Electrochemistry

and its uses

Muhammad Abtahee 32
Abdullah Kiani 72
Introduction
 The branch of chemistry that deals with the chemical
changes produced by electricity and the production of
electricity by chemical changes.
 It is the study of interconversion of chemical energy and
electrical energy.
 Study of redox reaction(transfer of electrons from one
substance to another).
Oxidation and Reduction

 It is the loss of electrons during a reaction by a molecule,

atom or ion.
 Oxidation occurs when the oxidation state of a molecule,
atom or ion is increased.
 Reduction occurs when there is a gain of electrons or the
oxidation state of an atom, molecule, or ion decreases.
 Example:
 H2 → 2 H+ + 2 e-
 F2 + 2 e- → 2 F-
 H2 + F2 → 2 HF
Reducing and oxidizing agent

 Oxidizing agents removes electrons from another

substance in a redox reaction.
 Reducing agents donates electrons to another substance in
a redox reaction.
 Example:
 Cu(s)+2 Ag+(aq) →Cu2+(aq)+2 Ag(s).
EMF and its relation with Gibbs
free energy ΔG
 Energy per unit electric charge that is imparted by an
energy source, such as an electric generator or a battery.
 Relation:
 Gibbs free energy is the change in the amount of energy
available in a chemical system to do work.
 In an electrochemical cell, the work done is dependent on
the number of coulombs of charge transferred and the
energy available.
 ΔG = –zFE
Entropy Change

 Entropy is the measure of disorder.

 Electrochemical measurements are easy and quick to
obtain thermodynamic data.
 -ΔS= ΔG/ΔT
Enthalpy Change

 Enthalpy is the total heat content of the system.

 ΔH= ΔG + TΔS
 To find ΔG, ΔH, ΔS :
 Set up an appropriate electrochemical cell
 Measure EMF at various temperatures (3 or 4
temperatures).
EMF Series

 An electromotive force series is a metal's ranking in

respect to inherent reactivity.
 All metals have arranged in a series according to their
standard potential values.
 The more positive value corresponds to noble metals and
the more negative value to more reactive metals.
 If two metals make up a cell , the more active metal acts as
the anode and the more noble metal of the two will act as
the cathode.
Electrochemical Series

 A serial arrangement of metallic elements or ions

according to their electrode potentials determined under
specified conditions.
 Metals are ranked in accordance with their potential in 1 N
solution of their solutions.
 Hydrogen is zero reference.
 If metal has positive value it is called noble metal or semi
noble such as silver, copper etc.
 If metal has negative value it is called active metal such as
iron, aluminum, magnesium and zinc.
Limitations of EMF series

 In real solutions, activities of metal ions in equilibrium with the

respective metals usually do not equal to unity.
 The position of a metal in EMF series with respect to another
metal may change because of complex formation.
 Alloys are not included in EMF series.
 In oxidizing environment, some metals undergo passivation.
Transition metals usually shows passive behavior in aerated
aqueous environment. This dual position of some metals is not
reflected in EMF series.
Pourbaix Diagram

 Pourbaix diagrams shows conditions of potential and pH under

which a metal either be:
 Immune.
 Passive.
 Corrode.
 If hydrogen ions are involved we will get pH.
 If electrons are involved we will get potential.
 Horizontal lines mean constant potential.
 Vertical lines mean constant pH.
 Inclined lines will have both pH and potential.
Pourbaix Diagram(Cont.)
Uses of Electrochemistry

 Electrochemistry can be useful in extraction, refining, plating,

corrosion and its control, power generation, melt composition,
thermo data etc.
 Electrolytic cells are used in the electro refining of many non-
ferrous metals. They are also used in the electro winning of these
metals.
 Electrochemistry is important for creating new technologies that
are ecofriendly.
 It bring about non-spontaneous chemical transformations.
Thank You