Bridge Program - Chemistry

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Module 1 Basics of Electrochemistry

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 Syllabus

Introduction-Redox Reactions-Oxidation and Reduction with examples-Galvanic cell (Daniel Cell)-Principle

& Working-Origin of single electrode potential-Nernst Equation (Numerical) – Reference Electrode-

Standard Hydrogen Electrode (SHE)-Determination of electrode potential using SHE-Electrochemical

Series-Applications (Numerical)-Cells &Batteries-Primary and Secondary Cells-Inorganic semiconductors-P

type and N-Type-Examples

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 Introduction
Father of modern electrochemistry: Allen Bard
****************************************
Interconversion of electrical and chemical energy

Which kind of substances can act as electrolytes?????????

 Aqueous solution or molten state

 Liberation of ions
 Allows electric current to pass through there by resulting in
its chemical decomposition.

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 Electrochemistry

Anode Cathode
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 Electrochemistry
An electrode is a solid electric conductor that carries electric current into
non-metallic solids, or liquids, or gases.

Electrodes : Two types An Ox

Anode: Oxidation – Loss of electrons Red Cat
Cathode: Reduction – Gain of electrons
Electrode representation

M M n+
+ ne-
Oxidation Anodic representation – Metal/Metal ion (M/Mn+)
M n+ + ne- M Reduction
Cathodic representation – Metal ion/Metal (Mn+/M)
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Electrochemistry

tV

Electrochemical cell Zn/Zn2+//Cu2+/Cu 7

 Electrochemistry
Cell representation

Oxidation half cell // Reduction half cell

OR

Anode// Cathode

OR

Metal/Metal ion // Metal ion/ Metal

Left – Oxidation half cell (Anode) Right- Reduction half cell (Cathode)
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Give the Oxidation and Reduction Reactions

Al Al -> Al3+ + 3e Al3+ + 3e -> Al H 1+

Li 1+
Mg Mg -> Mg2+ + 2e Mg2+ + 2e -> Mg Mg 2+
Fe 2+
H H2 -> 2H+ + 2e 2H+ + 2e -> H2
Ag 1+
Pb -> Pb2+ + 2e Pb2+ + 2e -> Pb Au 3+
Pb Cl 1-
Au Au -> Au3+ + 3e Au3+ + 3e -> Au Al 3+
Pb 2+
Ag Ag -> Ag+ + e Ag+ + e -> Ag Mn 2+
Br 1-
Br 2Br- -> Br2 + 2e Br2 + 2e -> 2Br-
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 Electrochemistry
An oxidation-reduction reaction is a type of chemical reaction that involves the
transfer of electrons between two species

Redox reaction

Electrochemical cell – Convert chemical energy into electrical energy

Electrolytic cell – Convert electrical energy into chemical energy

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 Types of Reactions

Redox

 Redox reactions are oxidation-reduction chemical reactions in which the reactants

undergo a change in their oxidation states

 CuSO4+Zn→Cu+ZnSO4

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 Electrode potential

Tendency of electrode to lose or gain electrons when it is in contact with its own ionic
solution

 Oxidation potential
Tendency of electrode to lose electrons when it is in contact with its own ionic solution
M -> Mn+ + ne-

 Reduction potential
Tendency of electrode to gain electrons when it is in contact with its own ionic solution
Mn+ + ne- -> M

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 Helmholtz Electrical Double Layer
M M n+ + ne- Oxidation Oxidation
 During oxidation metal ions enter into the
M n+ + ne- M Reduction
electrolyte leaving behind electrons
 The anode becomes negatively charged
 Negative anode attracts positive metal ions
due to electrostatic force to form a double
layer of charges

Reduction
 Positive metal ions from solution takes
electrons from electrode and gets deposits
as metal
 Electrode becomes positively charged
 It attracts negative charges to form a double
layer
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 Write the cell representation
Anode Cathode Cell Representation

Zn in Zinc Sulphate Ag in Silver chloride Zn/Zn2+ // Ag+ /Ag

Cd in Cadmium chloride Au in Gold chloride Cd/Cd2+ // Au3+ /Au

Mg in Magnesium sulphate Cu in Copper sulphate Mg/Mg2+ // Cu2+ /Cu

Fe in Ferrous chloride Cu in Cupric chloride Fe/Fe2+ // Cu2+ /Cu

Al in Aluminium chloride Ag in Silver nitrate Al/Al3+ // Ag+ /Ag

Li in Lithium Chloride Nickel in Nickel Chloride Li/Li+ // Ni2+ /Ni

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 Design & sketch a reversible cell for the reaction
2Al (s) + 3Fe2+ (aq) 2Al3+ (aq) + 3Fe (s)
Design –Cell representations and reactions
Sketch – Schematic representation e-

Anode – Oxidation Potentiometer

2Al (s) 2Al3+ (aq) + 6e-

KCl

Cathode – Reduction
3Fe2+ (aq) + 6e- 3Fe (s) Salt bridge
Al Fe
Cell Representation
Al2(SO4)3
Al/Al3+// Fe2+/Fe Solution
FeSO4
Anode Cathode Solution
Oxidation half cell Reduction half cell
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Differences between electrochemical cell & electrolytic cell

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Identify the oxidation & reduction half cell for the following reaction

2H+(aq) + 2Li (s) 2Li+ (aq) + H2 (g)

 Identify the Oxidation & reduction reaction  Write the Oxidation & reduction half cell

Oxidation - Loss of electrons Oxidation half cell – Li/Li+

Reduction – Gain of electrons
Reduction half cell – 2H+/H2
Oxidation - 2Li (s) 2Li+ (aq) + 2e-
Reduction - 2H+(aq) + 2e- H2 (g)

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Standard Hydrogen Electrode (SHE)

Primary reference electrode

Example of gas electrode
Electrode Potential = 0 V

Apparatus

 Inert platinum electrode

coated with platinum black
 Dipped in 1M HCl
 Hydrogen gas passed at 1atm

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 Standard Hydrogen Electrode (SHE)
Depending on the potential of coupled electrode it can act as anode or
cathode

If the potential of coupled electrode is less than zero SHE act like cathode

2H+ + 2e- -> H2 (reduction)

If the potential of coupled electrode is greater than zero SHE act like anode

H2 -> 2H+ + 2e- (Oxidation)

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 Determination of potential using SHE
e- Ecell = E cathode – E anode
Potentiometer = Ecu – ESHE

KCl
Ecu = Ecell + 0
H2 (1atm) Ecu = Ecell
Salt bridge Anode : H2 -> 2H+ + 2e-
Pt wire
Cu
Cathode : Cu2+ + 2e- -> Cu
H+ solution CuSO4
(1M) at 298 K Anode Cathode Solution Cell Reaction : H2 + Cu2+ -> 2H+ + Cu
Oxidation half cell Reduction half cell

Nernst Equation
Pt/H2/H+ // Cu2+/Cu20
 Limitations of SHE

 Requires considerable volume of test solution

 Hydrogen electrode will be poisoned by compounds like Hg, As, S etc
 Cannot be used in solution containing redox systems
 Difficult to maintain pressure at 1 atm
 Expensive due to Pt

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 Nernst Equation for a single Electrode
Nernst Equation for a single electrode
Nernst equation is

E = Eo - 2.303RT/nF log Keq

General reduction reaction

Mn+ + ne- -> M(s)

E = Eo - 2.303RT/nF log [M]/[Mn+]

E = Eo - 2.303RT/nF log 1/[Mn+]

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 Nernst Equation for a cell

E = Eo - 2.303RT/nF log Keq (Keq = [P]/[R] )

Eg. Daniel cell

Zn + Cu2+ -> Zn2+ + Cu

Eocell = EoCathode – EoAnode n=2

E = (EoCu – EoZn ) - 2.303RT/2F log [Zn2+]/ [Cu2+]

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 Prediction of spontaneity
Predict whether the reaction occurs spontaneously and why ?

Ni + Cu2+ -> Ni2+ + Cu , Given E0Ni = -0.25 V and E0Cu = 0.34 V

Higher potential value - reduction potential
Eocell = EoC – EoA

Eocell = EoCu – EoNi

Eocell = 0.34 - -0.25 = 0.59 V

Positive Eo value, So reaction spontaneous (∆Go = -nFEo)

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Determination of equilibrium constant

At equilibrium:

∆Go = -RT ln Keq (1)

∆Go = -nFEo (2)

-nFEo = -RT ln Keq

ln Keq = nFEo/RT
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 Determination of equilibrium constant
For a cell reaction at 298K, the equilibrium constant is 104. Calculate E0cell (n=2)

ln Keq = nFEo/RT

ln 104 = 2 x 96500 x E / 8.314 x 298

E = 0.118 V

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 Determination of electrical energy
Calculate the amount of electrical energy available from a dry cell
corresponding to the consumption of 6.55gm of Zn metal. Given EMF = 1.5V,
atomic weight of Zn = 65.5gm

Electrical energy corresponding to 65.5 g of Zn = - ∆G = nFE

= 2 x 96500 x 1.5

= 289500 J
Electrical energy corresponding to 6.55 g of Zn = 289500 x 6.55/65.5

= 28950 J
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 Determination of electrode potential
Calculate the electrode potential of Cu if the concentration of CuSO4 is 0.206 M at
23.10C. Given E0 Cu = 0.34 V
Cu2+ + 2e -> Cu

E = Eo - 2.303 RT/nF log Keq

E = EoCu - 2.303 RT/nF log 1/[Cu2+]

E = 0.34 – 2.303 x 8.314 x 296.1/2 x 96500 log 1/[0.206]

= 0.319 V
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 Electrochemical series
Standard reduction potentials are arranged in increasing order
Li+ + e- Li -3.045 V
Increasing tendency for
Increasing tendency for oxidation
+
K +e -
K -2.930 V (reducing agents)
oxidation – Reducing agent

Mg2+ + 2e- Mg -2.370 V Increasing tendency for

Zn2+ + 2e- Zn -0.763 V reduction – Oxidising agent

2H+ + 2e- H2 0V
2+ -
Electrodes above hydrogen
Cu + 2e Cu +0.34 V
have negative reduction
Ag+ + e- Ag +0.79 V
Increasing tendency for
reduction (oxidising agents)
potential, while those
F2 + 2e- 2F-
placed below have positive
+ 2.87V
reduction potential

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 Applications of electrochemical series

1. Relative ease of oxidation and reduction

Greater the reduction potential – Electrode undergo reduction
Lower the reduction potential – Electrode undergo Oxidation
F2 (2.87 V) – Reduction – Act as Cathode
Li+ (-3.05 V) – Oxidation – Act as anode

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 Applications of electrochemical series

Oxidising agents have positive Eo

Higher the positive value, stronger will be the oxidising agent
Reducing agents have negative Eo
Higher the negative value, stronger will be the reducing agent

H+ can oxidise Zn, Mg, K , Li etc.

H2 can reduce Cu2+, Ag+, F2 etc.

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 Applications of electrochemical series

2. Displacement Reactions
Metal with lower E0 value (highly reactive) will displace metal with higher
E0 value (less reactive)
Zn + CuSO4 -> ZnSO4 + Cu
Zn will displace Cu from its solution spontaneously

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 Applications of electrochemical series

3. To predict spontaneity of a reaction

∆G = -nFE

Spontaneous reaction - ∆G will be negative

For all positive values of Eo reaction will be spontaneous

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 Applications of electrochemical series

4. Reactivity with acid to produce H2 gas

Elements with reduction potential value lesser than hydrogen (0 V) will
react with acid and liberate H2 gas

Zn + H2SO4 -> ZnSO4 + H2 (Zn -0.76 V)

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 Applications of electrochemical series

5. Determination of standard EMF of the cell

EMF – maximum potential difference between the electrodes of a cell
Standard EMF = Eo cathode - Eo anode

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 Applications of electrochemical series

6. Prediction of correct metallurgical methods

 Eo values of Cu, H2O & Al are +0.34 V, -0.83 V & -1.66 V respectively

 Copper gets easily reduced than water ( Cu +0.34 V & H2O -0.83 V)

Higher reduction potential for copper

 Water gets more easily reduced than Aluminium (H2O -0.83 V & Al -1.66 V)

Higher reduction potential for water

 Copper can be produced by the electrolysis of aqueous copper sulphate but

not Al
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 Oxidising & Reducing Agents
Identify the oxidising & reducing agent in the following reaction
Zn + Cu2+ -> Zn2+ + Cu
Reducing agent- Zn
Reduction
Zn undergoes self oxidation by reducing

Zn + Cu 2+ Zn 2+
+ Cu Cu2+
to Cu
Oxidising agent- Cu2+
Oxidation Cu2+ undergoes self reduction by oxidising
Zn to Zn2+ - Oxidising agent

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 Displacement tendency

Can iron rod placed in a solution of AgCl undergoes replacement reaction. Given
E0 Ag = 0.80 V and E0 Fe = -0.44 V ?

Reduction potential of Fe is less than Ag.

Fe is more reactive than Ag
So replacement reaction takes place

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 Displacement tendency
Arrange the following metals in the order in which they displace each other: Al,
Cu, Fe, Mg, Zn. The standard reduction potentials of these metals are -1.66 V,
+0.34 V, -0.44 V, -2.37 V & -0.76 V respectively.

Lower the reduction potential higher the tendency to get oxidised & can be
displaced easily.
Mg>Al>Zn>Fe>Cu

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 Spontaneity of redox reactions
When potassium permanganate solution is added drop-wise to an acidified
mixture of NaCl & KI, predict the oxidation product. Given that Eo Cl2/Cl- = 1.36 V,

Eo I2/I- = 0.54 V, Eo MnO4/H+/Mn2+ = 1.51 V

More spontaneous reaction is having maximum EMF

EMF = E cathode – E anode
In the formation of chlorine, EMF = 1.51 - 1.36 = +0.15 V
In the formation of iodine, EMF = 1.51 – 0.54 = +0.97 V
 I- from KI will oxidise to I2 first.
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 Displacement tendency
Can a nickel spatula be used to stir copper sulphate solution? Standard
potentials of Ni= -0.23 V & Cu= 0.34 V

 Standard potentials of Ni is lower than that of Cu.

 If Ni spatula is used to stir copper sulphate solution, it will displace Cu from
copper sulphate
Ni + Cu2+ -> Ni2+ + Cu

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 Displacement tendency
Can we use a copper vessel to store 1M silver nitrate solution? Standard
potentials of Ag= 0.80 V & Cu= 0.34 V

 Standard potentials of Ag is higher than that of Cu.

 If 1M silver nitrate solution is stored in a copper vessel, copper will displace
Ag from silver nitrate
 We cant use a copper vessel to store 1M silver nitrate solution

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 Displacement tendency
When a Zn rod is dipped in a copper sulphate solution, the blue colour of copper
sulphate is slowly discharged. Why? Standard potentials of Zn= -0.76 V & Cu=
0.34 V
 Standard potentials of Zn is lower than that of Cu.
 If Zn rod is dipped in a copper sulphate solution, Zn will displace Cu from
copper sulphate
 Decrease in concentration of Cu2+ ions
 Slow discharging of blue colour
Zn + Cu2+ -> Zn2+ + Cu 43
 FUNDAMENTALS OFWORKING OF A CELL

 Anode – Oxidation occurs at this electrode

 Cathode – Reduction occurs at this electrode

 Salt bridge – Contains electrolytes which are required to complete the circuit in

a galvanic cell

 Half-cells – reduction and oxidation reactions are separated into compartments

 External circuit – Conducts the flow of electrons between electrodes

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 GALVANIC CELL
 An electrochemical cell that converts the chemical energy of spontaneous redox

reactions into electrical energy is known as a galvanic cell or a voltaic cell

 Electric work done by a galvanic cell is mainly due to the Gibbs energy of spontaneous

redox reaction in the voltaic cell

 It generally consists of two half cells and a salt bridge

 Each half cell further consists of a metallic electrode dipped into an electrolyte

 These two half-cells are connected to a voltmeter and a switch externally with the help

of metallic wires 45
 GALVANIC CELL
 In a galvanic cell, when an electrode is exposed to the electrolyte at the electrode-

electrolyte interface, the atoms of the metal electrode have a tendency to generate

ions in the electrolyte solution leaving behind the electrons at the electrode

 Thus, making the metal electrode negatively charged

 While at the same time metal ions in the electrolyte solution too, have a tendency

to deposit on a metal electrode

 Thus, making the electrode positively charged

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 GALVANIC CELL
 Under equilibrium condition, charge separation is observed and depending on the

tendencies of two opposing reactions, the electrode can be positively or

negatively charged

 Hence, a potential difference is developed between the electrode and electrolyte

 This potential difference is known as electrode potential

 Out of two electrodes, the electrode at which oxidation takes place is called

anode while the electrode at which reduction takes place is called cathode
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 GALVANIC CELL
 The anode has a negative potential with respect to the solution while the cathode

has a positive potential with respect to the solution

 Thus, a potential difference develops between two electrodes of the galvanic cell.

This potential difference is known as cell potential

 When no current is drawn from the galvanic cell, cell potential is known as the

electromotive force of the galvanic cell

 Example: Daniel Cell

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Daniel Cell
Anode (Oxidation)
Zn  Zn2+ + 2e-

Cathode (Reduction)
Cu2+ + 2e-  Cu

Cell Reaction
Zn + Cu2+  Zn2+ + Cu

Cell Representation
Zn/Zn2+//Cu2+/Cu
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Functions of salt bridge

 Salt bridge is an inverted ‘U’ tube

containing an inert electrolyte

Functions
 Provides continuity of electrical circuit
 Prevents diffusion of interfering ions
 Maintains electrical neutrality
 Eliminate liquid junction potential

Examples for inert electrolytes– KCl, NH4NO3

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 Classification of Cells

Serial No. Primary cells Secondary cells

1 Cell reaction Non-reversible Reversible

2 Recharge ability No Yes
3 Example Daniel cell Lithium ion cell

Battery: Combination of cells

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 Inorganic Semiconductors
 Inorganic semiconductors such as silicon, germanium, and gallium arsenide are

widely employed in electronic devices such as transistors, diodes, and integrated

circuits

 semiconductor material has an electrical conductivity value falling between

that of a conductor, such as metallic copper, and an insulator, such as glass

 Extrinsic semiconductors are semiconductors that are doped with specific

impurities
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 Inorganic Semiconductors

 A p-type semiconductor is an intrinsic semiconductor doped with boron or indium

 The majority of carriers in p-type semiconductors are holes

 Electrons are minority carriers in a p-type semiconductor

 The acceptor energy level of the p-type is close to the valency bond and away from the

conduction band

 Examples: Trivalent impurities such as Aluminium, Gallium, and Indium

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 Inorganic Semiconductors
 In an n-type semiconductor an intrinsic semiconductor doped with phosphorus or

antimony as impurity

 The majority of charge carriers in n-type semiconductors are electrons

 Holes are minority carriers in a n type semiconductor

 The donor energy level of n-type is close to the conduction band and away from the

valency band

 Examples: Pentavalent impurities such as Arsenic, Antimony, Phosphorus, Bismuth

etc.
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THANK YOU

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