CHM 4102

Electrochemistry
Electrochemical Methodologies and Instrumentation
Members:
1. Chan Keng Fuong 162597
2. Chee Wei Jian
163325
3. Ho Meng Choon
163760
4. Lee Shin Xuan
161363
5. Lee Xin Jie
162434
6. Nurul Nadia binti Basiron 170114
7. Maizatul Nurhafiqah binti Mohd Jupri 170202
8. Intan Nur Balqis binti Mohd Khalid Wong
170207
9. Nur Aisyah Nasuha binti Mohd Azam 170214
10. Yew Yen Pin
163244

ACTIVITY
1

(a) Discuss the main features, functionalities and

characteristics of a potentiostat.
Main
features
Electric potential range (measured and applied): while the
potential window is mostly based on the solvent window the electronics
can also limit the possible range.
Accuracy in potential (measured and applied): limits of deviations
between the actual and reported.
Range of scan rate: how slow or fast a potential window can be
scanned this is most important for experiments that require high scan
rates such as those involving ultramicroelectrodes.
Sample rate: the rate at which potential or voltage can be accurately
sampled. This can be important for experiments that need high scan
rates such as those involving ultramicroelectrodes.
File size: a limiting factor can be the file size limit. This would most
likely affect the choice of the potential range swept or the potential
sample rate.
Electric current range (measured and applied): the maximum
range over which current can be sampled. Applying large currents is
important for experiments that pass a great deal of current like a large

 Current resolution: determines the operational range of a

specific experiment and the bit resolution of that data in the
current dimension.
Accuracy in current (measured and applied): limits of
deviations between the actual and reported.
Number of working channels: how many working
electrodescan the instrument control. Abipotentiostatis
necessary to controlling systems with two working electrodes like
a rotating ring-disk electrode.A polypotentiostatmay be
important for controlling some biological experiments with three
or more working electrodes.
Footprint: potentiostats include small devices of about 20 x 10 x
5cm weighing well under a kilogram or a simple board that can
be installed in a desktop computer. A large bench-top model would
be on the order of 50 x 20 x 10cm and weigh up to or more than
5 kilograms.
Interface: can the instrument run independently or must they be
slaved to a personal computer.
Sweep generator: can the system apply an analogue sweep or
does it use a digital staircase generator as an approximation. If it
does use a digital staircase then the resolution of the staircase is
important.

Functionaliti
es
A potentiostat is an electronic instrument that controls the voltage
difference between a Working Electrode and a Reference Electrode. Both
electrodes are contained in an electrochemical cell. The potentiostat
implements this control by injecting current into the cell through an Auxiliary
or Counter electrode.

Characteristi
cs
Highly stable operation over a wide range of loads with up to
5mA output.
A useful frequency range from dc to greater than 2 kHz.
A precision low noise voltage reference source variable from 5 V,
having a stability of better than 10 V for periods greater than 1 hr.
A faster recovery, low-noise, ac current signal amplifier with a
frequency respose between 5 x 10-2 and 2 x 103 Hz.

b) Draw the electronic circuit involved in a potentiostat.

Discuss the function of all of the main components in
potentiostat.
Control amplifier
- maintaining the voltage
between the reference and
the working electrode as
closely as possible to the
voltage of the input source
. -- It adjusts its output to
automatically control the
cell current so that a
condition of equilibrium is
satisfied.

Reference Electrode
- measuring the working electrode potential. A Reference Electrode
should have a constant electrochemical potential as long as no
current flows through it.
- The most common lab Reference Electrodes are the Saturated
Calomel Electrode (SCE) and the Silver/Silver Chloride (Ag/AgCl)
electrodes. In field probes, a pseudo-reference (a piece of the
Working Electrode material) is often used.

Input source

Working Electrode
- electrode where the potential is controlled and where the
current is measured. For many physical electrochemistry
experiments, the Working - -Electrode is an "inert"
material such as gold, platinum, or glassy carbon. In these
cases, the Working Electrode serves as a surface on which
the electrochemical reaction takes place.

Counter (Auxiliary) Electrode

- Conductor that completes the
cell circuit.
- The Counter Electrode in lab
cells
is
generally
an
inert
conductor
like
platinum
or
graphite. In field probes, it's
generally another piece of the
Working Electrode material. The
current that flows into the solution
via the Working Electrode leaves
the solution via the Counter
Electrode.
- The electrodes are immersed in
an electrolyte (an electrically
conductive
solution).
The
collection of the electrodes, the
solution,
and
the
container
holding the solution are referred
to as an electrochemical cell

c) Why a Faraday cage is needed in the

potentiostatic set up?

to improve shielding against external current noise.

to remove noise that can make low current measurements difficult.

d) Before any electrochemical measurement, oxygen

needs to be removed from the electrochemical cell.
Why?
Oxygen is electroactive, and can be reduced quite easily.
Therefore, it must be removed from the solution if the system
under study is reducible.
Oxygen is typically removed by bubbling an inert gas (e.g.,
nitrogen or argon) through the solution for about 10 minutes.
If a stationary solution experiment is to be performed, it is
important that the stirring is stopped and the solution is allowed
to become quiescent before the experiment is started (although a
blanketing layer of inert gas over the solution can be maintained
during the experiment).

ACTIVITY
2

Main component in
Electrochemical cell

Electrode system
1. Two electrodes system
CE

and RE are shorted on one of the

electrodes while the WE and S (Sense) are
shorted on the opposite electrode.
Measured the potential across the complete
cell.
Used when:
the measurement of the whole cell voltage is
significant
the CE potential can be expected not to drift over
the course of the experiment

2. Three electrode system

Most

common electrochemical cell setup.

Current flow between CE and WE.
Potential difference controlled between WE and CE
and measured between RE and S.
The potential changes of the WE are measured
independent of changes that may occur at the CE.
This isolation allows for a specific reaction to be
studied with confidence and accuracy.

Type of Electrodes
Working Electrode (WE)

ACTIVITY
3

WORKING ELECTRODE
is

the
electrodein
an
electrochemical system on which
the
reaction
of
interest
is
occurring
often used in conjunction with
anauxiliary
electrode,
and
areference electrodein athree
electrode system.
Depending
on
whether
the
reaction on the electrode is a
reduction or an oxidation, the
working
electrode
is
calledcathodic
oranodic,
respectively.

Type of Working
Electrode
Ultramicroelectrode(UME)
Rotating disk electrode(RDE)
Rotating ring-disk electrode(RRDE)
Hanging
mercury
drop

electrode(HMDE)
Dropping mercury electrode(DME)

Example of Reference
Electrode
Standard hydrogen electrode(SHE) (E=0.000 V) activity of H +=1
Normal hydrogen electrode(NHE) (E 0.000 V)concentration H +=1
Reversible hydrogen electrode(RHE) (E=0.000 V - 0.0591*pH)
Saturated calomel electrode(SCE) (E=+0.241 V saturated)
Copper-copper(II) sulfate electrode(CSE) (E=+0.314 V)
Silver chloride electrode(E=+0.197 V saturated)
pH-electrode(in case ofpHbuffered solutions, seebuffer solution)
Palladium-hydrogen electrode
Dynamic hydrogen electrode(DHE)

Both of these types of electrode seem to be used in neuronal activation

Macroelectrode and microelectrode

Both of these types of electrode seem to be used in neuronal
Macroelectrode
Microelectrode
activation
Macroelectrodes are small
conductors of electrical currents
used in machinery . it is also
used in DBS technique

definition

Microelectrode is an electrode
of very small size used in
electrophysiology for recording
neural signals or electrical
stimulation of nervous tissue.

The size is bigger than

microelectrode, the diameter is
~1mm and surface area ~6mm

size

The dimension of this electrode

is typically smaller than about
20m and small as 30nm in
diameter and 2m long.

Used in recording cellular

spiking activity to measure the
collective sum of slow potentials
from multiple cells near the
electrode.
Used in

application

to monitor neurotransmitter
dopamine in rat brains
inresponse behaviour of
change
use in scanning
electrochemical
microscope(SECM)

Pretreatment process of electrode

Mechanical polishing is carried out with metallographic papers of

increasing fineness.

The electrodes is polished by using alumina or diamond powder

of 0.05
size. This would remove all surface impurities.

After rinsing thoroughly with water, the electrode was washed

ultrasonically with absolute alcohol and double-distilled water
respectively.

Electrochemically pretreated electrode was obtained by

successive potential sweep between 1.5 and 2.5V at 100mVs1
for four cycles in
pH 7.0 buffer solutions.

Care must be taken to clean the electrode thoroughly afterwards

to ensure that the polishing materials are completely removed.
Otherwise, these polishing material themselves may show some
specific catalytic or
inhibitive effects.

Electrolyte
Electrolyte solutions are normally formed when a salt is placed into a
solvent such as water and the individual components dissociate due
to the thermodynamic interactions between solvent and solute
molecules, in a process called solvation.

Properties:
will freely dissolve metal to be refined
able to dissolve the major portion of the anode
should be incapable of dissolving metals more electro-negative
than that to be
refined
good conductor of electricity, and should not be altered chemically
by exposure
to air the proportion of soluble electro-positive impurities must not
be
excessive, or these substances will accumulate too rapidly in the
solution and
necessitate its frequent purification

Functions:
In batteries, two materials with different electron affinities are used as
electrodes;
electrons flow from one electrode to the other outside of the battery,
while inside
the battery the circuit is closed by the electrolyte's ions. Here, the
electrode
reactions convert chemical energy to electrical energy.
In some fuel cells, a solid electrolyte or proton conductor connects the
plates
electrically while keeping the hydrogen and oxygen fuel gases
separated.
In electroplating tanks, the electrolyte simultaneously deposits metal
onto the
object to be plated, and electrically connects that object in the circuit.
In electrolytic capacitors the chemical effect is used to produce an
extremely thin
dielectric or insulating coating, while the electrolyte layer behaves as
one capacitor
plate.

Supporting electrolyte

Electrolyte containing chemical species that are not electroactive

and which has an high ionic strength and conductivity.
Properties:
Impart conductivity to the solvent and hence enable the continuous
current flow
in solution
If the concentration is very low, they can form a space charge near
the surface
and the space charge potential can influence the charge transfer
kinetics.
If the ions of the supporting electrlytes are adsorbed in the surface,
they can
catalyse or inhibit other reactions.
Generally control the acidity of the ionic solution
Some ions may form complexes with the reactants and products.

Functions:
To reduce the ohmic IR voltage drop in the cell to a minimum and
effectively
eliminate the contribution of the analyte to the migration current
Modifies the solvation behavior of the redox couple and the acid-

Solvent

A solvent is a substance that dissolves a solute and resulting in a

solution.

Properties:
liquid in room temperature
soluble for ionic substance to form solution or electrolyte
solvent itself will undergo oxidation or reduction in potential region
possess the required acid-base properties

Functions:
To dissolve ionic components and form highly conducting solutions.
Easily dissolve compounds of electrochemical interest

What to consider in choosing an electrolyte?

Electrolyte is a substance that ionizes when dissolved in suitable
ionizing
solvents. It conducts electricity when ions present in the solvent.
The electrolyte substance must able to dissolve in the solvent and
dissociate to
form free moving ions.
The concentration of electrolyte must suit with the chemical
reaction
The type of electrolyte used is suitable with the electrode used.
The type of electrolyte use must be suitable with the instrument.
eg: Fuel cell use solid electrolyte
Electrolyte in batteries must be clear of debris or any discolouration.

ACTIVITY
4

BASIC PRINCIPLE OF
DISCHARGE BATTERY:BATTERY
electrons flow from the

anode to the cathode in

the external circuit and a
current is produced.
Once all the active
material at the cathode
has been reduced, and/or
all the active anodic
material is oxidised, and
the battery cannot
provide any more power

Charged battery
Rechargeable batteries are

(re)charged by applying
electric current, which
reverses the chemical
reactions that occur during
discharge/use.
When a current is applied

to the cell in the opposite

direction the anode
becomes the cathode, and
vice versa which forcing the
chemical reactions into

Basic principle of fuel cell

fuel cell is are

a device
that
generates
AElectrons
drawn
from
the electricity by a chemical reaction.

anode to the cathode through

an external circuit, producing
direct currentelectricity.
hydrogen atoms enter a fuel

cell at the anode

The hydrogen atoms are now

"ionized," and carry a positive

electrical charge.

The negatively charged

electrons provide the current

through wires .
Oxygen enters the fuel cell at
the cathode.
oxygen picks up electrons and
travels through the
electrolyte to the anode,
where it combines with
hydrogen ions.
Water will form , which drains
from the cell.
As long as a fuel cell is
supplied with hydrogen and
oxygen, it will generate
electricity.

Introduction to Biosensors
A biosensor is an analytical device which is used to determine
the presence and concentration of a specific substance in a
biological analyte.
Desired molecule

Bioreceptor

Transducer

Biosample
Biosensor

Signal

Processing

Display

Biosensor composed of two elements.

1. A bioreceptor that is an immobilized sensitive biological element
(e.g. enzyme, DNA probe, antibody) recognizing the analyte (e.g.
enzyme substrate, complementary DNA, antigen). Although
antibodies and oligonucleotides are widely employed, enzymes are
by far the most commonly used biosensing elements in biosensors.

2. A transducer is used to convert (bio)chemical signal resulting from

the interaction of the analyte with the bioreceptor into an electronic
one. The intensity of generated signal is directly or inversely
proportional to the analyte concentration. Electrochemical
transducers are often used to develop biosensors. These systems
offer some advantages such as low cost, simple design or small
dimensions. Biosensors can also be based on gravimetric,
calorimetric or optical detection.

Bioreceptor

Antibody

Transducer

Optical

Enzyme

Electrochemical

Nucleic Acid (DNA)

Mass based

Cell

Temperature based

MIP

Electric &
Magnetic

Absorption
Fluorescence
Interference
potentiometric
amperometric
conductimetric

Dielectric properties
Permeability properties
Voltage or Current

Biosensor
Analyte

Response

Analysis

Detection

Signal

Sample
handling/
preparati
on

Components of a Biosensor

Detector

Basic Characteristics of a
Biosensor
1. LINEARITY
Linearity of the sensor should be high
for the detection of high substrate
concentration.
2. SENSITIVITY Value of the electrode response per
substrate concentration.
3. SELECTIVITY Chemicals Interference must be
minimised for obtaining the correct
result.
4.RESPONSE TIME Time necessary for having 95%
of the response.