PART 23

VOLTAMMETRY

1
• In voltammetry, the indicator electrode is studied under polarized
conditions.

• Voltammetry is a method of obtaining information about the analyte by

measuring the current formed as a function of the applied potential.

• To ensure full polarization, the working electrodes used in voltammetry

are microelectrodes with a very small surface area.

• The voltametry is based on the measurement of the current generated

in an electrochemical cell under full concentration polarization
conditions.

2
• However, potentiometric measurements are made under conditions
where the current approaches zero and there is no polarization.

• In addition, various measures are taken to eliminate or minimize

concentration polarization in electrogravimetry and coulometry.

• In electrogravimetry and coulometry, almost all of the analyte is

converted to another state, while in voltammetry, a minimum amount is
consumed.

• Voltammetry is used for;

(1) investigation of various oxidation and reduction phenomena

(2) investigation of adsorption phenomena on surfaces

(3) elucidation of electron transfer mechanisms

3
A. EXCTATION SIGNALS IN VOLTAMMETRY

• In voltammetry, the current in the cell is measured while the voltage of the
working (indicator) electrode is systematically changed (!).

• In voltammetric applications, very different time-varying voltages can be

applied to a working electrode.

• These time-voltage functions are called excitation signals.

• The simplest of the excitation signals is linear sweep, in which the

potential of the working electrode changes linearly with time.

• Pulsed waveforms and triangular waveforms are other commonly used

excitation signals.

4
Voltage versus time excitation signals used in voltammetry

5
B. VOLTAMMETRIC INSTRUMENTATION

• The classical voltammetric application signal is linear sweep. Here, the

potential applied to the cell is increased as a function of time.

• At this time, the current of μA in the cell as a function of the applied

potential is recorded (E = IR).

• In the linear sweep method, the potential of the working electrode is

generally increased or decreased at a rate of 2-5 mV/s.

• The current generated as a function of the potential applied to the working

electrode is plotted, which is called a voltammogram.

6
B.1. Voltammetric Instrumentation

• The voltammetric cell consists of three electrodes immersed in a solution

containing the analyte and an excess of the electrolyte called the supporting
electrolyte.

• One of these electrodes is the microelectrode or working electrode, whose

potential changes linearly with time.

• The dimensions of this electrode are small to increase its tendency to polarize.

• The second is the reference electrode whose potential remains constant

throughout the experiment, and the potential between it and the working
electrode is controlled.

• The third is the counter electrode, which is in the form of a Pt wire or Hg

pool, which allows the current to be transferred from the solution to the
microelectrode.
7
 Potantiometry
Measures the current
that develops against
the changed potential

Pt wire or
[Microelectrode]
Hg pool

Controls the
potential of Resistance > 1011 Ω
the working Current is zero
electrode

A manual potentiostat for voltammetry

8
• The signal source is a variable power source consisting of a battery
connected in series with a variable resistor R.

• The voltammogram is obtained by recording the current that occurs as a

function of the potential between the working electrode and the reference
electrode.

• This is achieved by the excitation signal generated by moving the slider C

between A and B at a constant speed.

• During the potential sweep, current and potential values are recorded at
equal time intervals.

• However, in modern voltammetric instruments all this is done

automatically and in a pre-programmed manner.
9
B.2. Voltammetric Electrodes

• Electrodes used in voltammetry are a variety of shapes and sizes.

1- It may be a small conductive disk attached to a rod made of an inert

material such as Teflon with a connecting wire inserted (a).

• This conductive disc can be a metal such as Pt, Au; a semiconductor

such as pyrolytic graphite, SnO2 or a metal covered with a mercury film.

2- Mercury electrodes (especially at large negative potentials) are widely

used due to hydrogen overvoltage (b, c, d).

• The preparation of a fresh metallic surface with a new drop that is easily
created each time is an important advantage of them.

10
Conductive disc
Pt, Au,
pyrolytic graphite,
SnO2

It can be Hg
film on
surface
Disc electrode Hanging mercury drop electrode Dropping mercury electrode
(HMDE) (DME)

Some common types of commercial voltammetric electrodes

11
• Also, amalgam-forming reduction of many metal ions on the surface of the
mercury electrode simplifies the chemistry of this phenomenon.

• The simplest of the mercury electrodes is prepared by coating the surface

of the disc electrode with a mercury film.

• Hg electrodes are prepared as (b) hanging mercury drop electrode, (c)

dropping mercury electrode, and (d) stagnant mercury drop electrode.

• Of these, the stagnant mercury drop electrode can be used as both a

hanging mercury and a dropping mercury electrode.

• In this SMDE, the polyurethane-tipped plug is opened and closed for the
desired time (50 - 200 ms) with a signal from the control unit.

12
Stagnant
mercury
drop
electrode (kontrol edilir tıkaç)

13
B.3. Voltammograms

• The linear sweep votamogram of an event in which an A species is

reduced to a P product on a mercury film microelectrode is as follows.

Positive
currents are
cathodic

Assumption:
[A] = 10-4 M i s = k cA
[P] = 0.0 M
[KCl] = 0.1 M

Negative E1/2 ≈ E0
currents are
anodic The electrode is
connected to the
negative terminal of the
power supply
14
• On voltammograms, positive (cathodic) currents are marked in the upper
half and negative (anodic) currents in the lower half.

• For historical reasons, more negative (less positive) values are written as
you go from left to right on the potential axis.

• The curve in the sigmoidal ( ʃ ) shape in the linear sweep voltammogram is

called the voltammetric wave.

• The current after the sharp increase is called the limiting current (is).
Because this current is determined by the rate of transport to the
surface of the analyte in the mass transfer event.

• Limiting currents are generally proportional to the analyte concentration.

is = k cA
15
• The limiting current plateau is an example of full concentration
polarization.

• Because, the analyte concentration on the electrode surface drops to zero

and, at this point, the mass transfer rate has reached its maximum value.

• The potential when the current value is equal to half of the limiting
current (iS/2) is called the half-wave potential (E1/2).

• The half-wave potential is closely related to the standard potential of

the half-reaction and is used to identify components in solution.

• Linear-scan voltammetry applications; (a) hydrodynamic voltammetry,

(b) polarography, and (c) cyclic voltammetry.

• However, triangular excitation signal is used in cyclic voltammetry.

16
B.4. Hydrodynamic Voltammetry

• Here, it is essential to obtain fast and repeatable limiting currents.

• Linear scan voltammetry in which the solution or electrode is in constant

motion is called hydrodynamic voltammetry.

• In hydrodynamic voltammetry, either the solution is stirred vigorously while

the electrode is stationary, or the electrode is rotated at a constant speed.

• Another way is to run the analyte solution through a tube in which the
electrode is placed (detector).

• By adding an excessive amount of supporting electrolyte to the medium,

the migration effect is minimized (diffusion controlled!).

17
 Concentration : cA

A + ne- P
In hydrodynamic voltammetry,
flow types and reactive Concentration : cA

concentrations near the working

electrode versus applied X, Y
and Z potentials

18
a) Anodic and Mixed (Anodic-Cathodic) Voltammograms

• Both anodic and cathodic waves are frequently encountered in

voltammetry.

• For example, the voltammogram given below shows waves of both

oxidation and reduction of the iron ion.

• Curve A is an example of an anodic wave. Fe2+ Fe3+ + e-

• As the potential is made negative, there is a decrease in anodic current

and when the oxidation of iron(II) stops, the current becomes zero (≈ - 0.2
V).

• The fact that the half-wave potentials of the C and A waves are the same
indicates that the reduction / oxidation of iron is reversible.
19
 Limiting current

anodic/cathodic wave
current

- 0.2 V

anodic wave
current

Limiting
current
0.1 V

Voltammetric behavior of iron(II) and iron(III) in citrate medium.

(three separate voltammograms)

20
• Curve B belongs to a mixture containing equimolar iron(II) and iron(III).

• The part below the zero streamline belongs to the oxidation of iron(II), and
the reaction ends when the applied potential is E1/2.

• The top of the curve corresponds to the reduction (cathode) of iron(III).

EFFECT OF OXYGEN ON VOLTAMOGRAM

• Dissolved oxygen is easily reduced at various electrodes.

• For example, two different cathodic waves of oxygen are observed in an

aqueous solution saturated with air.

• The first of these belongs to the reduction of oxygen to hydrogen peroxide,

and the second to the reduction of hydrogen peroxide to water.

21
 Voltammogram for the
reduction of oxygen in an
air-saturated 0.1 M KCl
Total : solution.

H2O2 + 2H+ + 2e- 2H2O

The lower curve is for 0.1
M KCl, where oxygen is
removed by passing
nitrogen gas through the
solution.
The cathodic wave around
-2.0 V belongs to the H2
output.

22
b) Applications of Hydrodynamic Voltammetry

10- Determination of chemical species from chromatographic columns or

flow injection devices (voltametric detector),

20- Routine determination of oxygen and biochemically important species

such as glucose, lactose, ethanol and sucrose (amperometric sensor)

30- As an indicator in determining the end point in coulometric and

volumetric titrations (amperometric titration)

40- It is used in basic studies about electrochemical events.

23
 10- Voltammetric detector

A voltammetric system for

the determination of
electroactive species
eliminating from a column.

The cell volume is 1 µL.

insulating
layer
The working electrode
potential is set to the limiting
current value of the analyte
and the limiting current value
is measured.

24
 20 - Amperometric sensors

• The technique based on measuring the limiting current at an applied

constant potential and relating this current to the concentration is called
amperometry.

• The determination of dissolved oxygen in various aqueous media is

extremely important for biomedical, medical, industrial and environmental
research.

• The Clark oxygen sensor used in the determination of O2 in blood and

other body fluids works on this basis.

• When this sensor is immersed in a flowing or stirred analyte solution, the

amount of O2 passing through the membrane to the disk cathode is
proportional to the concentration.
25
(constant) Clark voltammetric oxygen sensor

Cathode reaction:

O2 + 4H+ + 4e- 2H2O

Anode reaction:

Ag(s) + Cl- AgCl(s) + e-

Equilibrium time of the sensor : 10 -

20 s

is = k cA

26
• The glucose sensor used in the routine determination of glucose in
blood serum samples is also a voltammetric oxygen sensor.

• The membrane is a three-layered polycarbonate film (1) that is

permeable to glucose, not to protein and other blood components.

• The middle layer is the immobilized enzyme (2) (glucose oxidase),

• And the inner layer is a cellulose acetate (3) membrane that allows small
molecules such as hydrogen peroxide.

(middle layer)

(current is proportional to concentration)

27
 30 - Amperometric titrations (indicator)

• The equivalence point of this reaction can be

determined if at least one of the reagent or
product is reduced / oxidized.

• Here, the resulting current is measured against

the titrant volume (time in the coulometric
process) by keeping the potential in the limiting
current region constant.

• In the amperometric titration curves rigth side,

(a) the analyte is reduced, (b) the titrant is
reduced, and (c) both the analyte and titrant are
reduced.

28
B.5. Polarography

• Linear scan voltammetry in which the medium is not stirred and a

dropping mercury electrode is used is called polarography.

• Since diffusion is the only mode of mass transfer, in polarography, the

currents are controlled only by diffusion, not convection.

• Therefore, polarographic limiting currents are called diffusion currents

(id) (10-1000 times smaller than hydrodynamic limiting currents).

• The diffusion current is read from the peak of the voltammetric waves
generated against the changed potential in each drop.

• That is, the Hg drop is formed and the current is measured at the last
moment of its life.

29
 Step hight
Potantial

Sampling
time

Drop time

Time

• First, the potential is increased by 4 mV. Then the mercury drop is formed.

• The limiting current is measured during the last 17 ms of this Hg drop life.

• But, the diffusion current is the difference between the limiting current and
the residual currents.
30
 One peak per
drop (wave)
Cd2+ + 2e- + Hg Cd(Hg)

(id)max = k cA

2H+ + 2e- H2

(A) 5x10-4 M Cd2+ in 1 M HCl

(B) Polarograms of 1 M HCl (recorded after
quenching of current fluctuations)
31
a) Residual Currents

• One of the reasons for the formation of this current is traces of oxygen and
impurities in the solution (supporting electrolyte, water).

• The other reason is that the mercury droplets are loaded with different
charges compared to the solution and these charges (e-) are separated
when the drop falls.

b) Effect of pH on Polarograms

• Most electrode reactions related with organic materials involve hydrogen

ions.

R + nH+ + ne- RHn

• Therefore, good buffering should be done in organic polarography.

32
c) Advantages and disadvantages of dropping mercury electrode

• This electrode exhibits overvoltage to the reduction of the hydrogen ion.

• A new metal surface is created with each drop. Therefore, the electrode
behaves independently of the previous states.

• It is possible to obtain instantly repeatable average currents at any

potential.

• The biggest disadvantage; since mercury is easily oxidized, its use as an

anode is limited (limit: + 0.4 V).

• Residual currents limit the sensitivity of the method to 10-5 M.

33
34
C. PULSE POLAROGRAPHIC AND VOLTAMETRIC METHODS

• Linear scan polarography method has lost its importance because of slow,
difficult to use and very low detection limits.

• The emergence of spectroscopic techniques is another reason.

• In addition, the development of the following types of stagnant mercury

drop electrodes has brought pulse techniques to the fore.

• Of these techniques, differential pulse polarography and square wave

polarography are the two most important.

• In applications, if electrodes other than mercury are used, it is called

differential pulse voltammetry and square wave voltammetry.

35
Cross section of a
stagnant mercury
drop electrode

(kontrol edilir tıkaç)

36
C.1. Differential Pulse Polarography (Voltammetry)
• The two most common excitation signals used in differential pulse
polarography devices are shown below.
• The first of these is used in analog devices, and the second is generally
used in digital applications.

Puls
period
Puls
period

37
ØIn these excitation signals, a 50 mV pulse is applied during the last 50 ms
of the mercury drop life.

• If a mercury electrode is used, the drop is mechanically dropped at a given

moment to coherence the drop and the pulse.

ØIn this process, two current measurements are made. One is just before
the pulse (S1) and the other is just before the end of the pulse (S2).

• The difference in current per pulse (Δi = iS2 – iS1) is recorded as a

function of linearly increasing potential.

• The resulting differential curve is in the form of a peak and the peak
height is proportional to the concentration.

38
• In a reversible reaction, the peak potential (Epeak) is approximately equal to
the standard potential (E0) of the half-reaction.

• Here, Δi = iS2 – iS1

Epeak = E0 • The peak potential is closely related

to the half-wave potential.

• These derivative polarograms

provide qualitative identification
of the analyte based on its peak
potential (Epeak).
Voltammogram for a differential-pulse

39
• It is seen below that differential pulse polarography significantly increases
the sensitivity of the linear-scan polarographic method.

Solution containing Solution containing

0.36 ppm antibiotics 180 ppm antibiotics

40
• That is, the detection limit of differential pulse voltammetry (polarography)
is 100 - 1000 times lower (!) and is between 10-7 - 10-8 M.

ØThis high sensitivity is due to an increase in faradaic current and a

decrease in non-faradaic charging current.

ØWhen the potential is suddenly increased by 50 mV, there is a current

increase (Nernst) that will reduce the analyte concentration around the
electrode to the required level.

ØWhen the equilibrium concentration required for this potential is reached,

the current decrease a level that meets the diffusion (diffusion controlled).

• In this case, the total current is several times greater than the diffusion
current in classical voltammetry (polarography).

41
ØAlso, when the potential pulse is applied, the charge on the drop
increases and a non-faradaic current (charging current) is generated.

ØThis current decreases exponentially with time and approaches zero

towards the end of the drop life, where the surface area changes very
little.

• Therefore, by measuring the current at this moment, the non-faradaic

current is minimized and the signal to noise ratio increases.

ØAs a result, an increase in faradaic current and a decrease in loading

current significantly increase the sensitivity of the method.

• As the drop falls (or under hydrodynamic conditions), the solution at the tip
of the electrode becomes homogeneous again with respect to the analyte.

42
C.2. Square-Wave Polarography (Voltammetry)

• Square wave polarography is a pulse voltammetry technique that has the

advantage of being extremely fast (1 V/s) and sensitive.

• Besides the hanging mercury drop, other types of electrodes are also
used.

• Scan with the hanging mercury drop electrode is performed during the last
few milliseconds of a drop's life with the charging current constant.

• In square wave voltammetry, the applied pulses are superimposed on the

stepped signal to obtain the excitation signal.

• For a reversible reduction reaction, the size of a pulse is great enough so

that oxidation of the product formed on the forward pulse occurs during the
reverse pulse.
43
 Stepped signal

τ ≈ 10 ms Uyarma sinyali

ΔES = 10 mV
forward

reverse
Puls (50 mV) application

ESW = 25 mV
2ESW = 50 mV The entire scan is done towards
the end of the hanging mercury
drop.

Generation of a square-wave voltammetry excitation signal. The staircase signal in (a)

is added to the pulse train in (b) to give the square-wave excitation signal in (c). The
current response, Di, is equal to the current at potential 1 minus that at potential 2. 44
 Epik = E1/2
Δi α cA

i1 : forward current-cathodic
i2 : reverse current-anodic

In fact, forward
and reverse
currents are
measured near
the half-wave
potential.

Variation of current against the excitation signal for a reversible reaction

45
• In the figure, the forward pulse generates the cathodic current (i1) and the
reverse pulse creates an anodic current (i2).

• Usually, the difference of these currents (Δi) is plotted to obtain

voltammograms, which is directly proportional to the concentration.

• The peak potential in the resulting graph also corresponds to the half-
wave potential (Epeak = E1/2).

• The detection limit of square-wave voltammetry, which can be measured

extremely fast, is between 10-7 and 10-8 M.

46
C.3. Applications of Puls Voltammetry

ØIn quantitative applications, calibration curves are often used, in which

the peak heights(!) are plotted against the analyte concentration.

• Instead, sometimes standard addition methods can be applied.

a) Inorganic applications

• Various metals and reducible anions are easily analyzed. Most of the
time, the selectivity of the electrode is increased with the supporting
electrolyte.

b) Organic polarographic analysis

• Many organic functional groups that can be reduced are analyzed.

47
D. CYCLIC VOLTAMMETRY

• Cyclic voltammetry (CV) is an important and widely used

electroanalytical technique. Its use for quantitative purposes is
infrequent.

ØIt is used a lot in the study of oxidation / reduction reactions and in the
observation of reaction intermediates.

• It is also widely used in capturing the post-formation reactions of the

products formed at the electrodes.

ØIn the cyclic voltammetry method, the current is measured while the
applied potential is first scanned in one direction and then in the opposite
direction.
48
 Swictching
potantial
50 mV/s

Rev
sca

ers
rd
20 second

es
wa

can
For Scan rate = 50 mV/s
Swictching
potantial

Cyclic voltammetric excitation signal

49
• In this triangular waveform; potentials where the scan reverses are
called switching potentials (- 0.15 V and + 0.8 V).

These return potentials are;

• It is selected to allow observing the diffusion-controlled oxidation or

reduction of one or more species.

• In general, scanning in the direction of more negative potentials is called

forward scan and in the other direction is called reverse scan.

• The scan time can range from 1 ms to 100 s or longer.

• The CV experiment is performed in a stationary solution with a

stationary electrode.

50
 reverse

- 0,15 V

+ 0,8 V
forward

(a) Potential versus time waveform.

(b) Cyclic voltammogram for a solution that
Concentration Current drop with
reaches
Nernst
diffusion layer
formation
is 6.0 mM in K3Fe(CN)6 and 1.0 M in
equilibrium
KNO3.
Fe(CN)63- + e- Fe(CN)64-

Anodic
current of
O2 output

51
• The very small anodic current at point A (at an initial voltage of +0.8 V) is
related to the oxidation of water to form O2.

• Since it is not a reducible or oxidisable type, the current from +0.7 V to

+0.4 V is zero.

• When the potential gets positive values less than +0.4 V, the cathodic
current starts to develop, which is related to the reduction of ferricyanide
(B). Fe(CN)63- + e- Fe(CN)64-

• While the current increases rapidly between B and D, the Fe(CN)63-

concentration on the surface decreases gradually and reaches the
equilibrium determined by the Nernst equation.

• The peak current can be thought of as the sum of two separate

components. These;

52
 1- The initial current increase required for the surface concentration of the
reactant to reach the equilibrium value determined by the Nernst equation.

2- Normal diffusion is controlled current.

• The initial current drops rapidly after the maximum (from D to F),
because the diffusion layer thickens rapidly from the electrode surface.

• At point F (-0.15 V) the scan reverses.

• But, the current is still cathodic as the electrode potential is still negative
enough for Fe(CN)63- reduction.

• As the potential shifts towards the positive, it reaches the region where
Fe(CN)63- is not reduced and the current becomes zero. Then the anodic
current starts.

53
• Important parameters in cyclic voltammogram; cathodic and anodic peak
potential (Epc, Epa) is the cathodic and anodic peak current (ipc, ipa).

• The difference of peak potentials (ΔEp) for a reversible electrode

reaction is ΔEp = I Epa – Epc I = 0.0592/n

• If ΔEp is larger, the reaction is irreversible because the electron transfer

kinetics is very slow.

• Cyclic voltammetry is widely used in the identification of various chemicals

in organic and inorganic chemistry.

• In this method, Pt electrodes are often used. Hg film electrodes can be

preferred in the negative potential region (?).

54
Example: Interpret the alternating voltammogram of the parathion
insecticide given below in sodium acetate/acetic acid buffer (pH=5) and
50% ethanol medium.

Answer: Here the switching potentials are – 1.2 and + 0.3 V. But the first
scan was started from 0.0 V.

1- The cathodic peak in A is related to the reduction of the parathion to the

hydroxylamine derivative.

ϕ-NO2 + 4e- + 4H+ ϕ-NHOH + H2O

55
 ϕ-NO2 + 4e- + 4H+ ϕ-NHOH + H2O

ϕ-NO + 2H+ + 2e- ϕ-NHOH

ϕ-NHOH ϕ-NO + 2H+ + 2e-

Cyclic voltammogram of the insecticide parathion in 0.5 M pH 5 sodium acetate buffer

in 50% ethanol. Hanging mercury drop electrode. Scan rate: 200 m V/s.
56
2- The anodic peak at B is related to the oxidation of the hydroxyl amine to
a nitroso derivative during reverse scanning.

ϕ-NHOH ϕ-NO + 2H+ + 2e-

3- The cathodic peak at C results from the reduction of the nitroso

compound back to the hydroxyl amine derivative.

ϕ-NO + 2H+ + 2e- ϕ-NHOH

4- With the cyclic voltammograms taken from the pure solutions of these
compounds, it can be confirmed that the B and C peaks belong to these
compounds.

57
E. STRIPPING METHODS

• Generally, in all stripping methods, the analyte is first deposited on an

electrode (electrolysis) in a stirred(!) solution.

• After the highly sensitively measured deposition time, the electrolysis

is interrupted and the deposited analyte is determined by a voltammetric
method.

• In this second step of the analysis, the analyte is back-dissolved or

stripped from the electrode surface; therefore the process is called the
stripping method.

• In anodic stripping methods, the working electrode acts as the cathode

in the deposition step and as the anode in the stripping process.
58
• In cathodic stripping methods, the working electrode acts as the anode
in the deposition step and as the cathode in the stripping process.

• However, it should be noted that only a small fraction of the analyte is

deposited on the electrode surface in the electrodeposition step.

• Quantitative results depend on the electrode potential and size, the

deposition time, stirring speed of the sample and calibration solutions.

• For example, the potential excitation schedule followed for the

determination of Cd and Cu in aqueous solution by an anodic stripping
method is given below.

• First, by applying a constant potential of -1.0 V (the solution is stirred),

both ions are deposited on the electrode in a few minutes.

59
 (a) Excitation signal for
stripping determination
of Cd2+ and Cu2+

(b) Anodic stripping

voltammogram.

(or time)

60
• To complete the analysis, the potential is reduced to less negative values by
applying the linear scan voltammetric method.

• At this time, the current in the cell is recorded as a function of time or

potential to obtain a working (stripping) voltammogram.

• At a potential more negative than -0.6 V, cadmium begins to oxidize and a

sharp increase in current is observed.

• When all the accumulated cadmium is consumed, the current drops to its initial
value.

• Cu begins to oxidize when the potential drops to about -0.1 V.

• The heights of these peaks are proportional to the masses of the deposited
metals, and calibration with standard solutions of cations is important.

61
E.1. Electrodeposition Step

• To detect a metal ion by anodic stripping, a fresh hanging mercury drop

(HMDE) is first formed (sometimes a mercury film).

• Next, a potential 10-20 mV more negative than the half-wave potential

value of the respective ion is applied by stirring the solution.

• It is continued to accumulate on the electrode for a certain period of time,

carefully measured 1-30 minutes (time is very important!).

E.2. Voltammetric Completion of the Analysis

• The analyte collected at the electrode can be determined by any of the

voltammetric methods. Do not stirring at this time!.

62
• For stripping, the potential is decreased (less towards the negative) from
the initial cathodic value at a constant and linear rate.

• The anodic current generated at this time is recorded as a function of the

applied potential.

• The analysis is interpreted by comparing the obtained curve with the

calibration graphs made with the standard solutions of the relevant
analyte.

• For example; in the determination of halogens, it can be first deposited

as Hg(II) salt on the mercury anode and then cathodically stripped.

• The differential pulse anodic stripping polarogram for a mixture

containing cations at 25 ppb concentrations is given below.

63
 Δi = iS2 – iS1

Differential pulse anodic stripping voltammograms of solution containing 25

ppb Zn, Cd, Pb and Cu
64
E.3. Adsorption Stripping Methods

• In the method, first, enough analyte is accumulated by immersing the

electrode (HMDE) in a stirred analyte solution for a few minutes.

• The accumulation of the analyte occurs by physical adsorption.

• The adsorption process is carried out by operating at the potential at which

the charging current of the electrode is zero (for mercury - 0.4 V).

• Then, the deposited material is determined by linear scanning or pulsed

voltammetric measurements without stirring the solution.

• With this method, many organic molecules of clinical and pharmaceutical

importance can be determined sensitively (such as 10-10 - 10-11 M) in a
short time.

65
 QUESTIONS AND PROBLEMS

23-1 23-2 23-3 23-4 23-5 23-8

THIS PRESENTATION HAS BEEN PREPARED FROM THE

FOLLOWING TEXTBOOK

SKOOG / WEST HOLLER/CROUCH

9th Edition

66
1) What does the excitation signal mean? Specify the excitation signals you know used in voltammetry and
explain each of them with a figure.

2) What do you understand by linear scanning voltammetry? How does the excitation signal used here
change? Draw a diagram of a manual potentiostat used in voltammetric measurement and indicate its main
parts and their functions on the figure.

3) Draw a diagram of a controlled-potential electrogravimetry (electrolysis) device or a manual potentiostat

used in voltammetric measurement, and indicate the basic parts and their functions on the figure. Briefly
explain the working principle of the methods by specifying the similarities and differences in the application
of both methods. (Part 22+23)

4) In linear scanning voltammetry, plot the voltammogram of a reduction event in the form of A + e P to
show the limiting current and half-wave potential. Describe how this voltammogram is used in a quantitative
analysis, and write down the main correlation used.

5) Briefly explain hydrodynamic voltammetry. Write down the application areas of hydrodynamic
voltammetry. Explain the working principle of the voltammetic detector system by drawing a figure.

6) Briefly explain hydrodynamic voltammetry. Write down the application areas of hydrodynamic
voltammetry. Explain the working principle of the Clark oxygen sensor by drawing what you know about the
amperometric sensor.
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7) Briefly explain hydrodynamic voltammetry. Write down what you know about amperometric titration,
which is one of the application areas of hydrodynamic voltammetry. Explain by drawing typical
amperometric titration curves.

8) Explain the basic principle of voltammetry and state how polarography is a voltammetric application.
Draw a simple polarographic voltammogram. Show the changes in current depending on the applied
potential and explain the reasons for these changes.

9) Explain the basic principle of the "differential pulse voltammetry-polarography" method, one of the
pulse voltammetric and polarographic methods, and write what you know about excitation signals and
voltammograms.

10) Explain the basic principle of the "square wave voltammetry-polarography" method, which is one of
the pulse voltammetric and polarographic methods, and write what you know about excitation signals and
voltammograms.

11) What is the basic working principle of cyclic voltammetry? Draw the excitation signal and explain by
considering certain points on this signal.

12) Write down the basic principle of stripping methods. What is understood by the anodic stripping and
cathodic stripping method?

13) Briefly explain the basic principle of adsorption stripping methods and the way they are applied.
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