NOTES

ELECTROCHEMISTRY

High Yield Notes

 NOTES
NOTES
ELECTROCHEMISTRY
INTRODUCTION TO
ELECTROCHEMISTRY
Electrochemistry is a branch of
chemistry which is concerned
with interconversion of chemical
energy and electrical energy.
Electrical energy is converted
into chemical energy through
electrolytic cells.
Chemical energy is converted
into electrical energy through
galvanic or voltaic cells.
Note: The interconversion of
electrical and chemical energy is
a redox reaction.

PreMed.PK 1
 NOTES OXIDATION AND REDUCTION
Difference between Oxidation and Reduction

Oxidation Reduction

Gain of Oxygen Atoms. Loss of Oxygen Atoms

Loss of Hydrogen Atoms. Gain of Hydrogen Atoms.

Gain of electrons including cathodic

Loss of electrons including anodic reactions.
reactions.

Product is more stable. Product is less stable.

Increase in Oxidation State. Decrease in Oxidation State.

Zn → Zn2+ + 2e- Cu2+ + 2e- → Cu

To remember oxidation or
reduction at anode and cathode
you can remember that,
Any type of cell whether it is
electrolytic or galvanic cell, in
which oxidation reduction
reactions take place, oxidation
always takes place at the anode
and reduction always takes
place at cathode.
You can also remember this by
this phrase AnOx RedCat
Where AnOx = Oxidation at
anode
RedCat = Reduction at Cathode

PreMed.PK 2
 NOTES OXIDISING AND
REDUCING AGENTS
Difference between Oxidizing Agents and Reducing
Agents
Oxidizing Agents
Carry out Oxidation Process.
Oxidizes other Species.
Gets Reduced themselves.
Gain Electrons themselves.
Mostly non metals.
"Relative Strength of Oxidizing agents
F2>Cl2>Br2>I2".
High reduction potential.
Oxidizing power is directly proportional to Reducing power is inversely proportional to
the reduction potential.
Oxidation Number or State
Apparent charge on an atom of
an element in a molecule or an
ion is called oxidation number or
oxidation state.
It may be positive, negative or
zero.
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Reducing Agents
Energy is absorbed.
Reactants are at low energy state.
Products are at high energy state.
Product is less stable.
Mostly metals.
Relative strength of Reducing Agents
Li<Na<K<Rb<Cs
Low reduction potential.
the reduction potential.
Rules of Assigning
Oxidation Number
1. The oxidation number is written
on the upper right side of the
symbol.
2. Elements in free state have an
oxidation state of zero. For
example: H2, Na, K, Mg, O2.,
Oxidation number is strictly 0.
3. The oxidation number of
monoatomic ion is same as the
charge on the ion. For example:
K, Ca, Al and S have +1, +2, +3, -1,
-2 oxidation number
respectively.
4. For ions having group of atoms,
the sum of oxidation numbers is
equal to the charge on the ion.
5. The sum of oxidation states of all
the elements in a compound is
always equal to zero.
3
 NOTES For Example:
K2Cr2O7
Similarly

(+1)2 + 2Cr -2(7) = 0 III-A IV-A V-A VI-A VII-A VIII-A

+2 + 2Cr -14 = 0
+3 +4 -3 -2 -1 0
2C = +14 -2 = +12
-3 -4 +3 +2 +1 +2
Cr = +6
+5 +4 +3 +4
NaBrO3 +6 +5 +6
1 + Br + (-2)(3) = 0 +7 +8
1 + Br -6 = 0
Br - 5 = 0 The oxidation state given in table
Br = +5 are variable oxidation states
possible in respective group.
6. Hydrogen has +1 oxidation state
in all its compounds with non-
metal. i.e HCl, HBr. In case of metal
hydrides, Hydrogen has -1 oxidation
State. i.e. Li(+1 )H(-1)
7. Oxygen in all its compounds has
Oxidation State -2. e.g H2O, Na2O
Oxidation State
Examples
of O
- 1 Oxidation State
H2O2, BaO2, Na2O2
(Peroxide)
-1/2 Oxidation State
KO2
(Superoxide)
+2 Oxidation State
OF2
(Only with F)

8. In case of neutral molecules, the

sum of all the oxidation states is
zero.
9. For simple ions of the same
group, the oxidations number will
have the same sign and same
charge which is equal to the group
number.
Note:
To remember the oxidation
state of various elements in a
periodic table, remember the
group number of respective
element.
For example:
Oxidation number of I-A=+1
Oxidation number of II-A=+2
Oxidation number of III-A=+3

PreMed.PK 4
 NOTES Difference between Oxidation State and Valency
Oxidation State
Numbers that represents an electric
charge which an atom appears to have
when combine with other atoms is
called oxidation state.
Oxidation number of an element may be
different in different compounds.
Oxidation number of an element may
have positive negative or zero value.
Oxidation number of an element may be
fractional.
Oxidation number may be whole number Example
Example
Oxidation number of Sulphur in
Na2S4O6 is + 2.5.
Oxidation number of Iron in FeCl3 and
FeCl2 is + 3 and + 2 respectively.
Conduction
Conduction is of two types:
1. Electronic or Metallic
conduction
2. Electrolytic conduction
Electronic or Metallic Conduction
Conduction of electricity due to
presence of free electrons in metals is
called electronic or metallic conduction.
Conduction through metals decrease
with the rise of temperature due to
oscillation of ions in the structure.
This conduction may be accompanied by
the physical change i.e surface metal
may becomes dull.
This condition is not a accompanied by
chemical change.
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Valency
Valency is the number of atoms of a
particular element that is combined
with one atom of another element to
form a molecule. Actually it is the
combining capacity of an element.
Valency of an element is usually fixed.
Valency of an element does not have
positive or negative value.
Valency of an element is always a whole
number.
Valency of Fe in FeCl3 is 3 and FeCl2 is 2
Electrolytic Conduction
Conduction of electricity due to
presence of free electrons in fused /
molten / aqueous electrolyte is called
electrolytic conduction.
Conduction through electrolyte
increases with the rise of temperature
due to increase in the ionization and
number of free ions.
This condition is not accompanied by
physical change.
This condition is a accompanied by
chemical change i.e redox reaction takes
place on the surface of anode and
cathode (electrolysis).
5
 NOTES Comparison between Ionization and Electrolysis
Ionization
Ionization is the process in which ionic
compound when used or dissolved in
water split up into charged particles
which are called ions.
Ionization is caused by process of
hydration of ions which remains in the
solution in the form of radicals.
Example:
NaCl(s) → Na+(aq) + Cl-(aq)
Ionization in the aqueous medium may
be exothermic or endothermic.
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Electrolysis
Electrolysis is the process in which Ions
of an electrolyte deposit at electrode
during an electrolytic conduction.
Electrolysis is caused by passage of
electric current through a solution
with the help of electrode(anode and
cathode).
Example:
Electrolysis of fused NaCl.
2NaCl(Fused) → 2Na(s) + Cl2(g).
(Deposit at Cathode and
anode).
6
 NOTES ELECTROLYSIS
The process in which non
spontaneous reaction take place at
the expense of electricity is called
electrolysis.
Electrolytic Cell
A cell in which a redox reaction
occurs at the expense of
electrical energy is called
electrolytic cell.
In this cell, electrical energy is
converted into chemical energy.
Oxidation and reduction
reactions occur in the same
compartment.
It is used for the extractions of
metal, purifications,
electroplating and an anodizing.
The process of electrolysis takes
place in the electrolytic cell.
Process of Electrolysis
Process of electrolysis is carried out
by using aqueous solution of salts
or molten salts.
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Electrolysis of Fused Salts
Reaction at Cathode
When fused salts are
electrolysed the metals ions
called cations carrying positive
charge move towards the
cathode.
Cathode provide electrons to
them and they get reduced.
For example:
In case of Fused PbCl2, Pb+2
ions being positively charged
move towards cathode and gain
electrons
Pb+2(l) + 2e- → Pb(s) (reduction)
Reaction at Anode
The ions move towards the
anode. They lose their electrons
at the anode and get oxidized.
For example:
In case of PbCl2, Cl- ions being
negatively charged move
towards anode and lose
electrons.
2Cl-(l) → Cl2(g)+2e- (oxidation)
Similarly, for fused NaCl and
fused PbBr2, electrolytes are
decomposed during electrolysis
Na and Pb are produced at
cathode while Cl2 and Br2 gases
are formed at anode.
Flow of Electrons and Ions
In the fused salt there is
electrolytic conduction in the
cell while there is electronic
conduction in the external
circuit in the cell ions move
towards anode and cathode to
get oxidized or reduced
respectively.
The flow of electrons take place
through external circuit from
anode to cathode.
7
 NOTES Note:
Current is conducted by
electrons outside the cell in the
external circuit from anode to
cathode. Current is conducted
by ions inside the cell from
cathode to anode.
Electrolysis of Aqueous
Solutions of Salts
The electrolysis of aqueous
solution of salt is not so simple
and is somewhat complicated.
The reason is that water
molecules are oxidized as well as
reduced, that is why product of
electrolysis of aqueous solution
of salt are not precisely
predictable.
Examples:
Let us take the example of
aqueous solution of NaNO3. It
dissociates in water as follows:
NaNO3 → Na+1 + NO3 1-
(oxidation)
Water molecules also get
ionized
H2O+H2O →H3O+(aq)+ OH-1(aq)
Reaction at cathode
H3O+ ions being positively
charged move towards cathode
and get reduced in competition
of Na+1 ions.
H3O+1 + 1e → H2O(l) +H2(g)
(reduction)
Similarly, one more hydrogen
atom is formed then both
Hydrogen atoms react to form
Hydrogen gas.
H(g) + H(g) →H2(g)
H2 gas is evolved at cathode.
Na+1 ion will remain as cathode
and does not get reduced
because H+1 ion has greater
tendency to gain electrons.
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Reaction at Anode
At anode both nitrate and
hydroxide are present.
Hydroxide ions are easier to
discharge than nitrate ions.
Nitrate ions will remain in the
solution.
The electrode reaction is as
follows:
(OH-1 → OH + e-)4 (oxidation)
The OH groups decompose to
give Oxygen and water
molecules. 4OH- → O2+2H2O
So, oxygen gas is obtained at
anode.
Na+1 ions and NO3-1 ions will
remain in the solution.
Expected Order of
Discharge of Ions
Expected order of discharge of
ions may also depend upon their
concentration.
If an ion with greater tendency
to discharge has low
concentration in comparison to
ion which has less tendency to
discharge itself then ion with
greater concentration may get
discharged.
Ease of Discharging of Anions:
SO4-2 < NO3-1 < Cl-1 < Br-1 < I-1 <
OH-1
Note:
The concentration of H3O+ is 10-
^7 mol/dm3 in water.
When these are discharged,
more H3O+ are formed by
dissociation of water molecules
to give continuous supply of
H3O+.
8
 NOTES Product of Electrolysis

Electrolyte Copper Cathode Copper Anode

Copper dissolves to form
CuSO4 Ions Solid Copper Deposits
Cu2+ Ions

Electrolyte Silver Cathode Silver Anode

Ag(s) dissolves to form Ag2+
AgNO3(aq) and HNO3 Ag Deposits
ions

Products of Electrolysis using Inert Electrodes like

Platinum and Graphite

Electrolyte Cathode Anode

PbBr2 (molten) Pb(s) Br2(g)

NaCl (molten) Na(s) Cl2(g)

NaCl (aq) H2(g) Cl2(g)

CuCl2 (aq) Cu(s) Cl2(g)

CuSO4 (aq) Cu(s) O2(g)

KNO3 (aq) H2(g) O2(g)

NaOH (aq) H2(g) O2(g)

H2SO4 (aq) H2(g) O2(g)

Application of Electrolysis Extraction of Aluminium Metals

Extraction of metal from their ores Aluminium is extracted by

Magnesium and Calcium metals
are extracted by the electrolysis
of their fused chlorides MgCl2
and CaCl2.
Mg and Ca metal in solid form
are collected at cathode while
Cl2 is collected as gas at anode.
electrolyzing fused Bauxite
(Al2O3.2H2O) in the presence of
fused Cryolite, Na3AlF6.
This process is called Hall
Beroult process.

PreMed.PK 9
 NOTES Purification of anodized
Aluminium
Galvanic Cell or Voltaic Cell
A cell in which redox reaction
Anodized Aluminium is generates electric current
prepared by making it an anode through a chemical reaction is
in an electrolytic cell containing called a voltaic cell or a galvanic
Sulphuric Acid or Chromic Acid cell.
which coats a thin layer of oxide In this cell, chemical energy is
on it. converted into electrical energy.
The Aluminium oxide layer Reduction reaction and
resists the attack of corrossive oxidation reaction occur in the
agents. separate compartment.
The freshly anodized aluminium It is used for the measurement
is hydrated and can absorb dyes. of the electrode potential.
It contains two half cells.
Left Half Cell (Oxidation Half Cell)
Purification of Metals
Zinc electrode is dipped in one
Electrolytic cell can also be used molar solution of ZnSO4.
for the purification of copper.
Impure copper is made the Right Half Cell (Reduction Half
anode and thin sheet of pure Cell)
copper is made the cathode.
Copper Sulfate solution is used Copper Electrode is dipped in
as electrolyte. one molar solution of CuSO4.
The atoms of Cu from impure Cu
anode are converted to Cu+2 Salt Bridge
ions by the process of oxidation
and migrate to cathode which is It is an aqueous solution of KCl in a
made of pure copper. gel.
At cathode these Cu+2 ions get
Working:
reduced and deposited at the
surface of cathode.
1. Connect both the half cell
In this way Cu anode is purified.
electrolytically through the salt
Impurities are left at anode.
Bridge.
2. Close external circuit by
Electroplating
connecting the Zinc and Copper
electrode.
Copper, silver, nickel and
3. The electrons will flow from Zinc
chromium plating is done by
to Copper through external
various types of electrolytic cells.
circuit.
One metal is deposited at the
surface of another metal.
The metal upon which the other
metal has to be deposited is
made cathode and that metal
which has to be deposited is
made the anode.

PreMed.PK 10
 NOTES At Anode
Zn(s)→ Zn+2(aq) + 2e- (oxidation)
For the zinc copper cell, the half cell
reactions are reversed to give:

At cathode: Zn+2(aq) + 2e- → Zn(s)

Cu+2(aq) +2e → Cu(s) (reduction) (reduction)
Cu(s) → Cu+2(aq) + 2e-
The voltaic cell reaction is (oxidation)
represented by
And the action being reversed,
Zn(s)/Zn+2(aq) 1M||Cu+2(aq) becomes:
1M/Cu(s)
Zn+2(aq) + Cu(s) → Zn(s) +
EMF of the Cell Cu+2(aq)
Eo=1.10V
Oxidation occurs at the copper
Function of Salt Bridge electrode and reduction takes
1. A salt bridge acts as an electrical place at the zinc electrodes and
contact between the two half the cell operates as an
cells. electrolytic cell in which energy
2. A salt bridge prevents the from an external source drives a
transfer of the electrolytes from non spontaneous reaction.
one half cell to the other. When a cell operate as a voltaic
3. A salt bridge helps in cell the electrode at which
maintaining the charge balance reduction occurs is called
in two half cells. cathode while the electrode at
4. A salt bridge minimizes / which oxidation takes place is
eliminates the liquid junction called anode.
potential. in a Voltaic cell zinc acts as an
anode and copper acts as a
Voltaic cell is a Reversible cathode.
Cell
If the external circuit in the
voltaic cell is replaced by a
source of electricity, the
electrode reaction can be
reversed.
Now external source of
electricity pushes electrons in
the opposite direction and
supplies energy or work to the
cell so that the reverse, non-
spontaneous reaction occurs.
Such a cell is called a reversible
cell.

PreMed.PK 11
 NOTES Standard Electrode Redox
Potential
The potential setup when an
electrode is in contact with one
molar solution of it’s own ions at
298 K is known as standard
electrode potential.
It is represented as Eo .
When a Zinc rod is dipped in the
solution of its own ions then zinc
rod will bear an accumulation of
negative charge.
This is due to a greater tendency
of zinc atoms to lose electrons.
The negative charge on the zinc
rod will attract an atmosphere of
positively charged zinc ions
around the rod to form an
electrical double layer as shown
in the figure.
Equilibrium can be represented as:
Zn(s) → Zn+2(aq) + 2e-
Electrode potential of an
element can be calculated by
comparing it with standard
hydrogen electrode (SHE).
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Types of Standard
Electrode Potentials
Standard Oxidation Potential
Zn → Zn+2 + 2e- E°ox = -0.76V
Standard Reduction Potential
Cu+2 + 2e- → Cu E°red = +0.34V
Standard Hydrogen
Electrode (SHE)
SHE consists of a glass tube
filled with H2 gas at 1 atm
pressure.
Platinum foil coated with finely
divided platinum black is
suspended in it.
The whole system mentioned
above is dipped in 1M solution of
HCl.
Electrode potential of SHE is
arbitrarily considered as zero.
Electrode potential of an
element can be calculated by
comparing it with standard
hydrogen electrode (SHE).
Reaction that take place in SHE are:
H2(g) → 2H+(aq) + 2e- (oxidation)
2H+(aq) + 2e- → H2(g) (reduction)
12
 NOTES Measurement of Electrode
Potential
For the measurement of the
electrode potential, standard
hydrogen electrode as reference
is coupled electrolytically with
other element and the cell
potential is taken as electrode
potential of the element.
An oxidation or reduction
reaction may take place at
standard hydrogen electrode,
depending on nature of
electrode which is coupled with
Measurement of Electrode
it.
Potential of Copper
Measurement of Electrode
Potential of Zinc The electrode potential of
copper can be measured by the
For the measurement of establishment of galvanic cell in
electrode potential of zinc, a which copper electrode is
galvanic cell is established dipped in one molar solution of
between zinc electrode in one its own ions and connected with
molar solution of its ions and the standard hydrogen
standard hydrogen electrode. electrode.
Under standard conditions, the Under standard condition the
voltmeter reads 0.76V and voltmeter reads 0.34V and the
deflection in such a direction deflection is in such a direction
that indicates that zinc acts as that copper acts as a cathode
an anode has a greater and has a greater tendency to
tendency to give off electrons, gain electrons and undergoes
undergoes oxidation. reduction.
Hydrogen acts as a cathode. Hydrogen acts as an anode.
0.76V is the oxidation potential 0.34V is the reduction potential
of zinc and is given the positive of copper and is given the
sign. positive sign.
The reduction potential of zinc is The oxidation potential of
-0.76V. copper is -0.34V.

At Anode At Anode

Zn(s) → Zn+2(aq) + 2e- (oxidation) H2(g) → 2H+(aq) + 2e- (oxidation)

At Cathode At Cathode

2H+(aq) + 2e- → H2(g) (reduction) Cu+2(aq) + 2e- → Cu(s)

(reduction)

PreMed.PK 13
 NOTES

PreMed.PK 14
 NOTES REDOX EQUATIONS
Oxidation and reduction always
takes place together.
There can be no oxidation
without reduction and vice
versa.
This combined process is called
redox reaction.
Redox reactions in terms of electron
transfer or change in oxidation
number is explained in the
following example:
Zn(s) + CuSO4(aq) → ZnSO4(aq) +
Cu(s)
Its ionic equation is:
Zn(s) + Cu+2(aq) → Zn+2(aq) +
Cu(s)
Balancing of Redox
Reaction by Ion Electron
Method
Example of Acidic Medium
Given Equation:
Cl- + MnO4- → Cl2 + Mn2+
Balanced Equation:
10Cl- + 2MnO4- +16H+-> 5Cl2+2Mn2+
+8H20
Example of Basic Medium
Given Equation:
MnO42+(aq) + C2042-(aq) + H2O
→ MnO2(s) + CO2(g) + OH-(aq)
Balanced Equation:
2MnO42+(aq) + 3C2042-(aq) + 4H2O
→ 2MnO2(s) + 6CO2(g) + 8OH-(aq)
PreMed.PK
Important Note
For Balancing Equation in Acidic
Medium
Oxygen is balanced by H2O
Hydrogen is balanced by H+
For Balancing Equation in Basic
Medium
Hydrogen is balanced by H+
Oxygen is balanced by OH-
For balancing equation in neutral
medium
Hydrogen is balanced by H+
Oxygen is balanced by H2O
Balancing of Redox
Equation by Oxidation
Number Method
The steps involved can be
memorized by following
sequence:
1. Skeleton Equation
2. Identification of Elements whose
oxidation number changed
3. Indication of number of
electrons gained or lost
4. Equating the increase or
decrease in oxidation number,
using a suitable multiplier
5. Balancing the rest of equation
by inspection method
6. Balancing the following
equation by oxidation number
method
Given Example
K2Cr2O7 + HCl → KCl + CrCl3 +
Cl2 + H2O
Balanced Equation:
K2Cr2O7 + 14HCl → 2KCl + 2CrCl3
+ 3Cl2 + 7H2O
15
 NOTES ELECTROCHEMICAL SERIES
When elements are arranged in the order of their increasing standard
reduction electrode potential on the Hydrogen scale, the resulting list is
known as electrochemical series.

Standard Reduction Potentials (E°) of substances

at 298 K

Standard
Element/Specie Electrode Reduction
Potential E°
Li Li+ + e- → Li -3.045
K K+ + e- → K -2.925
Ca Ca2+ + 2e- → Ca -2.87
Na Na+ + e- → Na -2.714
Mg Mg2+ + 2e- → Mg -2.37
Al Al3+ + 3e- → Al -1.66
Zn Zn2+ + 2e- → Zn -0.76
Cr Cr3+ + 3e- → Cr -0.74
Fe2+ + 2e- → Fe
increasing strength as an oxidising agent

Fe increasing strength as an reducing agent -0.44

Cd2+ + 2e- → Cd
increasing reduction potential

decreasing reduction potential

Cd -0.403
Ni Ni2+ + 2e- → Ni -0.25
Sn Sn2+ + 2e- → Sn -0.14
Pb Pb2+ + 2e- → Pb -0.126
H2 2H+ + 2e- → H2 0.00 (SHE)
Cu Cu2+ + 2e- → Cu +0.34
Cu Cu+ + e- → Cu +0.521
I2 I2 + 2e- → 2I- +0.535
Fe Fe3+ + 3e- → Fe +0.771
Ag Ag+ + e- → Ag +0.7994
Hg Hg2+ + 2e- → Hg +0.885
Br2 Br2 + 2e- → 2Br- +1.08
Cl2 Cl2 + 2e- → 2Cl- +1.360
Au Au3+ + 3e- → Au +1.50
F2 F2 + 2e- → 2F- +2.87

PreMed.PK 16
 NOTES Mnemonics Lower Elements of
To help learn the electrochemical Electrochemical Series
series
1. Smaller negative value of
Upper Elements reduction potential
2. Gains electrons easily
Lithium (Li) Little 3. Acts as oxidizing agent
Potassium (K) Kinza 4. Acts as cathode in cells
Calcium (Ca) Can 5. Less reactive metal
Sodium (Na) Send 6. Can't replace the lower metal
Magniseum (Mg) Monkey 7. Does not cause release of H2 gas
Aluminium (Al) Elephant from mineral acids
Zinc (Zn) Zebra 8. Include as Ered
Chromium (Cr) Crows
Iron (Fe+2) In Applications of
Cobalt (Co) Cubic Electrochemical Series
Nickel (Ni) Nickel
Tin (Sn) Tin 1. Prediction of feasibility of
Lead (Pb) Lead chemical a reaction
Hydrogen (H2) Hut 2. Calculation of voltage or
electromotive force (EMF) of
Lower Elements cells
3. Comparison of relative tendency
Copper (Cu2+) Cute of metals and non metals to get
Copper (Cu+1) Curly oxidized or reduced
Iodine (I2) Imported 4. Relative chemical activity of
Iron (Fe2+) Iron metals
Silver (Ag) Silver 5. Reaction of metals with dilute
Mercury (Hg+2) Hyderabadi acids
Bromine (Br2) Bangles 6. Displacement of one metal by
Chlorine (Cl2) Collected an other from its solution
Gold (Au) All over
Fluorine (F2) Finland Predict the Feasibility of a
Reaction
Upper Elements of
The cell potential helps us to
Electrochemical Series
determine the feasibility of a
1. Larger negative value of reaction by knowing the
reduction potential standard reduction potential of
2. Looses electrons easily reacting elements for given
3. Acts as reducing agent reaction.
4. Acts as anode in cells If the value of the cell potential
5. More reactive metal is positive then the reaction is
6. Can replace the lower metal feasible otherwise not.
7. Causes release of H2 gas from
mineral acids
8. Include as Eoxi

PreMed.PK 17
 NOTES The self potential can be calculated
from given value of standard
reduction potential of elements as
follows:
Zn+2(aq) + 2e- → Zn(s) E°= -0.76V
Cu+2(aq) + 2e- → Cu(s) E°= +0.34V
The given reaction is:
Zn(s) + Cu+2(aq) → Zn+2(aq) +
Cu(s)
The cell potential is calculated by
the sum of standard oxidation
potential and standard reduction
potential of the respective element:
E°cell = E°oxi + E°red
E°cell = 0.76V + 0.34V
E°cell = 1.10V
Since the cell potential is positive,
above reaction is feasible.
Another Example
Zn+2(aq) + Cu(s) → Zn(s) +
Cu+2(aq)
E°cell = E°oxi + E°red
E°cell = -0.76V - 0.34V
E°cell = -1.10V
Since the cell potential is negative
above reaction is not feasible.
Calculation of Voltage or
Electromotive Force (EMF)
of Cells
The cell potential helps us to
determine the electron flow in
the external circuit of a cell.
If the value of the cell potential
is positive then the electron will
flow spontaneously from anode
to cathode in the external circuit
of a cell otherwise the electrons
can not flow spontaneously.
PreMed.PK
The cell potential can be calculated
from given values of standard
reduction potential of elements as
follows:
Zn+2(aq)+2e- → Zn(s) E° = -0.76V
Cu+2(aq) +2e- → Cu(s) E° = +0.34V
The cell potential is calculated by
the sum of standard oxidation
potential and standard reduction
potential of respective elements:
E°cell = E°oxi + E°red
E°cell = 0.76V + 0.34V
E°cell = 1.10V
Since cell potential is positive,
electron can flow from anode to
cathode spontaneously.
Comparison of Relative
tendency of Metals and
Non-Metals to get Oxidized
or Reduced
The value of reduction potential
of a metal or a non metal tells us
the tendency to lose electrons
and act as a reducing agent.
It also gives us the information
about the tendency of species to
gain electrons and act as
oxidizing agents.
Greater the value of standard
reduction potential of a given
species, greater is its tendency
to accept electrons to undergo
reduction hence to act as an
oxidizing agent.
For example, ions like Au3+, Pt2+
Hg2+, Ag+, Cu2+, and the non-
metal elements like F2, Cl2, Br2
and I2 which lie below the SHE
have a stronger tendency to
gain electron and undergoes
reduction.
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 NOTES In the electrochemical series
strong oxidizing agents like F2,
Cl2, Br2 and I2 etc, have a large
positive value of standard
reduction potential while strong
reducing agents like Li, K ,Ca
and Na have large negative
value and lie above the SHE.
Relative Chemical
Reactivity of Metals
Greater the value of standard
reduction potential of a metal,
the smaller is its tendency to
lose electrons to change into
positive ions, the lower will be its
reactivity.
For example metals like Lithium
(Li), Potassium(K), Sodium (Na)
and Rubidium (Rb) are highly
reactive.
Coinage metals like Copper (Cu),
Silver (Ag) and Gold (Au) are the
least reactive because they have
positive reduction potential.
Similarly metals like Lead (Pb),
Tin (Sn), Nickel (Ni), Cobalt (Co)
and Cadmium (Cd) which are
very close to SHE react very
slowly with steam to liberate
hydrogen gas while the metals
like Iron (Fe), Chromium (Cr),
Zinc (Zn), Manganese (Mn),
Aluminium (Al) and Magnesium
(Mg) which have more negative
reduction potential react with
steam to produce metallic
oxides and hydrogen gas.
PreMed.PK
Reaction of Metals with
Dilute Acids
Greater the value of standard
reduction potential of a metal,
lesser is its tendency to lose
electrons to form metal ions and
so, weaker is its tendency to
displace H+ ions from acid as
Hydrogen (H2) gas.
For example metals like Silver
(Ag), Gold (Au), Platinum (Pt)
and Copper (Cu) which have
sufficiently high positive values
of reduction potential do not
liberate hydrogen gas from
acids while metals like Zinc (Zn),
Magnesium (Mg) and Calcium
(Ca) which are close to the top of
the series, have very low
reduction potential and liberate
hydrogen gas when they react
with acids.
Displacement of one Metal
by another Metal from its
Solution
One metal will displace another
metal from the aqueous
solution of its salt if it lies above
it in the electrochemical series.
For example Iron (Fe) can
displace Copper (Cu) from
CuSO4. Zinc (Zn) cannot
displace Magnesium (Mg) from
solution of MgSO4.
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 NOTES TYPES OF ELECTROCHEMICAL
CELLS
The cells consisting of electrode dipped into an electrolyte which makes
the interconversion of electrical energy and chemical energy possible are
called electrochemical cells.
There are two types of electrochemical cells:
1. Electrolytic Cell
2. Voltaic or Galvanic cell
Comparison between Electrolytic Cell and Galvanic Cell
Electrolytic Cell
A cell in which a redox reaction occurs
at the expense of electrical energy is
called electrolytic cell
Anode is positively charged
Cathode is negatively charged
Electrical energy is converted into
chemical energy
Both Oxidation and Reduction reactions
occur in the same compartment
Non-spontaneous Redox reaction
occurs
Salt Bridge is not used
It is used for:
1. Extraction of metals
2. Purification of metals
3. Electroplating
4. Anodizing
It consumes heat (endothermic)
Example:
Nelson's Cell
Down's Cell
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Voltaic/Galvanic Cell
A cell in which a redox reaction
generates electric current through
chemical reaction is called galvanic cell
Anode is negatively charged
Cathode is positively charged
Chemical energy is converted into
electrical energy
Reduction and Oxidation reactions
occur in separate compartments
Spontaneous Redox reaction occurs
Salt Bridge is used
It is used for the measurement of
electrode potential
It generates heat (exothermic)
Example
Daniel Cell
Ni-Cd Cell
Fuel Cell
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