28/03/2017

KENYATTA UNIVERSITY
SCHOOL OF PURE AND APPLIED SCIENCES
DEPARTMENT OF CHEMISTRY

For DSVOL

SCH 401 ELECTROCHEMISTRY

Series -3 (Applications: Batteries, Polarography and Voltammetry)

Dr. Eric Masika

Physical Chemistry and Nanotechnology
Office: Biochemistry Room 31 1

Introduction to Batteries
Batteries consist of two or more voltaic cells that are
connected in series to provide a steady dc voltage at the
batterys output terminals.
The voltage is produced by a chemical reaction inside
the cell. Electrodes are immersed in an electrolyte,
which forces the electric charge to separate in the form
of ions and free electrons.
REDOX Reaction
Oxidation, the loss of electrons, occurs at the anode.
Reduction, the gain of electrons, occurs at the
cathode.
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Characteristics of Batteries:
Practical applications of Galvanic cells is their use in batteries. In
multicell batteries like those in automobiles, the individual
galvanic cells are linked in series with the anode of each cell
connected to the cathode of the adjacent cell.

The voltage provided by the battery is the sum of the individual

cell voltages.

Features in a battery largely depend on the application. Though a

commercially successful battery should be:
Compact
Lightweight
Inexpensive!
Provides source of power for relatively long periods of time.

.
3

Common Types of Commercial Batteries:

Lead storage battery

Dry-cell Batteries

Nickel-Cadmium Batteries
e-
Nickel-Metal Hydride Batteries M M e-

Lithium and Lithium-Ion Batteries M+

M+
electrolyte
(Fuel Cell)
Anode Oxidation Reaction (-)
M M+ + 1e-

Cathode Reduction Reaction (+)

M+ + 1e- M 4
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Lead storage battery

Most familiar of all galvanic cells because it has been used as a
reliable source of power for starting automobiles for nearly a
century. A typical 12 V consist of six cells connected in series,
each cell providing a potential of about 2 V. The cell design is
illustrated below:

Lead storage battery (cont.):

The anode, a series of lead grids packed with a spongy lead.
The cathode, a second series of grids packed with lead dioxide,
dip into electrolyte; an aqueous solution of sulphuric acid (38%
by weight).
Discharging process
Anode:
Pb(s) + HSO4- (aq) PbSO4(s) + H+(aq) + 2e- E= 0.296 V

Cathode:
PbO2(s) + 3H+(aq) + HSO4- (aq) (aq) PbSO4(s) + H2O(l) E= 1.628 V
Overall:
Pb(s) + PbO2(s) + 3H+(aq) + 2HSO4-(aq)PbSO4(s) + H2O(l) E= 1.924 V
Note that the cell does not need to have separate anode and
cathode compartments because the oxidising and reducing agents
are both solids (Pb and PbO2 )that are kept from coming in
contact by the presence of insulating spacers between the grids.
6
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Schematic of discharging process Lead battery:

Connection to an electrical load allows the electrons to flow from

negative to positive terminals. This reduces the charge and
consequently the voltage at the electrodes.
Electrodes become coated with PbSO4 on discharging process. 7

Schematic of Charging process Lead battery:

Connection to an electrical power source forces electrons to flow from

positive to negative terminal. This in turn increase the charge and the
voltage at the electrodes.
The PbSO4 coating is removed upon charging and the acid electrolyte
becomes stronger. 8
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Voltage vs Electrolyte concentration Lead battery:

ln Q
9

Dry-cell Batteries:
Consists of a zinc can, which serves as the anode and an inert graphite
rod surrounded by a paste of solid Manganese dioxide and carbon
black, which functions as a cathode as illustrated in the figure below.

Typical NH4Cl/ZnCl2 Typical Alkaline cell

dry cell
10
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Dry-cell Batteries-(cont.):
Note that surrounding the MnO2-containing paste is the electrolyte, a
moist paste of ammonium chloride and zinc chloride in starch.
Simplified form of electrode reactions:
Anode:
Zn(s) Zn2+ (aq) + 2e-
Cathode:
2MnO2(s) + 2NH+(aq) + 2e- Mn2O3 +2NH3(aq)+ H2O(l)

Advantages of alkaline dry cells;

Cell has longer life because Zn corrodes more slowly.

Produces more power and a more stable current and voltage

because of the efficient ion transport in the alkaline electrolyte.
With the voltage of alkaline cell approximately 1.5 V.

11

Nickel-Cadmium Batteries
They are often referred to as ni-cad, used in calculators and
portable tools because unlike most dry cells, they are rechargeable.
The anode is cadmium metal and the cathode is nickel (III) compound
(NiO(OH) supported on nickel metal. The electrode reactions are:

Anode:
Cd(s) + 2OH-(aq) Cd(OH)2(s) +2e-

Cathode:
NiO(OH)(s) + H2O + 2e- Ni(OH)2(s) + OH-(aq) 12
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Nickel-Cadmium Batteries (cont.)

Ni-cad batteries can be recharged hundreds of times because the solid
products of the electrode reactions adhere to the surface of the
electrodes.

Main advantages:
Operational within a wide range of temperature (up to 70 C for
Philips Bodine).
Completely sealed construction, maintenance free and can be
mounted in any orientation.
Long storage life and long service, can be stored in a fully
discharged condition without deterioration with over 500
charge/discharge cycles.
Ability to withstand over-charge and over-discharge.

13

Nickel-Metal hydride Batteries

Because Cadmium is an expensive, toxic, heavy metal; ni-cad has
been replaced in many applications by lighter, more environmentally
friendly nickel-metal hydride or NiMH, batteries. The anode is a
special metal alloy such as LaNi5 that is capable of absorbing and
releasing large amounts of hydrogen at ordinary temperatures.
Involved reactions are as follows:
Anode:
MHab(s) + OH-(aq) M(s) + H2O(l) +2e-
Cathode:
NiO(OH)(s) + H2O + 2e- Ni(OH)2(s) + OH-(aq)
Overall
MHab(s) + NiO(OH)(s) M(s) + Ni(OH)2(s

Where M represents the hydrogen-absorbing metal alloy and Hab

denotes the absorbed hydrogen.
Some of the kinetic energy which would be dissipated as heat, in
these systems, converted to electrical energy. 14
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Nickel-Metal hydride Batteries (cont.)

Main advantages:
Variety of schemes to state-of-charge has been suggested

Minimal memory/voltage depression

The electrodes are economical and rugged exhibiting high-rate

performance, long cycle life and good capacity.

Designed so that the oxygen recombination cycle is capable of

recombining gases during overcharge under normal operating
conditions.

15

Lithium and Lithium-Ion Batteries:

They are more popular for portable electronic products than the
previous batteries because, they are light weight and high voltage
up to about 3.0 V. For example only 6.94 g is needed to provide 1
mole of electrons.
Anode: Lithium batteries use Li metal anode and electrolyte
consisting of Lithium salt such as LiClO4, in an organic solvent.
Cathode: Most Lithium batteries have manganese dioxide
cathode, which can absorb a variable number of Li+ into its solid-
state structure.
Electrode Reactions involve oxidation of Lithium at the anode
and reduction of MnO2 at the cathode.
Anode:
xLi(s) xLi+(aq) + xe-

Cathode:
MnO2(s) + xLi+(aq) + xe- LixMnO2(s) 16
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Lithium and Lithium-Ion Batteries:

The main distinction between a lithium and Lithium ion, lies in
the nature of the anode;
Lithium battery uses a lithium metal anode
Lithium-ion uses a graphite anode that has Lithium atoms
inserted between the layers of carbon atoms, (LixC6). Usually
the cathode in Lithium-ion battery is CoO2.

17

Lithium and Lithium-Ion Batteries (cont.):

Lithium-ion batteries are used in cell phones, laptops, digital
cameras, power tools and Tesla motors. Recent concerns about the
safety in plug-in electric are being addressed by development of
alternative electrodes such as Lithium titanate ( Li2TiO3), Lithium
iron phosphate (LiFePO4) which have greater thermal stability
than LixC6 and LiCoO2. While Lithium battery are largely used in
calculators, watches and other small consumer products.

Apples lithium-ion batteries

iWatch!

18
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Lithium and Lithium-Ion Batteries (cont.):

Advantages:
High energy density - potential for yet higher capacities.

Does not need prolonged priming when new. One regular

charge is all that's needed.

Relatively low self-discharge - self-discharge is less than half

that of nickel-based batteries.
Limitations:
Requires protection circuit to maintain voltage and current
within safe limits.
Subject to aging, even if not in use - storage in a cool place
at 40% charge reduces the aging effect.
Expensive to manufacture - about 40 percent higher in cost
than nickel-cadmium.
Not fully mature - metals and chemicals are changing on a 19
continuing basis.

Fuel Cells:
A fuel cell is an electrochemical device that converts chemicals
(such as hydrogen and oxygen) into water and produces
electricity in the process.
As long as the reactants (H and O) are supplied to the fuel cell,
it will continually produce electricity and never go dead, unlike
conventional batteries.

Example:
H2O(g) + CH4 CO(g) + H2(g)
H = +206 kJ
Conditions of reaction:
Ni catalyst and 1100 C.

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Fuel Cells (cont.):

The cell contains porous carbon electrodes impregnated with
metallic catalysts and an electrolyte consisting of hot aqueous
KOH. The fuel, gaseous, H2 and the oxidising agent, O2, do not
react directly but instead flow into separate compartments
where H2 is oxidised at the anode and O2 reduced at the
cathode.
The cell reactions are as follows:
Anode:
2 H2(g) 4H+(aq) + 4e-
Cathode:
O2(g) + 4H+(aq) + 4e- 2H2O(l)
Overall reaction: 2 H2(g) + O2(g) 2H2O(l)
In this case, protons pass through the membrane from the anode
to the cathode, while electrons move through the external
circuit.
21

Fuel Cells (cont.):

Examples

Alkali fuel cells operate on Proton Exchange Membrane

compressed hydrogen and
oxygen. They generally use a
solution of potassium hydroxide
(chemically, KOH) in water as
their electrolyte.
(PEM) fuel cells work with a
polymer electrolyte in the form of
a thin, permeable sheet
22
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Fuel Cells (cont.):

Examples

Molten Carbonate fuel cells Solid Oxide fuel cells (SOFC)

(MCFC) use high-temperature
compounds of salt (like sodium
or magnesium) carbonates
(chemically, CO3) as the
electrolyte.
use a hard, ceramic compound
of metal (like calcium or
zirconium) oxides (chemically,
O2) as electrolyte.
23

Fuel Cells (Question):

Question:
In a fuel cell which consumes methanol and oxygen, the
reactions are:
CH3OH(aq) + H2O(l) CO2(g) + 6H+(aq) + 6e-
and
1.5 O2(g) + 6H+(aq) + 6e- 3H2O(l)

a) Write overall cell reaction

b) Calculate the standard free energy change of the overall

reaction (kJ mol-1), assuming the standard cell potential is
+1.210 V

c) Calculate the potential of this fuel cell (in Volts) at -50oC if

[CH3OH(aq)] = 10.0 mol L-1, = 0.2 atm and = 0.001 atm.
24
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Current Batteries: Issues

High Charge Capacity (per unit mass)

High Power Discharge (P=IV)
High Energy Storage (E=QV)
Environmentally Friendly
Examples: Low cost
The storage capacities of alkaline and metal hydride batteries
are largely cathode limited, and both use potassium hydroxide
electrolyte.
Safety problems in Li ion batteries , mainly due to the dendritic
deposition of Li metal during charging process.

Musk says battery cell capacity will need to double worldwide for Tesla to produce a
mass-market electric car. ( http://www.technologyreview.com/view/521201/for-tesla-
motors-success-is-all-about-the-batteries/ )
25

Current Batteries: Way forward!

The new flow battery design from a Harvard team uses organic (carbon-based)
materials instead of a rare metal. Eliza Grinnell/ Harvard School of Engineering
and Applied Sciences

http://www.ibtimes.com/new-battery-technology-could-help-unlock-solar-wind-
power-potential-1532480
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Carbon nanotube Fibers:

http://phys.org/news/2014-02-carbon-nanotube-fibers-outperform-copper.html
27

References
http://dbhs.wvusd.k12.ca.us/Gallery/Gallery0.html
pictures of scientists
http://www.eere.energy.gov/hydrogenandfuelcells/fuelcells/fc_
types.html types of fuel cells
http://www.corrosion-doctors.org/Biographies/GroveBio.htm
sir william grove
http://chem.ch.huji.ac.il/~eugeniik/history/nicholson.html
willliam nicholson
http://inventors.about.com/library/weekly/aacarselectric2a.htm
history of BEVs
http://americanhistory.si.edu/fuelcells/phos/pafcmain.htm fuel
cell history
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Activity and Concentration

Activity effective concentration
Ion-ion and ion-H2O interactions (hydration shell)
cause number of ions available to react chemically
("free" ions) to be less than the number present
Concentration can be related to activity using the
activity coefficient g, where [a] = g (c)

Until now we have assumed that activity, a, is equal to

concentration, c, by setting g = 1 when dealing with
dilute aqueous solutions

But ions dont behave ideally . . .

Concentration related to activity using the activity
coefficient g, where [a] = g (c)
The value of g depends on:
Concentration of ions and charge in the solution
Charge of the ion
Diameter of the ion
Ionic strength, I = concentration of ions and charge in
solution
I = 1/2 Smizi2
where mi = concentration of each ion in moles per L,
zi = charge of ion
Activity coefficient gz 1 as concentrations 0 and tend
to be <1 except for brines
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Corrosion and Electrochemical reactions:

Corrosion is the spontaneous dissolution of a metal by a reaction i.e. the
metals are converted into thermodynamically preferred compounds (e.g.
ores).

Examples of Reduction potentials for common metals as compared to O2.

Reduction Equation E (V)
O2(g) + H+(aq) + 4e- 2H2O(l) 1.23
Cu+ + 2e- Cu(s) 0.34
Pb2+ + 2e- Pb(s) -0.13
Fe2+ + 2e- Fe(s) -0.44
Zn2+ + 2e- Zn(s) -0.76
Al3+ + 2e- Al(s) -1.66

Note that most common metals have reduction potentials less than of O2,
therefore oxidation will be spontaneous (produce a positive cell potential).
31

Potentiometric Measurements:

Measurements using membrane electrodes (Ion Selective Electrodes)

32
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Ion selective Electrodes (ISE):

An ideal ISE consists of a thin membrane
across which only intended ion can be
transported. Note, the transport of ions from
a high concentration to a low one through a
selective binding with some sites within the
membrane creates a potential difference.

i.e. when the membrane of the electrodes is

in contact with a solution containing a
specific ion (e.g. Ca2+), a voltage, dependent
on the level of that ion in solution, develops
at the membrane.

All of ISEs are in combination style; i.e. the

voltage develops in relation to an internal
Ag/AgCl reference code.
33

Principles of Ion selective Electrodes (ISE):

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Principles of Ion selective Electrodes (ISE) (cont.):

Based on Nernst expression (equation 3), the ISE response is a
linear equation in the form of E = E + m* ln(a),
Where E = Measured voltage
E= The standard potential for the combination of the two
half cells
m = slope
ln(a)= natural logarithm of the activity ratio of the meaasured
ion species.
Assuming, ionic strength is

Potential, V/mV
fairly constant, the Nernst
equation may be writtten to
describe the electrode response
to the concentration, C, of the
measured ionic species. Ploted
as potential, V, as a function of
ln(C) as illustrated on the RHS. ln(C) 35

Characteristics Ion selective Electrodes (ISE) (cont.):

Selectivity; The selectivity is one of the most important characteristics
of an electrode, as it often determines whether a reliable measurement
in the sample is possible or not.
Slope of the linear part of the measured calibration curve of the
electrode. The theoretical value according to the Nernst equation is:
59.16 [mV/log(ax)]at 298 K for a single charged ion or 59.16/2 = 29.58
[mV per decade] for a double charged ion.
Range of linear response; At high and very low target ion activities
there are deviations from linearity. Typically, the electrode calibration
curve exhibits linear response range between 10-1M and 10-5M.
Detection limit; According the IUPAC recommendation the detection
limit is defined by the cross-section of the two extrapolated linear parts
of the ion-selective calibration curve. In practice, detection limit on the
order of 10-5-10-6 M is measured for most of ion-selective electrodes.
The observed detection limit is often governed by the presence of other
interfering ions or impurities.
Response time; In earlier IUPAC recommendations, it was defined as
the time between the instant at which the ion-selective electrode and a
36
reference electrode are dipped in the sample solution.
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Types of Ion selective Electrodes (ISE):

Glass membrane (i.e. H+ electrode)

Crystalline/Solid-state electrode (e.g. F- electrode uses Eu2+-doped

LaF3 crystal).

Liquid-based electrodes (e.g. Ca2+ electrode uses a liquid

chelator).

Compound electrode (e.g. CO2 gas sensing electrode).

37

Glass Membrane Electrodes

Ag(s)AgCl(s)Cl-(aq)H+(aq, outside) H+(aq, inside), Cl-(aq)AgCl(s) Ag(s)

Outer reference Analyte Inner H+ Inner reference

electrode solution solution electrode
Glass
electrode

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Glass Membrane Electrodes (cont.):

39

Crystalline/Solid-state electrode :
The membrane is composed of an insoluble inorganic salt. An ion-
exchange process leads to the formation of a potential at the membrane.
Single crystal LaF3 is widely used to determine F-. The crystal is
usually doped with Europium to improve the conductivity. At each
membrane-solution interface, the following equilibrium takes place.
LaF3(s) LaF2+(aq) + F-(aq)
Note that crystalline electrodes may be homogeneous or heterogeneous.

Homogeneous membrane electrodes:

These are ion-selective electrodes in which the membrane is a
crystalline materials prepared from either a single compound or a
homogeneous mixture of compounds (i.e. Ag2S, AgI/Ag2S).

Heterogeneous membrane electrodes:

Formed when an active substance / active mixture of substances is
mixed with an inert matrix, such as silicone rubber or PVC or on
hydrophobized graphite. This leads to formation of heterogeneous
40
sensing membrane.
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Polarizable and Non-polarizable electrodes :

The observed half-cell potential at Electrode-electrolyte interface is
often due to polarization, then an over-potential occurs, which can be
studied by means of current-voltage curves. With, the help of current-
voltages curves, the solution can be analysed by a method called
voltammetry.
Overvoltage
Difference between observed and zero-current half-cell potentials

Resistance Concentration Activation

Current changes Changes in The activation energy
resistance of distribution of ions at barrier depends on the
electrolyte and thus a the electrode- direction of current and
voltage drop electrolyte interface determines kinetics

VP = VR + VC + VA + EO : where EO is standard half-cell potential.

Note: Polarization and impedance of the electrode are the most
important electrode properties. 41

Polarizable and Non-polarizable electrodes (Definition):

Perfectly Polarizable Electrodes:
No actual charge crosses the electrode-electrolyte interface when
current is applied. The current across the interface is a
displacement current and the electrode behaves like a capacitor.
Example:
Platinum Electrode ( Noble metal)

Perfectly Non-polarizable Electrodes:

These are electrodes where current passes freely across the
electrode-electrolyte interface, requiring no energy to make the
transition. These electrodes do not experience over-potentials.
Example:
Ag/AgCl electrode.

42
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Polarography and Voltammetry:

Liquid
Polarography
Electrodes
Working
Electrode
Solid
Voltammetry
electrodes

Thus working electrode refers to an electrode in an electrochemical

system on which the reaction of interest occurs. Note that its
regularly used in conjunction with an auxiliary electrode and/or a
reference electrode.

The reaction on the electrode determines the nature of electrode i.e

oxidation and reduction will be referred to as anodic and cathodic,
respectively.
43

Polarography :
In polarography, the electrolysis is usually carried between mercury
electrodes where the interest lies in cathodic processes. The
working electrode consists of Mercury (Hg) drop from a capillary
into a solution under test as illustrated in the figure below: Thus the
name dropping mercury electrode (DME).
As the name suggests, the
electrode is mercury in the form
of a succession of droplets
coming out from a glass capillary
with internal diameter 0.03 to
0.05 mm.
By varying potential applied to
the working electrode (Hg) and
measuring the resulting current
passing thro the solution;
concentration of metal ions can
readily and accurately be
44
determined
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Principles of Polarography (DME):

Applying electrolytic solution (e.g. CdCl2) in a titration assembly
with excess of supporting electrolyte e.g. KCl. Nitrogen gas has
been bubbled through the electrolytic solution to remove dissolved
oxygen.
When a small negative potential is applied to DME, positively
charged ions move towards DME due to electrostatic force of
attraction, however, applied potential is not sufficient hence no
reaction takes place at the DME. This is illustrated as a polarogram
below:
Current A - B is called
residual current.
Current B - C is called
diffusion current (is directly
proportional to the
concentration of the Analyte).
Current C D is called
Limiting current. 45

Dropping Mercury Electrode (cont.):

46
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Half Wave Potential (E):

E = have wave potential when Id is half and is unique for each
cation. For example, polarographic analysis of a solution of 0.1 M
CaCl2 containing impurities, different species will occupy their
characteristic positions with respect to the voltage in the polarogram,
as shown below: Forms the basis of qualitative analysis.

Polarogram of 0.1M CaCl2 containing Cu2+ , Pb2+, Cd2+, Mn2+ etc.

47

Advantages of DME :
I. The drops are reproducible so that the currents flowing, although
varying with drop-growth and detachment from the capillary are also
reproducible.
II. A fresh surface of electrode is continuously presented to the
electrolyte solution, almost eliminating chemical polarisation effects.
III. The hydrogen overvoltage for mercury as an electrode material is
extremely high.
IV. The extent of electrolysis is small owing to the small surface area, so
the solution may be electrolysed many times without measurable
reduction in concentration.
Note that the voltage range of electroactivity in polarography depends on
the type of electrode in use on the electrolytic support. The preferential
choice of Mercury and potassium chloride as electrode and electrolyte,
respectively is due to the appreciably wider window over which
electrochemical reduction may be studied. For example, at the more
positive end, the limit is given by dissolution of mercury which occurs in
the vicinity of +0.25 V vs SCE. On the other end, Potassium ion occurs
48
at a more negative potential (-1.5 V vs SCE).
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Disadvantages of DME:
I. Mercury dissolution occurs at about 0.4 V

II. Oxygen is reduced by a two stage process over most of the

cathodic working range. Dissolved oxygen must therefore be
removed.

III. Mercury is costly and toxic.

IV. Hg is oxidised, it therefore restricts the use of electrode as anode.

V. DME generates some current like residual current, migration

current and kinetic current which add error in current
measurement.

49

Polarographic Current- Potential Equation:

50
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Polarographic Wave Diffusion controlled:

a) 1F HCl acid
with 0.5 mM
Cadmium ion.

b) 1F HCl acid
alone.

According to Ficks Law of Diffusion, the rate of diffusion is

proportional to the concentration gradient. Given that diffusion in
polarography, the rate controlling (determining) step; then the rate of
electrode reaction is proportional to the concentration gradient. 51

Magnitude of Diffusion controlled:

52
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The Half-wave potential and its Significance:

This is the most important constant in polarography. Chemical
thermodynamics and structural information may be obtained from the
measurements of half-wave potentials of reversible and irreversible
waves under varying experimental conditions.

The manner in which the current is affected by the electrode potential

on the rising part of the wave is to be noted. On the plateau, the
electron transfer is so fast that the ions or molecules of the
electroactive substances are reduced or oxidized as rapidly as they
arrive or formed at the electrode surface.
The electrode reactions are conveniently divided into:
Reversible reactions: Such reactions are so rapid that the
thermodynamic equilibrium is very nearly attained at every
instant during the life of a drop at any potential.
Irreversible reactions: The reactions are so slow that they
proceed only by a fraction of the way to the equilibrium during
the life of each drop. 53

Influence of Ionic strength on Half-wave potential

54
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Polarography Quantitative Analysis.

55

Polarography Quantitative Analysis (cont.)

56
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Polarography Quantitative Analysis (Example.)

Example:
The following data obtained from a linear scan of hydrodynamic
polarogram of a reversible reduction reaction.
Potential Current
(V vs SCE) (A)
-0.358 0.37
-0.372 0.95
-0.382 1.71
-0.4 3.48
-0.41 4.2
-0.435 4.97
The limiting current is 5.15 A. Determine the values of n and half-
wave potential.
57

Polarography Quantitative Analysis (Solution.)

Potential Current Log (i/ilim-i)
(V vs SCE) (A)
-0.358 0.37 -1.1112
-0.372 0.95 -0.6455
-0.382 1.71 -0.3036
-0.4 3.48 0.31886
-0.41 4.2 0.64553
-0.435 4.97 1.44108

58
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Factors that Affect the Half-wave Potentials.)

The temperature coefficient of the half-wave potential is mostly
between 2 and + 2 mV/degree. For reversible wave it is
usually positive and may exceed several millivolts per degree.

The half wave potential is almost always independent of the

concentration of electroactive species ( i.e. of the diffusion
current) after proper correction is applied for the iR drop.

Changes in the nature and concentration of supporting

electrolyte may affect the half-wave potential. For example, in
reversible waves, it may be due to formation of complexes.

59

VOLTAMMETRY
Comparison of Voltammetry to Other Electrochemical Methods

1.) Voltammetry: electrochemical method in which information about an analyte is

obtained by measuring current (i) as a function of applied potential
- only a small amount of sample (analyte) is used

Instrumentation Three electrodes in solution

containing analyte

Working electrode: microelectrode whose

potential is varied with time

Reference electrode: potential remains constant

(Ag/AgCl electrode or calomel)

Counter electrode: Hg or Pt that completes

circuit, conducts e- from signal source through
solution to the working electrode

Supporting electrolyte: excess of nonreactive

electrolyte (alkali metal) to conduct current
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Apply Linear Potential with Time Observe Current Changes with Applied Potential

2.) Differences from Other Electrochemical Methods

a) Potentiometry: measure potential of sample or system at or near zero
current.

voltammetry measure current as a change in potential

b) Coulometry: use up all of analyte in process of measurement at fixed current

or potential

voltammetry use only small amount of analyte while vary potential

Principles of stripping Analysis

Cell and Sample Considerations
Anodic stripping measurements are carried out in an electrochemical cell,
which is usually a covered beaker ( 10 to 200-ml volume) of glass, quartz,
or Teflon.

Electrodes
The working electrode is the electrode of small area at which the
reaction of interest occurs.
The reference electrode provides a known and stable potential with
which the potential of the working electrode is compared.
The counter electrode minimizes the error from the cell resistance.

Supporting Electrolyte
The sample for stripping analysis must be a solution. If the sample is a solid,
it must be dissolved. minimization of electrical migration by adding
supporting electrolyte.
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Issues with Oxygen and its Removal

The half-wave potentials of these steps are approximately -0.05 and -0.9
V versus the saturated calomel electrode (SCE)

(a) oxygen may oxidize the metals in the electrode amalgam;

(b) hydroxyl ions formed during the reduction of oxygen in neutral or
basic media can precipitate metal ions in the vicinity of the working
electrode;
(c) Oxygen reduction can compete with most of the redox processes of
interest
The method most frequently used for removing oxygen from a solution
consists of bubbling an electro-inactive gas (nitrogen, argon, etc) through the
solution.

Dissolved oxygen also can be removed chemically from the sample

solution by addition of sodium sulfite or ascorbic acid. However, these
procedures are restricted to a certain solution pH and may introduce
impurities to the sample.

STRIPPING ANALYSIS
Two step technique
Deposition Step

The extremely low detection limit of stripping analysis is attributable to the

preconcentration that takes place during the deposition step. At the
mercury working electrode used for measurement of amalgam-forming
metals the electrode deposition reaction is:

At solid electrodes, used for measurement of ions with less noble redox
potentials, the corresponding electrochemical reaction is:
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The Deposition Step Contd

In all cases, the deposition potential imposed on the working electrode is
chosen according to the species to be determined and is maintained for a
deposition period depending on their concentrations. The formation of an
amalgam, i.e., the feasibility of depositing metal ions into mercury electrodes,
depends mainly on the solubility of the metal in mercury.

STRIPPING ANALYSIS
Stripping Step
Usually the stripping step consists of scanning the potential
anodically (toward more positive potentials), linearly, or
in another potential-time waveform. When the potential
reaches the standard potential of a metal-metal ion couple,
that particular metal is reoxidized back into solution and a
current is flowing.

Whereas the deposition step of the analysis is

usually the same for the different stripping
techniques, the primary differences are
associated with the approach used during the
stripping step.

Thermodynamics of the stripping process

Stripping processes interference
Background removal The potential-time sequence used in linear
scan anodic stripping experiment along
Fast measurements with the resulting voltammogram.
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Stripping Step with Medium Exchange

The medium-exchange procedure involves a
deposition of the metals from the sample solution,
followed by stripping them into a more suitable
electrolyte. The method improving the selectivity of
stripping measurements and minimizing
interferences

Targeted effects:
Better stripping peak resolution using complex stripping
solutions to resolve better some metal ions.
Minimizing background interference by using blank
supporting electrolytes.
Disadvantages:
Exposing the electrode to the atmosphere;
Breaking the electrical circuit;
Co-transfering the sample solution, associated with the
solution exchange step.
As a result, considerable losses ( 10-15%) of the deposited
metals have been reported.

STRIPPING ANALYSIS

- Very sensitive for detection of trace metals

- Favorable signal to background ratio

- About four to six metals can be measured simultaneously

at levels as low as 10-10 M

- Low cost instrumentation

- There are different versions of stripping analysis depending

on the nature of the deposition and stripping steps