ELECTROCHEMISTRY

Electrochemistry:
It is the branch of physical chemistry. It deals with the interactions between electrical energy and chemical species.
These interactions are two types:
1) Conversion of electrical energy into chemical energy.
2) Conversion of chemical energy into electrical energy.
Conductor: the substance which allows the passes of electric current through it is called an electrical conductor.
Electrical conductors are classified into two types.
1) Metallic or Electronic conductors.
Ex: all metals, graphite.
2) Electrolytic conductors.
Definition of Electrolytic conductor: The substances which don’t conducts electricity in its solid state but conduct
electricity in its molten or fused or aqueous solution state.
Ex: fused NaCl, HCl, NaOH, CH3COOH, H2SO4 etc.
Conductance of Electrolytes:
Electrolytic conduction involves transfer of electrons through the migration of positive and negative ions towards
the electrodes.
In an ionic solutions the cations and anions are free to move and can transport charge, when current is passed
through the solution so, the ions carry current.

Conductance of Solution: the ability of all the ions in solution to carry current is called its conductance.
Or
The conducting power of all the ions those are present in the solution.

As metallic conductors, electrolytic conductors obey Ohm’s law.

According to Ohm’s law, the resistance (R) of a uniform conductor is directly proportional to its length (l) and
inversely proportional to its cross sectional area (a).
In Electrolytic conductors,
Length of the conductor (l) = separation between two electrodes.
Cross sectional area (a) = area of electrodes.
R α l --------------------1
R α 1/a -------------------2
R α l/a
R =ρ l/a (ρ = specific Resistance)
1/ρ = l/a × 1/R
1/ρ = specific conductance
Specific conductance denoted by K(kappa)
K = l/ × 1/R
K = l/a × C
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K = cell constant × C
 Units:
Resistance (R) = Ohm or Ω
Conductance (C ) = 1/R = ohm-1 or Ω-1
Specific Resistance (ρ) = R × a/ l = ohm × cm2/cm = ohm.cm (CGs)
= ohmmeter (MKS)

Cell constant = l/a = cm/cm2 = cm-1

Specific conductance (K) = cell constant × C
= ohm-1 × cm-1 (CGs)
= ohm-1× meter-1(MKS)
Specific conductance (K)
It is the conductance of the 1 cm3 of electrolytic solution.
Or
The conducting power of all the ions those are present in 1cm3 of solution.
Effect of dilution on specific conductance:
Up on dilution the number of ions increases. So the conductance increases but number of ions present per unit
volume decreases. Therefore specific conductance decreases.
Units:
Specific conductance (K) = cell constant × C
= ohm-1 × cm-1 (CGs)
= ohm-1× meter-1(MKS)

Equivalent conductance.(λ):
It is the conductance of electrolytic solution, which contains the one gram equivalent of electrolyte.
Or
The conducting power of all the ions of one gram equivalent of an electrolyte present in a solution is called
equivalent conductance.
It is denoted with λ.
Relationship between λ and K
Case 1: let us assume one gram equivalent of an electrolyte is present in one Cm3 of electrolytic solution.
Therefore λ = K
Case 2: let us assume one gram equivalent of electrolyte present in V Cm3 of electrolytic solution.
Therefore λ = VK (v = volume of electrolytic solution containing one gram equivalent of electrolyte)
Units: λc = VK = ohm-1 cm-1 cm3/gram.equivalent.
λc = ohm-1 cm2/gram.equivalent.

Relationship between λc & Normality(N)

If k is expressed in ohm-1 cm-1.
Let us assume Normality of solution is N of GEN of electrolyte present in 1liter.
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 N GEN is present in 1000cm3 of solution.

 1 GEN of electrolyte is present in 1000/N cm3 of solution.
 λc = K × 1000/N

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  if k is expressed in ohm-1 meter-1
 λc = k × 1/1000N.

Molar conductance: ( μc Or λm)

It is the conductance of electrolytic solution which contains one mole electrolyte is called molar conductance. It is
denoted by ( μc Or λm).

Relationship between (μc & K)

μc = K × V ( v = volume of electrolytic solution containing one mole of electrolytic solution.)

Relationship between μc & M:

If K is expressed in ohm-1 cm-1 ,the molarity of solution is M.
Then μc = K × 1000/M.

APPLICATIONS OF CONDUCTANCE (CONDUCTROMETRIC TITRATIONS)

Conductivity measurements have been frequently used in determining the end points of different type of titrations,
viz. titration involving
Acid – alkali,
Displacement and precipitation.
Conductometric titrations defined as those titrations in which end – point is detected with the help of conductivity
measurements.
Conductometric titrations are based on the fact that the conductance of a solution at a constant temperature
depends upon the number and mobility (velocity) of ions presents in it.
Examples:

1.Titration of a strong acid (Hcl) with a strong base (NaOH):

In these titration alkali solution is generally taken in the burette and a know volume of the acid solution taken in conductivity
cell. The conductance of acid solution is noted initially. Since the acid solution contains the fastest moving H+ ions, its
conductivity will be very high. By adding certain amount of NaOH solution to Hcl solution following reaction takes place.
(H+ + Cl-) + (Na+ + OH-) (Na+ + Cl-) + H2O
The addition of NaOH solution to the HCl solution replaces some of the fast moving H+ ions by slow moving Na+
ions with the result conductance of the resulting solution (40ml HCl+1ml NaOH) will be low than that of the pure HCl (40ml)
solution.
Thus more and more H+ ions are replaced by Na+ ions with the addition of more
and more NaOH to Hcl solution and hence conductivity keeps on falling till all the H+ ions
from HCl are replaced by Na+ ions from NaOH. After complete neutralization of HCl further
addition of NaOH to the conductivity solution will introduce the OH- ions which are fast
moving among all the ions (Na+, cl-, OH-) present at this stage. Thus conductivity of
solution obtained on addition of NaOH to neutral solution increases and this goes on
increasing with the addition of NaOH.
Graph: the conductance values are plotted against the volume of alkali added, the points
will lie on two straight lines(AB and BC). The point of intersection of these two lines gives
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end point.

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 Titration of a weak acid (CH3COOH) against a strong base (NaOH):
The initial conductance of the acetic acid solution (taken in the conductivity cell) is low because its poor
dissociation.
On adding NaOH solution, highly ionized sodium acetate is formed.
CH3COOH + [Na+ + OH-] CH3COO- + Na+ + H2O
Due to formation of highly ionized sodium acetate the conductivity increases. The conductance goes on increasing with the
addition of NaOH solution.
When whole of the acetic acid taken in the conductivity cell has been
neutralized, further addition of NaOH solution increases the conductance sharply
because the addition of NaOH introduces the fast moving OH- ions.
Graph: if we plot a graph between conductance values on y - axis and volume of alkali
on x - axis two lines intersecting at the point B. the point B corresponds to the end
point and hence gives the volume of alkali required for the neutralization of the given
volume of acid.

Titration of weak acid (CH3COOH) against a weak base (NH4OH):

Conductometric method is particularly suitable for such titrations because they do not give
a sharp end point with indicator.
In this titration the initial conductance of the CH3COOH solution is low due to the poor
dissociation of the acid(weak). However, the conductance start increasing on the addition
of base(NH4OH). The increase in conductance is due to formation of ammonium salt.
After equivalence point, the conductivity remains almost constant because of free base
(NH4OH) is also a weak electrolyte. The end point is quite sharp and obtained by the
intersecting point of the two curves.

Titration involving precipitation:

Precipitation reaction: AgNO3 against KCl

Ag+ + NO3- + K+ Cl- AgCl + K+ + NO3-

Since the mobility of potassium and silver ions is nearly similar, replacement of Ag+ ion
by K+ ion will not affect the conductance will remain more or less constant till the
equivalent point is reached. However, when more KCl is added progressively after the
end point the conductance start increasing because the addition of excess
of KCl introduces the ions of K+ and Cl-. In this the conductance increases due to
increasing of number of ions.

Titration of a mixture of weak and strong acids (CH3COOH + HCl) against a strong base (NaOH):
(In this mixture of acid taken in conductivity cell, NaOH is taken in burette).
The ionization of the weak acid (CH3COOH) remains suppressed in the presence of the
strong acid because of the ion effect. Hence at first only the strong acid is neutralized.
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The neutralization of the weak acid will commence only when HCl has been completely
neutralized. Hence here a curve of the type ABCD is obtained. The point B corresponds
to the end point for the complete neutralization of the strong acid and the point C
corresponds to the end point for the complete neutralization of the mixture.

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 Advantages of conductometric titrations: these have several advantages over the conventional titrations
involving the use of indicators. This technique used in case of
i) Colored solution where selection of proper indicator is difficult;
ii) Very dilute solutions.
iii) Weak acid against weak base.
iv) Acids and bases and their mixtures.
v) Precipitation reactions.

Electrochemical cell:
Cell: cell is a single arrangement of two electrodes and an electrolyte.
Electrochemical cell is a cell which produces electric current due to chemical action.
Ex: galvanic (or voltaic), dry cell, lead storage battery, lithium ion battery.
Galvanic cell:
Construction of galvanic cell:

It is designed to make use of the spontaneous redox reaction between zinc and cupric ions to produce an electric current. It
consists of two half-cells. The half-cell on the left contains a zinc metal electrode dipped in ZnSO 4 solution. The half-cell on
the right consists of copper metal electrode in a solution CuSO 4. The half-cells are joined by a salt bridge that prevents the
mechanical mixing of the solution. When the zinc and copper electrodes are joined by wire, the following observations are
made:
(i) There is a flow of electric current through the external circuit.
(ii) The zinc rod loses its mass while the copper rod gains in mass.
(iii) The concentration of ZnSO4 solution increases while the concentration of copper sulphate solution decreases.
(iv) The solutions in both the compartments remain electrically neutral.

During the passage if electric current through external circuit, electrons flow from the zinc electrode to the copper electrode.
At the zinc electrode, the zinc metal is oxidized to zinc ions which go into the solution. The electrons released at the
electrode travel through the external circuit to the copper electrode where they are used in the reduction of Cu 2+ ions to
metallic copper which is deposited on the electrode.

Oxidation half reaction, Zn(s) Zn2+(aq) + 2e-

Reduction half reaction, Cu (aq) + 2e 2+ - Cu (s)
----------------------------------------------------------------------------------------------
Net reaction Zn(s) + Cu2+ (aq) Zn2+(aq) + Cu(s)
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-----------------------------------------------------------------------------------------------

Thus, the overall redox reaction is:

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 Zn(s) + Cu2+ Cu(s) + Zn2+(aq)

Thus, indirect redox reaction leads to the production of electrical energy. At the zinc rod, oxidation occurs. It is the
anode of the cell and is negatively charged while at copper electrode, reduction takes, place; it is the cathode of the cell and
is positively charged.
Salt bridge: it is inverted U shaped glass tube filled with paste of KCl or KNO3 or NH4NO3; with agar-agar gum
Use of salt bridge in the galvanic cell: it completes the circuit and allows the passes of ions from one half cell to other half
cell. It maintains the electrical neutrality in both the half cells.

Representation of electrochemical cell

1. Anode must be written on the left hand side, cathode on the right hand side.
2. Left hand side electrode is written by writing the metal first and then electrolyte.
These two are separated by vertical line or a semicolon. The electrolyte may be written by the formulae of the compounds
or by ionic species.
Zn/Zn2+ (or) Zn; Zn2+ (or) Zn; ZnSO4
3. Cathode is written on the right hand side. In this first case, electrolyte is represented then only electrode; these two are
separated by a vertical line or a semicolon.
Cu2+ / Cu (or) Cu2+; Cu (or) CuSO4 / Cu
4. A salt bridge is denoted by two vertical lines, which separates the two half cells.
Eg: Daniel cells
Zn; Zn2+ || Cu2+; Cu
Constructs the cells in which following reactions are taking place.
i) Fe + CuSO4  FeSO4 + Cu
ii) Zn + H2SO4 ZnSO4 + H2
iii) Fe + SnCl2 FeCl2 + Sn
iv) ½ H2 + ½ Cl2  HCl

Electrode potential:

When a metal is dipped in a solution of its own ions; the metal atom tends either to loss electrons or gain to
electrons
In this process there develops a potential difference between metal atom and corresponding ions is called electrode
potential.
Case 1: if metal loss electrons (oxidation process)
MMn+ + ne-
In this process the developed potential is called Oxidation potential of electrode represented with Eox or Em/m+
Case 2: if metal gain electrons (reduction process)
Mn+ +ne- M
In this process the deve
loped potential is called Reduction potential of electrode represented with Ered or Em+/m
Note: for a particular electrode for a particular condition the magnitudes of oxidation and reduction potentials are equal, but
the signs are opposite.
OP = -Red
Eox = - Ered
Em/m+ = - Em+/m

Standard electrode potential:

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The Electrode potential measured at 250c temp and 1Molar concentration electrolytic solution is called standard
electrode potential.
In case of gasses electrode 1 atm pressure is taken as standard
Standard O.p is represented as E0 ox, E0 m/m+

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 Standard reduction potential is represented as E0 red, E0 m+/m

EMF of Electrochemical cell:

The difference of potential, which causes flow of electrons from the electrode of higher potential to the electrode of lower
potential, is called electromotive force (EMF). The emf of galvanic cell is calculated from the reduction half-cell potentials
using the following relation.

E(cell) = E(right) – E(left)

or
Ecell = E cathode – E anode
Where E(cell) = e.m.f of cell
E(right) = reduction potential of right hand side electrode
E(left) = reduction potential of left hand side electrode
Calculate the e.m.f of the following cells.
i) Zn/zn2+(0.1m) // Cu2+ (0.01m)/Cu ; Ezn = -0.7623volts, Ecu= +0.337 [1.0993volts]
ii) Cd / Cd2+ // Cu2+ / Cu ; standard reduction potential cd and cu are -0.04, and +0.34 [0.74volts]
iii) Pb / Pb2+ // Cd2+ / Cd ; standard reduction potential of cd and pb are 0.408 and -0.126volts[0.534]
iv) Calculate the standard EMF of cell which involves the following cell reaction.
Zn + 2Ag+  Zn 2+ + 2Ag; E0zn/zn2+ = 0.76 volts and E0Ag,Ag+ = -.0.80 volts[1.56]

Nernst equation:
This is the relationship between electrochemical reaction and corresponding cell emf.
Let us consider a galvanic cell whose cell reaction is written as
aA + bB cC + dD
Here lower case latters a , b , c , d represent the number of moles of A,B,C,D respectively at equilibrium.

RT [C]c[D]d
Ecell = E0cel – ln
nF [A]a[B]b
Ecell = emf of the cell
Eocell = standard emf of the cell
R = universal gas constant (8.314JK-1
T = temperature in Kelvin
F = faraday (96500c)

Ecell = E0cell – 2.303RT/nF × log ([C]c [D]d/ [A]a [B]b)

Ecell = Eocell – 0.05916/n × n log ([C]c [D]d/ [A]a [B]b) at 25 oc
Nernst equation is also applicable to half cell reactions.
Ex: MMn+ + ne-

EM/Mn+ = E0 m/m+ - 0.05916/n × log [Mn+]/[M]

Activity (concentration) of all pure solids is unity
EM/Mn+ = E0 m/m+ - 0.05916/2 × log [Mn+]

Types of electrodes:
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Metal/metal ion electrode – Zn /Zn 2+ electrode

Gas electrode – Hydrogen electrode
Redox electrode – Quinhydrone electrode
Metal/Metal insoluble salt electrode – Calomel electrode.

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 Ion selective electrode – Glass electrode

REFERENCE ELECTRODE
(STANDARD HYDROGEN ELECTRODE, SHE OR NHE)
Hydrogen electrode is the primary standard electrode. It consists of a
small platinum strip coated with platinum black as to adsorb hydrogen
gas. A platinum wire is welded to the platinum strip and sealed in a glass
tube as to make contact with the outer circuit. The platinum strip and glass
tube is surrounded by an outer glass tube which has an inlet for hydrogen
gas at the top and a number of holes at the base for the escape of excess
of hydrogen gas. The platinum strip is placed in an acid solution which has
H+ ion concentration 1 M. pure hydrogen gas is circulated at one
atmospheric pressure. A part of the gas is adsorbed and the rest escapes
through holes. This gives equilibrium between the adsorbed hydrogen and
hydrogen ions in the solution.
H2 <--> 2H+ + 2e-
The temperature of the cell is maintained at 250C. By international
agreement the standard hydrogen electrode is arbitrarily assigned a
potential of exactly ± 0.000. .. Volts.

Calomel electrode:

It consist of a glass tube having side tube on each side. Pure sample of
mercury is placed at the bottom of the tube and connected to the circuit by a
platinum wire, sealed in a glass tube. A paste of mercurous chloride (Hg 2Cl2)
or calomel and mercury in KCl solution is placed on the surface of mercury.
Potassium chloride solution is used as electrolyte.

1/2 Hg2Cl2 + e- Hg + Cl-

According to nernest equation:

Ecalomel = E0c - 0.05916 log [Cl-]

Quin-hydrone electrode: This is a redox electrode. The electrode consists of a shiny platinum electrode dipped in a acid /
base test solution, which is saturated with quinhydrone. Quinhydrone is a 1:1 molar mixture of quinone and hydroquinone.
Quinhydrone is slightly soluble in water, formed by equi – molar mixture of hydroquinone and quinine.

Each one of the two substances can be easily oxidized or reduced to the other. In this case, the electrode reaction may be
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represented as follows:

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 Using Nernst equation, the potential of quinhydrone electrode EQ may be written as

EQ = E0Q – 2.303RT/2F × log [QH2] /[Q] [H+]2

[QH2] : [Q] is 1:1 ratio
EQ = E0Q + 0.05916 log [H+] at 250c
EQ = E0Q – 0.05916pH this equation is used to calculate pH of a solution.
Advantages:
1 the electrode is very easy to setup
2 the pH value obtained is very accurate
3 Very small quantity of solution is sufficient for the measurement.
Disadvantages: the electrode cannot be used in more alkaline solution (pH.> 8.5) and also with solution that react with
quinine or hydroquinone.
Ion selective electrode: ion selective electrode is a sensor which converts the activity of a specific ion dissolved in a solution
in to an electrical potential.

Glass electrode:
A glass electrode is a type of ion – selective electrode; this is H+ ion sensitive
electrode. It consists of a thin walled glass bulb attached to a glass tube. This glass
tube contains a dilute solution of constant pH of HCl(0.1N) solution. A silver wire
covered with silver chloride is immersed in this solution.

When a glass surface is in contact with a solution, there developed a potential

difference between the glass surface and the solution. The magnitude of potential
depends on the H+ ion concentration of the solution and the nature of glass.
Glass electrode may be represented as
Ag, AgCl (s) / 0.1N HCl /glass/H+
The electrode potential, of the glass electrode depends upon the concentration of H+ ions contained in the
experimental solution.

Eg = E0g – 2.303RT/F logH+

= E0g – 0.059 logH+
= E0g + 0.059pH

Concentration cell:
A concentration cell is an electrochemical cell in which electrical energy arises from the transfer of
substances from the solution of high concentration (around an electrode) to low concentration (around other
electrode).
This cell has two equivalent half cells of the same material differ only in concentrations.
Types of concentration cell:
These are two types
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1) Electrolyte concentration cell

2) Electrode concentration cell
Electrolyte concentration cells:

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 It is a cell made up of two half cells having identical electrodes with same electrolyte at different concentration, the
two half cells are joined by salt bridge.
Ex: a cell is formed by two Ag electrodes with two different concentration having AgNO3 solutions.
Cell representation:
Ag/AgNO3 (C1)//AgNO3 (C2)/Ag
Diluted concentrated
Let us consider C2 > C1
To maintain equilibrium between these two C1
and C2 concentration solution, at C1 concentration solution,
metal atoms (Ag) from electrode are dissolved
as metal ion (Ag+) in the solution.
Means at C1 concentration electrode oxidation takes place.
Ag Ag+ (C1) + e ----------------1
At the same time at C2 concentration electrode metal ions (Ag+) from the solution deposited as metal (Ag) on Ag
electrode to decrease concentration of solution.
Ag+ (C2) + e Ag------------------2
From 1 + 2 we get net reaction.
Ag Ag+ (C1) + e
Ag+ (C2) + e Ag
------------------------------
Ag+ (C2)  Ag+ (C1) -------------------3
-------------------------------
So the emf is developed due to transfer of Ag+ ions at C2 concentration to C1 concentration.
Emf of the cell:

Ecell = -0.05916/1 log (Ag+(c1)/Ag+(c2)

Ecell = 0.05916log C2/C1
Note: the standard cell potential of concentration cell is zero because a cell can’t derive a current through a circuit
with identical electrodes.
Electrode concentration cell:
Ex: two hydrogen electrodes at different gas pressure in the same solution of H+ ions
In this cell two hydrogen electrodes at unequal gas pressures (say P1 and P2) are immersed in
the same solution of hydrogen ions at 25oc is represented as
Pt, H2 (P2) / H+ / H2 (p1), Pt
If P2 > P1 oxidation occurs at LHS electrode
H2 2H+ 2e ---------------- 1
Reduction occurs at RHS electrode
2H + + 2e H2 ----------------2
Net reaction 1+ 2
H2 (p2) H2 (p1)
Net reaction shows that H2 gas transferred from P2 pressure electrode
to P1 pressure electrode. Due to transfer of gas potential is developed.
Nernes’t equation for this gas electrode is
Ecell = - 0.05916/2 log (P1/P2)
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Ecell = 0.05916/2 log (P2/P1)

Applications of EMF (Potentiaometric titrations):

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 These are the titrations in which end point is detected with the help of emf measurements.
In this a cell is constructed in which at least one of the electrodes is reversible with respect to one of the
ions taking part in the titration.
We know that potential of an electrode dipped in a solution of an electrolyte depends up on the concentration of
active ions.
E = E0 + RT/nF log C
By change in the active ion concentration in the solution, changes the electrode potential correspondingly.
During the course of titration the concentration of active ion decrease there by electrode potential of indicator
electrode decrease. Thus measurement of indicator electrode potential can give a good indication of end point of titration
reaction.
The potential of indicator electrode is usually measured potentiometrically by connecting with a reference electrode
(Ex: Calomel,SCE)

Detection of end point: the emf of the cell changes by the addition of titrant, due to concentration of reversible ion in
contact with indicator electrode. We thus record the change in emf with every small addition.
Change of potential will be low at first but equivalent point change will be sharp and quite sudden.
 The values are plotted against corresponding volume changes.
 A curve like the one show in figure is obtained the end point corresponds to the point of inflexion.

 Another graph ∆E/∆V Vs volume of alkali(V) is like

In this maximum of the curve gives end point.

Acid – Base titration:
In acid base titration quinhydrone electrode is employed as indicator electrode. The reference electrode is calomel
electrode. The reference electrode is, generally, the saturated calomel electrode.
A definite volume of the given acid solution is taken in a large beaker. To it a pinch of hydroquinone is added and a
stirrer and a platinum electrode are dipped in it. This electrode is then connected to a saturated calomel electrode through a
potentiometer. On adding standard alkali solution from burette, the emf of the cell decreases at first gradually, but end point
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the change of potential will be suddenly quite large. The end point of the titration is then located by plotting ∆E/∆V versus.
 Precipitation titration: titration involving precipitation
Ex: AgNO3 with KCl
In this titration a silver electrode (Ag) dipped in AgNO3 solution used as indicator electrode, saturated
calomel electrode as reference electrode. These two are combined by salt bridge, and are connected to potentiometer.
By the addition of KCl from burette to AgNO3 solution, the concentration of Ag + ions decreases, due to precipitation of Ag+
ions as AgCl.
Ag+NO3- + K+Cl-  AgCl + K+NO3-
Due decreasing of concentration of Ag+ ions the reduction potential of indicator electrode decreased. This is
decreasing progressively on addition of KCl. At end point the concentration of Ag+ is quite rapid. At end point the Ag+
concentration becomes very small on account of slight solubility of AgCl. If addition of Ag+ is continued, the Ag+ ion
concentration is not affect, except a very small decrease, due to decrease in solubility of AgCl on account of common
ion(Cl) effect. Therefore, addition of KCl beyond end point causes only a very small decrease in electrode potential or emf
of the cell.

Electrochemical series:
Standard electrode potential of system is constant; IUPAC has suggested that the standard electrode potential
means its reduction potential. i.e potential developed between Mn+ and M.
Arrangement of elements in the increasing order of their standard electrode potential is called electrochemical
series.
Metal ion potential in volts
Li + + e  Li -3.05
K +eK
+ -2.93
Ca + 2e  Ca
++ -2.90
Na++ e  Na -2.74
Mg + 2e  Mg
++ -2.37
Al + 3e  Al
+3 -1.66
Zn+2+ 2e  Zn -0.76
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Cr + 3e  Cr
+3 -0.74
Fe+2+ 2e  Fe -0.44
Ni + 2e  Ni
+2 -0.23
Sn + 2e  Sn
+2 -0.14

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 Pb+2 + 2e  Pb -0.13
Fe+3 +3e  Fe -0.04
H+ + e  1/2H2 0.00
Cu+2+2e  Cu +0.34
Ag++ e  Ag +0.80

Pt+4 + 4 e  Pt +0.86
Au + e  Au
+ +1.69
1/2F2 + 2e  2F - +2.87
Applications of Electrochemical series:
The electrochemical series provide valuable information.
1) Relative ease of Oxidation or reduction:
A system with high reduction potential has a great tendency to undergo reduction, so we can easily
interpret the behavior of different elements.
Ex: F2 is easily reduced to F-
Li+ is easily reduced with greater difficult to Li
2) Replacement tendency:
Lower reduction potential metals can displace higher reduction potential metals from their salts.
Ex: iron displace cu from CuSO4
3) Predicting spontaneity of redox reactions:
Spontaneity of redox reaction can be predicted from the emf value of complete cell reaction.
Positive value of Ecell indicates the reaction is spontaneous.
Ecell is negative indicates the reaction is non spontaneous.
4) Calculation of equilibrium constant:
The standard electrode potential
E0 = RT/nF ln keq

Determination of pH by using glass electrode:

Electrode potential of glass electrode
Eg = Eg0 + 0.05916 pH
Eg0 is the standard electrode potential.
 The pH of the solution can be determined if the potential
of glass electrode is know.
 To determine glass electrode glass electrode is combined
with a reference electrode such as calomel electrode.
 The EMF of the cell is
Ecell = Ec – Eg
= Ec – [E0g + 0.05916pH]
= Ec – Eg – 0.05916pH
pH = Ec – E0g – Ecell / 0.05916.
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 BATTERIES:
 In common use Battery is a storage device, used for storage of chemical energy
 Battery is a combination of two or more electrochemical cells, these electrochemical cells connected in series.
Batteries are three types.
i) Primary battery: (primary cells): these are non rechargeable batteries; cell reaction in this battery is non
reversible. Ex: Dry (or Laclanche cell), lithium cells.
ii) Secondary battery (secondary cells): these are rechargeable batteries; cell reaction in this battery is
reversible. Ex: lead – storage battery, Ni – Cd battery, Lithium ion battery.
iii) Flow battery and fuel cell: in which materials (reactants, products, and electrolytes) pass through the
battery, which is simply an electrochemical cell that converts chemical to electrical energy. Ex: H2 – O2
fuel cell, CH3OH & O2 fuel cell.

Dry cell (or Leclanche cell):It is a cell without fluid component.

It contains a zinc vessal, act as anode, and it contains a graphite rod in middle of
the zinc vessal act as cathode.Graphite rod is sourrounded by MnO2 powder, and the
space between Graphite rod and Zn vessal is filled with paste of NH4Cl and ZnCl2 act as
electrolyte.

The anodic halfcell reaction is

Oxidation: Zn(s)  Zn+2 + 2e --------------------------1

The cathod half cell reaction: cathode reaction is quite complex.

Readuction: 2MnO2 + H2O + 2e Mn2O3 + 2OH-(aq) -----------------------------2

2OH-(aq) + 2NH4+ 2NH3 (g) + 2H2O (l) ---------------------------------3
Here NH3 doesn’t liberated as gas, it is immidiatly combine with ZnCl2 and form the complex ion
[Zn(NH3)2]Cl2
2NH3(g) + ZnCl2 [Zn(NH3)2]Cl2-------------------------------4
Reaction at cathode is 2+3+4
2MnO2 + H2O + 2e Mn2O3 + 2OH-(aq)
2OH-(aq) + 2NH4+ 2NH3(g) + 2H2O (l)
2NH3(g) + ZnCl2 [Zn(NH3)2]Cl2
------------------------------------------------------------------------------------
2MnO2 + 2NH4++ ZnCl2+ 2e Mn2O3 + [Zn(NH3)2]Cl2 + H2O ----------------------5
-----------------------------------------------------------------------------------
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Net reaction 1+ 5
Zn(s) Zn+2 + 2e
2MnO2 + 2NH+ + Zn2+ + 2Cl- + 2e Mn2O3 + [Zn(NH3)2]Cl2 + H2O
---------------------------------------------------------------------------------------------

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 Zn(s)+ 2MnO2 + 2NH+4 + 2Cl- Mn2O3 + [Zn(NH3)2]Cl2 + H2O
---------------------------------------------------------------------------------------------
Dry cell is primary cell; since various reactions involved can’t be reversed by passing electricity though cell.
Emf of this cell is 1.2 volts.

Lead – storage battery:

It is a rechargeable battery. Generally it is combination of six lead – storage cells; each cell has 2volts
emf total emf of the battery is 12 volts.
Lead – storage cell: in this cell one of the electrode is made of lead act as anode and other electrode made of lead
dioxide (PbO2) or rather a paste of PbO2 is pressed into a grid, made of lead act as cathode. These two electrodes are
dipped in 20% H2SO4 solution, this solution act as electrolyte.

Discharging: When cell operating as voltaic cell, it is said to be discharging.

At anode oxidation takes place, pb loses electrons
Pb Pb+2 + 2e
The Pb+2 ions combine with sulphate ions
Pb+2 + SO4-2 PbSO4 (precipitate)
Therefore Pb + H2SO4 PbSO4 + 2H+ + 2e --------------------------------------1
The electrons released at anod flows to PbO2 electrode from externally, at PbO2 electrode lead undergo reduction.
At cathode
PbO2 + 2H+ 2e + H2SO4 PbSO4 + 2H2O -------------------------2

‘So the Net reaction during use is 1 + 2

Pb + H2SO4 PbSO4 + 2H+ + 2e

PbO2 + 2H 2e + H2SO4
+ PbSO4 + 2H2O
------------------------------------------------------------------------
Pb + PbO2 + 2H2SO4 2 PbSO4 + 2H2O + energy
----------------------------------------------------------------------------
Note: at both electrodes PbSO4 is precipitated.
 The voltage of this single cell is 2 volts at a concentration of 20% H2SO4 at 250C\
Charging: when both anode and cathode become covered with PbSO4, the cell ceases the function as a voltaic
cell. To reacharge a lead storage cell, the reactions taking place during discharging are reversed by passing an
external emf greater than 2 volts from external Dc source.
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Reaction at – ve terminal:
PbSO4 + 2e Pb + SO4-2 ----------------------- 3
Reaction at + ve terminal

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 PbSO4 + 2H2O – 2e PbO2 + 4H+ + SO4-2 --------------------4
Net reaction during charging 3 + 4
2 PbSO4 + 2H2O + energy Pb + PbO2 + 4H+ + 2SO4-2

Ni – Cd Battery:
 In this cell, cadmium act as anode and NiO2 act as cathode:
 Aqueous potassium hydroxide KOH act as electrolyte.
 The cathode is Nickel – plated woven mesh, and the anode is cadmium – plated net.
 The electrolyte KOH, act only as an ion conductor and doesn’t contribute significantly to cell reaction.
Reaction at anode:
Cd Cd+2 + 2e
Cd + 2OH - Cd(OH)2 + 2e
Reaction at cathode:
NiO2 + 2H2O + 2e Ni(OH)2 + 2OH-
Net reaction is 1 + 2
Cd + 2OH- Cd(OH)2 + 2e
NiO2 + 2H2O + 2e Ni(OH)2 + 2OH-
-------------------------------------------------------------------------------------------------

Cd + NiO2 + 2H2O Ni(OH)2 + Cd(OH)2

---------------------------------------------------------------------------------------------------
The emf of this cell is 1.26 volts, it is a rechargeable battery, and all reactions involved in this cell are reversible.
Applications: calculators, digital cameras, Laptops, flashlights.

Lithium ion Battery:

In these batteries, carbon material (C) is used in the anodes, and metal
oxide material (LiCoO2) containing lithium is used in the cathodes. Lithium ions
migrate between the two electrodes via an organic electrolyte they doesn’t deposit
as metal, they exist as metal ions.
Charging and discharging mechanism
Battery charging and discharging occur through the migration of lithium
ions between the cathode and anodes and exchange of electrons through doping
and de doping. More specifically, during charging lithium is de doped from
cathode consisting of a lithium containing compound, and internal layer of carbon
in anode is doped with lithium. Conversely during discharging lithium is de doped
from between the carbon layers in anodes and the compounds layers in cathodes
are doped with lithium.
Anode: carbon material (C)
Cathode: LiCoO2 (lithium cobalate) or LiMnO2 (lithium manganate)
Electrolyte: LiBF4 or LiPF6 with Organic solvents or polymer gell
Reaction at charging:
initial charge
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C + LiCoO2 CLix + Li1-xCoO2

Reaction at discharging:
discharge

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 CLix + Li1-xCoO2 CLix-dx + Li1-x +dxCoO2
Average emf of this battery is 3.7 volts
Applications: used in laptops, mobile phones, digital cameras,

Fuel cell: a fuel cell is an electrochemical cell, which converts chemical energy contained in readily available fuel oxidant
system into electrical energy.
H2 – O2 fuel cell:
This is a common type of fuel cell. Similar to galvanic cell, fuel cells also have half cells. Both half cells have
porous graphite electrode with a catalyst and contains proton exchange membrane. The electrodes are placed in the
aqueous solution of NaOH or KOH , this solution act as electrolyte.
Hydrogen and Oxygen are supplied at anode and cathode, respectively, at about 50atm pressure. The gasses
diffuse at respective electrodes and following reactions taking place at electrodes.
Reaction at anode: At anode in presence of catalyst (Pt) H2 gas is split into H+ and e’s
2H2 4H+ + 4e
4H+ + 4OH- 4H2O
At anode reaction: 2H2 +4OH - 4H2O + 4e --------------1
Released electrons are passed through the external circuit to cathode to create current in external circuit.

Reaction at cathode:
4e + O2 + 2H2O 4OH- -------------------2

Net reaction is 1+ 2
2H2 +4OH- 4H2O + 4e
4e + O2 + 2H2O 4OH-
---------------------------------------
2H2 + O2 2H2O
---------------------------------------
 Emf of this cell is 1 volts.

Methanol – Oxygen fuel cell;

 Methanol oxygen fuel cell has a unit cell composed of a

membrane electrode assembly (MEA).
 The MEA is composed of a solid polymer electrolyte
membrane sandwiched between an anode and cathode.
 The anode and cathode includes a catalyst layer and
diffusion layer.
 Such a methanol oxygen fuel cell generates power by
supplying a methanol and water to the anode, and
supplying an oxidant to cathode.
Reaction at anode:
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CH3OH + H2O CO2 + 6 H+ + 6e

Generated electrons at anode are passed through the external circuit and create electric current in
external circuit. H+ ions are transferred through membrane to cathode, CO2 gas is escaped from anode chamber.
Reaction at cathode:

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 6 H++ 6e + 3/2 O2 H2O

Net reaction:
CH3OH + H2O CO2 + 6 H+ + 6e
6 H++ 6e + 3/2 O2 H2O
-------------------------------------------------------------------
CH3OH + 3/2 O2 2 H2O + CO2
--------------------------------------------------------------------

Advantages of fuel cells:

o No emission of toxic gasses and chemical wastes are in safe
limits. The reactants and products are environmental friendly.
o High efficiency ( 75% - 85%) of energy conversion from chemical
energy to electrical energy.
o No noise pollution like in generators and low thermal pollution.
o Low maintenance costs.
o Fuel cell are operable to high temperature ( <2000C)
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CVR - 2014