UNIT-III

ELECTROCHEMISTRY AND APPLICATIONS

ELECTROCHEMICAL CELLS
▪ It is device, which converts chemical energy into electrical energy and vice
versa.
▪ Oxidation – reduction reactions take place in electrochemical cells for
the generation ofelectrical energy.
These are of two types.
1. Galvanic Or Voltaic Cells:
⯌ These are devices which convert chemical energy into electrical energy.
⯌ These are spontaneous.
2. Electrolytic Cells:
⯌ These are devices which convert electrical energy into chemical energy.
These are non
- spontaneous.
⯌ Both types of cells contain electrodes where the oxidation and reduction reactions
occur. Oxidation occurs at anode (- ve) and reduction occurs at cathode (+ ve).
GALVANIC OR VOLTAIC
CELLS
🞻 It is an electrochemical cell that converts chemical energy into electrical
energy byspontaneous redox reaction within the cell.
🞻 It generally consists of two different metals connected by a salt bridge, or
individual halfcells separated by a porous membrane.
🞻 A common electrochemical or voltaic cell is Daniel cell.
🞻 It consists of two half cells i.e., one half cell on the left contains a zinc
metal electrode dipped in ZnSO4 solution and two half-cell on the right
contains a copper metal electrode dipped in CuSO4 solution.
🞻 These two half cells are separated by a salt bridge, and two electrodes are joined
by wire.
When these reactions take place, following observations can be made:
1. Electrical current flows from Zn electrode to Cu electrode through
external circuit.
2. Zinc loses its mass while the copper rod gains its mass.
3. Concentration of ZnSO4 solution increases while the concentration of
CuSO4 solutiondecreases.
4. Solutions in both the compartments remain electrically neutral.
REPRESENTATION OF A
GALVANIC CELL
Galvanic cell is represented as follows:
 Anode half cell is written on left hand side and cathode half cell is written on
right hand side.
 Anode is represented by writing the metal first and then the electrolyte. The
two are separated by a vertical line or semicolon. Concentration of an
electrolyte is represented in brackets.
Anode Half cell: Zn/ Zn+2 or Zn: Zn+2 or Zn/ ZnSO4 (1M)
 Cathode is represented by writing the electrolyte first and then metal.
Cathode Half-cell: Cu+2/Cu or Cu+2: Cu or CuSO4 (1M)/ Cu
 The salt bridge is represented by two vertical lines, separating the two half-
cells.
Galvanic cell: Zn/ Zn+2(1M)// Cu+2(1M)/Cu
 ELECTROMOTIVE FORCE
(EMF)
▪ The flow of electrons from one electrode to another electrode is due to
difference in electrodepotential.
▪ The difference in electrode potential which causes the flow of current from
one electrode to another electrode is called electromotive force of
electrochemical cell.

Ecell = Eright − Eleft

ECell - e.m.f of cell

Eright - electrode potential of right
hand side electrode

Eleft - electrode potential of left hand

side electrode
SINGLE ELECTRODE
POTENTIAL
▪ When Zinc metal (rod) is placed in the solution of its own ions, Zinc ions
move into solutionleaving behind electrons.
▪ Zinc metal gets –ve charge. This process is oxidation.
▪ Conversely, when Copper metal (rod) is placed in the solution of its own
ions, Cu2+ ionsdeposit on the metal surface by gaining electrons from the
metal.
▪ Copper metal gets +ve charge. This process is reduction.
 ▪ The rate of above two reactions depends upon
o The nature of the metal
o The temperature
o The concentration of the metal ions in the solution.
▪ A positive layer of Zinc ions is developed around Zinc metal and –ve layer of
sulphate ions is developed around copper metal. This layer is known as
Helmholtz double layer.

▪ A difference of potential is developed between the metal and the solution. This
potentialis called single electrode potential.
▪ The electrode potential is the measure of tendency of metal to lose or gain of
electrons, whenthe metal is in contact with its own ions of 1M concentration
at 25oC.
▪ Electrode potentials are of two types
• Oxidation potential: It shows the tendency of metal to lose electrons.
• Reduction potential: It shows the tendency of metal to gain electrons.
• For a metal both of these potentials have same numerical value with opposite
signs.
• If the oxidation potential of a metal is +x volts
• Its reduction potential will be –x volts.
ELECTRODE POTENTIAL
• Electrode potential is the tendency of metal electrode to lose or gain electrons,
when it is contacted with a solution of its own salt. It is represented by E.
 • Standard electrode potential is the electrode potential measured at standard
conditions i.e at 298K and 1M concentration of the electrolyte and
1atmosphere pressure. It is represented by E0.
EXPRESSION FOR ELECTRODE POTENTIAL (NERNST EQUATION)
Statement:

The reduction potential of two electrodes is directly proportional to the concentration

of electrolyte which we taken.
Consider a general redox reaction
M n+ + ne−  M

For a reversible reaction, free energy change and equilibrium constant are related as
This is Nernst equation.
Electrode potential depends on
a) Concentration of ions b) Temperature and c) Nature of the electrode

Cell potential calculations:

The driving force of the electron flow from anode to cathode shows a
potential drop in the energy of the electrons moving into the wire. The
difference in potential energy between the anode and cathode is known
as the cell potential in a voltaic cell.
Potentiometry: Potentiometry is a technique that is used in analytical
chemistry, usually to find the concentration of a solute in solution.
(or)
 The measurement of electrical potential as a technique in chemical
analysis.
In this technique, the potential between two electrodes is measured using
a high-impedance voltmeter (Wang, 2000). Use of a high-impedance
voltmeter ensures that current flow is negligible.

Potentiometric titrations:
A titration in which the equivalent or end point of a reaction is determined with
the help of the measurement of the potentials of the reaction mixture is known
as potentiometric titrations.
These are two types (i) Acid- base titrations.
(ii) Red- ox titrations.

(i) Acid- base titrations:

The acid solution whose strength has to be determined is take in a
beaker and the hydrogen electrode and calomel electrode were dipped in
the solution. The electrodes were connected to the potential meter and the
EMF is measured.

A known volume of standard alkali solution is added from the burette,

stirred thoroughly and the EMF of cell is recorded. Like these 10 to 15
readings are recorded by repeating the procedure of the additional
standard alkali. The volume of alkali added he's plotted again this is the
EMF absurd as shown in the figure. The steepest portion aftercare
indicates the equivalent point of the titration.
(ii) Red- ox titrations (or) oxidation reduction titrations:
This procedure adopted for oxidation reduction titration is the same as in acid
base titrations, the only difference is that the electrode reversible to hydrogen
ions is replaced by a bright platinum electrode. The EMF of the electrode is
determined by the activity of ratio of the substance being oxidized are
reduced. For example 𝐹𝑒 2+ Iterated against potassium dichromate. The
ferrous iron solution is taken in the beaker, treated with dilute sulfuric acid and
platinum electrode and the calomel electrode are dipped. The electrodes are
connected to the potential meter and the EMF of the solution after the addition
of potassium dichromate is recorded. A graph is plotted with EMF and volume
of potassium dichromate.
The steep rise is the endpoint of the titration.
Conductance: ➢ ease with which current flows per unit area of conductor per unit
potential applied & is reciprocal to resistance(R)
concept of conductivity:
Conductivity is the measure of the ease at which an electric charge
or heat can pass through a material. A conductor is a material which
gives very little resistance to the flow of an electric current or thermal
energy.
Conductivity cell:
Conductometric titrations:
Those titrations in which conductivity measurements are made use of in
determining endpoint off acid alkali reactions, some displacement reactions or
precipitation reactions are called conductometric titrations. The fact that the
conductance of a solution at a constant temperature depends upon the number of
ions present in it and their mobility is taken as advantage.

Types of conductometric titrations:

Acid-base titrations:

(i) String acid with strong base:

Consider the reaction in which hydrochloric acid is titrated against a solution of

sodium hydroxide. 20ml of my acid solution is taken in a conductivity cell placed
in a thermostat and the conductivity of the solution is measured. 1ml of NaOH
solution is added to the solution to this solution and the conductance is measured.
The process is repeated after every edition of 1ml of NaOH and the values are
plotted as shown below. The endpoint of interaction of two curves is the end point
of the titration.
(ii) Weak acid and strong base:

When a weak acid like acetic acid is titrated against a strong alkali like sodium
hydroxide a carve shown below is obtained .

The initial conductivity of the solution is low because of the poor dissociation
of the weak acid. On adding alkali, highly ionized sodium acetate is formed.
The acetate ions at first tend to suppress the ionization acetic acid due to
common effect. Later the conductivity begins to increase due to the conducting
power of the who highly ionized salt exceed that of the weak acid. After
endpoint the addition of sodium hydroxide contribute sharp increase in the
conductivity of the solution the point of intersection two curves gives the
endpoint of the titration.
Strong acid with weak base:

The curve obtained for the titration of a strong acid with a weak base is shown
in the below figure.
 In this case the conductivity of the solution will first decrease due to the fixing
up of the first moving H+ ions and their replacement by slow moving NH4+
ions. After the end point has been reached, the addition of access drops of
ammonium hydroxide will not cause any appreciable change in conductivity,
as ammonium hydroxide is a weak electrolyte.
(iV) weak acid with weak base:
The titration of a weak acid with weak base does not give a sharp endpoint.
Consider the titration of acetic acid with ammonium hydroxide.

The complete titration curve is as shown below.

The initial conductance of the solution is low due to the poor dissociation of the
week acid, but it starts rising as CH3COONH4 is farmed after the equivalent
point, the conductivity remains almost constant, because the freebase
ammonium hydroxide is weak electrolyte. The endpoint he is quite sharp in this
case by this conductometric titration.
Photo chemical sensors:
They are photochemical and photometric, and are used to find the
concentration or changes in the chemical reactions with most
accuracy. The chemical sensors are highly sensitive in nature.
A Photoelectric Sensor consists primarily of an Emitter for emitting light
and a Receiver for receiving light. When emitted light is interrupted or
reflected by the sensing object, it changes the amount of light that arrives
at the Receiver. The Receiver detects this change and converts it to an
electrical output.

Potentiometric sensors:
A potentiometric sensor is a type of chemical sensor that may be
used to determine the analytical concentration of some components
of the analyte gas or solution. These sensors measure the electrical
potential of an electrode when no current is present.

A potentiometric sensor is a type of electrochemical sensor that may be

used to measure the potential difference of an electrode.
Ex: PH meter
Principle:
• The signal is measured as the potential difference(voltage) between
the working electrodes and the reference electrodes. The working
electrodes potential must depend on the concentration of the
analyte in the gas or solution phase.
• In the potentiometric sensors the ion selective electrode is coupled
with the reference electrode to complete the circuit end the sensor
measure the potential difference between two electrodes.
Use of potentiometric sensors:
The potentiometric sensors are used in analysis of glucose in blood.
Glucose is converted into ions, which is detected by the ion selective
electrode. Glucose is oxidized into gluconic acid which is further
undergoes decomposition and gives H+ ions which are detected by PH
electrode.

positive ions measured by pH meter, a potential difference is set up

between glass electrode and reference electrode which is sense by
potentiometric sensor which analyze the glucose level in blood.
PH meter:
• The measuring system consists of a PH measuring electrode
(indicating electrode) and reference electrode.
• The potential difference between the two electrodes is a function of
the pH value of the measured solution.
Working:
Reference electrodes:

1. Hydrogen Electrode:-
➢ It consists of a small platinized platinum foil, which is sealed through
theend of a glass tube. This tube is surrounded by another co-axial
tube, which is sealed to the inner glass tube at the top.
➢ The outer glass tube is provided with a side arm for passing hydrogen
gas.
➢ The bottom of the outer tube is blown into a bell around the platinum
electrode. Openings in the bell allow the escape of hydrogen gas.
➢ The platinum foil is coated with a layer finely divided platinum
(platinumblack), which absorbs the hydrogen gas and it also speeds
up the equilibrium between hydrogen gas and the hydrogen ions (H+
(or) H3O+).

Standard Hydrogen Electrode

This electrode, when dipped in a 1M HCl and when hydrogen at 1 atm is
passed through, yields a Normal (or) Standard hydrogen electrode. The e.m.f. of
such cell has arbitrarily been fixed at Zero. Hydrogen electrode may be employed
to find the pH value of an unknown solution.
Limitations:
1. The hydrogen electrode is readily affected by compounds of Hg, As,
S andoxidizing agents like, Fe3+, MnO4-, Cr2O7-2 etc., and consequently,
this electrode cannot be used in solutions containing these ions.
2. It cannot be used in the presence of ions of many metals.
 3. It cannot be used in solutions containing redox systems.
4. It is quite inconvenient to setup a hydrogen electrode.
Calomel Electrode:-
It is the most commonly used mercury- mercurous chloride electrode. The
potential of the calomel electrode, on the hydrogen scale, has been found to vary
with the concentration of the potassium chloride solution used. The potential of
this electrode is equal to the e.m.f. of the cell.

Diagram:-

Saturated Calomel Electrode

Construction: It consists of tube in the bottom of which is a layer of mercury, over
which is placed a paste of Hg+Hg2Cl2. The remaining portion of cell is filled
with a solution of normal or decinormal or saturated solution of KCl. A
platinum wire dipping into the mercury layer is used for making electrical
contact. The side-tube is used for electrode is formulated as:

The calomel electrode can acts as anode or cathode depending on the nature of
the other electrode of the cell.
The net cell reversible electrode reactions,

Therefore electrode potential of calomel electrode is depending upon the

concentration of KCl. The electrode is reversible with chloride ions.
The electrode can be coupled with hydrogen electrode containing solution of
unknown pH.
The potential of the calomel electrode depends upon the concentration ofKCl solution used.
Following table gives the values of std. oxidation potentials for different concentrations of KCl solution
used.( measured at 298K).

Concentration of KCl Saturated KCl 1M KCl 0.1M KCl

E0 [v] 0.241 0.281 0.334

Applications:-
1. It is used as secondary reference electrode in the measurement of
singleelectrode.
2. It is used as reference electrode in all potentiometer determinations
and tomeasure pH of the given solution.
Amperometric sensors:
Amperometric sensors measure the current response to detect the concentration of an analyte
at a fixed potential.
Principle:

Amperometry involves the measurements of currents at constant voltage applied at the

dropping mercury electrode. The value of electrode potential is chosen in such a way that only
the metal ion is reduced. This method is generally used for the determination of metal ion
present in aqueous solution.

Examples:
The most prevalent examples of the amperometric method employ an enzyme-catalyzed
redox reaction, where the resulting redox electron current is measured at a working electrode
for high sensitivity.

Applications:
• This method is generally used for the determination of metal ion present in aqueous
solution.
• Amperometry involves the measurements of currents at constant voltage applied at
the dropping mercury electrode.

• The value of electrode potential is chosen in such a way that only the metal ion is
reduced.
Advantages:
High sensitivity, selectivity, low cost, and the ability to integrate easily into continuous analysis
systems are some general advantages of amperometric biosensors .

CELLS (OR) BATTERIES

• Cell is a device in which chemical energy is converted into electrical energy.
• Many cells connected in series are called battery.
• Cells are of two types.
Primary Battery or Primary Cells
▪ Cells in which electricity is continuously generated till all the reactants
areconverted into products.
▪ These reactions are irreversible.
▪ Hence cell becomes dead after the conversion of reactants into
products. Suchcells cannot be charged.
1. Secondary Cells Or Secondary Battery
▪ Secondary cells may be used through a large number of cycles of
discharging andcharging.
▪ Cell reactions are reversible.
▪ As and when required the cell can be discharged and
charged.Ex: Lead acid storage battery.
ZINC –AIR BATTERIES

Zinc air batteries are receiving a significant attention in the last years. They have
a high capacity, low cost, low toxicity and they are competitive with state of the
art batteries (Li-ion, NiMH). In zinc-air batteries, zinc is oxidized by oxygen
taken from the surrounding air. Battery is constructed from four components: zinc
anode, air cathode, separator and electrolyte.
Applications:
• Very small battery used in hearing aids.
• Larger battery used in cameras.
• Very larger battery used in electric vehicles.
SECONDARY CELLS

LITHIUM ION BATTERY

➢ These batteries contain lithium ions instead of metallic lithium hence they
are called lithium ion cells.
➢ In these cells, oxidation and reduction reactions does not takes place, but
transport of Li+ ions from one electrode to another electrode through the
electrolyte (like LiBF4, LiPF6 or organic solvent).
➢ In this battery, lithium ions interchange between two layers of graphite and
LiCoO2.
 ➢ During charging process, lithium ions leave LiCoO2 and travel through the
electrolyte to the graphite (C6).
LiCoO2 + graphite(C6 ) → Li1−xCoO2 + LixC6

➢ During discharging process, lithium ions leave move back through the

electrolyte to the cobalt oxide.

Li1−xCoO2 + LixC6 → Li1−x+ y CoO2 + Lix− y C6

➢ Thus, charging and discharging cycle is simply migration of Li+ ions

from oneelectrode to another electrode with flow of electrons through the
external circuit.
Applications:
These are used in electronic circuit boards, military and space applications,
medicaldevices.

FUEL CELLS

❖ A fuel cell is an electrochemical cell which converts chemical energy

intoelectrical energy by available oxidant.
❖ The fuel and oxidizing agents are continuously supplied to the
electrodes of thecell, at which they undergo reactions.
❖ Fuel cells are capable of supplying current as long as reactants are
supplied.
❖ Fuel cells are characterized by
✓ High efficiency
✓ Low noise
✓ Free from vibration and pollution

HYDROGEN – OXYGEN FUEL CELL

CONSTRUCTION
1. Electrodes are made of two porous graphite rods impregnated with
finepowder of Pt or an alloy of Pb with Ag or Ni.
2. Electrolyte solution 2.5% KOH.
3. H2 gas is bubbled through anode and O2 gas is bubbled through the
cathode.
Polymer Electrolyte Membrane fuel cells (PEMFC):
A polymer electrolyte membrane containing water has acidity comparable
to a solution with 10 wt% sulfuric acid. The anode side is a hydrogen
ambient atmosphere, while the cathode side is air. Because of
humidification and water produced by the reaction, the reactive gas
contains saturated water vapor.
The electrolyte material used in PEMFCs is a copolymer of
poly(tetrafluoroethylene) and polysulfonyl fluoride vinyl ether. The polymer
is stable in both oxidative and reductive environments and has high
protonic conductivity (0.2 S/cm) at typical PEMFC operating
temperatures.

PEM fuel cell directly converts chemical energy of a fuel into electricity by
the reaction of hydrogen with oxygen over a proper catalyst with water as
by-product.
The PEMFC typically operates at 160 F (70 ◦C) to 185 F (85 ◦C). About 50% of
the maximum power is available immediately at room temperature. Full operating
power is available within about 3 min under normal conditions. The low
temperature of operation also reduces or eliminates the need for thermal
insulation to protect personnel or other equipment.