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POLAROGRAPHY,
AMPEROMETRIC TITRATIONS
AND VOLTAMMETRY
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
Structure
9.1
Introduction
Objectives
9.2
9.3
9.4
Applications of Polarography
Applications of Amperometric titrations
Polarography Experiments
Determination of ascorbic acid in citrus fruits
Determination of ascorbic acid (Vitamin C) in the citrus juice by the standard addition
and calibration curve methods
Other industrial important determinations for traces or minor constituents
Determination of lead and copper in carbon steels
Determination of the amount of Cd2+ present in the unknown solution
Determination of the nature of the ion (E1/2)
9.5
Applications of voltammetry
Voltammetry Instrument
Practical methods: steps involved in voltammetry
9.6
9.7
9.8
9.9
9.1
INTRODUCTION
While going through Unit 7 and Unit 8 of this course (Electroanalytical Methods), you
have learnt about the different electroanalytical methods like Polarography,
Voltammetry and Amperometric titrations. In this unit (Unit 9), we will discuss the
applications of the previously discussed electroanalytical methods.
In this unit we will start our discussion with the different applications of Polarography,
followed by those of Amperometric titrations. A number of polarography experiments
are then discussed. This is followed by the different applications of cyclic
voltammetry.
Objectives
After studying this unit you should be able to:
give examples of the species determined with the help of amperometric titrations
for different titrations and electrodes,
67
Electroanalytical
Methods-III
9.2
APPLICATIONS OF POLAROGRAPHY
Most metal ions are reducible at DME, and multicomponent mixtures can often be
analysed by selecting an appropriate supporting electrolyte so that the half-wave
potentials of two ions are differed by about -0.2 V vs SCE or by using complexing
agents by taking the advantage of complexing ability of the metal ions.
Based on this, polarography is used predominantly for trace metal analysis of alloys,
ultra-pure metals, minerals/metallurgy, environmental analysis (air, water, soil and sea
water contaminants), foodstuffs, beverages and body-fluids, toxicology and clinical
analysis. Reducible anions such as BrO 3 , IO3-, Cr2O72- and NO2- can also be
determined using well buffered solutions.
Type of sample
Foodstuffs
high purity aluminium
Steels
Beer and soft drinks
High-purity salts
Petroleum fractions
Fuels
Milk, pharmaceuticals
Fruit and vegetables
Sea water, gases
Ketone
-C=N
Nitrile
-NO2
Nitro
-CHO
Aldehyde
-N=N-
Azo
-NO
Nitroso
>C=C<
Alkene
-NO=N-
Azoxy
-NHOH
Hydroxylamine
-C
Aryl alkyne
-O-O-
Peroxy
-ONO-
Nitrite
Azomethine
-S-S-
Disulfide
-ONO2
Nitrate
C-
>C = C-
68
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
Girard T and D
Semicarbazide
Hydroxylamine
Active Polarographic
Group
Azomethine
Carbazide
Hydroxylamine
Primary amine
Peperonal
CS2
Cu3(PO4)2 suspension
Azomethine
Dithiocarbonate (anodic)
Copper(II) amine
Secondary amine
HNO2
Nitrosoamine
Alcohols
Chromic acid
Aldehyde
1,2-Diols
Periodic acid
Aldehyde`
Carboxyl
- SH (anodic)
Phenyl
Nitration
- NO2
Reagent
SAQ 1
a)
...
...
...
...
b)
...
...
...
...
9.3
69
Electroanalytical
Methods-III
Zn2+ determination) the diffusion current will decrease. This is the fundamental
principle of amperometric titrations or polarographic titrations.
The diffusion current at an appropriate applied voltage is measured as a function of the
volume of the titrating solution. The end point is the intersection of two lines giving
the change of current before and after the equivalence point.
Table 9.4: Examples of amperometric titrations
Titrant
Electrode
Species determined
DME
Dimethylglyoxime
DME
Ni2+
Lead nitrate
DME
SO42-, MoO42-, F
DME
I-
Silver nitrate
Rotating Pt
Thorium(IV) nitrate
DME
F-
Potassium dichromate
DME
Pb2+, Ba2+
Iodine
Rotating Pt
Potassium bromate/KBr
Rotating Pt
Additions
Rotating Pt
Alkenes
Substitutions
Rotating Pt
Complexation reactions
EDTA
Precipitation reactions
Oxidation reactions
SAQ 2
What is the fundamental principle of amperometric or polarographic titration?
...
...
...
...
9.4
POLAROGRAPHY EXPERIMENTS
70
9.4.2
For the analytical determination use both the calibration curve method and standard
addition method.
i)
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
ii)
iii)
Second polarogram
Place 10 cm3 of unknown solution, 5 cm3 of known stock solution [of method
(i)], 50 cm3 of 2M KCl and 2.5 cm3 of 0.2% gelatin solution in a volumetric
flask and dilute to the mark with distilled water and record the polarogram of
this solution in a polarographic cell after removing dissolved oxygen with
nitrogen. Determine its wave height and calculate the concentration of unknown
solution as described under Unit 8 (polarography).
9.4.3
In the application of the polarographic method of analysis to steel, ferric ion interferes
due to its reduction near zero potential in sodium tartrate supporting electrolyte.
Fe(III) has to be reduced to Fe(II) with hydrazinium chloride in a hydrochloric acid
medium so that Fe(II) is reduced at much negative potential of -1.4 V vs SCE which is
more negative than lead and copper.
Procedure: Dissolve accurately weighed 5.0 g of the steel in a mixture of 25 cm3 of
water and 25 cm3 of concentrated hydrochloric acid and heat gently. Add few drops of
standard potassium chlorate solution to dissolve carbides and boil the mixture until the
solution is clear. Cool and dilute to 50 ml with water in a volumetric flask. Pipette 2
ml of this solution into a polarographic cell and add 1.0 cm3 of 20% hydrazine
hydrochloric solution to reduce Fe(III) to Fe(II) ion, 1.0 cm3 of 0.2% methyl cellulose
to act as maximum suppressor and 5.5 cm3 of 2.0 M sodium formate solution. Keep
the cell in a nearly boiling water bath for 10 minutes in order to complete the
reduction. Cool and take the polarogram using SCE. The polarogram will have two
steps. The first one at E1/2 of - 0.25 V vs SCE is due to the reduction of cuprous to
copper metal. The second step at E1/2 of - 0.45 V vs SCE is due to lead. Use standard
addition method for determination. For this carry out a calibration by adding known
amounts of copper and lead ions to a solution of steel of low copper and lead content
and determine the increase in wave heights due to addition. Calculate the percentage
of copper and lead in the sample.
71
Electroanalytical
Methods-III
Analysis of steel and ferro-alloys for minor constituents (Cu, Ni, Co, Mn, Cr,
Mo, W, V, Ti, Sn, Pb, and Al).
ii)
iii)
Analysis of high purity zinc and of zinc alloys (Cu, Pb, Cd, Sn, Mn, Al).
iv)
v)
vi)
vii)
viii) Analysis of refined metallic tin and of tin base alloys (Cu, Bi, Pb, Cd, Zn, Fe).
ix)
x)
Analysis of refined metallic lead and of lead base alloys (Bi, Fe, Cu, Cd, Zn,
Sb).
xi)
xii)
xiii) Analysis of high purity zinc and zinc base alloys (Cu, Pb, Cd, Sn, Bi, Mn).
xiv) Analysis of pure strontium salts (Ba).
HO
HO
HO
OH
HO
-
-2e
Ascorbic acid
+ 2 H+
Dihydro ascorbic acid
O
Prepare a fresh stock solution of 50 cm3 of 0.2% ascorbic acid. Prepare 5 standard
solutions of ascorbic acid in volumetric flasks of 25 cm3. To each one add 0.5 cm3 of
0.5 M acetate buffer and different volumes of 0.2% ascorbic acid, 0, 200, 400, 600 and
800 dm3 . Dilute to the mark with distilled water. For each solution record
polarograms over the potential range -150 to + 200 mV vs Ag/AgCl/1M KCl reference
electrode.
Plot id vs c of ascorbic acid (calibration curve).
Standard addition methods
Squeeze an orange, grape fruit or lemon until about 10 cm3 of juice is obtained. Filter
the juice through a porous funnel (pore size about 1 mm).
Prepare four 25 cm3 volumetric flasks. Add to each 0.5 cm3 of 0.5M acetate buffer, 2.0
cm3 of the juice and standard addition of 0, 200, 400, and 600 dm3 of 0.2% ascorbic
72
acid. Dilute to mark with distilled water. Record polarograms under the same
conditions as in the calibration step. Draw the standard additions plot and determine
the concentration of ascorbic acid. Report the concentration of ascorbic acid (Vitamin
C) in the original sample (juice) in mol/l and also ppm.
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
SAQ 3
Complete the sentence by selecting the correct alternatives:
a)
...
...
...
...
b)
How can the ferric ion interfere in the polarographic analysis of steel and how is
its interference prevented?
...
...
...
...
9.5
APPLICATIONS OF VOLTAMMETRY
All these techniques can be applied quantitatively for the analysis of large variety of
samples (environmental samples, steels, clinical samples etc). The choice of a
particular technique will depend on the analyte's characteristics, expected
concentration, other constituents present and location of the sample.
Pulse polarography is better for analyzing a wide range of inorganic/organic analytes.
While in the case of stripping methods the analyte is to be preconcentrated at the
electrode surface. Further the concentration of the analyte in the sample, the accuracy
and precision required will decide the technique to be selected.
The analysis of a sample component is quite simple and any of the methods can be
used and from the linear relationship between the current and concentration, the
unknown concentration in the sample can be obtained. In case of samples containing
more than one analyte; if the components behave independently, the analysis will be a
simple addition of the respective individual separation voltammograms. However if
the id or ip is sufficient they can be determined independently as if they were only a
single component.
The amount of separation between these potentials will depend on the type of the
potential, technique used, concentration of the components. If the difference is less
than minimum separation and there is overlap between the voltammograms of the two
components, independent analysis is not possible and a simultaneous analysis method
is to be followed by taking the sample and simultaneous equations for the current at
two potential be formed and by solving these equations, the concentrations of both the
analytes can be obtained.
The analysis has been explained in detail in the numericals given in the terminal
questions.
73
Electroanalytical
Methods-III
1.
2.
ii)
iii)
The potentiostat allow to impose the potential scanning between the working
and reference electrodes while the current flowing through the circuit is
recorded between the working and auxiliary electrodes.
The computer CVA Trace analyzer from Metrohm Ltd. can be used as an
intergrated instrument with keyboard or a commercially available personal
computer interface to measuring system (with software):
i)
ii)
74
1.
Sample treatment: For this analysis the sample must be in a solution form. If
solid, it has to be brought into solution by dissolving in a suitable solvent.
Liquids or solids with low solubility are to be digested or extracted.
2.
3.
4.
Electrode cleaning.
5.
6.
Scanning/registration of voltammograms.
7.
8.
9.
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
SAQ 4
Give the schematic diagram of the basic instrument for voltammetry.
...
...
...
9.6
There are inorganic ions, metal complexes and a few organic compounds which
undergo electron transfer reactions without the making or breaking of covalent bonds.
The vast majority of electrochemical reactions involve an electron transfer step which
leads to a species which rapidly reacts with components of the medium via so called
coupled chemical reactions. One of the most useful aspects of CV is its applications to
the qualitative diagnosis of these homogeneous chemical reactions that are coupled to
the electrode surface provides the capability for generating a species during the
forward scan and then probing its fate with the reverse scan and subsequent cycles, all
in a matter of seconds or less.
In addition, the time scale of the experiment is adjustable over several order of
magnitude by changing the potential scan rate, enabling some assessment of the rates
of various reactions. There are several examples of the coupled chemical reactions,
however two are given below.
A cyclic voltammogram for the popular antibiotic chlor-amphenicol is illustrated in
Fig. 9.2. The scan was started in a negative direction from 0.0 V. Three peaks are
observed, peak A for the initial reduction, peak B for oxidation of a product of this
reduction and peak C for oxidation of a product resulting from the events accounting
for peak B. All three peaks or waves involve more than a simple electron transfer
reaction.
peak A
peak B
peak C
RNO 2 + 4e + 4 H + RNHOH + H 2 O
RNHOH RNO + 2H + + 2e
RNO + 2e + 2H + RNHOH
75
Electroanalytical
Methods-III
Fig. 9.2: Cyclic voltammogram of 3.3 mg/25 cm3 chloramphenicol in 0.1 M acetate
buffer, pH 4.62. Carbon paste electrode. Scan rate = 350 mV/s
Its oxidative CV on a carbon paste electrode is illustrated in Fig. 9.3. In this case the
scan is initiated in a positive direction from 0.0 volts. The initial two-electron
oxidation (peak A) generates a proton and an organic cation which is readily
hydrolyzed to benzoquinone and tyrosine.
OH
OH
H2N
COOH
H2N
2e + H
COOH
OH2
OH
O
+
O
Peak A
H2N
COOH
The tyrosine thus produced is subsequently oxidized at peak B (no product from peak
B is detected on the reverse scan).
76
OH
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
O
H
+ 1e
H2N
H2N
COOH
COOH
Coupling Products
Peak B
Fig. 9.3 Cyclic voltammogram of 5 mg/25 cm3 Lthyronine in 1 M H2 SO4. Carbon paste
electrode, scan rate = 200 mV/s
+ 2e + 2 H
O
Peak C
OH
77
Electroanalytical
Methods-III
OH
+ 2H+ + 2e
OH
Peak D
SAQ 5
What are Coupled chemical Reactions?
...
...
9.7
SUMMARY
In this unit we have discussed about the elements or compounds determined with the
help of polarography in different types of samples like food stuff, sea water, fuels etc.
We discussed the polarographic analysis of organic compounds. We studied the given
examples of the species determined with the help of amperometric titrations for
different titrations and electrodes. We discussed the different polarography
experiments using both the calibration curve method and standard addition method.
We discussed other industrial important determinations for traces or minor
constituents. Lastly we discussed about the application of cyclic voltammetry.
9.8
TERMINAL QUESTIONS
1.
2.
3.
4.
5.
9.9
ANSWERS
78
a)
The commonly used supporting electrolytes which are easily mixed with
organic solvents are various quaternary ammonium salts such as tetrabutyl
ammonium iodide.
b)
2.
3.
a)
b)
4.
Fig. 9.1
5.
There are inorganic ions, metal complexes and a few organic compounds which
undergo electron transfer reactions without the making or breaking of covalent
bonds. The vast majority of electrochemical reactions involve an electron
transfer step which leads to a species which rapidly reacts with components of
the medium via so called coupled chemical reactions.
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
Terminal Questions
1.
2.
Most of the organic compounds are insoluble in pure aqueous medium and also
in mercury to form amalgam. Therefore, the solvent in which the organic
compound and its electrode product is soluble is added to the supporting
electrolyte.
3.
4.
5.
Species determined
Ni2+
SO42-, MoO42-, F-
79
Electroanalytical
Methods-III
Further Reading
Websites
S.No.
Topic
An article in Resonance
on Polarography by the
eminent scientist
V. Lakshminarayanan
http://dspace.rri.res.in/bitstream/2289/856/1/2004
%20RES%209%20p51-61.pdf
2.
Anodic Stripping
voltammetry
http://www2.chemistry.msu.edu/courses/cem837/
Anodic%20Stripping%20Voltammetry.pdf
3.
Anodic Stripping
voltammetry, a very
detailed presentation
http://ocw.kfupm.edu.sa/user/CHEM54201/Anodi
c%20stripping%20good.pdf
4.
Cyclic Voltammetry
http://www.chemistry.nmsu.edu/studntres/chem43
5/Lab13/
5.
Cyclic Voltammetry
http://www.biol.paisley.ac.uk/marco/Enzyme_Ele
ctrode/Chapter1/Cyclic_Voltammetry1.
6.
Details of
http://faculty.uml.edu/david_ryan/84.514/Electroc
hemLecture11.pdf
polarography, pulse
polarography and cyclic
voltammetry
7.
Linear sweep
voltammetry
http://www.chemistry.adelaide.edu.au/external/so
c-rel/content/linsweep.htm
8.
Polarography
http://electrochem.cwru.edu/ed/encycl/art-p03polarography.htm
9.
Polarography
http://www.drhuang.com/science/chemistry/electr
ochemistry/polar.doc.htm#_Toc172448509
10.
Polarography
http://www.drhuang.com/science/chemistry/electr
ochemistry/polar.doc.htm#_Toc172448509
11.
Voltammetry
http://www.amelchem.com/download/items/volta
mmetry/manuals/eng/manual_eng.pdf
12.
Voltammetry
http://new.ametek.com/contentmanager/files/PAR/App%20Note%20E-4%20%20Electrochemical%20Analysis%20Techniques
1.pdf
1.
80
Web Sites/Books
Books
1.
2.
3.
Instrumental Analysis, Editors, H.H. Bauer, G.D. Christian and J.E.O Reilly,
2nd Edn, Allyn and Bacon, Inc., Boston (1991).
4.
5.
6.
7.
8.
9.
10.
11.
Applications of
Polarography,
Amperometric
Titrations and
Voltammetry
81