particular supporting electrolyte (0.1 mol/L citric acid, 0.1 mol/L HCl,
acetate buffer, 0.1 mol/L NaF) and 50 µL Bi standard solution in the measuring cell and record
the voltammetric curves using the following parameters (Fig. 10.1.).
Measuring solution
20 mL supporting electrolyte solution (0.1 mol/L citric acid, 0.1 mol/L HCl, acetate buffer or
0.1 mol/L NaF)
+ 50 µL Bi standard solution
Exercise
Explain why the electrolyte solution has such an influence on the position of the potential!
Experiment 10.2.
Influence of the concentration of hydrochloric acid on the peak separa-

tion of copper and bismuth
Now optimize the determination of bismuth in the presence of lead and copper with respect
to the supporting electrolyte solution by adding various concentrations of hydrochloric acid
(0.01 mol/L, 0.1 mol/L, 1 mol/L, 1.5 mol/L, 2 mol/L) and an excess of copper to the solution.
Add 20 mL of the particular hydrochloric acid to the voltammetric measuring cell followed by
20 µL Bi standard solution, 100 µL Cu standard solution and 20 µL Pb standard solution.
Measuring solution
20 mL hydrochloric acid (at the corresponding dilution)
+ 100 µL copper standard solution
+ 20 µL lead standard solution
+ 20 µL bismuth standard solution
The measuring parameters are the same as shown in Fig. 10.1.
Exercise
Suggest a suitable concentration of HCl for the determination of bismuth in the presence of
copper!
Experiment 10.3.
Detection of bismuth in the presence of copper and lead

Transfer the measuring parameters from Experiment 10.1 to the Determination mode and draw
up a method using a 2-fold standard addition of bismuth. The voltammograms should only be
recorded up to an end potential of 0 V. Analyze a solution with the following composition: 20 mL
2 mol/L HCl, 20 µL Bi standard solution, 100 µL Cu standard solution and 20 µL Pb standard
solution. The solution is spiked twice with 20 µL Bi standard solution.
Measuring solution
20 mL supporting electrolyte [c(HCl) = 2 mol/L]
+ 100 µL copper standard solution
+ 20 µL lead standard solution
+ 20 µL bismuth standard solution
Optimize the evaluation of the curves! Vary the evaluation type between “linear” and “polynomial”
and shift the foot points manually! Observe the changes in the automatically calculated result
and determine the recovery rate in each case!
Exercise
Discuss the advantages and disadvantages of automatic peak evaluation!
References
[1] R. Neeb, Inverse Polarographie und Voltammetrie, Akademie-Verlag, Berlin, 1969.
In the analysis of bismuth it can be seen that a reversible reduction can be achieved in numer-
ous electrolyte solutions, although interference as a result of the overlapping of the copper
and antimony(III) peaks also occurs. In solutions with a high hydrochloric acid concentration
the copper and bismuth peaks at the mercury drop electrode are still adequately separated. In
addition, interference resulting from very high copper concentrations can be minimized by the
suitable selection of the deposition potential, if this suppresses the deposition of the copper.
Experiment 10.1.
Influence of various electrolyte solutions on the formal potential of

bismuth
In halogen acids and other mineral acids the peak potential lies between 0 and -0.2 V. Bismuth
salt solutions tend to hydrolyze in weakly acidic solutions. This is why the peak potential shifts
in comparison to strongly acidic solutions. In solutions of organic or inorganic complexing
agents the formal potentials may also undergo a considerable shift.
Electrolyte solution Peak potential vs. Ag/AgCl (3 mol/L KCl)

0.1 mol/L citric acid -359 mV
0.1 mol/L HCl -112 mV
0.1 mol/L NaF -121 mV
0.1 mol/L acetic acid/sodium acetate 10 mV
Experiment 10.2.
Influence of the concentration of the hydrochloric acid on the peak

separation of copper and bismuth
In weak hydrochloric acid solutions strong interference occurs as a result of peak overlapping
with copper. As the hydrochloric acid concentration increases peak separation also becomes
better, and the determination of bismuth in the presence of copper is possible. However, HCl
concentrations which are too high make it difficult to evaluate the bismuth peak as a result of
the beginning final rise (oxidation of mercury with the formation of mercury chloride).
Fig. 10.2. Dependency of the peak separation of copper and bismuth on the concentration of the hydrochloric acid
used
Experiment 10.3.
Detection of bismuth in the presence of copper and lead

Figure 10.3. shows the voltammograms of the determination of bismuth in the presence of
copper and lead. For the evaluation a baseline approximation of the “polynomial” type was
selected, in which the foot points were optimized for each spiking process. This baseline ap-
proximately follows the estimated basic current curve corresponding to a solution containing
no bismuth. The concentration determined under these conditions corresponds to the standard
amount added.
Concentration found: β(Bi) = 1.95 mg/L
Standard concentration: β(Bi) = 2 mg/L
Recovery rate: 97%
The evaluation with an automatically determined “linear” baseline gave incorrect results. The
recovery rate was considerably lower than 100%.
Fig. 10.3. Determination of bismuth in the presence of copper and lead with standard addition
Experiment 11
Determination of thallium in the presence of cadmium and lead
Thallium is well soluble in mercury and can be determined electrochemically in almost all sup-
porting electrolytes. However, interference to the determination process can occur, for example
in an acetate buffer with the lead and cadmium peaks. By the addition of strong complexing
agents such as EDTA the lead and cadmium peaks can be suppressed. As thallium does not
form a complex with EDTA, it can be determined very selectively together with numerous other
elements.
Nature of the task

This Experiment demonstrates the basic principles behind the determination of thallium in the
presence of lead and cadmium by the addition of a complexing agent.
Reagents
• Supporting electrolyte: c(NaCl) = 0.25 mol/L
c(acetic acid) = 0.025 mol/l
• Lead standard solution ß(Pb2+) = 10 mg/L
• Cadmium standard solution ß(Cd2+) = 1 mg/L
• Thallium standard solution ß(Tl+) = 10 mg/L
• EDTA solution ß(EDTA) = 100 mg/L
Procedure
The Experiment is carried out in the Exploratory mode.
Measuring solution
10 mL water
+ 10 mL supporting electrolyte
Add 10 mL bi-distilled water and 10 mL supporting electrolyte to the cell and record a first
voltammogram of the electrolyte solution using the parameters shown in Fig. 11.1. Add 40 µL
each of the lead, cadmium and thallium standard solutions step by step and record a voltammogram
each time. Then add 100 µL EDTA solution and record a further voltammogram.
Exercise
Explain the influence of complexing agents on the position of the formal potentials of redox
systems!
References
^
[1] I. Šinko, S. Gomišcek, Mikrochimica Acta, 10, 1972, 163-172.

[2] J. E. Bonelli, H. E. Taylor, R. K. Skogerboe, Anal. Chim. Acta, 118, 1980, 243-256.
[3] L. K. Hoeflich, R. J. Gale, M. L. Good, Anal. Chem., 55, 1983, 1591-1595.
The lead and thallium peaks are not separated under the selected conditions. The addition of
EDTA complexes the cadmium and lead and therefore shifts the peaks to more negative potentials
so that only the thallium peak appears. It is now possible to determine thallium in the solution
by a normal standard addition method.
Fig. 11.2. Determination of thallium in the presence of cadmium and lead by the addition of EDTA
a) supporting electrolyte + c(Pb2+) = 9.6·10-8 mol/L + c(Cd2+) = 1.8·10-8 mol/L
b) solution a) + c(Tl+) = 9.8·10-8 mol/L
c) solution b) + β(EDTA) = 0.5 mg/L
Experiment 12
Complexation capacity of a water sample
As already shown in Experiment 6, natural water samples often contain organic compounds that
can form complexes with heavy metals. These compounds are frequently able to form chelate
complexes; these have a particularly high stability. This can lead to the heavy metals bound in
the complexes becoming electrochemically inactive and therefore impossible to determine.
The complexation capacity of an aqueous sample can be determined in a voltammetric titration
by adding a standard solution of the metal in µL steps to a sample solution and recording a
voltammogram after each addition. As natural waters can also contain organic substances
that interfere with the voltammetric determination of a heavy metal, not by the formation of
complexes but by adsorption processes on the mercury surface, this is known as the apparent
complexation capacity.
Nature of the task

Record a voltammetric titration curve in a synthetic and a natural water sample.
Experiments
12.1. Complexation capacity of a synthetic water sample
12.2. Complexation capacity of a natural water sample
Reagents
• Supporting electrolyte c(KCl) = 1.5 mol/L
• ETDA standard solution ß(EDTA·2 H2O) = 10 mg/L
• Lead standard solution ß(Pb2+) = 10 mg/L
Procedure
All Experiments in this Experiment are carried out in the Exploratory mode of the 757 VA
Computrace.
Experiment 12.1.
Complexation capacity of a synthetic water sample

This part-experiment is intended to familiarize you with the problems of a voltammetric titration.
Place 22.5 mL bi-distilled water, 2 mL potassium chloride-sodium acetate electrolyte and 500 µL
EDTA solution in the cell. Use the following parameters (Fig. 12.1.) to record the voltammogram
of the electrolyte solution. Then add the Pb2+ standard solution in 25 µL steps and use the same
parameters to record a voltammogram after each addition.
Measuring solution
22.5 mL bi-distilled water
+ 2 mL electrolyte
+ 0.5 mL EDTA solution
Use the function Signal → Peak search to evaluate the peak currents of the lead oxidation and
plot these against the concentration of lead in the solution.
Exercises
What type of curve do you expect?
How would you evaluate the expected curve?
Experiment 12.2.
Complexation capacity of a natural water sample

Repeat Experiment 12.1. with a natural water sample. As natural water samples from lakes or
ponds normally have a sufficiently high concentration of salts it is not necessary to add an
electrolyte and the water sample can be measured directly. Add 25 mL of the water sample to
the voltammetry vessel and proceed in a similar manner to Experiment 12.1. If a noticeable
peak is seen after the first addition of 25 µL Pb2+ standard solution then repeat the Experiment
with a smaller volume of standard solution or dilute the Pb2+ standard solution accordingly. On
the other hand a natural water sample can have a high content of complexing agents such as
humic materials; in this case the water sample must be diluted accordingly.
Reference
[1] P. Weidenauer, K. H. Lieser, Fresenius Z. Anal. Chem., 320, 1985, 550.
Experiment 12.1.
Complexation capacity of a synthetic water sample
Fig. 12.2. Titration curve for the determination of the complexation capacity of a synthetic water sample
When small amounts of lead are added these are initially completely complexed and no peak
for the lead oxidation is seen. A lead peak is only seen when a certain concentration has been
exceeded; its peak height should then increase linearly with the lead concentration in the solu-
tion. By applying tangents to both curves and determining their intersection point it is possible
to determine the complexation capacity of a water sample. The synthetically prepared water
sample shows a complexation capacity for lead of 59 µg/L.
Experiment 12.2.
Complexation capacity of a natural water sample

The water sample used here was taken from a pond on the outskirts of Greifswald and could
be investigated without any dilution by using the parameters given in Fig. 12.1. The apparent
complexation capacity of this water is 37 µg/L.
Fig. 12.3. Titration curve for the determination of the complexation capacity of a natural water sample
The method described in this Experiment can also be used for the determining the concentration
of complexing agents.
Experiment 13
Cyclic voltammetry
In recent years cyclic voltammetry has achieved a particularly great popularity among the dy-
namic measuring methods used in electroanalytical chemistry. Its applications range from the
investigation of simple redox processes in organic and inorganic chemistry up to biochemistry
and macromolecular chemistry. Two aspects have primarily contributed to this development: the
theoretical principles of the method have been exactly analyzed and described mathematically.
Many numerical methods have also been developed in recent years that allow the simulation
of complex electrode processes.
With the aid of cyclovoltammetry it is possible to determine both the thermodynamic and
kinetic parameters of electrode processes; these include the electron transfer steps and also
the coupled chemical reactions.
Nature of the task

The following Experiment demonstrates the basic principles of cyclovoltammetry. Primary in-
terest is given to discussing the possibilities which cyclovoltammetry provides of determining
reaction mechanisms and kinetic parameters.
Experiments
13.1. Basic principles of cyclic voltammetry
13.2. Statements about the reversibility of electrode reactions
13.3. Kinetic statements about redox reactions
Reagents
• Cadmium standard solution ß(Cd2+) = 1 g/L
• Zinc standard solution ß(Zn2+) = 1 g/L
• Ascorbic acid solution: ß(ascorbic acid) = 1 g/L
• Acetate solution: c(KCl) = 1.5 mol/L
Procedure
All Experiments in this Experiment are carried out in the Exploratory mode of the 757 VA
Computrace.
Experiment 13.1.
Basic principles of cyclic voltammetry

Add 20 mL KNO3 to the voltammetry vessel. Add 200 µL Cd2+ standard solution to it and use
the following parameters (Fig. 13.1.) to record a cyclovoltammogram.
Measuring solution
20 mL potassium nitrate solution
+ 0.2 mL cadmium standard solution
Fig. 13.1. Instrument settings for measuring cadmium
Exercises
Sketch the curve of the applied potential as a function of time for the CV mode!
Explain the typical curve of a cyclovoltammogram for a simple, reversible electron transfer
mechanism!
What characteristic quantities can be derived from a cyclovoltammogram?
How can the number of transferred electrons be determined for reversible systems?
Experiment 13.2.
Statements about the reversibility of electrode reactions

This experiment is intended to explain the meaning of the terms “reversible”, “quasi-reversible”
and “irreversible”. In the first experiment you have already become acquainted with a reversible
system. Now record a cyclic voltammogram for an electrolyte solution containing 20 mL acetate
solution and 200 µL Zn2+ standard solution. Use the parameters shown in Fig. 13.2. Then repeat
the experiment with an electrolyte solution consisting of 20 mL potassium nitrate solution and
200 µL ascorbic acid standard solution under the conditions given in Fig. 13.3. In each case
determine the peak potentials for the forward and reverse reactions.
20 mL acetate solution + 0.2 mL zinc standard solution
Fig. 13.2. Instrument settings for measuring zinc
20 mL potassium nitrate solution + 0.2 mL ascorbic acid solution
Fig. 13.3. Instrument settings for the measurement of ascorbic acid
Exercises
What are the causes of the differences in the cyclovoltammograms of reversible, quasi-revers-
ible and irreversible systems?
What are the causes of the oxidation and reduction peaks often not being symmetrical to each
other?
Experiment 13.3.
Kinetic statements about redox reactions

In experiment 13.2. you have already become acquainted with an example of a quasi-reversible
reaction. The distinctive feature is that both the mass transport and the charge transfer determine
the current. The time scale of the CV experiment can be greatly varied by the potential sweep rate.
This means that an electrode reaction can be controlled both by the charge-transfer reaction and
the diffusion. If the rate of the charge transfer is comparable to the potential sweep rate then the
difference in the peak potentials will be greater than 59 mV/n. From the peak separation the rate
of the electrode reaction can be determined by using the help function Ψ from a formalization
developed by Nicholson and Shain:
γαks(RT)1/2
Ψ=
(πnFs D )1/2
where r ox
γ =
() Dox ½
Dred
α = Charge transfer coefficient
ks = Reaction rate constant (cm/s)
Dox = Diffusion coefficient of the oxidized species (cm2/s)
Dred = Diffusion coefficient of the reduced species (cm2/s)
n = Number of transferred electrons per formula conversion
s r = Potential sweep rate(V/s)
F = Faraday constant
R = Universal gas constant
T = Absolute temperature (K)
Nicholson and Shain calculated values (see Fig. 13.4.) for Ψ as a function of the peak potential
difference multiplied by n under the assumption that α = 0.5. The value of n∆Ep does not
depend significantly on α, when α lies approximately between 0.3 and 0.7 and Ψ is not smaller
than 0.5.
From a graphical plot of the values in the table below for Ψ as a function of n∆Ep the value
of Ψ can be obtained from the experimentally determined peak potential differences. For the
calculation of ks only those values of Ψ which lie between 0.3 and 0.8 should be used, with
0.5 representing the optimum value.

Ψ n∆Ep / mV Record the cyclovoltammograms for an electro-
lyte solution consisting of 20 mL KNO3 and 200
20 61 µL Zn2+ standard solution. Use the conditions
7 63 given in Fig. 13.2. and vary the potential sweep
6 64 rate from 10-100 mV/s in steps of 10 mV/s.
5 65 Determine the peak potentials for the forward
and reverse reactions.
4 66
3 68 Measuring solution
2 72 20 mL potassium nitrate solution
1 84 + 0.2 mL zinc standard solution
0.91 86
Exercises
0.80 89
Plot the values of Ψ against n∆Ep!
0.75 92
Use the experimentally determined values for
0.61 96
n∆Ep to determine the Ψ values for the individual
0.54 104 potential sweep rates and use these to calculate
0.50 105 the rate constant for the electrode reaction
0.38 117 (α = 0.25, DZn = 7.2 · 10-6 cm2/s, DZn(Hg) =
2+
1.57 · 10-5 cm2/s)!

0.35 121
0.26 140 References
0.25 141 [1] Y. Okinata, Talanta, 11, 1964, 203.
0.16 176 [2] R. S. Nicholson, I. Shain, Anal. Chem.,
0.14 188 36, 1964, 706
[3] R. S. Nicholson, Anal. Chem., 37, 1965,
0.12 200
1351.
0.11 204 [4] J. Heinze, Angew. Chem., 96, 1984,
0.10 212 823-840.
0.077 240 [5] D. A. Skoog, J. J. Leary, Instrumentelle
0.074 244 Analytik, Springer-Verlag, Berlin, 1996.
0.048 290
Fig. 13.4. Values for Ψ (for α = 0.5)

Experiment 13.1.
Basic principles of cyclic voltammetry
Fig. 13.5. Characteristic quantities of a cyclic voltammogram
The most important values which can be obtained from a cyclic voltammogram are:
Ep,a = Peak potential (anodic)
Ep,c = Peak potential (cathodic)
ip,a = Peak height (anodic)
ip,c = Peak height (cathodic)
∆Ep = Peak potential difference
Ep/2 = Potential at which i = ip/2
Ef = Formal potential
For reversible and quasi-reversible systems the following applies:
Ep,a – Ep,c
Ef =
2

The number of transferred electrons can be determined for reversible systems as follows:
∆Ep = 57 mV/n (bei 25 °C)

Fig. 13.6. Cyclic voltammogram of a Cd standard solution
Experiment 13.2.
Statements about the reversibility of electrode reactions
Fig. 13.7. Cyclic voltammogram of a Zn standard solution

Fig. 13.8. Cyclic voltammogram of an ascorbic acid solution
Reversible case (example: Cd2+)

The speed of the heterogeneous charge transfer is so great that a dynamic equilibrium is formed
at the phase boundary (ks > 10-1 cm s-1). The current, as the measured quantity for the charge
flow at the electrode surface, is controlled solely by the mass transport as the slowest step
(diffusion-control). Under these conditions ∆Ep is approximately 59 mV/n.
Quasi-reversible case (example: Zn2+) (10-1 > ks > 10-5 cm s-1)

In addition to the mass transport the charge transfer also determines the current. The conditions
of the Nernst equation are only approximately fulfilled. The difference of the peak potentials is
greater than 59 mV/n at higher potential sweep rates. By varying the potential sweep rate the
electrode reaction can be carried out controlled by both charge-transfer and diffusion.
Irreversible case (example: ascorbic acid)

The charge transfer at the electrode is extremely slow (ks <10-5 cm s-1). Depending on the
potential, only the cathodic or anodic charge-transfer reaction has a measurable rate. Under
these conditions the Nernst equation can no longer be used.

Experiment 13.3.
Kinetic statements about redox reactions
Fig. 13.9. Ψ function
Calculation of the reaction rate constant for zinc:

ks = 4.628 · 10–2 Ψ sr1/2
Measuring series:
sr / Vs–1 sr1/2 / (Vs–1)1/2 n∆Ep / mV Ψ ks / cm s–1

0.04 0.2 104 0.514 4.76·10–3
0.05 0.224 110 0.435 4.51·10–3
0.06 0.245 114 0.405 4.59·10–3
0.07 0.265 120 0.363 4.45·10–3
0.08 0.283 124 0.330 4.32·10–3
0.09 0.3 124 0.330 4.58·10–3
Mean value: ks = (4.54 ± 0.15) · 10–3 cm s–1

Practical help
Electrode potentials of various reference electrodes
Table 1: Electrode potentials of the silver-silver chloride electrode at various temperatures and various concentrations
of KCl (the concentrations refer to 25°C) calculated with respect to the standard hydrogen electrode [1]
E / mV
T / °C m(KCl) c(KCl)
1 mol/kg 1 mol/L 3 mol/L 3.5 mol/L saturated
0 236.6 249.3 224.2 222.1 220.5
5 234.1 246.9 220.9 218.7 216.1
10 231.4 244.4 217.4 215.2 211.5
15 228.6 241.8 214.0 211.5 206.8
20 225.6 239.6 210.5 207.6 201.9
25 222.3 236.3 207.0 203.7 197.0
30 219.0 233.4 203.4 199.6 191.9
35 215.7 230.4 199.8 195.4 186.7
40 212.1 227.3 196.1 191.2 181.4
45 208.4 224.1 192.3 186.8 176.1
50 204.5 220.8 188.4 182.4 170.7
55 200.6 217.4 184.4 178.0 165.3
60 196.5 213.9 180.3 173.5 159.8
65 210.4 176.4 169.0 154.3
70 187.8 206.9 172.1 164.5 148.8
75 203.4 167.7 160.0 143.3
80 178.7 199.9 163.1 155.6 137.8
85 196.3 158.3 151.1 132.3
90 169.5 192.7 153.3 146.8 126.9
95 165.1 189.1 148.1 142.5 121.5

Table 2: Electrode potentials of the calomel electrode at various temperatures and various concentrations of KCl
(the concentrations refer to 25°C) calculated with respect to the standard hydrogen electrode [2]
E / mV
T / °C m(KCl) c(KCl)
1 mol/kg 0.1 mol/L 1 mol/L 3.5 mol/L saturated
0 333.8 285.4 260.2
5 272.90
10 271.94 334.3 283.9 254.1
15 270.87 250.9
20 269.62 334.0 281.5 247.7
25 268.23 333.7 280.1 244.4
30 266.61 333.2 278.6 241.1
35 264.90 237.7
40 263.06 331.6 275.3 246.6 234.3
45 261.04
50 329.6 271.6 242.8 227.2
60 322.9 267.3 237.7 219.9
70 262.2 233.1 212.4

Table 3: Half-wave potentials of important inorganic ions in various electrolyte solutions at the mercury electrode [calculated with respect to the silver-silver chloride
108
electrode with c(KCl) = 3 mol/L] [3, 4]
Electrolyte solution
Substance
Symbol
c(acetic acid) = 2 mol/L
+ c(ammonium acetate) = 2 mol/L
c(NH3) = 1 mol/L
+ c(NH4Cl) = 1 mol/L
c(KCl) = 1 mol/L
c(HCl) = 1 mol/L
c(NaOH) = 1 mol/L
c(KNO3) = 0.1 mol/L
c(KSCN) = 1 mol/L
c(Na2EDTA) = 0.1 mol/L
c(Na2-tartrate) = 0.5 mol/L
c(Na3-citrate) = 0.1 mol/L
+ c(NaOH) = 0.1 mol/L
c((NH4)2-oxalate), pH = 2 with
c(H2SO4) = 1 mol/L
c(H2SO4) = 1 mol/L
c(NH3) = 2 mol/L
c(NH3) = 2 mol/L
Aluminum(III) Al3+ NR NR -1.59 i NR NR NR NR NR NR NR

Antimony(III) Sb3+ -0.39 -0.81 w -0.07 -0.12 w -0.42 -0.19 w -0.58 w -0.64 w NR -0.33 -0.33 w -0.46 w -0.41 w -0.76 w
-0.50 w -0.15 w -1.18 -0.70 -0.95 w -0.57 w
Arsenic(III) As3+ -0.95 -1.62 i -0.07 i -0.38 w -0.25 -0.11 w NR -1.23 w NR -0.22 w NR -1.56 w -1.70 i -1.58 i
-0.62
Bismuth(III) Bi3+ -0.21 w NR -0.06 w -0.07 w -0.68 -1.17 i ↓ NR -0.54 w -0.31w -0.77 w -0.13 w -0.21 w -0.22 w -0.26 w ↓
chw
Cadmium(II) Cd2+ -0.63 w -0.77 w -0.62 w -0.61 w -0.82 i -0.55 w -0.62 w NR chw -0.64 -0.68 i -0.56 w -0.61 w -0.62 w -0.62 w
Chromium(III) Cr3+ -1.20 -1.34 w↓ -1.03 -1.00 w NR ↓ -0.87 -1.01 w -1.20 w -1.58 i NR NR NR -1.73 i NR
-1.01
Chromium(VI) Cr6+ NR -0.28 w -0.38 -1.03 i -0.85 w -0.32 -0.41 -1.20 w -0.33 -0.73 w NR NR -0.02 w -1.14 w
-1.45 w -0.88 w -1.10 -1.00 w -0.86 -1.72 i
-1.68 -1.71
Cobalt(II) Co2+ NR -1.26 -1.38 NR NR ↓ -1.27 w -1.11 NR -1.53 NR NR NR NR -1.52 i
-1.54
Copper(II) Cu2+ -0.25 w -0.20 w -0.18 -0.20 -0.35 NR -0.64 -0.26 w -0.08 w -0.41 w -0.05 w -0.15 w -0.18 w -0.18 w
-0.46 w -0.43
Germanium(IV) Ge4+ -1.34 i -1.41 NR NR NR -1.26 i i chw NR NR NR NR NR -1.38 w -1.38 w
chw
Indium(III) In3+ -0.67 w -1.08 -0.57 -0.57 -1.12 w -0.90 i -0.59 w NR NR -1.17 -0.61 w -0.67 w -0.68 w -0.70 w
-0.84 w -0.87 w -1.18
Iron(II) Fe2+ NR -1.44 w -1.57 i i chw -1.55 i ↓ -1.31 -1.59 w -0.09 w -1.51 i -0.83 w -0.02 w -0.17 -0.18 w -0.18 w
chw -1.56 i -1.57 w -1.61 i
chw
Iron(III) Fe3+ -0.02 NR ↓ -1.42 i NR NR ↓ -1.29 i -1.56 w -0.11 w -0.19 -0.85 w -0.18 w -0.17 w -0.19 w -0.19 w
-0.24 -1.53 w -1.59 w
Lead(II) Pb2+ -0.47 w -0.47 w -0.41 w -0.41 w -0.73 ↓ -0.36 w -0.39 w -1.03 w -0.59 -0.69 w -0.40 w -0.45 w -0.56 w -0.57 w
Manganese(II) Mn2+ NR -1.59 w -1.55 w NR -1.68 i ↓ -1.46 i -1.56 i NR -1.52 w NR NR NR -1.61 i -1.60 i
Molybdenum Mo6+ -0.63 w NR NR -0.08 i NR NR NR -0.52 NR NR -0.02 -0.17 w NR NR
(VI) -1.15 -0.75 w -0.11 -0.29
-1.30 -0.33 w -0.59
-0.74 w
Nickel(II) Ni2+ -1.09 w -1.07 w -1.03 NR NR ↓ -1.00 w -0.66 w NR NR NR NR NR NR -1.32
Selenium(IV) Se4+ -0.70 w -1.54 w NR -0.06 NR NR NR -0.67 w -1.21 NR -0.03 -0.68 w -1.35 -1.35
-1.19 -0.47 -1.20 w -0.60 w -1.11
Thallium(I) Tl+ -0.44 w -0.46 w -0.47 -0.46 w -0.45 -0.43 w -0.50 w -0.44 w -0.45 w -0.47 w -0.44 -0.44 -0.44 -0.44
Tin(II) Sn2+ -0.13 w -0.72 -0.43 w -0.45 w -0.83 -0.35 w -0.45 w -0.13 -0.54 -0.83 w -0.12 w -0.15 w -0.26 w -0.51 i
-0.63 w -1.15 w -1.59 w -0.83 -1.08 w -0.51 w -0.62 w -0.62 w -0.64 i
-1.06
Tin(IV) Sn4+ NR NR NR ↓ -0.45 NR ↓ NR -1.57 -1.16 i NR NR -0.51 w NR NR NR
Tungsten(VI) W6+ -0.26 i NR NR -1.01i NR NR NR -1.26 i NR NR
chw
Vanadium(V) V5+ i chw -1.12 -1.10 i -1.11 i -0.40 i -1.03 i -0.50 w -1.23 -0.33 i -0.76 NR NR -0.90 -0.19 w
-1.29 i chw -1.11 w -1.30 w -0.88
-1.29 w
Zinc(II) Zn2+ -1.05 -1.32 w -0.99 w -0.99 i -1.58 -0.97 -1.01 w NR -1.27 w -1.38 w NR NR -1.38 -1.29
w – very well marked wave or peak

i – poor or not evaluable wave (e.g. in rise of supporting electrolyte)
chw – catalytic hydrogen wave (in some cases can be used for quantitative analysis)
↓ - precipitate formation, consider solubility product!
NR – no wave or peak

Table 4: Potential windows at mercury and platinum in selected aqueous electrolytes
Potential / V vs. Ag/AgCl/3 mol/L KCl

+3 +2 +1 0 –1 –2 –3
1 mol/L H2SO4
1 mol/L KCl
1 mol/L NaOH
Mercury
0.1 mol/L acetate buffer, pH 4.6
0.01 mol/L LiCl

Platinum
1 mol/L H2SO4
1 mol/L NaOH
References
[1] Galster H, pH-Messung, VCH, Weinheim, 1990.
[2] Ives D. J. G., Janz G. J., Reference Electrodes, Theory and Practice, Academic Press,
New York, 1961.
[5] Meites, L., Polarographic Techniques, Interscience Publishers, John Wiley & Sons, New
York, 1965.


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Monograph

Dr. U. Schröder and Dr. H. Kahlert

Ernst Moritz Arndt University, Greifswald

Advised by Prof. Dr. F. Scholz (Ernst Moritz Arndt University, Greifswald,

All rights reserved to the publisher, including translation.

Practical help . ..............................................................................................................106

Nature of the task

Influence of oxygen on polarographic measurements

Fig. 1.1. Instrument settings for measuring in the DC mode

Fig. 1.2. Instrument settings for measuring in the DP mode

The basic polarographic curve

Fig. 1.3. Instrument settings for measuring in the DC mode

Discharging a depolarizer / SMDE – HMDE

Fig. 1.5. Instrument settings for measuring at the SMDE

The polarographic spectrum

Fig. 1.7. Instrument settings for measuring in the DC mode

Fig. 1.8. Instrument settings for measuring in the DP mode

Influence of oxygen on polarographic measurements

The basic polarographic curve

Discharging a depolarizer / SMDE - HMDE

The polarographic spectrum

Nature of the task

Measuring the capacitive current

Fig. 2.1. Instrument settings

Measuring the faradaic current

Fig. 2.2. Instrument settings

Nature of the task

Fig. 3.1. Instrument settings for measuring in the DC mode

Determining the 3σ detection limits of Pb2+ and Zn2+ in electrolytes by

Determining the 3σ detection limits of Pb2+ and Zn2+ by DC polarography

Fig. 3.3. Polarograms of electrolyte solutions with the following composition:

Nature of the task

Basic principles of the determination

Fig. 4.1. Instrument settings for measuring in the DC mode

Fig. 4.2. Instrument settings for measuring in the DP mode

Polarographic determination of vitamin C in fruit juices

Fig. 4.3. Data transfer

Basic principles of the determination

In this reaction the redox potential depends on the pH:

Polarographic determination of vitamin C in fruit juices:

Fig. 4.6. Determination of ascorbic acid in the Determination mode

Nature of the task

Phase-selective current recording – possibility of eliminating the capaci-

Fig. 5.1. Instrument settings

Phase-selective current recording – possibility of isolating the capaci-

Phase-selective current recording – possibility of eliminating the capaci-

An alternating current polarogram is obtained by plotting the alternating current amplitude

Phase-selective current recording – possibility of isolating the capaci-

Fig. 5.4. Dependency of the adsorption peak on the concentration of n-pentanol

1.2. Wet digestion in a closed system

The use of anodic stripping voltammetry for the determination of heavy

Basic principles of anodic stripping voltammetry: influence of the de-

Fig. 6.1. Instrument settings

Basic principles of anodic stripping voltammetry: influence of the deposi-

Determining the concentration of zinc, cadmium, lead and copper in

Fig. 6.2. Instrument settings

Determination of the concentration of cadmium, lead and copper in

Fig. 6.3. Instrument settings

Basic principles of anodic stripping voltammetry: influence of the deposi-

Basic principles of anodic stripping voltammetry: influence of the de-

The dependency shown is known as a pseudopolarographic curve. The maximum increase in

Determination of the concentration of zinc, cadmium, lead and copper

Determination of the concentration of cadmium, lead and copper in