Electrochemistry

Introduction
• Electrochemistry is the branch of physical chemistry
that studies the relationship between electricity, as
a measurable and quantitative phenomenon, and
identifiable chemical change, with either electricity
considered an outcome of a particular chemical
change or vice versa. These reactions involve
electric charges moving between electrodes and an
electrolyte (or ionic species in a solution). Thus
electrochemistry deals with the interaction
between electrical energy and chemical change.
 Potentiometric titration
• Potentiometric titration is a technique similar
to direct titration of a redox reaction. It is a
useful means of characterizing an acid. No
indicator is used; instead the potential is
measured across the analyte, typically an
electrolyte solution.
Concentration or potential Concentration or potential is
is known to us unknown to us
 Principle
• We can find out the concentration of solution
by measuring the potential difference
between the two electrodes
• When electrodes are dipped in an ionic
solution oxidation or reduction will take place
on indicator electrode
• Because of redox reaction, potential
difference is created between the two
electrodes and measured by voltmeter
Components of a Potentiometric
Cell
1. Reference electrode
2. Salt bridge
3. Analyte
4. Indicator electrode
 Electrode Potentials
• Ecell = Eindicator-Ereference
• Standard potential for cell, E0 cell, follows Nernst
Equation:
E0 cell = (RT/nF) lnK
E0 cell = (RT/nF) ln(reduced/oxidized)
R is gas law constant, T is temperature, K is equilibrium
constant, F is the Faraday, and n is number of
equivalents of electricity Electrode potential is sum
of two half-reactions. Cannot determine potential of
a single electrode, measure differences in potential.
 Reference electrode
•Half-cell with known potential (Eref)
•Left hand electrode (by convention)
•Easily assembled
•Unaffected by small variations
•Insensitive to analyte concentration
▫Constant potential
Indicator electrode
• Generates a potential
(Eind) that depends on
analyte concentration
• Selective
• Rapid and reproducible
response
 Salt bridge
• Prevents mixing up of analyte components with
components of electrode
• 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. This
movement of ions in the salt bridge completes the
electrical circuit.
• Generates potential (Ej) = negligible
• A salt bridge of saturated potassium chloride,
potassium nitrate or ammonium nitrate is used to
prevent possible contamination of the reference
electrodes with the test solutions.
• When two solutions of electrolytes are brought into
contact, a potential difference is set up between
them due to transference of ions across the
boundary. This potential difference is known as
liquid junction potential. The salt bridge reduces
this potential almost to zero.
 Liquid Junction Potential
• Liquid junction - interface between
two solutions containing different
electrolytes or different
concentrations of the same
electrolyte
• A junction potential occurs at every
liquid junction.
– Caused by unequal mobilities of the +
and - ions.
Reference Electrodes
1. Standard Hydrogen Electrode
2. Calomel Reference Electrode
3. Silver/Silver Chloride
Reference Electrode
 SHE
• Hydrogen Gas Electrode

• Pt (H2 (1 atm), H+ (1M)

• SHE is not often used because of

fire hazard
• Inconvenient to use and
maintain
• Although we rarely use the standard hydrogen
electrode (SHE) for routine analytical work, it is the
reference electrode used to establish standard-
state potentials for other half-reactions. The SHE
consists of a Pt electrode immersed in a solution.
• As the hydrogen gas flows over the porous
platinum, an equilibrium is set up between
hydrogen molecules and hydrogen ions in solution.
The reaction is catalysed by the platinum.
Saturated Calomel Electrode
Hg2Cl2(s)+2e-2Hg(l)+2Cl-(aq)

•SCE
•Easy to prepare
•Easy to maintain
•+246 mV potential at 25C
•Toxic
SCE
 Saturated calomel electrode
• saturated calomel electrode (SCE) the
concentration of Cl– is determined by the solubility
of KCl. The electrode consists of an inner tube
packed with a paste of Hg, Hg2Cl2, and KCl, situated
within a second tube containing a saturated
solution of KCl. A small hole connects the two tubes
and a porous wick serves as a salt bridge to the
solution in which the SCE is immersed. A stopper in
the outer tube provides an opening for adding
addition saturated KCl.
Ag/AgCl Ref. Electrode
• Another common reference electrode is
the silver/silver chloride electrode, which is
based on the following redox couple between
AgCl and Ag.
• AgCl(s)+e−⇋Ag(s)+Cl−(aq)
• As is the case for the calomel electrode, the
activity of Cl– determines the potential of the
Ag/AgCl electrode; thus
• +200 mV potential at 25C
 Indicator Electrodes
I. Metallic IE
II. Membrane IE
III. Gas Sensing Probes
METALLIC INDICATOR ELECTRODES
 Direct Indicator Electrodes
(Metallic Indicator Electrodes)
• The simplest type of direct indicator electrode is a
metal, M, in contact with a solution containing its
own cation, M+. At the metal-solution interface, a
potential develops that is proportional to the
activity of the metal ion in solution. The potential
can be measured directly with respect to a
reference electrode.
• The voltage measured is simply the difference
between the potential at each electrode:
• Ecell=Eindicator−Ereference
Metallic Indicator Electrode
Inert metal electrodes like Pt or Au can be used
as indicator electrodes for ions involved
in redox reactions that occur in solution
 MEMBRANE ELECTRODES

• In 1901 Fritz Haber discovered that there is a change in

potential across a glass membrane when its two sides are in
solutions of different acidity.
• Consist of a thin membrane separating 2 solutions of
different ion concentrations
• Most common: pH Glass electrode
• The existence of this membrane potential led
to the development of a whole new class of
indicator electrodes called ion-selective
electrodes (ISEs). In addition to the glass pH
electrode, ion-selective electrodes are
available for a wide range of ions.
• The development of new membrane
electrodes continues to be an active area of
research.
• A glass electrode is a type of ion-selective electrode made
of a glass membrane that is sensitive to a specific ion. The
most common application of ion-selective glass electrodes
is for the measurement of pH.
• The pH electrode is an example of a glass electrode that is
sensitive to hydrogen ions. Glass electrodes play an
important part in the instrumentation for chemical
analysis and physico-chemical studies. The voltage of the
glass electrode, relative to some reference value, is
sensitive to changes in the activity of certain type of ions.
Glass pH Electrode
 Theory Glass pH electrode
It consists of a silicate matrix based on
molecular network of silicon dioxide
(SiO2) with additions of other metal
oxides, such as Na, K, Li,
 Theory of the glass membrane potential
• 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:
• 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+]
GAS SENSING PROBES
• A number of membrane electrodes have been developed that
respond to the concentration of dissolved gases.
• They consists of a thin membrane separating the sample from
an inner solution containing an ion-selective electrode.
• The membrane is permeable to the gaseous analyte, but isnot
permeable to nonvolatile components in the sample matrix.
• Once the gaseous analyte passes through the membrane,
• it reacts in the inner solution, producing a species
whose concentration can be monitored by an appropriate ion
selective electrode.
• For example, in the CO2 electrode, CO2 reacts in the inner
 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