ELECTROCHEMICAL SENSORS

A chemical sensor is a small device that can be used for

direct measurement of the analyte in the sample matrix.
Ideally, such a device is capable of responding continuously
and reversibly and does not perturb the sample. By
combining the sample handling and measurement steps,
sensors eliminate the need for sample collection and
preparation.

Electrochemical sensors represent an important subclass of

chemical sensors in which an electrode is used as the
transduction element.
 ELECTROCHEMICAL BIOSENSORS

Electrochemical biosensors combine the analytical power

of electrochemical techniques with the specificity of
biological recognition processes. The aim is to biologically
produce an electrical signal that relates to the
concentration of an analyte.
Potentiometry
 Potentiometric Methods
• In potentiometry we measure the potential of an
electrochemical cell under static conditions.
• Because no current—or only a negligible current—flows
through the electrochemical cell, its composition remains
unchanged.
• For this reason, potentiometry is a useful quantitative method.
• The first quantitative potentiometric applications appeared
soon after the formulation, in 1889, of the Nernst equation,
which relates an electrochemical cell’s potential to the
concentration of electroactive species in the cell.
Potentiometric method include two type of measurement these are ;

• 1.Direct measurement of an electrode potential from which

concentration of an active ion may be found

• 2.Indirect measurement - Change of E.M.F. of an electrode cell

brought about by the addition of titrant

Both methods are based on quantitative measurement of E.M.F. of cell

is given by
E cell = E reference + E indicator + E junction
• As the reference electrode potential is independent of solution and
junction potential is constant so the cell potential is measure of
indicator electrode potential and can give information on the nature
and concentration of substance under test.
 POTENTIOMETRIC ELECTROCHEMICAL CELLS
• A schematic diagram of a typical potentiometric electrochemical cell is
shown in Figure.
• The electrochemical cell consists of two half-cells,,each containing an
electrode immersed in a solution of ions whose activities determine the
electrode’s potential.
• A salt bridge containing an inert electrolyte, such as KCl, connects the two
half-cells. The ends of the salt bridge are fixed with porous frits, allowing the
electrolyte’s ions to move freely between the half-cells and the salt bridge.
 POTENTIOMETRIC ELECTROCHEMICAL CELLS

• This movement of ions in the salt bridge completes the electrical circuit.
• By convention, we identify the electrode on the left as the anode and
assign to it the oxidation reaction; thus

• The electrode on the right is the cathode, where the reduction reaction
occurs.
 Reference Electrodes

CALOMEL ELECTRODES, and SILVER/SILVER CHLORIDE

ELECTRODES, and GLASS ELECTRODE
Theory of the glass membrane potential:
The pH electrode functions as a result of ion exchange on the surface of a
hydrated layer. The membrane of a pH glass electrode consists of chemically
bonded Na2O and SiO2. For the electrode to become operative, it must be
soaked in water. During this process, the outer surface of the membrane
becomes hydrated. When it is so, the sodium ions are exchanged for
protons in the solution:
SiO─ Na+ (solid) + H+ (solution) ↔ SiO─H+ (solid) + Na+ (solution)
The protons are free to move and exchange with other ions.

Charge is slowly carried by

migration of Na+ across glass
membrane

Potential is determined by
external [H+]
 Potentiometric Measurements

As shown in Figure, we use a

potentiometer to determine the
difference between the potential of
two electrodes.

The potential of one electrode— the

working or indicator electrode—
responds to the analyte’s activity,
and the other electrode—the
counter or reference electrode—has
a known, fixed potential.

Schematic diagram of a manual potentiometer:

C is the counter electrode; W is the working
electrode; SW is a slide wire resistor; T is a tap
key and i is an ammeter for measuring current.
 Potentiametric Titration
In the potentiometric titration the titration reaction is followed by measurement of
concentration of one or more species potentiometrically. The beaker or flask becomes
one of the half cells and the reference electrode is the other halfcell.

There is a different between titration reaction and cell reaction; in titration reaction
the reactant and products be in the same half cell and the titration reaction always at
equilibrium while in cell reaction is not at equilibrium.

In potentiometric titration the change in electrode potential upon the addition of

titrant are noted by the volume of titrant added. At the end point the rate of change of
potential is maximum

The potentiometric end point has been applied to all types of chemical reaction. It can
be used with colored or opaque solution

Types of Potentiometric titration

acid –base, oxidation reduction, precipitation, complexmetirc
 Advantages of Potentiometric titrations

• Can be used for coloured, turbid or fluorescent analyte solution.

• Can be used if there is no suitable indicator or the colourchange is

difficult to ascertain.

• Can be used in the titration of polyprotic acids, mixtures of acids,

mixtures of bases or mixtures of halides.

• The apparatus required is inexpensive, reliable and readily available

• It is easy to interpret the titration curve.

 Potentiometric Titration
• Involves measurement of the potential
of a suitable indicator electrode as a
function of titrant volume
• Provides MORE RELIABLE data than
the usual titration method
• Useful with colored/turbid solutions
• May be automated
• More time consuming
Potentiometric Titration Curves
 Conductometry
Conductometry:
is the simplest of the electroanalytical
techniques; by Kolthoff in 1929.
Conductivity is:
“the ability of the medium to carry electric
current”.
 Introduction
Conductors are:
either metallic (flow of electrons) or electrolytic
(movemenmt of ions).

Conductance of electricity:
migration of positively charged ions towards the cathode and
negatively charged ones towards the anode

(i.e.) current is carried by all ions present in solution.

Conductance depends on the number of ions in solution.
Conductivity measurements

1.Electrodes
Two parallel platinized Pt. foil electrodes or Pt. black with
electrodeposited a porous Pt. film which increases the surface
area of the electrodes.

2.Primary standard solutions

Primary standard KCl solution ,at 25℃, 7.419g of KCl in 1000g
of solution has a specific conductivity of 0.01286Ω-1/cm.
Equivalent conductance (o ):

“It is the conductance of a solution of one-gram

equivalent of solute (with no respect of its volume)
contained between two electrodes placed 1 cm
apart.”

Due to the interionic effects,

the equivalent conductance (o ) is concentration
dependant.
Factors affecting conductivity:
 Size of ions
 Temperature
 Number of ions
 Charge of ions

 Specific conductivity:-It is conductivity offered

by a substance of 1cm length and 1sq.cm surface
area. units are mhos/cm.

 Equivalent conductivity:-it is conductivity offered

by a solution containing equivalent weight of
solute in it.
Molar conductance of various ions at infinite
dilution at 25℃

ions molar conductance

K+ 73.52
Na+ 50.11
Li+ 38.69
H+ 349.82
Ag+ 61.92
Cl- 76.34
Br- 78.4
OH- 198
APPLICATIONS OF CONDUCTOMETRY

It can be used for the determination of:-

 Solubility of sparingly soluble salts
 Ionic product of water
 Basicity of organic acids
 Salinity of sea water (oceanographic work)
 Chemical equilibrium in ionic reactions
 Conductometric titration
CONDUCTOMETRIC TITRATIONS:

 The determination of end point of a titration by

means of conductivity measurements are known
as conductometric titrations.
Types of conductometric titrations:

 Acid-base titration
 Precipitation titration
 Replacement titration
 Redox (oxidation-reduction) titration
 Complexometric titration
ACID-BASE TITRATIONS
• Titration of strong acid
(a) with strong base.g. HCl with NaOH
(b) with weak base e.g. HCl with NH4OH
• Titration of weak acid
(c) with strong base e.g. CH3COOH with NaOH
(d) with weak base e.g. CH3COOH with NH4OH
 ADVANTAGES OF
CONDUCTOMETRIC TITRATIONS
 No need of indicator
 Colored or dilute solutions or turbid suspensions
can be used for titrations.
 Temperature is maintained constant throughout the
titration.
 End point can be determined accurately and errors
are minimized as the end point is being determined
graphically.
 Polarography

 The earliest voltammetric technique

 Heyrovsky invented the original polarographic
method in 1922, conventional direct current
polarography (DCP).
 It employs a dropping mercury electrode (DME) to
continuously renew the electrode surface.
 Diffusion is the mechanism of mass transport.
Introduction
 Theory of polarography
When an external potential is applied to a cell
containing a reducing substance such as CdCl2,
The following reaction will occur:

Cd2+ + 2e + Hg = Cd(Hg)
The technique depends on increasing the applied
voltage at a steady rate and simultaneously
record photographically the current-voltage
curve (polarogram)
The apparatus used is called a polarograph .
 A typical polarograph
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 Outlet of inert gas
Inlet of inert gas
(H2 or N2 to expel
dissolved oxygen
 Dropping Mercury Electrode
(Working electrode)
 Capillary tube about 10-15cm
 Int. diameter of 0.05mm
 A vertical distance being
maintained betwwen DME and the
solution
 Drop time of 1-5 seconds
 Drop diameter 0.5mm
Supporting electrolyte
The supporting electrolyte
is a solution of (KNO3, NaCl, Na3PO4) in which the
sample (which must be electroactive) is dissolved.

Function of the supporting electrolyte

It raises the conductivity of the solution.
It carries the bulk of the current so prevent the
migration of electroactive materials to working
electrode.
It may control pH
It may associate with the electroactive solute as
in the complexing of the metal ions by ligands.
Polarographic measurements
Polarography measurement is governed by
ilkovic equation:
id= 708 nD1/2m2/3t1/6C
n= no. of electrons
t= drop time (second/drop)
D= diffusion coefficient of analyte (cm2/s)
m= rate of flow of Hg through capillary (mg/s)
C= analyte’s concentration in mM
 Polarogram
0.001 M Cd2+ in 0.1 M KNO3 supporting electrolyte

All Cd2+ around the electrode has already

Electrode become more and more
been reduced. Limiting Current at the
reducing and capable of reducing Cd2+
electrode is reached by limiting the
Cd2+ + 2e- Cd diffusion rate of Cd2+ from the solution to
Current starts to be registered at the the electrode. Thus, current stops rising and
Current i (A)

levels off at a plateau

electrode (decomposition potential)
id
Current at the working electrode
Working electrode is no yet continue to rise as the electrode
capable of reducing Cd2+  become more reducing and more Cd2+
only small residual around the electrode are being
current flow through the reduced. Diffusion current of
electrode Cd2+ is not limited Base line
of residual
current
E½ Half –wave potential
-0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4
Applied potential, V vs SCE
Polarogram
The Polarogram is characterized by the
following parameters:

• Residual current
• Limiting current
• Diffusion current
• Half wave potential (E1/2)
 Advantages and disadvantages of DME
Advantages of DME
Its surface is reproducible, smooth and continuously
renewed, this eliminates the poisoning effect.
Mercury forms amalgams (solid solution) with many metals.
The diffusion current assumed a steady value immediately
after each change of applied potential and is reproducible.
The large hydrogen over-potential of mercury renders
possible deposition of substance that difficult to reduce.
The surface area can be calculated from the weight of drop.
Disadvantages of DME
At potential more positive than + 0.4 V vs SCE, mercury
dissolves producing anodic polarographic wave which
masks other waves, therefore DME can be used only for the
analysis of reducible or easily oxidizable substances.
The capillary is very small so easy to be blocked→ malfunction
of the electrode
Mercury is very toxic and easily oxidized
 Application of Polarography
A. Qualitative: by using the half wave potential which is
characteristic to each substance

B. Qualitative
INORGANIC ANALYSIS ORGANIC ANALYSIS

– Analysis of metals – Analysis of

• Zn carbonyl,peroxide,
• Cd nitro, azo group, etc.
– Analysis of anions as
dromate, iodate, etc. – Biochemical analysis
 Application of Polarography
Advantages of using polarography in pharmaceutical analysis
•1- Only small volume of sample is required.
•2- Turbid and coloured solutions can be analyzed.
•3- It can be used for the determination of
substances, which are not electrochemicall active
(indirect).
•4- Prior separation of excepients is not required.
•5- Its sensitivity is sufficient for the determination
trace elements and toxic impurities.
6- Samples of natural origin
7- high speed analysis which is important for QC