ELECTROCHEMISTRY
MARKS = 05
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UNIT 3
ELECTROCHEMISTRY
Conductors:
Any substance, which allows the electric current to pass through it, is called an
electrical conductor.
There are two types of conductors.
Types of Conductors
Metallic conductors
Substances, which allow the passage of electricity through them without
undergoing any chemical change.
Example: Cu, Ag, Al etc.
Electrolytic conductors
Substances that allow the passage of electricity through their molten state or
aqueous solutions and undergo chemical decomposition.
Difference between metallic and electrolytic conduction
Metallic Conduction
Electrolytic Conduction
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UNIT 3
Types of Electrolytes
There are three types of electrolytes: Strong, weak and non electrolytes.
Strong electrolytes
A strong electrolyte is one which undergoes complete ionization when
dissolved in water.
The solution contains only the ions and not molecules.
Examples:
HCl, HNO3, H2SO4, NaOH, Ca(OH)2, NaCl, KCl, CH3COONa etc.
Weak electrolytes
A weak electrolyte is one which undergoes partial ionization or dissociation.
Here, in solution the ions and the dissociated molecules will be in equilibrium
with each other. When such a solution is diluted, the degree of ionization
increases. It becomes complete at infinite dilution.
Examples:
Non-electrolytes
A substance which doesn't allow the electric current to pass through it is called
a non electrolyte.
These substances have no ions. Therefore they do not ionize in water.
(Covalent compounds).
Examples:
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The inter-ionic attraction
It is the interactions between the ions of the solute at low concentrations. At
low
concentrations the inter-ionic attraction is very less, but at high
concentrations it is appreciable.
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UNIT 3
BASIC CONCEPTS
Ohm's law
The potential difference across the conductor is directly proportional to the
current flowing through it.
Solutions obey Ohm's law like metallic conductors.
Resistance (R)
It is the hindrance to the passage of current. It is the ratio of potential
difference (V) across the conductor to the current (I) flowing through it.
It is expressed in ohm.
Conductance (C)
It is the ease provided by a solution to the flow of current.
R = resistance
l = Length of conductor
a = area of cross section
Then,
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Units: ohm.cm
Specific Conductance
It is the reciprocal of specific resistance.
Units:
ohm-1 cm-1 or
S/cm-1
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This is
at
because
higher
concentration there is greater inter ionic attraction which retards the motion of
the ions as conductance falls
is that conductance at infinite dilution
where the ions are far apart and there is no inter-ionic attraction. This can be
obtained by extrapolation of the graph to zero concentration.
Weak electrolytes:
A weak electrolyte dissociates to a much lesser extent so its conductance is
lower than that of a strong electrolyte at the same concentration.
The very large increase at infinite dilution is because the ionization increases
and so the number of ions in solution increases.
The value of
cannot be obtained by extrapolation as can be seen
on the graph. It is obtained by applying Kohlrausch's law.
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UNIT 3
values for strong electrolytes is larger than weak electrolytes for the same
concentration. Increase in
to that for weak electrolyte.
Kohlrausch's Law:
At infinite dilution when the dissociation of the ions is complete each ion makes
a definite contribution to the total molar conductance irrespective of the nature
of the other ion.
Mathematically,
where
are the molar conductance of A+ and B- at infinite
dilution x and y are the ions provided by one formula unit of the electrolyte.
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UNIT 3
The value of
for KCl, CH3COOK and HCl can be obtained by extrapolation
(they are strong electrolytes).
or
If 0.1M acetic acid has 25% degree of dissociation, what is the concentration of
H2 ion.
For weak electrolytes the increase of molar conductance with dilution is due to
the increase in dissociation.
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Faradays First law of Electrolysis:
The mass of substance deposited is directly proportional to the quantity of
current passed.
If
Wg =
I
=
t =
mass of substance
Current in amperes
time in seconds
electrochemical equivalent.
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Galvanic Cells (Voltaic Cell):
It is a device used to convert the chemical energy produced in a redox reaction
into electrical energy.
Example: The redox reaction between Zn and CuSO4 is
If a redox reaction is allowed to take place in such a way that the oxidation half
reaction takes place in one beaker and the reduction half reaction in another
beaker, then electrons will flow from the former to the latter and a current will
flow.
Salt
is
bridge
an
inverted U-tube filled with a strong electrolyte like KCl in Agar-Agar gel.
Anode (Negative terminal) is Zn at which oxidation takes place.
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UNIT 3
energy
Electrolytic Cell
into It coverts electrical
chemical energy
energy
into
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The two aqueous solutions are interlinked through a salt bridge which is an
inverted 'u' tube which is filled with saturated semi solid paste of Agar Agar
saturated in KCl or KNO3 solution.
Note: Agar agar is a carbohydrate which forms a jelly like substance when
dissolved in hot water]
Working:
At the Zn electrode, oxidation takes place:
The 'electrons' (e-) removed or lost by the metal move through the material of
the electrode and reach the Cu electrode at which they are accepted by Cu 2+
ions of the solution to form neutral copper atoms.
In an electrochemical cell, each electrode constitutes one half of the cell and
the reaction taking place at the electrode is called half-cell reaction. The
overall cell reaction is obtained by adding the two half-cell reactions (1) and
(2).
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would have been liberated appears in the form of electrical energy. Hence the
electrochemical cell acts as a source of current although for a short interval.
The electrode at which oxidation takes place or the metal rod becomes negative
charged is called negative electrode.
The electrode at which reduction takes place or the metal rod becomes positive
charged is called positive electrode.
ii.
iii.
In general KCl salt bridge is used while KNO 3 salt bridge is used when silver
electrode is involved as one of the electrodes.
Representation of the electrochemical cell:
An electrochemical cell is a device in which oxidation and reduction reactions
take place indirectly and the decrease in the potential energy is converted into
electrical energy.
In representation of an electrochemical cell, the electrode at which reduction
takes place is written on the RHS of the salt bridge and the electrode at which
oxidation takes place is written on the LHS of the salt bridge. The salt bridge
linking the aqueous solutions is represented by two vertical parallel lines
having ions on both sides.
LEFT HAND SIDE
Anode
Cathode
Oxidation
Reduction
In the above system, Zn electrode is written on the LHS while the Cu electrode
on the RHS of the salt bridge.
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UNIT 3
Metal
Where,
C1 and C2 are the concentrations of Zinc (Zn 2+) and Copper (Cu2+) ions
respectively.
Double vertical lines ( || ) represent the salt bridge.
Electrode Potential
Origin of Electrode Potential:
Consider a zinc rod being dipped in ZnSO 4 solution. The zinc atoms on the
surface of the metal with in the solution have tendency to release Zn +2 into
solution retaining the electrons on the surface of the metal. This process is
called dissolution or solution pressure of the metal and it is oxidative in nature.
The zinc ions of the solution have a tendency to accept the electrons on the
surface of zinc rod to form neutral zinc atoms and get deposited on the zinc
rod. This process is called deposition or the osmotic pressure of solution and it
is reductive in nature.
These two processes will be taking place simultaneously at different rates. In
this case, the rate of dissolution is found to be greater than the rate of
deposition. Consequently, by the time equilibrium is reached, more of
dissolution would have occurred and the solution becomes positively charged
whereas rod becomes negatively charged. Due to the attractive electrostatic
forces, the Zn ions accumulate around the Zn rod and an electrical double
layer of opposite charges is formed and between the Zn rod and the solution
the potential developed is called Zinc Electrode Potential
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UNIT 3
Consider a copper rod being dipped in CuSO4 solution. Even in this case, both
dissolution and deposition will be taking place simultaneously at different
rates. Here, the rate of deposition is found be greater than the rate of
dissolution. Hence, by the time the equilibrium is reached, the solution
becomes negatively charged while the rod becomes +vely charged. Due to the
attractive electrostatic forces, the negatively ( vely) charged SO 4-2 ions
accumulate around the positively (+vely) charged metal, resulting in the
formation of an electrical double layer. The potential developed at the interface
is called copper electrode potential.
Metal Electrodes:
A metal-ion system in which the metal is in equilibrium with its own ions in
solution is called a metal electrode.
Example:
Zn rod dipped in ZnSO4 solution constitutes a Zn electrode, which is
represented as Zn/Zn+2.
Similarly,
Cu electrode
Iron electrode
Cu/Cu2+
Fe/Fe2+ or
Fe/Fe3+
When equilibrium is established between a gas and its ions in solution a gas
electrode is formed. For this, the gas has to be retained in solution which is
achieved by having a metal like platinum capable of adsorbing the gas and
also should not react with the components of the system. An equilibrium is
established between the gas adsorbed on the metal and the ions of the gas in
solution,.
For example:
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UNIT 3
When H2 gas is bubbled through HCl containing a Pt foil, the H 2 gas gets
adsorbed and between the H2 gas on the metal and H+ of the solution, an
equilibrium is established. This constitutes Hydrogen electrode represented as
pt, H2/H+.
(Since the oxide ion in solution forms OH- instead of remaining as O-2).
The Electrical potential difference set up between the metal and its ions in the
solution is called electrode potential.
Or
It may be defined as the tendency of an electrode to lose or gain electrons
when it is in contact with solution of its own ions.
The magnitude of the electrode potential depends on:
1.
2.
3.
Temperature.
Oxidation Potential:
If an electrode undergoes spontaneous oxidation when coupled with a standard
hydrogen electrode (SHE) it is said to have a positive value of oxidation
potential and vice versa.
Reduction Potential:
If an electrode undergoes spontaneous reduction when coupled with a
standard hydrogen electrode (SHE) it is said to have a positive value of
reduction potential and vice versa.
Standard Electrode Potential (Eo)
It is the potential developed when the pure metal is in contact with its ions at
one molar
(1 M) concentration at a temperature of 25oC or 298 K.
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UNIT 3
Example:
When a Zn rod of any length is dipped in 1M ZnSO 4 solution, standard
electrode is formed and the potential developed is called standard zinc
electrode potential (EoZn). The standard zinc electrode is represented as
Zn/Zn+2 (1 M).
In case of a gas electrode, the standard electrode potential (E o) is defined as
the potential developed at the interface of the gas and solution containing its
own ions when an equilibrium is established between the gas at a pressure of
760 mm of Hg (1 atm or 1 bar) and the ions in solution of unit concentration (1
M).
When the H2 gas at a pressure of 1 atm is bubbled through HCl of 1 M standard
H2 electrode is formed and the potential developed is called standard hydrogen
electrode potential (E0H2) whose magnitude is considered to be 0.
The standard H2 electrode is represented as
Pt, H2 / H+ (760 mm of Hg)/ (IM)
The magnitude of the standard electrode potential is independent of
temperature since it depends only on the concentration of the ions.
Cell Potential or EMF of a Cell:
The difference between the electrode potentials of two half cells is known as
electromotive force (E.M.F.) or cell potential or cell voltage.
It is represented as Ecell .
Potential Difference
using
Electrochemical Series:
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UNIT 3
It is the arrangement of metals in increasing order of standard reduction
potential.
Characteristics of Electrochemical Series:
1.
Reactive metals are placed on top (e.g., Li) and they have a great
tendency to get oxidized. Non-reactive metals like Ag and Au are placed
at the bottom.
2.
3.
Any metal which is above another can displace that from its salt
solutions
Example:
4.
If two metals form a cell, the metal that is above undergoes oxidation
and forms the anode while the one below forms the cathode.
Example:
Zn - Anode
(-0.76V)
Cu - Cathode
(+ 0.34V)
Higher the SRP, greater is the tendency to accept e-, higher is the
tendency to get reduced and greater is the oxidizing power. Fluorine
system (F2/F)- has the highest SRP and hence it possesses highest
oxidising power and this increases down the group.
2.
Lower the SRP, lesser is the tendency to accept e-, higher is the tendency
to donate electrons, higher is the tendency to get oxidized and greater is
the reducing power.
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UNIT 3
In the ECS, Lithium has the lowest SRP. Hence, it has the highest
reducing power and this goes on decreasing down the series.
3.
4.
Lower the SRP, lesser is the tendency to accept the electrons, greater is
the tendency to donate the e - to form cations and higher is the electro
positive nature. In the ECS, Li system has the lowest SRP and is highly
electro positive which goes on decreasing down the series.
5.
A metal system occurring above H2, displaces H2 from dilute acids, from
water steam depending on its position and gets tarnished.
6.
More electronegative
More electropositive
Exercise Questions:
Q 1: The electrode potentials A, B, C and D are 2.52 V, 0.16V, + 1.3V and
3.01V
respectively. On the basis of this name the following:
D = 3.01 V
A = 2.52 V
B = 0.16 V
C = + 1.3
V
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UNIT 3
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(l)
Most electropositive
Most electronegative
Highest reducing power
Highest oxidizing power
Lowest oxidizing power
Displaced by all other systems
Does not displace any other system
Displace H2
Always acts as negative electrode
Always acts as positive electrode
System which is not displaced by any other
Which electrode will act as positive and which one as negative in
the following combinations:
i.
ii.
iii.
iv.
A
B
C
D
and
and
and
and
B
C
D
A
A 1:
(a)
Most electropositive
(b)
Most electronegative
:
(c)
Highest reducing power
:
(d)
Highest oxidizing power
:
(e)
Lowest oxidizing power
:
(f)
Displaced by all other systems
(g)
Does not displace any other system:
(h)
Displaces H2
(i)
Always acts as a negative electrode:
(j)
Always acts as positive electrode
(k) System which is not displaced any other
(l)
i.
A is negative and B is positive
ii.
B is negative and C is positive
iii.
D is negative and C is positive
iv.
D is negative and A is positive
:
C
D
C
D
:
C
:
D
:
:
C
D, A and B
C
D
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UNIT 3
The minimum potential which causes the flow of the electrons from the
negative electrode to the positive electrode is called e.m.f.
The emf of a cell is defined as the algebraic difference between the SRP of the
positive electrode and the SRP of the negative electrode even though oxidation
is taking place at the negative electrode.
E0Cathode
E0Anode
OR
ERight or
ER
ELeft or
EL
= 0.35 ( 0.76)
= 1.10 V
Nernst Equation:
Effect of temperature and change in electrolytic concentration on electrode
potential is determined by using Nernst equation.
For the reduction reaction,
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UNIT 3
Where,
[M]
[M
n+
=
]
E0
Gas constant
Temperature in K
F = 96500 coulombs
At T = 298 K,
Example:
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UNIT 3
For the Zn - ZnSO4 electrode:
[Zn] = [Cu] = 1
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Zn (s) | ZnSO4 (aq) ||
2.
3.
SO42 moves through the salt bridge from CuSO4 to ZnSO4 solution.
The concentration of Cu2+ and Zn2+ at this stage are the equilibrium
concentration.
Significance of Kc
It tells us about the extent to which the reaction has been completed. Kc for
Zn-Cu cell at 298K is 2 x 107 which shows that the reaction has nearly gone to
completion.
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UNIT 3
Gibb's Free Energy and Cell Potential (EMF):
When a cell reaction takes place electrical energy is produced which results in
decrease in the free energy of the system.
Electrical work = Decrease in free energy
In an electrochemical cell,
Electric work done =
E.M.F.
For equilibrium,
= RT ln KC
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UNIT 3
2.
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3.
4.
Note:
Na+, Ca2+ and Al3+ have lower reduction potential than water so H 2 gas is
evolved at the cathode.
ii.
Cu2+, Ag+ have much higher reduction potential than that of water. So
these ions are deposited at the cathode.
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UNIT 3
BATTERY
A number of cells connected in series forms a battery.
Primary battery:
In these the redox reactions occur only once and cannot be used again.
Example: dry cells, mercury cells.
Secondary battery:
These can be recharged by passing current and can be used again and again.
Example: Lead storage battery, Ni-Cd storage cell.
Fuel cell:
Energy produced by combustion of fuels like H 2, CO, CH4 can be directly
converted to electric energy.
Primary Cells:
Dry Cells
It is the compact form of the Leclanche cell.
Anode
Cathode
:
:
Cylindrical Zn container.
The space in between is filled with NH 4Cl and ZnCl2. The graphite rod is
surrounded by MnO2 and carbon.
Reactions:
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It does not have a long life because the acidic NH 4Cl corrodes the Zinc
container.
Mercury
Cell:
Used
in
electric
hearing
watches.
small
devices like
aids
and
Anode
Zinc
:
container
Cathode
Electrolyte :
:
Carbon rod
moist HgO mixed with KOH.
Reactions:
The cell shows a constant potential of 1.35 V throughout as it does not involve
any ion whose concentration changes.
Secondary Cell:
Lead Storage Battery:
Anode
Lead
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UNIT 3
Cathode
PbO2
dilute H2SO4.
:
:
Cadmium
NiO2
Reactions:
It can be recharged.
Fuel Cell:
These are devices which convert the energy produced during the combustion
of fuels like H2, CO and CH4 directly into electrical energy. The most successful
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UNIT 3
fuel cell is the H2-O2 fuel cell. It was used in the Apollo space programme and
the water produced used as drinking water for the astronauts.
Working:
H2 and O2 are bubbled through a porous carbon rod into concentrated NaOH.
Catalysts are present in the electrodes.
Advantages:
1.
More efficient than conventional cells because the energy of the fuel is
converted directly into electric energy. Efficiency = 60-70%.
2.
CORROSION
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UNIT 3
The process of slowly eating away of the metal due to attack of the
atmospheric gases on the surface of metals; forming oxides, carbonates,
sulphides is called corrosion.
For example:
Tarnishing of Ag.
Development of a green coating on Cu and bronze etc.
Water on the metal surface dissolves CO2 and O2 from the air.
2.
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3.
4.
Reactivity of metal
Presence of impurities
Presence of air, moisture, gases like SO2 and CO2
Presence of electrolytes
Prevention of Rusting:
1. Barrier protection:
The metal surface is not allowed to come in contact with moisture, O2 and CO2.
i.
ii.
iii.
iv.
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2. Sacrificial protection:
Covering the surface with a more electro positive metal than Fe. The more
electro positive metal loses electrons and as long as this coating is present Fe
is protected.
Example:
Galvanization
Important Suggestion:
First of all, prepare Intext &
Exercise Questions as well as Solved Examples from NCERT
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UNIT 3
and then only prepare questions from Previous Years
Papers.
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