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Electro-Chemistry
Electrochemistry is the branch of physical chemistry. This deals with the relation between electrical energy
& chemical energy & with the method of their inter-conversion i.e. how electrical energy is converted into
chemical energy & vice-versa.
(1) Conductors: - Substance, which can conduct electric current are called conductors. Conductors are of two
types.
(i) Metallic or Electronic conductors: - Those substances which conduct electricity due to free
electrons without any chemical change. eg. Metals such as Ag, Au, Cu, Al, graphite etc. Metallic
conductivity decreases when temperature is increased.
(ii) Ionic or Electrolytic conductors: - Those substances which conduct electricity due to free ions in
it’s dissolved or fused state with change chemical change. eg. KCl & polar covalent compounds like
HCl behave as electrolytes.
Electrolytic conductors are further classified on the basis of their degree of dissociation as
Strong electrolytes: - Are those substances which are completely (or almost completely) ionized or
dissociated in their solution or in molten state. eg. NaCl, CuSO4, HCl, HNO3, KOH, NaOH etc.
Weak electrolytes: - Are those substances which are dissociated only to a small extent in their
solution (in polar solvents) or in molten state. eg. NH4OH, CH3COOH etc.
Strong electrolytes exhibit high electrical conductivity because of high ionization, whereas weak
electrolytes exhibit low conductivity as they ionized less.
Conductivity depends on the following factors.
(a) Inter-ionic attraction (solute-solute interaction): - Inter-ionic attraction high conductivity low.
(b) Polarity of solvent: - The substance gets ionized more in a polar solvent & therefore its
conductivity is also being high.
(c) Viscosity of the solvent: - Larger the solvent-solvent interaction larger will be the viscosity &
lesser will be the conductivity.
(d) Temperature: - Conductivity increase with temperature increase because ionization increase.

Metallic conduction Electrolytic conduction

(i) It is due to the flow of electrons. (i) It is due to the flow of ions.
(ii) It is not accompanied by decomposition of the (ii) It is accompanied by decomposition of the
substance.(Only physical changes occurs) substance. (Physical as well as chemical change occur)
(iii) It does not involve transfer of matter. (iii) It involves transfer of matter in the form of ions.
(iv) Conductivity decreases with increase in (iv) Conductivity increases with increases in temperature
temperature. and degree of hydration due to decreases in viscosity of
medium.
(2) Non-conductors or Insulators: - Substances which do not conduct electric current are called Insulators.
eg. Non-metal, gases, ceramics, glass, wood, rubber & organic compounds such as cane-sugar, urea,
naphthalene & glycerin etc.
(3) Conductance of electrolytic solutions: - Ohm’s Law : - According to Ohm’s Law, if potential difference
is V & a current (I), is passed in the solution of resistance (R), then
𝑽 𝒍 𝒍
V∝𝑰 or V = IR or I=𝑹 Where R ∝ R = 𝝆𝒂
𝒂
Where 𝜌 = Specific resistance or resistivity. It depends on the nature of the substance.
𝑙
l = Length of conductor, a = Cross section area or thickness. & 𝑎 = Cell constant.
If l = 1cm & a = 1cm2 then R = 𝝆
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Therefore resistance of a substance having 1cm length & 1cm2 transverse section area, called specific
resistance of that conductor or the resistance of 1cm3 of a substance is called specific resistance.
𝑎
𝜌=𝑅𝑙 Unit = Ohm×cm2/cm = Ohm × cm
Conductance: - It is a measure of the ease with which current flows through a conductor. It is an additive
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property. It is expressed as C. It is reciprocal of the resistance, i.e., C
R
Units: - The units of conductance are reciprocal Ohm (ohm 1 ) or mho. Ohm is also abbreviated as  so that
Ohm 1 may be written as  1 .
According to SI system, the units of electrical conductance is Siemens, S (i.e., 1S  1  1 ).
Conductivity: - The inverse of resistivity is called conductivity (or specific conductance). It is represented by
the symbol,  (Greek kappa). The IUPAC has recommended the use of term conductivity over specific
conductance. It may be defined as, the conductance of a solution of 1 cm length and having 1 sq. cm as
the area of cross-section. In other words, conductivity is the conductance of one centimetre cube of a
solution of an electrolyte
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κ=𝜌 Unit = ohm–1cm–1 or siemen cm–1
1 𝑙 1
κ=𝑅×𝑎 or conductivity = 𝑅𝑒𝑠𝑖𝑠𝑡𝑎𝑛𝑐𝑒 × Cell constant.
𝑆𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒
Cell constant = 𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑛𝑑𝑢𝑐𝑡𝑎𝑛𝑐𝑒

Equivalent conductivity: - If one equivalent of an electrolyte is dissolved in a solution & conductivity of two
parallel electrodes situated at 1-cm distance is called equivalent conductivity.
𝟏𝟎𝟎𝟎
λ=κ×V=κ× Unit = ohm–1cm2equivalent–1 or siemen cm2equivalent–1
𝑵
Molar conductivity: - If one mole of an electrolyte is dissolved in a solution, then the conductivity of that
solution between two parallel electrodes situated at 1-cm distance is called molar conductivity.
𝟏𝟎𝟎𝟎
µ = κ × V = κ × 𝑴 𝒐𝒓 𝑪 Unit = ohm–1cm2 mole–1.
Measurement of conductivity: - Conductivity & resistance are opposite to each other. Therefore, we can
calculate the Conductivity by determining resistance of the solution. For this Wheatstone bridge is used.

Faraday's laws of electrolysis: - The laws, which govern the deposition of substances (In the form of ions) on
electrodes during the process of electrolysis, is called Faraday's laws of electrolysis. These laws given by
Michael Faraday in 1833
(a) Faraday’s First Law: - According to this law, the amount of the substance produced at any electrodes
during electrolysis is directly proportional to the quantity of electricity passed through the solution.
𝑴
w∝Q or w = ZQ or w = 𝒏𝑭 × It
𝐌 𝐄
Where Z =Electrochemical equivalent of the solution. Z = 𝐧𝐅 = 𝐅
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F = Faraday (96500)
Q = It & n = electron released or accepted.
When a current of 1 Ampere is passed for 1 second (i.e., Q  1 ), then, W  Z
Thus, electrochemical equivalent (ECE) may be defined as “the mass of the ion deposited by passing a
current of one Ampere for one second (i.e., by passing Coulomb of electricity)”. It's unit is gram per
coulomb.
Coulomb is the unit of electrical charge.
96500 Coulombs  6.023  10 23 electrons = 1 mole electrons.
6 .023  10 23
1 Coulomb   6 .28  10 18 electrons, or 1 electronic charge  1 .6  10 19 Coulomb
96500
Number of electrons passed
Number of Faraday 
6.023  10 23
Quantity of electricity is required = Number of electron change × mole × 96500
One faraday is equal to the total charge of one mole electrons ie. equal to 96500 coulomb.
1F (faraday) = N × e– = 6.022×1023 × 1.60219 × 10–19 = 96500 coulomb/mole.
(b) Faraday’s Second Law: - According to this law, when same amount of electric current is passed through
many electrolyte solutions, then the amount of substances obtained on various electrodes are proportional
to their equivalent weights.
𝑾𝟏 𝑬𝟏 𝒁𝟏 𝑰𝒕 𝑬𝟏 𝒁𝟏 𝑬𝟏
w∝E w = kE = = =
𝑾𝟐 𝑬𝟐 𝒁𝟐 𝑰𝒕 𝑬𝟐 𝒁𝟐 𝑬𝟐
Number of electrons passed
Number of Faraday 
6.023  10 23
Variation of conductivity& molar conductivity with dilution: - We know that conductance of ions is due to
the presence of ions in the solution. The greater the number of ions, the greater is the conductance. As with
dilution, more ions are produced in solution so conductance also increase on dilution. Conductivity always
decreases with decreases in concentration or increase in dilution both for weak & strong electrolyte because the
no. of ions per unit volume decreases. In general molar conductivity of the electrolyte decreases with
increase in concentration. This is because the total volume of solution containing one mole of electrolyte
increases with increase in dilution. The λ & µ-increase with dilution, because number of ions dissociated from
1-mole substance increases.
Molar conductivity for strong electrolyte at infinite dilution is calculated by Debye- Huckel-Onsager
equation.
µ = µ° – b√𝒄 Where c = Molar concentration & b = Constant
Molar conductivity for weak electrolyte at infinite dilution is calculated by Kohlraush’s law.
𝟏𝟎𝟎𝟎 × 𝜿
µ= 𝑪
Strong electrolyte (KCl)

Weak electrolyte (CH3COOH)

µ

Concentration
The curve for strong electrolytes becomes linear at high dilution & thus can be extrapolated to zero
concentration to obtain the value of µ-at infinite dilution.
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But for weak electrolytes curve does not become linear at any stage, it is not possible to obtain the limiting
value of its molar conductivity by extrapolating the curve to zero concentration.

Kohlraush’s law: - At infinite dilution the difference of equivalent conductivities of the pair of salts in which
one common ion is present, remain constant at constant temperature.
When positive ion is common then µ => 2.06 eg. NaCl & NaBr ; KBr & KCl.
When negative ion is common then µ => 23.41 eg. NaNO3 & KNO3 ; KBr & NaBr.
Therefore the value of λ & µ- depends on the nature of ions.
“At infinite dilution, the molar conductivity of an electrolyte can be expressed as the sum of the positive &
negative ions present in the solution”.
µ∞ = ʋ+λ+∞ + ʋ–λ–∞ Where ʋ+ & ʋ– are the number of positive & negative ions.
∞ ∞ ∞
λ = λ+ + λ–
Application of Kohlraush’s law: -
(i) Calculation of molar conductivity at infinite dilution for weak electrolyte. Eg.
∞ ∞ ∞ ∞
𝜆∞ ∞ ∞ ∞ ∞
𝐶𝐻3 𝐶𝑂𝑂𝐻 = 𝜆𝐻 + + 𝜆𝐶𝐻3 𝐶𝑂𝑂 − = 𝜆𝐻 + + 𝜆𝑁𝑎 + + 𝜆𝐶𝐻3 𝐶𝑂𝑂 − + 𝜆𝐶𝑙 − –𝜆𝑁𝑎 + – 𝜆𝐶𝑙 −
𝜇 cm cm
(ii) Determination of the degree of ionization of a weak electrolyte: - 𝛼 = 𝜇∞ c  
m (     )
𝐶𝛼2
(iii) Determination of the ionization constant of a weak electrolyte: - K = 1−𝛼
(iv) Calculation of the solubility of sparingly soluble salt: -
(𝜅𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 −𝜅𝑤𝑎𝑡𝑒𝑟 )×1000 (𝜅𝑠𝑎𝑙𝑡 )×1000
S= =
ʋ+ 𝜆∞ ∞
+ + ʋ− 𝜆− 𝜇∞
(4) Electrolytes: - The substances which produce ions in solution are called electrolytes.
(a) True electrolytes: - Which consisting ions in its purest form. E.g. NaCl, KCl, BaSO 4, KNO3 etc.
(b) Potential electrolytes: - Do not contain ions in their purest form, the ions, however, are formed only
when these are dissolved in water. E.g. HCl, CH3COOH. Etc
(5) Cells are two types: -
(a) Electrolytic cells or Voltameter: - In these cells, electrical energy is converted into chemical energy.
i.e. chemical reactions (oxidation-reduction reaction) occur due under the effect of electric current.
 The electrode on which oxidation takes place is called anode (or +ve pole) and the electrode on
which reduction takes place is called cathode (or –ve pole).
 During electrolysis in voltameter cations are discharged on cathode and anions on anode.
 In voltameter, outside the electrolyte electrons flow from anode to cathode and current flow
from cathode to anode.
(b) Electrochemical cells: - In these cells, chemical energy is converted into electrical energy. i.e. electric
current is generated by oxidation-reduction reaction. Voltaic or galvanic cells are the examples of this
type.
S.No. Electrolytic cells Electrochemical cells
1. The redox reaction in this case is non-spontaneous & takes In this case, the redox reaction responsible for the
place only when the electrical energy is supplied. production of electrical energy is spontaneous.
2. Both the electrodes are placed in the solution in the same The two electrodes are dipped in different
beaker. electrolytes taken in different beakers.
3. Only one electrolyte is used. Both the beakers contain different electrolyte.
4. Electrodes may be of the same or different materials. Both the electrodes are of different materials.
5. No salt bridge is required. Salt bridge is required.
6. Anode (connected to +ve terminal) is taken as positive & cathode Anode (oxidation) = –ve.
(connected to –ve terminal) is taken as negative pole. Cathode (reduction) = +ve.
7. The electrons are supplied by the battery & they enter The electrons move from the anode to cathode in
through the cathode & come out through the anode. the external circuit.
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e– e–
Voltmeter Salt bridge
Cu cathode
Zn anode

Porous plug
ZnSO4 CuSO4

L.H.Electrode R.H.Electrode
(i) Oxidation take place (i) Reduction take place.
(ii) –ve pole (ii) +ve pole
(iii) Anode (iii) Cathode
(iv) El = –ve (iv) ER = +ve
 Electrochemical cell consists of two vessels, two electrodes, two electrolytic solutions and a salt
bridge.
 The two electrodes taken are made of different materials and usually set up in two separate vessels.
 The electrolytes are taken in the two different vessels called as half - cells.
 A metal dipped in the solution of its own ions is called an electrode or a redox couple.
 The two vessels are connected by a salt bridge/porous pot.
 The electrode on which oxidation takes place is called the anode (or – ve pole) and the electrode on
which reduction takes place is called the cathode (or + ve pole).
 In electrochemical cell, ions are discharged only on the cathode.
 Like electrolytic cell, in electrochemical cell, Electrons flow from anode to cathode in the external
circuit while current flows from cathode to anode.
 In a electrochemical cell, cell reaction is exothermic.
 For electrochemical cell, Ecell  ve, G  ve.
 The tendency of an electrode to lose or gain electrons is called electrode potential. Since each
electrode potential represent a half cell, therefore electrode potential is also called potential for half-
cell.
 Electrode potential depends upon the nature of the metal, concentration of ions in solution & the
temperature, therefore electrode potentials are usually measured under standared conditions. i.e.
one molar concentration of metal ions & a temperature of 298K. The electrode potentials measured
under these conditions are called standard electrode potential & denoted by E0.
 The electrode potential has to be measured against some reference electrode or SHE.
 EMF (electromotive force) or the cell potential is the potential difference between the two
0 0 0
electrodes of the cell when no current is following in the circuit. 𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
 Put single lines to separate the electrode from solution & double line or a dashed line to separate the
solutions.
 Potential difference (P.D.) is not responsible for the flow of steady current.
 EMF-is responsible for the flow of steady current in the circuit.
 A salt bridge helps in maintaining the charge balance in the two half-cells.
 Salt bridge: - Provides electrical communication. The function of the salt bridge is to allow the
movement of ions from one solution to the other without mixing of the two solutions (when the con.
of Zn2+-ions around anode increases, sufficient number of Cl- -ion migrate from the salt bridge to
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the anode half cell. Similarly, to neutralize the excess negative charge due to the additional SO42-
ions in cathode, sufficient number of K+ ions migrates from the salt bridge to the cathode half cell.).
Salt bridge consists of a U-tube containing a semi-solid paste obtained by adding agar-agar or
gelatin to the solution of a strong electrolyte such as KCl, KNO 3, K2SO4 etc. The following are the
functions of the salt bridge
(i) It connects the solutions of two half - cells and completes the cell circuit.
(ii) It prevents transference or diffusion of the solutions from one half cell to the other.
(iii)It keeps the solution of two half - cells electrically neutral.
(iv) It prevents liquid – liquid junction potential i.e. the potential difference which arises between
two solutions when they contact with each other.
 Standard hydrogen electrode (SHE) or Normal hydrogen electrode (NHE): - The absolute
value of potential of a single electrode can not be measured since a half cell reaction can not take
place independently. Therefore, electrode potential has to be measured against a reference
electrode called SHE or NHE.
A NHE consists of a pt-wire sealed in a glass tube & has a pt-foil attached to it. The foil is
coated with finely divided pt & acts as the pt-electrode. It is dipped in 1M solution of H+-ions (i.e
1M HCl) at 298K & pure H2-gas maintained at a pressure of 1-atmosphere is bubbled over pt-
electrode.
Hydrogen electrode consists of hydrogen gas in equilibrium with H+-ion in a solution. The EMF of
hydrogen electrode depends upon (i) Pressure of the H2-gas. (ii) Concentration of H+-ion in a
solution.
Pt, H2(gas) | H+

It acts as anode, if the other electrode can accept the electrons. i.e H2 (g) 2H+ (aq.) + 2e–

It acts as cathode, if the other electrode donates electrons. i.e 2H+ (aq.) + 2e– H2 (g)

The electrode potential of a SHE is taken to be zero.

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 Oxidising character ∝ Reduction character ∝ Reduction electrode potential.

𝟏
 Reducing character ∝ Oxidation character ∝ 𝐑𝐞𝐝𝐮𝐜𝐭𝐢𝐨𝐧 𝐞𝐥𝐞𝐜𝐭𝐫𝐨𝐝𝐞 𝐩𝐨𝐭𝐞𝐧𝐭𝐢𝐚𝐥
 EMF = +ve then the cell reaction will take place.
 EMF = –ve then reaction will take place in opposite direction.
 The metals whose electrode reduction potential are positive, can not release H 2 gas from acids. The
metals, whose electrode reduction potentials are negative, liberate H 2-gas from acids.
 Higher the negative value of electrode reduction potential of a metal, more will be its tendency to
release electrons, & the metals will be more reactive.
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Emf Potential difference

It is the potential difference between two electrodes It is the difference of the electrode potentials of the two
when no current is flowing in the circuit. electrodes when the cell is under operation.
It is the maximum voltage that the cell can deliver. It is always less then the maximum value of voltage which
the cell can deliver.
It is responsible for the steady flow of current in the It is not responsible for the steady flow of current in the
cell. cell.
 Cell EMF and the spontaneity of the reaction: - We know, G  nFEcell

Nature of reaction ΔG(or ΔG o ) E cell (or E ocell )

Spontaneous – +
Equilibrium 0 0
Non – spontaneous + –
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Types of electrochemical cells: - Two main types of electrochemical cells have been reported, these are,
(i) Chemical cells: - The cells in which electrical energy is produced from the energy change
accompanying a chemical reaction or a physical process are known as chemical cells. Chemical cells
are of two types,
(a) Chemical cells without transference: - In this type of chemical cells, the liquid junction potential is
neglected or the transference number is not taken into consideration. In these cells, one electrode is
reversible to cations while the other is reversible to the anions of the electrolyte.
(b) Chemical cells with transference: - In this type of chemical cells, the liquid-liquid junction
potential or diffusion potential is developed across the boundary between the two solutions. This
potential develops due to the difference in mobilities of  ve and  ve ions of the electrolytes
(ii) Concentration cells: - “A cell in which electrical energy is produced by the transference of a
substance from a system of high concentration to one at low concentration is known as concentration
cells”. Concentration cells are of two types
(a) Electrode concentration cells: - In these cells, the potential difference is developed between two
electrodes at different concentrations dipped in the same solution of the electrolyte. For example,
two hydrogen electrodes at different gaseous pressures in the same solution of hydrogen ions
constitute a cell of this type.
Pt, H 2 (pressure p1 ) H 2 (pressure p 2 ) Pt 0.0591 (p )
| H | ; Ecell  log 1 at 25 o C If p1  p2 , oxidation occurs at
Anode Cathode 2 (p 2 )
L. H. S. electrode and reduction occurs at R. H. S. electrode.

In the amalgam cells, two amalgams of the same metal at two different concentrations are
immersed in the same electrolytic solution. M (Hg C1 ) | M n | Zn(Hg C 2 ) The emf of the cell is given by
0 .0591 C
the expression, Ecell  log 1 at 25 o C
n C2
(b) Electrolyte concentration cells: - In these cells, electrodes are identical but these are immersed
in solutions of the same electrolyte of different concentrations. The source of electrical energy in
the cell is the tendency of the electrolyte to diffuse from a solution of higher concentration to that
of lower concentration. With the expiry of time, the two concentrations tend to become equal.
Thus, at the start the emf of the cell is maximum and it gradually falls to zero. Such a cell is
represented in the following manner ( C 2 is greater then C1 ).
M | M  n (C1 )| | M n  (C 2 )| M

Zn | Zn2  (C1 ) Zn2  (C2 )| Zn

or ||
Anode Cathode
The emf of the cell is given by the following expression,
0.0591 C
Ecell  log 2(R. H .S ) e at 25o C
n C1(L. H .S .)

The concentration cells are used to determine the solubility of sparingly soluble salts, valency of
the cation of the electrolyte and transition point of the two allotropic forms of metal used as
electrodes, etc
Electrochemical series: - The standard reduction potentials of a large number of electrodes have been
measured using standard hydrogen electrode as the reference electrode. These various electrodes can be
arranged in increasing or decreasing order of their reduction potentials. The arrangements of elements in
order of increasing reduction potential values are called electrochemical series. It is also called activity
series, of some typical electrodes.
Characteristics of Electrochemical series
(i) The negative sign of standard reduction potential indicates that an electrode when joined with SHE acts
as anode and oxidation occurs on this electrode. For example, standard reduction potential of zinc is –
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0.76volt, When zinc electrode is joined with SHE, it acts as anode (–ve electrode) i.e., oxidation occurs on
this electrode. Similarly, the +ve sign of standard reduction potential indicates that the electrode when
joined with SHE acts as cathode and reduction occurs on this electrode.

(ii) The substances, which are stronger reducing agents than hydrogen are placed above hydrogen in the
series and have negative values of standard reduction potentials. All those substances which have positive
values of reduction potentials and placed below hydrogen in the series are weaker reducing agents than
hydrogen.
(iii) The substances, which are stronger oxidising agents than H  ion are placed below hydrogen in the
series.
(iv) The metals on the top (having high negative value of standard reduction potentials) have the tendency
to lose electrons readily. These are active metals. The activity of metals decreases from top to bottom. The
non-metals on the bottom (having high positive values of standard reduction potentials) have the tendency
to accept electrons readily. These are active non-metals. The activity of non-metals increases from top to
bottom.
Table : 12.3 Standard reduction electrode potentials at 298K
Element Electrode Reaction Standard Electrode Reduction
0
(Reduction) potential E , volt
Li Li++ e– = Li –3.05
K K++ e– = K –2.925
Ba Ba+++ 2e = Ba –2.90
Sr Sr+++ 2e = Sr –2.89
Increasing tendency to accept electrons Increasing strength as

Ca Ca 2   2e   Ca –2.87
Increasing strength as reducing agent Increasing tendency to

Na Na   e   Na –2.714
Mg Mg 2   2e   Mg –2.37
Al Al 3   3 e   Al –1.66
oxidising agent

++
–1.18
lose electrons

Mn Mn + 2e = Mn
Zn Zn2+ +2e–=Zn –0.7628
Cr Cr3++3 e– = Cr –0.74
Fe Fe2++ 2e– = Fe –0.44
Cd Cd2++2e– = Cd –0.403
Co Co+++ 2e = Co –0.27
Ni Ni2++2e– = Ni –0.25
Sn Sn2++2e– = Sn –0.14
Pb Pb+++ 2e = Pb –0.12
H2 2H++2e– = H2 0.00
Cu Cu2++ 2e– = Cu +0.337
I2 I2+2e– = 2I– +0.535
Hg Hg2++2e– = Hg +0.885
Ag Ag++ e– = Ag +0.799
Br2 Br2+2e– = 2Br– +1.08
Pt Pt+++ 2e = Pt +1.20
Cl2 Cl2+2e– = 2Cl– +1.36
Au Au 3++3e– = Au +1.50
F2 F2+2e–= 2F– +2.87
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Application of Electrochemical series

(i) Reactivity of metals: - The activity of the metal depends on its tendency to lose electron or electrons,
i.e., tendency to form cation (M n  ) . This tendency depends on the magnitude of standard reduction
potential. The metal which has high negative value (or smaller positive value) of standard reduction
potential readily loses the electron or electrons and is converted into cation. Such a metal is said to be
chemically active. The chemical reactivity of metals decreases from top to bottom in the series. The metal
higher in the series is more active than the metal lower in the series. For example,
(a) Alkali metals and alkaline earth metals having high negative values of standard reduction
potentials are chemically active. These react with cold water and evolve hydrogen. These readily
dissolve in acids formingcorresponding salts and combine with those substances which accept
electrons.
(b) Metals like Fe, Pb, Sn, Ni, Co, etc., which lie a little down in the series do not react with cold
water but react with steam to evolve hydrogen.
(c) Metals like Cu, Ag and Au which lie below hydrogen are less reactive and do not evolve
hydrogen from water.
(ii) Electropositive character of metals: - The electropositive character also depends on the tendency to
lose electron or electrons. Like reactivity, the electropositive character of metals decreases from top to
bottom in the electrochemical series. On the basis of standard reduction potential values, metals are divided
into three groups
(a) Strongly electropositive metals: - Metals having standard reduction potential near about – 2.0 volt or
more negative like alkali metals, alkaline earth metals are strongly electropositive in nature.
(b) Moderately electropositive metals: - Metals having values of reduction potentials between 0.0 and
about – 2.0 volt are moderately electropositive Al, Zn, Fe, Ni, Co, etc., belong to this group.
(c) Weakly electropositive: - The metals which are below hydrogen and possess positive values of
reduction potentials are weakly electropositive metals. Cu, Hg, Ag, etc., belong to this group.
(iii) Displacement reactions: -
(a) To predict whether a given metal will displace another, from its salt solution: - A metal higher in
the series will displace the metal from its solution which is lower in the series, i.e., The metal having
low standard reduction potential will displace the metal from its salt's solution which has higher
value of standard reduction potential. A metal higher in the series has greater tendency to provide
electrons to the cations of the metal to be precipitated.
(b) Displacement of one nonmetal from its salt solution by another nonmetal: - A non-metal higher in
the series (towards bottom side), i.e., having high value of reduction potential will displace another
non-metal with lower reduction potential, i.e., occupying position above in the series. The non-metal's
which possess high positive reduction potentials have the tendency to accept electrons readily. These
electrons are provided by the ions of the nonmetal having low value of reduction potential,. Thus, Cl 2
can displace bromine and iodine from bromides and iodides.
Cl2  2 KI  2 KCl  I2

2 I   I2  2e  .....(Oxidation)
Cl 2  2e   2Cl  .....(Reduction)
[The activity or electronegative character or oxidising nature of the nonmetal increases as the value of
reduction potential increases.]
(c) Displacement of hydrogen from dilute acids by metals: - The metal which can provide electrons to
H  ions present in dilute acids for reduction, evolve hydrogen from dilute acids.
Mn  Mn n  ne  .....(Oxidation)
 12

2 H   2e   H 2 .....(Reduction)
The metal having negative values of reduction potential possess the property of losing electron or
electrons.
Thus, the metals occupying top positions in the electrochemical series readily liberate hydrogen from
dilute acids and on descending in the series tendency to liberate hydrogen gas from dilute acids
decreases.
The metals which are below hydrogen in electrochemical series like Cu, Hg, Au, Pt, etc., do not
evolve hydrogen from dilute acids.
(d)Displacement of hydrogen from water: - Iron and the metals above iron are capable of liberating
hydrogen from water. The tendency decreases from top to bottom in electrochemical series. Alkali and
alkaline earth metals liberate hydrogen from cold water but Mg, Zn and Fe liberate hydrogen from hot
water or steam.
(iv) Reducing power of metals: - Reducing nature depends on the tendency of losing electron or electrons.
More the negative reduction potential, more is the tendency to lose electron or electrons. Thus
reducing nature decreases from top to bottom in the electrochemical series. The power of the reducing
agent increases, as the standard reduction potential becomes more and more negative. Sodium is a
stronger reducing agent than zinc and zinc is a stronger reducing agent than iron. (decreasing order of
reducing nature)
Element : Na  Zn  Fe
Reduction potential :  2.71  0.76  0 .44
Alkali and alkaline earth metals are strong reducing agents.
(v) Oxidising nature of non-metals: - Oxidising nature depends on the tendency to accept electron or
electrons. More the value of reduction potential, higher is the tendency to accept electron or electrons.
Thus, oxidising nature increases from top to bottom in the electrochemical series. The strength of an
oxidising agent increases as the value of reduction potential becomes more and more positive.
F2 Cl 2 , Br2 I 2 Cl 2 Br 2 I2
(Fluorine) is a stronger oxidant than and , (Chlorine) is a stronger oxidant than and
I2 Br2 Cl 2 F2
 0 .53  1.06  1.36  2 .85
Element : 
Reduction potential : Oxidising nature increases
Thus, in electrochemical series
(Strongest reducing agent)
Top
Highest negative reduction potential
Reducing
nature
Oxidising

or
nature

(Minimum reduction potential)

(Strongest oxidising agent)
Highest positive value of reduction potential
Bottom

(vi) Thermal stability of metallic oxides: - The thermal stability of the metal oxide depends on its
electropositive nature. As the electropositivity decreases from top to bottom, the thermal stability of the
oxide also decreases from top to bottom. The oxides of metals having high positive reduction
potentials are not stable towards heat. The metals which come below copper form unstable oxides,
i.e., these are decomposed on heating.
1 
BaO 

Ag 2 O  2 Ag  O2 2 HgO  2 Hg  O2 ; Na 2 O  

No decomposit ion
2 ; 
Al 2 O3 
(vii) Extraction of metals: - A more electropositive metal can displace a less electropositive metal from its
salt's solution. This principle is applied for the extraction of Ag and Au by cyanide process. Silver from
 13

the solution containing sodium argento cyanide, NaAg (CN )2 , can be obtained by the addition of zinc as it
is more electro-positive than Ag . 2NaAg(CN ) 2  Zn  Na2 Zn(CN ) 4  2 Ag
(6) Nernst equation: - The equation which gives the effect of electrolyte concentration & temperature on
the electrode potential or the EMF of a cell is called Nernst equation.
The potential of an electrode depends upon (i) temperature (ii) Concentration of the material involved in
the electrode reaction.
Mn+(aq.) + ne– M(s)

0 2.303𝑅𝑇 𝑀(𝑠) 0 0.0591 𝑀(𝑠)

𝐸𝑀𝑛+/𝑀 = 𝐸𝑀 𝑛+ /𝑀 – log𝑀𝑛+(𝑎𝑞.) or 𝐸𝑀𝑛+/𝑀 = 𝐸𝑀 𝑛+ /𝑀 – log𝑀𝑛+ (𝑎𝑞.)
𝑛𝐹 𝑛

Where 𝐸𝑀𝑛+/𝑀 = Potential of the electrode at a given concentration.

0
𝐸𝑀 𝑛+ /𝑀 = Standard potential of the electrode at a given concentration.

R = 8.314JK–1mol–1.
n = Number of electrons involved in the electrode reaction.
F = Faraday constant (96500Cmol–1.)
Concentration of solid is always taken to be unity.
(a) Nernst’s equation for cell EMF: - For a cell in which the net cell reaction involving n electrons is,
aA  bB  cC  dD
The Nernst equation is written as,
RT [C]c [D]d
Ecell  Ecell
0
 ln
nF [ A]a [B]b
Where, 0
E cell  E cathode
0
 E anode
0
.
o
The E cell is called the standard cell potential.
2 . 303 RT [C ]c [D]d
or Ecell  Ecell
o
 log
nF [ A]a [B]b
At 298 K, above eq. can be written as,
0 . 0592 [C ]c [D]d
or Ecell  Ecell
o
 log
n [ A]a [B]b
It may be noted here, that the concentrations of A, B, C and D referred in the eqs. are the
concentrations at the time the cell emf is measured.
(b) Nernst’s equation for Daniells cell : Daniell’s cell consists of zinc and copper electrodes. The
electrode reactions in Daniell’s cell are,
At anode : Zn(s)  Zn2  (aq)  2e 
At cathode : Cu 2  (aq)  2e   Cu(s)

Net cell reaction : Zn(s)  Cu 2  (aq)  Cu(s)  Zn 2  (aq)

Therefore, the Nernst equation for the Daniell’s cell is,
2.303 RT [Cu (s)][Zn 2  (aq)]
Ecdll  Ecell
0
 log
2F [Zn(s)][Cu 2  (aq)]
Since, the activities of pure copper and zinc metals are taken as unity, hence the Nernst equation for
the Daniell’s cell is,
2.303 RT [ Zn 2  (aq]
Ecdll  Ecell
0
 log
2F [Cu 2  (aq)]

The above eq. at 298 K is,

 14

0.0591 [ Zn 2 (aq]
Ecdll  Ecell
o
 log V For Daniells cell, 0
E cell  1 .1 V
2 [Cu 2 (aq)]

Relationship between potential, Gibbs energy and equilibrium constant: - The electrical work
(electrical energy) is equal to the product of the EMF of the cell and electrical charge that flows through the
external circuit i.e.,
Wmax  nFEcell ......(i)
According to thermodynamics the free energy change (G) is equal to the maximum work. In the cell work
is done on the surroundings by which electrical energy flows through the external circuit, So
 Wmax,  G ......(ii)
from eq. (i) and (ii) G  nFEcell In standard conditions G 0   nFEcell
0
&
Where G 0  standard free energy change
2.303 2.303𝑅𝑇 𝑛𝐸0
0
But Ecell  RT log K c or E0 = 𝑛𝐹 log.Kc or Kc = Antilog.0.0591
nF
2.303
 G 0  nF  RT log K c or G 0   2.303 RT log K c or G  G  2.303RT log Q
nF
G   RT ln K c (2.303 log X  ln X )
0
Or ∆G = –nFEcell. = – 2.303RTlogKc.
(7) Some Commercial cells: - Any battery or cell that can be used as a source of electrical energy is
basically an electrochemical cell.
A battery or a commercial cell must have the following requirements.
 It should be reasonably light & compact.
 It should be rechargeable.
 It should have reasonably long life.
 Its voltage should not vary appreciably during the use.
There are mainly three types of cells. (a) Primary cells (b) Secondary cells (c) Fuel cells.
(A) Primary cells: - Primary cells are those in which the redox reaction occurs only once & cell becomes
dead over a period of time & can-not be recharged & used again.
(a) Dry cell: - This is the most familiar & compact from of Leclanche cell. It is used in daily life in
torches, toys, transistor etc. It consists of a zinc cylinder filled with a paste of NH 4Cl & little of
ZnCl2. A graphite rod, placed in the centre but not touching the base & surrounded by powdered
manganese dioxide & carbon acts as cathode while zinc cylinder acts as anode.
+ Seal
Graphite (cathode)
Cell reaction: - MnO +C (Depolariser) 2

Anode Zn(s) –2e– Zn2+ Paste of NH Cl+ZnCl 4 2

Cathode MnO2(s) + NH4+(aq.) + 2e– MnO(OH) + NH3 –

Voltage 1.25 to 1.5V Zinc anode

 Even though not in use, a dry cell becomes dead after some time because the acidic NH 4Cl
corrodes the zinc container.
 ZnCl2 combines with the NH3 produced to form the complex salt [Zn(NH3)2Cl2] otherwise the
pressure developed due to NH3 would crack the seal of the cell. Electrons flow
e –
(b) Daniel cell: - e
– Key
–
+
Ammeter Current

Anode (Zn) Salt bridge Cathode (Cu)

Cathode : Cu rod Anode : Zn rod
Electrolyte : dil. H2SO 4 Emf : 1.1 V
Cotton Plugs

Zn2+ Cu2+
 15

At cathode : Cu 2  2e   Cu
At Anode : Zn  Zn2  2e 
Over all reaction : Zn  Cu 2  Zn2  Cu

(c) Mercury cell: - Mercury cell, consisting of Zn-Hg amalgam as anode & a paste of HgO & carbon
as the cathode. The electrolyte is a paste of KOH & ZnO. The electrode reaction are: -
Anode: - Zn(Hg) + 2OH- -2e- ZnO(s) + H2O
-
Cathode: - HgO(s) + H2O +2e Hg(l) + 2OH-
The cell potential is approximately 1.35V & remains constant as the ionic concentration of the
solution is not changed during its life.
Unlike dry cell, the mercury cell has a constant cell potential throughout its useful life because in
mercury cell the ions are not involved in the overall cell reaction.
(d)
(B) Secondary cells: - Secondary cells are those cells which can be recharged by passing a direct current
through them & can be used again as a source of electric current. E.g. (a) Lead-storage battery (b)
Nickel cadmium storage cell (c) Lithium ion cell battery.
(a) Lead-storage battery: - It is most frequently used battery in automobiles. It consists of six voltaic
cells connected in series. Sufficient to give a voltage of 12-volts.
+ –
Glass vessel

PbO2

Pb
dil. H2SO4

Anode: - Lead or an alloy of lead & antimony. or Perforated lead plates coated with pure lead
Cathode: - Finely powdered PbO2 or Perforated lead plates coated with PbO .
Electrolyte: - dil. H2SO4
Efficiency: - 80%
Chemical reaction: -
(i) During charging: -
At anode : PbSO4 + 2H+ + 2e–  Pb + H2SO4
At cathode : PbSO4 + 2H2O – 2e–  PbO2 + H2SO4 + 2H+
Overall reaction: - 2PbSO4 (s) + 2H2O Pb(s) + PbO2(s) + 4H+(aq.) + 2SO42–(aq.)
Specific gravity of H2SO4 increases and when specific gravity becomes 1.25 the cell is fully
charged.
Emf of cell: When cell is fully charged then E = 2.2 volt
(ii) During discharging : -
At anode : Pb + H2SO4 – 2e–  PbSO4 + 2H+
At cathode : PbO2 + 2H+ + 2e– + H2SO4  PbSO4 + 2H2O
Overall reaction: - Pb(s) + PbO2(s) + 4H+(aq.) + 2SO42–(aq.) 2PbSO4 (s) + 2H2O
Specific gravity of H2SO4 decreases and when specific gravity falls below 1.18 the cell
requires recharging.
Emf of cell : When emf of cell falls below 1.9 volt the cell requires recharging
The battery can be recharged by connecting it to an external source of direct current & the chemical
reaction is reverse.
 16

(b) Nickel cadmium storage cell: - Larger life than the lead storage cell. It is more expensive to
manufacture. The cell has a voltage of about = 1.4V & electrolyte = aq.KOH.
Anode: - Cd(s) + 2OH–(aq.) Cd(OH)2(s) + 2e–
Cathode: - NiO2(s) + 2H2O(l) +2e– Ni(OH)2(s) + 2OH–(aq.)
Overall: - Cd(s) + NiO2(s) + 2H2O(l) Cd(OH)2(s) + Ni(OH)2(s)
Maximum voltage = 1.4-volt & used in calculators & electrical watches.
(C) Fuel cells: - The electrochemical source of power in which the reactants are fed continuously into the
cell & the products are continuously removed is called a fuel cell.
The H2O2 fuel cell is also known as Bacon cell. In this cell, hydrogen and oxygen are bubbled through
a porous carbon electrode into concentrated aqueous sodium hydroxide or potassium hydroxide.
Hydrogen (the fuel) is fed into the anode compartment where it is oxidised. The oxygen is fed into
cathode compartment where it is reduced. The diffusion rates of the gases into the cell are carefully
regulated to get maximum efficiency. The net reaction is the same as burning of hydrogen and oxygen
to form water. The reactions are
Anode: - H2 + 2OH– 2H2O + 2e–
Cathode: - O2 + 2H2O + 4e– 4 OH–
Overall: - 2H2 + O2 2H2O(l)
Each electrode is made of porous compressed carbon containing a small amount of catalyst
( Pt, Ag or CoO) . This cell runs continuously as long as the reactants are fed. Fuel cells convert the
energy of the fuel directly into electricity EMF of fuel cell is 1.23 V. This cell has been used for
electric power in the Apollo space programme. The cell works continuously as long as the gases H2
& O2 are supplied continuously at 50-atmosphere pressure & at a temperature of 525K.
The important advantages of fuel cells are (i) High efficiency (ii) Continuous source of energy if the
supply of gases is maintained (iii) Pollution free working (no harmful products are formed) &
(iv) These cells are light in weight as compared to electrical generators to produce corresponding
quantity of power.
 Methyl alcohol & Methane are materials other than hydrogen that can be used as fuels in fuel cells.
H2O
Anode – + Cathode

Porous carbon electrode

OH–
H2 O2
Electrolyte

(D)
S.No. Cell/ Battery Anode Cathode Electrolyte
1. Dry cell Zinc Graphite (MnO2+C) touching cathode, (NH4Cl+ZnCl2) touching Anode
2. Mercury cell Zinc Graphite (HgO + KOH)-moist.
3. Lead storage Lead Lead oxide H2SO4 (38%)
4. Ni-Cd cell Cd NiO KOH (aq.)
 17

(8) Corrosion: - Decay process of the metal is called corrosion of metals.

Metallurgical process or reduction Corrosion or oxidation

Ore of metal Pure metal Metallic compound + Energy.

Thermodynamically stable state thermodynamically unstable state thermodynamically stable state

Unwanted degradation or deterioration of metal by chemical or electrochemical reaction by the

environment, it starting at the surface & resulting in loss of solid metallic compound due to formation
of other metallic compounds & energy. Eg.
(i) Formation of a layer of reddish brown scale of (Fe2O3.xH2O) on the surface of iron or rusting of
iron.
(ii) Reaction of Cl2- gas with Mg or Sn.
(iii)Tarnishing of silver black due to coating of silver sulphite.
(iv) Formation of green layer of basic carbonate containing {CuCO3 + Cu(OH)2} on the surface of
copper. When exposed to moist air containing CO2 .

Corrosion is an oxidation process. This includes destruction of materials by forming oxide, chloride,
sulphide, silicate, carbonate, sulphate, nitrate etc. The corrosion product may be solid or liquid. The
solid may be soluble or insoluble. The insoluble product generally form a compact layer protecting the
metal from further attack because the products are generally inert to atmosphere & do not allow air,
moisture, chemicals to penetrate & attack on fresh metal. Eg are coating on Al, Ag. & the soluble or
liquid products are easily removed from the surface as soon as they are formed, so the process of
corrosion continues.
Due to corrosion (Effect of corrosion) or Significance: - Corrosion is the reverse process of metal
extraction. It is universal reaction form all metals. The rate of corrosion of alkali metal is fastest &
coinage metals corrode slowly. Losses due to corrosion include not only the cost of metal but also the
cost of fabrication of machines, wastage of time & also the following.
 The strength of material is reduced.
 Amount of iron wasted each year by corrosion is about 25% of its annual world production. (2 to
2.5- billions dollars per annum.)
 It increases the maintenance & production cost.
 Reduction in metal thickness leading to loss of mechanical strength.
 Possibility of accidents (Injuries to people from structure failure or breakdown.)
 Loss of metallic properties & thus loss of efficiency.
 The efficiency of machinery decrease which results in the decrease in production rate.
 Loss of metallic mass.
 Blockage of pipes by solid corrosion products.
 Corrosion may cause leakage of inflammable gas from the corroded pipe line resulting into fire
hazards & leakage of toxic products.
Factor responsible for corrosion: -
 Reactivity of metal: - more reactivity more corrosion.
 Presence of air & moisture: - Air & moisture increases the chances of corrosion.
 Presences of impurities: - The impurities help in setting up electrochemical cells which increase
the speed of corrosion.
 Presence of electrolyte: - Electrolytes in water also increase corrosion. Iron corrodes more in sea
water than in pure water.
 Strain in metals: - Because of strain, the exposed surface area increase, which increases corrosion.
 18

The process of rusting is more common when the surface of metal is uneven. It suggests that the uneven
surface of iron behaves like small electro-chemical cells in the presence of water, which contains dissolved
oxygen or CO2. This water serves as the electrolyte.
Chemical reaction: -
Fe –2e– Fe2+ [Anode] ……. (i)
CO2 + H2O H2CO3 [Cathode]
– +
H2CO3 HCO3 + H
H2O OH– + H+
H+ + e– H
4H + O2 2H2O
–
+
4 H +O2 + 4e 2H2O ………. (ii)
+
Overall redox reaction 2Fe + 4H +O2 2 Fe2+ + 2H2O
4Fe2+ + O2 + 2H2O 2Fe2O3 + 8H+
Fe2O3 + x H2O Fe2O3x H2O (rust)
Drop of moisture
4H++O2+4e–2H2O
Rust (Cathode)

Fe2+
+
Fe anode 2e–
Flow of
electrons
Iron
Schematic representation of mechanism of rusting of iron

Corrosion protection: - Corrosion of metals can be prevented in many ways. Some commonly used
methods are
(i) By surface coating: -
(a) By applying, oil, grease, paint or varnish on the surface.
(b) By coating/depositing a thin layer of any other metal which does not corrode. For example, iron
surface can be protected from corrosion by depositing a thin layer of zinc, nickel or chromium on
it. Copper/brass can be protected by coating it with a thin layer of tin. Tinning of brass utensils is a
very common practice in our country.
(c) By Galvanization: - Prevention of corrosion of iron by Zn coating.
(ii) By connecting metal to a more electropositive metal: - As long as the more electropositive metal is
there, the given metal does not get corroded. For example, iron can be protected from corrosion by
connecting it to a block/plate of zinc or magnesium. This method of corrosion protection is called
cathodic protection.
(iii) By forming insoluble phosphate or chromate coating: - Metal surfaces are treated with phosphoric
acid to form an insoluble phosphate. Formation of a thin chromate layer also prevents the corrosion of
metals.
(iv) Using anti-rust solutions: - Solutions of alkaline phosphates and alkaline chromates are generally
used as anti-rust solutions. For example, iron articles are dipped in boiling alkaline sodium phosphate
solutions, when a protective insoluble sticking film of iron phosphate is formed.
 19

 Corrosion will occur rapidly if gaseous impurities such as SO2, SO3 etc are present in the atmosphere.
 It the potential of a cell for a metal is –ve, then corrosion will not occur & if it is positive then corrosion
will occur.
 Metals that are on the top of the reactivity series such as sodium, potassium, calcium, lithium,
magnesium, aluminium are extracted electrolytically.
 Methane and methanol can be used as fuels in fuel cells other than hydrogen that can be used as fuels
in fuel cells.
 Standard reduction potential of water is greater than that of sodium so aqueous solution of NaCl on
electrolysis gives H2 gas at the cathode not Na metal.
 Dry cell become dead after a long time even if it has not been used because the acidic NH4Cl corrodes
the zinc container.
 Main role of ZnCl2 in a dry cell because ZnCl2 combines with the NH3 produced to form the complex
salt [Zn(NH3)2Cl2] otherwise the pressure developed due to NH3 would crack the seal of the cell.
 Rusting of iron is quicker in saline water than in ordinary water because in saline water, the presence of
Na+ & Cl- ions increases the conductance of the solution in contact with the metal surface. This
accelerates the formation of Fe2+ ion & hence that of rust Fe2O3.xH2O.
 Cathodic protection is the process in which a metal is connected with a more reactive metal which acts
as anode & the metal to be protected acts as a cathode.
 Unlike dry cell, the mercury cell has a constant cell potential throughout its useful life because in
mercury cell the ions are not involved in the overall cell reaction.
 Platinum foil in the hydrogen electrode is used for inflow & outflow of electrons.
 Hydrogen-oxygen fuel cell is used in Apollo space programme.
 Antirust solutions are those which retard the corrosion of iron. For example, solutions of alkaline
phosphates.
 We can not store copper sulphate in an iron vessel because Cu (E.P. = +0.34V) & Fe (E.P. = -0.44V)
respectively. This means Cu2+ will be reduced to Cu & Fe will be oxidized to Fe2+. In other words, the
vessel will dissolve.
 Reduction potential of an electrode can be increase by increasing the concentration of the ions.
