Submitted To: Ma’m Mubeen

Submitted By: Ali Saif

Roll No: 18026223-004

Assignment: Electrochemistry

Semester: 2nd

Course Title: Physical and organic chemistry

Department of Chemical Engineering

 ELECTROCHEMISTRY
ELECTROCHEMISTRY
Electrochemistry is the study of production of electricity from the energy released during a
spontaneous chemical reaction and the use of electrical energy to bring about non-spontaneous
chemical transformations.

ELECTROCHEMICAL CELLS

A spontaneous chemical process is the one which can take place on its own and in such a process
the Gibb’s energy of the system decreases. It is this energy that gets converted to electrical
energy. The reverse process is also possible in which we can make non-spontaneous processes
occur by supplying external energy in the form of electrical energy. These inter conversions are
carried out in equipments called Electrochemical Cells.

TYPES:

Electrochemical Cells are of two types:

Galvanic Cells Converts chemical energy into electrical energy.

Electrolytic Cells Converts electrical energy into chemical energy.

GALVANIC CELL
Cell energy is extracted from a spontaneous chemical process or reaction and it is
converted to electric current.
For example,

Daniel Cell is a Galvanic Cell in which Zinc and Copper are used for the redox reaction to take
place.

Zn (s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)

Oxidation Half :

Zn (s) Zn2 + (aq) + 2e–

Reduction Half :

Cu2 + (aq) + 2e– Cu(s)

Zn is the reducing agent and Cu2+ is the oxidizing agent. The half cells are also known as
Electrodes. The oxidation half is known as Anode and the reduction half is called Cathode.
Electrons flow from anode to cathode in the external circuit. Anode is assigned negative polarity
and cathode is assigned positive polarity. In Daniel Cell, Zn acts as the anode and Cu acts as the
cathode.

ELECTROLYTIC CELL
These electrodes are dipped in and electrolytic solution containing cations and anions. On
supplying current the ions move towards electrodes of opposite polarity and simultaneous
reduction and oxidation takes place.

Preferential Discharge of ions

Where there are more than one cation or anion the process of discharge becomes competitive in
nature. Discharge of any ion requires energy and in case of several ions being present the
discharge of that ion will take place first which requires the energy.
ELECTRODE POTENTIAL
It may be defined as the tendency of an element, when it is placed in contact with its own ions to
either lose or gain electrons and in turn become positively or negatively charged. The electrode
potential will be named as oxidation or reduction potential depending upon whether

oxidation or reduction has taken place.

Characteristics:

(a) Both oxidation and reduction potentials are equal in magnitude but opposite in sign.

(b) It is not a thermodynamic property, so values of E are not additive.

STANDARD ELECTRODE POTENTIAL

It may be defined as the electrode potential of an electrode determined relative to standard
hydrogen electrode under standard conditions. The standard conditions taken are :

(i) 1M concentration of each ion in the solution.

(ii) A temperature of 298 K.
(iii) 1 bar pressure for each gas.

ELECTROCHEMICAL SERIES

The half cell potential values are standard values and are represented as the standard reduction
potential values as shown in the table at the end which is also called Electrochemical Series.
CELL POTENTIAL OR EMF OF A CELL

The difference between the electrode potentials of two half cells is called cell potential. It is
known as electromotive force (EMF) of the cell if no current is drawn from the cell.

Ecell = Ecathode + Eanode

For this equation we take oxidation potential of anode and reduction potential of cathode. Since
anode is put on left and cathode on right, it follows therefore,

= ER + EL

For a Daniel cell, therefore

E cell = ECu - EZn = 0.34 (-0.76) = 1.10 V

CELL DIAGRAM OR REPRESENTATION OF A CELL

The following conventions or notations are applied for writing the cell diagram in accordance
with IUPAC recommendations.

The Daniel cell is represented as follows:

Zn(s) | Zn2+ (C1 ) || Cu2+ (C2 ) | Cu (s)

(a) Anode half cell is written on the left hand side while cathode half cell on right hand side.

(b) A single vertical line separates the metal from aqueous solution of its own ions.

Zn (s) | Zn (aq) ; Cu (aq) | Cu (s)

(c) A double vertical line represents salt bridge

(d) The molar concentration (C) is placed in brackets after the formula of the corresponding ion.

(e) The value of e.m.f. of the cell is written on the extreme right of the cell.

For example,

Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu EMF = +1.1V

(f) If an inert electrode like platinum is involved in the construction of the cell, it may be written
along with the working electrode in bracket say for example, when a zinc anode is connected to a
hydrogen electrode.
SALT BRIDGE
Salt bridge is used to maintain the charge balance and to complete the circuit by facilitating the
flow of ions through it. It contains a gel in which an inert electrolyte like Na2 SO4 or KNO3 etc
are mixed. Negative ions flow to the anode and positive ions flow to the cathode through the salt
bridge and charge balance is maintained and cell keeps on functioning.

SPONTANEITY OF A REACTION

ΔG = – nFECELL

For a spontaneous cell reaction ΔG should be negative and cell potential should be positive.

If we take standard value of cell potential in the above equation we will obtain standard value of
ΔG as well.

ΔGo = – nFE0 CELL

TYPES OF ELECTRODES

Metal-Metal Ion electrodes:

A metal rod/plate is dipped in an electrolyte solution containing

metal ions. There is a potential difference between these two phases and this electrode can act as
a cathode or anode both.
Anode:

M Mn+ + ne–

Cathode:

Mn+ + ne– M

Gas Electrodes
Electrode gases like H2 , Cl2 etc are used with their respective ions. For example, H2 gas is used
with a dilute solution of HCl (H+ ions). The metal should be inert so that it does not react with
the acid.

Anode: H2 2H+ + 2e–

Cathode: 2H+ + 2e– H2

The hydrogen electrode is also used as the standard to measure other electrode potentials. Its
own potential is set to 0 V as a reference. When it is used as a reference the concentration of dil
HCl is taken as 1 M and the electrode is called “Standard Hydrogen Electrode (SHE)”.

Metal-Insoluble salt electrode

We use salts of some metals which are sparingly soluble with the metal itself as electrodes. For
example, if we use AgCl with Ag there is a potential gap between these two phases which can be
identified in the following reaction:

AgCl(s) + e– Ag(s) + Cl–

This electrode is made by dipping a silver rod in a solution containing AgCl(s) and Cl– ions.
Calomel Electrode

Mercury is used with two other phases, one is a calomel paste (Hg2 Cl2 ) and electrolyte
containing Cl– ions.

Cathode :

Hg2Cl 2 (s) + 2e– 2Hg(l) + 2Cl – (aq)

Anode :

2Hg(l) + 2Cl – (aq) Hg2Cl 2 (s) + 2e–

This electrode is also used as another standard to measure other potentials. Its standard form is
also called Standard Calomel Electrode (SCE).

Redox Electrode
In these electrodes two different oxidation states of the same metal are used in the same half cell.
For example, Fe2+ and Fe3+ are dissolved in the same container and an inert electrode of
platinum is used for the electron transfer. Following reactions can take place:

Anode:

Fe2+ Fe3+ + e–

Cathode:

Fe3+ + e– Fe2+
BATTERIES
When Galvanic cells are connected in series to obtain a higher voltage the arrangement is called
Battery.

Primary Batteries
Primary cells are those which can be used so long the active materials are present. Once they get
consumed the cell will stop functioning and cannot be re-used.

Example:

Dry Cell or Leclanche cell and Mercury cell.

Dry cell:
Anode :

Zn container

Cathode:

Carbon (graphite) rod surrounded by powdered MnO2 and carbon.

Electrolyte :

NH4 Cl and ZnCl2

Reaction :

Anode : Zn Zn2+ + 2e–

Cathode : MnO2 + NH4 + e – MnO (OH) + NH3

The standard potential of this cell is 1.5 V and it falls as the cell gets discharged continuously
and once used it cannot be recharged.

Mercury cells:
These are used in small equipments like watches, hearing aids.

Anode :

Zn – Hg Amalgam

Cathode :

Paste of HgO and carbon

Electrolyte:

Paste of KOH and ZnO

Anode :

Zn (Hg) + 2OH– ZnO (s) + H2O + 2e–

Cathode :

HgO (s) + H2O + 2e– Hg (l) + 2OH–

Overall Reaction :

Zn (Hg) + HgO (s) ZnO (s) + Hg (l)

The cell potential is approximately 1.35V and remains constant during its life.

Secondary Batteries
Secondary cells are those which can be recharged again and again for multiple uses. e.g. lead
storage battery and Ni – Cd battery.

Lead Storage Battery:

Anode :

Lead (Pb)

Cathode :

Grid of lead packed with lead oxide (PbO2 )

Electrolyte :

38% solution of H2 SO4 Discharging Reactions

Anode:

Pb(s) + SO4 (aq) PbSO4 (s) + 2e–

Cathode:

PbO2 (s) + 4H+ (aq) + SO4 2– (aq) + 2e– PbSO4 (s) + 2H2O(l)

Overall Reaction :

Pb(s) + PbO2 (s) + 2H2 SO4 (aq) 2PbSO4 (s) + 2H2O(l)

 To recharge the cell, it is connected with a cell of higher potential and this cell behaves as an
electrolytic cell and the reactions are reversed. Pb(s) and PbO2 (s) are regenerated at the
respective electrodes.These cells deliver an almost consistent voltage.

Recharging Reaction :

2PbSO4 (s) + 2H2O(l) Pb(s) + PbO2 (s) + 2H2 SO4 (aq)

FUEL CELLS

A fuel cell differs from an ordinary battery in the sense that the reactants are not contained inside
the cell but are externally supplied from an external reservoir. Fuel cell is used in space vehicles
and in this cell the two gases are supplied from external storages. In this cell carbon rods are
used as electrodes with KOH as the electrolyte.

Cathode :

O2 (g) + 2H2O (l) + 4e– 4OH– (aq) E = 0.40V

Anode :

2H2 (g) + 4OH– (aq) 4H2O (l) + 4e– E = -0.83V

Overall Reaction :

2H2 (g) + O2 (g) 2H2O (l) Ecell = 1.23V

Efficiency of fuel cell is 70%

Reference:
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