INTRODUCTION TO

ELECTROCHEMICAL METHODS

INSTRUMENTAL ANALYSIS AND TECHNIQUES-II

PHC-804
Course Incharge: Prof. Dr. Somia Gul
 Learning Objectives of Current Lecture
 To learn about Rotating Platinum Electrode.
 To learn about the design, construction and uses of rotating platinum electrode.
 To learn about the rotating platinum micro-electrode.

 To learn about the concept of rotating platinum electrode and reason for its rotation.
 To make students familiar with different advantages of rotating platinum electrode and its
comparison with DME.
 To learn about the pharmaceutical applications of rotating platinum electrode.
 To learn about Gold Electrode and about its pharmaceutical applications in electrochemistry.
 To make students familiar with gold electrodes (CDtrodes) using recordable CDs as the gold source.
 To learn about Carbon Electrode and about its pharmaceutical applications in electrochemistry.
 To make students familiar with advances in the field of electrochemical devices.
 Previous Lecture
• Before going further, recall that we have learnt that
 Membrane potential led to the development of a new class of indicator electrodes which are called as “Ion
Selective Electrodes” or ISEs.
 A membrane potential results from a chemical interaction between the analyte and active sites on the
membrane surface.
 As signals depends on a chemical process, most membranes are not selective toward a single analyte. Instead,
the membrane potential is proportional to the concentration of each ion that interacts with the membrane’s
active sites.
 A solid state ion selective electrode has a membrane that consists of either a polycrystalline inorganic salt or
a single crystal of an inorganic salt.
 Unlike a glass membrane ion-selective electrode, a solid state ISE does not need to be conditioned before it is
used, and it may be stored dry.
 A number of membrane electrodes respond to the concentration of a dissolved gas. The basic design of a gas-
sensing electrode, consists of a thin membrane that separates the sample from an inner solution that contains
an ion-selective electrode.
 The approach for developing gas-sensing electrodes can be modified to create potentiometric electrodes that
respond to a biochemically important species.
 The most common class of potentiometric biosensors are enzyme electrodes which are able to trap or
immobilize an enzyme at the surface of potentiometric electrode.
 Rotating Platinum Electrode

Platinum (Pt) is a noble metal that is very stable and

resistant to corrosion. Because of its stability, like Au, it is
often used to make jewelry. As an electrode, it is used to
oxidize organics or to generate hydrogen or reduce oxygen.

Amperometric titration can be carried out with a rotating

platinum electrode. The electrode is mounted on shaft of the
motor and rotated at constant speed of 600 RPM . Electrical
connection is made to the electrode by copper wire passing
through the tubing to the mercury covering
the platinum wire seal.
 Rotating Platinum Electrode

Rotating platinum electrode is capable of operating at variable

speeds, 100 to 1200 r.p.m., as shown in figure. It requires no
great skill to make and no insulation, since it is made of glass.
Rotating Platinum Electrode
Rotating Platinum Electrode
Rotating Platinum Electrode
Rotating Platinum Micro-Electrode
Rotating Platinum Electrode
Construction and Working of Rotating Platinum
Electrode

Construction: The electrode includes a

conductive disk embedded in an inert non-
conductive polymer or resin that can be
attached to an electric motor that has very fine
control of the electrode's rotation rate. The disk,
like any working electrode, is generally made of
a noble metal (in this case its made of Platinum)
or glassy carbon, however any conductive
material can be used based on specific needs.
 Construction and Working of Rotating Platinum
Electrode
Working: The disk's rotation is usually described in terms of
angular velocity. As the disk turns, some of the solution described
as the hydrodynamic boundary layer is dragged by the spinning
disk and the resulting centrifugal force flings the solution away
from the Centre of the electrode. Solution flows up, perpendicular
to the electrode, from the bulk to replace the boundary layer. The
sum result is a laminar flow of solution towards and across the
electrode. The rate of the solution flow can be controlled by the
electrode's angular velocity and modelled mathematically. This
flow can quickly achieve conditions in which the steady-state
current is controlled by the solution flow rather than diffusion.
This is a contrast to still and unstirred experiments such as cyclic
voltammetry where the steady-state current is limited by the
diffusion of species in solution.
Rotating Platinum Electrode
 Rotating Platinum Electrode
PHARMACEUTICAL APPLICATIONS
(1) To identify and quantify Dissolved oxygen and peroxides.
(2) For determination of Trace metals and metal-containing drugs.
(3) To identify and quantify Antiseptics and insecticides.
(4) To identify and quantify Vitamins.
(5) To identify and quantify Hormones.
(6) To identify and quantify Antibiotics.
(7) Identification and quantifying of Alkaloids.
(8) To identify Miscellaneous pharmaceutical substances.
(9) Blood serum and cancer diagnosis.
 Gold Electrode
• Gold electrodes are widely used in electrochemistry and
electroanalytical chemistry.
• The notable performance when used in stripping analysis of
many ionic species and the extraordinary affinity of thio
compounds for its surface make these electrodes very suitable
for many applications.
• A simple and novel way to construct gold electrodes (CDtrodes)
using recordable CDs as the gold source.
• The nanometer thickness of the gold layer of recordable disks
(50−100 nm) favors the construction of band nanoelectrodes
with areas as small as 10-6 cm2.
• The plane surface can be easily used for the construction of
conventional-sized gold electrodes for batch or flow injection
analysis or even to obtain electrodes as large as 100 cm 2.
• The low price of commercial recordable CDs allows a “one way
use”. The evaluation and applicability of these electrodes in the
form of nanoelectrodes, in batch and associated with flow cells.
 Gold Electrode
• Nanoporous gold prepared by dealloying Au: Ag alloys
has recently become an attractive material in the field of
analytical chemistry.
• This conductive material has an open, 3D porous
framework consisting of nanosized pores and ligaments
with surface areas that are 10s to 100s of times larger
than planar gold of an equivalent geometric area.
• The high surface area coupled with an open pore
network makes nanoporous gold an ideal support for the
development of chemical sensors.
• Important attributes include conductivity, high surface
area, ease of preparation and modification, tunable pore
size, and a bicontinuous open pore network.
• Specifically they relate to the development of
immunosensors, enzyme-based biosensors, DNA sensors,
Raman sensors, and small molecule sensors.
 Advances in the Field of Electrochemical Devices
Over the years, electrochemical devices have been proposed for the detection
of organic and biomolecules due to their easy and low-cost manufacturing
processes as well as for the possibility to realize a multi-panel system for the
simultaneous detection of several human metabolites, also “in continua”
instead of one-shot measurements. Moreover, they also allow easy assembly
with electronic systems for reading and transmitting acquired data.
On the other hand, electrochemistry is in continuous progress: enzyme-based
biosensors have been largely developed for sensing metabolites like glucose and
lactate, but also for the detection of drugs (e.g., cytochromes-based biosensors
proposed for the detection of etoposide, ifosfamide, cyclophosphamide and
ftorafur, four well known used anti-cancer compounds largely used in
chemotherapy). However, enzymes possess some intrinsic limitations, such as the
lowering of their activity in time once attached onto electrode surfaces, which
may also result in decreasing-in-time the performance of enzyme-based
biosensors as, for example, registered in the continuous monitoring of the
naproxen a well-known anti-inflammatory compound.
Advances in the Field of Electrochemical Devices
new sensing strategies have been considered and
cyclodextrins (CDs) have been selected as potential
candidates to provide selectivity to future electrochemical
sensing-devices. Cyclodextrins are oligosaccharides
composed of six (α), seven (β) or eight (γ) glucose units.
Their inner hydrophobic cavity and hydrophilic exterior
are enabled to form a “host–guest inclusion complex”
targeting different organic or inorganic molecules, toward
which usually show high molecular selectivity. Particularly
for electrochemical devices, β-CDs are the most commonly
used since their ring-size well matches with a large number
of target diagnostic-molecules and since, usually, they are
enough low-costs material.
 Carbon Electrode

Carbon electrode is the general

term for an electrode formed
from the element carbon. It can
be divided into natural graphite
electrode, artificial graphite
electrode, carbon electrode and
special carbon electrode.
 Carbon Electrode
Carbon electrodes have excellent
electrical and thermal conductivity,
heat resistance, chemical resistance,
high mechanical strength, and easy
processing and forming. Widely used
in metallurgy, chemical industry,
electrochemistry and other industries,
such as electrodes for electric arc
furnaces, electrodes for electrolysis,
electrodes for batteries, etc.
 Carbon Electrode
Carbon electrodes are made by mixing
pitch coke, petroleum coke and
adhesives and then carbonized. The
degree of graphitization is not high
and the conductivity is not as good as
graphite electrodes. It can be used for
electrolysis electrodes such as
What is the meaning of coke?
aluminum and magnesium, and distilled to dryness
battery electrodes. : the residue of coal left after destructive
distillation and used as fuel also : a similar
residue left by other materials (such as
petroleum) distilled to dryness. coke.
 Carbon Electrode
A non filler-metal electrode consisting
of carbon or a graphite rod; sometimes contains
copper powder for increased electrical
conductivity; used in carbon arc welding.

Carbon electrodes are used in electrolysis due to

their competence as a conductor and the number of
free electrons they have available for transfer. Not
only is carbon an efficient conductor, it also has a
very high melting point. This means it can be used
to facilitate a wide range of different reactions.
 Carbon Electrodes for Electrolysis

Most of the scientists have suggested that

carbon electrode has several freely moving
electrons within their structure so it acts as the
highly conductive material. They are more
stable at high temperatures, durable and
consider being tough material. So it is utilized
as a key ingredient in electrolysis. Another
special feature of this electrode is a high melting
point. Due to this factor, it can be utilized for a
wide range of reactions. Many people prefer to
use it because of its longevity, low cost.
 Carbon Electrodes for Electrolysis

The solution of electrolysis contains two rods.

Each of them carries different chemical or
physical reactions when current is passed
through the solution. Then positively charged
ions flow towards cathode since it receives
electrons. On the other side, the negatively
charged ions move towards positive ones or
anode and loss electron. Usually, it is made
out of an allot rope of carbon compound
called graphite. They are made from joining
many carbon atoms in a hexagonal shape
and linked with more number of hexagonal
to make a layer and it will be one atom thick.
Summary
 Platinum (Pt) is a noble metal that is very stable and resistant to corrosion. As an electrode, it is
used to oxidize organics or to generate hydrogen or reduce oxygen.

 Amperometric titration can be carried out with a rotating platinum electrode. The electrode is
mounted on shaft of the motor and rotated at constant speed of 600 RPM.

 The rotating platinum electrode includes a conductive disk embedded in an inert non-
conductive polymer or resin that can be attached to an electric motor that has very fine control
of the electrode's rotation rate. .

 Rotating platinum electrode is to identify and quantify Dissolved oxygen and peroxides, trace
metals and metal-containing drugs, antiseptics and insecticides as well as for blood serum and
cancer diagnosis.

 Gold electrodes used in stripping analysis of many ionic species and the extraordinary affinity
of thio compounds for its surface make these electrodes very suitable for many applications.

 A simple and novel way to construct gold electrodes (CDtrodes) using recordable CDs as the
gold source.
25
 Summary
 The high surface area coupled with an open pore network makes nanoporous gold an ideal
support for the development of chemical sensors.

 Specifically Gold electrodes relate to the development of immunosensors, enzyme-based

biosensors, DNA sensors, Raman sensors, and small molecule sensors.

 New sensing strategies have been considered and cyclodextrins (CDs) have been selected as
potential candidates to provide selectivity to future electrochemical sensing-devices.

 Particularly for electrochemical devices, β-CDs are the most commonly used since their ring-size
well matches with a large number of target diagnostic-molecules and since, usually, they are
enough low-costs material.

 Carbon electrodes are used in electrolysis due to their competence as a conductor and the
number of free electrons they have available for transfer.

 Carbon electrodes have excellent electrical and thermal conductivity, heat resistance, chemical
resistance, high mechanical strength, and easy processing and forming and they are widely used
in metallurgy, chemical industry, electrochemistry and other industries.
26
Further Reading and References
• Pharmaceutical Analysis Vol II by Dr. Anees Ahmad Siddiqui.

• A.H Beckett, J.B. stenlake, Practical Pharmaceutical Chemistry,

Fourth edition -part two

• Pharmaceutical Analysis Vol I & II by Asotosh Kar.

https://pubs.acs.org/doi/pdf/10.1021/ac60086a053

https://www.mdpi.com/2311-5629/5/4/78/htm

https://www.orientcarbongraphite.com/carbon-electrode-c-20.html