Electrochemistry

Electrochemistry is defined as the branch of chemistry that studies

chemical reactions which take place at the interface of an electrode and an
ionic conductor (electrolyte). These reactions involve electric
charges moving between the electrodes and the electrolyte. Thus
electrochemistry deals with the interaction between electrical energy and
chemical change.
The electrical properties of solutions are measured using electrodes in
arrangements known as electrochemical cells. There are two main types of
electrochemical cells: i) Electrolytic cells ii) Voltaic or Galvanic cells
Electrolytic Cells: When a potential difference is applied across two
electrodes that dip into a solution, a current will flow between them. The
amount of current that flows depends upon the voltage applied and the
electrochemical properties of the solutions.
Voltaic or Galvanic Cells: In some cells the chemical nature of the
electrodes and solutions results in a chemical reaction taking place at the
electrode with the production of electrical energy (batteries) but without
the need for an external voltage. This type of cell is used in potentiometric
methods where they develop a potential relative to the solution due to the
nature of the electrodes and the solution. This potential can be measured on
the basis of the concentration of the ions in the solution.

Electrochemistry based analytical methods in clinical laboratory

are:
(1) Potentiometry,
(2) Voltammetry
(3) Conductometry and
(4) Coulometry
Potentiometry
Potentiometry is the measurement of an electrical potential
difference between two electrodes in an electrochemical cell
which consists of two electrodes that are connected by an
electrolyte solution and conducts ions.
An electrode, or half-cell, consists of a single metallic conductor
that is in contact with an electrolyte solution.

There are two fundamental types of half cell reactions: Oxidation

reactions and Reduction reactions .
Electrode at which the oxidation reaction occurs is called the
anode and electrode at which the reduction reaction occurs is
called the cathode.
Potentiometric sensors are widely used clinically for the
measurement of pH, PCO2 and electrolytes (Na+, k+, Cl-, Ca2+, Mg2+,
Li+) in whole blood, serum, plasma, and urine.
The potential developed by a single electrode in a solution is caused by the
tendency of the solution either to donate or accept electrons and can be
calculatecd using the Nernst equation:
E = E0 - (2.3026RT/nF) X log a
Where, E is the electrode potential at the specified condition
E0 is the standard electrode potential
R is the gas constant (R = 8.314  J K−1 mol−1)
T is the absolute temperature
n is the number of electrons involved
F is the Faraday constant, (F = 9.648 5×104 C mol−1)
a, activity of the ion
At 250 C, the equation simplifies to
E = E0 – (0.059/n) log a

Each of these electrode systems is known as a half –cell and the potential
developed by a half-cell can not be measured in absolute terms but only
compared with that of another half-cell which is known as reference
electrode. The chemical reaction occurring at each half-cell is known as a
half-reaction.
 Reference electrode
• It has a standard potential on its own and its potential does not
change to whichever solution it is dipped.

• Example of reference electrode :

– Standard hydrogen electrode (SHE)
– Saturated calomel electrode
– Silver-silver chloride electrode
 Standard hydrogen electrode (SHE)
• The Standard hydrogen electrode is a redox electrode which forms the basis of
the oxidation-reduction potentials. It is defined as the potential that is
developed between H2 gas adsorbed on the Pt metal and H+ of the solution. The
electrode is dipped in an acidic solution and pure hydrogen gas is bubbled
through it at 1atm pressure. The concentration of both the reduced form and
oxidised form is maintained at unity.
• It is used for
– determination of electrode potential of metal electrode system
– determination of pH of the solution
Pt,H2 (g, 1atm) | H+ (aq, a = 1.00) ||2 H+ (aq) + 2 e- ↔ H2 (g)

Its absolute electrode

potential is estimated to be
4.44 ± 0.02 V at 25 °C
Saturated calomel (Hg2Cl2) Electrode (SCE)
• Contains of an inner jacket and outer sleeve.
• Inner jacket has wire contact with Hg and plugged with a mixture of
calomel Hg2Cl2 & KCl.
• Outer sleeve has crystals of KCl & porous plug of asbestos
• Application: pH measurement, cyclic voltammetry and general
aqueous electrochemistry.
• Advantages: easy of construction and stability of potential.
Hg | Hg2Cl2, KCl || Hg2Cl2 +2e– ↔2Hg+ + 2Cl-(aq)

The Saturated calomel electrode (SCE) is a

reference electrode based on the reaction
between elemental mercury and mercury
chloride. The aqueous phase is a saturated
solution of potassium chloride in water. When
saturated the redox potential of the calomel
electrode is +0.2444 V
 Membrane electrodes
It is used in Glass pH electrode
• Advantages over other electrodes for pH
measurements:
– Its potential is essentially not affected by the
presence of oxidizing or reducing agents.
– It operates over a wide pH range.
– It responds fast and functions well in physiological
systems.
Glass pH electrode
 Theory of the glass membrane potential
• Both the inside and outside surfaces of the glass
membrane in the GE bulb have SiOH groups.
• The interior surface of the glass membrane is in
contact with a constant concentration of HCl, and so
the number of SiO– groups on the interior surface
remains constant.
• By contrast, the number of SiO– groups on the
exterior of the glass membrane will change when the
pH of the solution the glass membrane is immersed in
changes.
• The difference in charge on the inside and outside of
the glass membrane results in a membrane potential.
• If we can set up an experiment to measure the
membrane potential, then this corresponds to
measuring the pH of the solution in which the glass
electrode is immersed.
Application of Potentiometric Measurement
• Clinical Chemistry
– Ion-selective electrodes are important sensors for clinical samples because
of their selectivity for analytes in complex matricies.
– The most common analytes are electrolytes, such as Na+, K+, Ca2+,H+, and
Cl-, and dissolved gases such as CO2.

• Environmental Chemistry
– For the analysis of of CN-, F-, NH3, and NO3- in water and wastewater.
– One potential advantage of an ion-selective electrode is the ability to
incorporate it into a flow cell for the continuous monitoring of wastewater
streams.

• Potentiometric Titrations
– Use a pH electrode to monitor the change in pH during the titration.
– For determining the equivalence point of an acid–base titration.
– Possible for acid–base, complexation, redox, and precipitation titrations, as
well as for titrations in aqueous and nonaqueous solvents.
• Agriculture
– NO3, NH4, Cl, K, Ca, I, CN in soils, plant material,
fertilizers and feedstuffs
• Detergent Manufacture
– Ca, Ba, F for studying effects on water quality
• Food Processing
– NO3, NO2 in meat preservatives
– Salt content of meat, fish, dairy products, fruit
juices, brewing solutions.
– F in drinking water and other drinks.
– Ca in dairy products and beer.
– K in fruit juices and wine making.
– Corrosive effect of NO3 in canned foods
Voltammetry
Voltammetric and amperometric methods are based on electrolytic
electrochemical cells, in which an external voltage is applied to a
polarizable working electrode and current of the cell is monitored,
and it is proportional to the concentration of the analyte present in
the test sample.

A number of voltammetric systems are produced commercially for the

determination of specific species that are of interest in industry and
research, better to referred to as sensors. These sensors can be
employed for the analysis of various organic and inorganic analytes in
various matrices.
The oxygen electrode for the determination of dissolved oxygen in a
variety of aqueous environments, such as sea water, blood, sewage,
effluents from chemical plants, and soils is of tremendous importance
to industry, biomedical and environmental research, and clinical
medicine.
Conductometry
Conductometry is an electrochemical technique used to determine
the quantity of an analyte present in a mixture by measurement of
its effect on the electrical conductivity of the mixture. It is the
measure of the ability of ions in solution to carry current under the
influence of a potential difference. In a conductometric cell,
potential is applied between two inert metal electrodes.

In clinical analysis, conductometry is frequently used for the

measurement of the fraction of erythrocytes in whole blood
(hematocrit) and as the transduction mechanism for some
biosensors.
Coulometry
Coulometry measures the electrical charge passing between two
electrodes in an electrochemical cell. The amount of charge passing
between the electrodes is directly proportional to oxidation or
reduction of an electroactive substance at one of the electrodes.
The number of coulombs transferred in this process is related to the
absolute amount of electroactive substance by Faraday's Law:

Where
Q = the amount of charge passing through the cell
C = coulomb = ampere. second)
n = the number of electrons transferred in the oxidation or
reduction reaction
N = the amount of substance reduced or oxidized in moles
F = Faraday constant (96,487 coulombs/mole)
Coulometric titration is one of the most accurate electrochemical
techniques since the method measures the absolute amount of
electroactive substance in the sample. Coulometry is considered the
gold standard for determination of chloride in serum or plasma.
 Biosensor
“Biosensor” – Any device that uses specific biochemical
reactions to detect chemical compounds in biological samples.

Current Definition:
A sensor that integrates a biological element with a physiochemical
transducer to produce an electronic signal proportional to a single
analyte which is then conveyed to a detector.
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 minimized for
obtaining the correct result.
4.RESPONSE TIME Time necessary for having 95% of the response.
 Types of Biosensors
1. Calorimetric Biosensor
2. Potentiometric Biosensor
3. Amperometric Biosensor
4. Optical Biosensor
DNA Biosensor
Steps involved in electrochemical DNA hybridization
biosensors:
 Formation of the DNA recognition layer

 Actual hybridization event

 Transformation of the hybridization event into
an electrical signal
 DNA biosensor
Application to clinical diagnosis and genome
mutation detection
Affinity type sensors based on oligonucleotide binding are available.
For example, a number of DNA sensors have been developed in which
a segment of DNA complementary to the target strand is
immobilized on a suitable electrochemical sensor. These devices
operate in the direct (based on electrochemical oxidation of guanine
in target DNA) or indirect (with exogenous electrochemical markers)
transduction modes.
A. Capture probe Sample Oxidation of guanine on target DNA

DNA biosensor: (A) direct elecrro-oxidation detection of guanosine bases in target DNA
after hybridization with immobilized capture probe on electrode surface
B. Capture probe Sample Reductionioxidation of
redox intercalation species

DNA Biosensor: (B) electrochemical detection of hybridization using exogenous redox

species that intercalates into hybridized complex between immobilized capture DNA
probe and target DNA.
 Application of Biosensor
 Food Analysis
 Study of biomolecules and their interaction
 Drug Development
 Crime detection
 Medical diagnosis (both clinical and laboratory use)
 Environmental field monitoring
 Quality control
 Industrial Process Control
 Detection systems for biological warfare agents
 Manufacturing of pharmaceuticals