Kuvempu University Electrolytic solutions: electrolytes are substances
Department of Chemistry
M.Sc. Chemistry Syllabus – 2019-2020
(CBCS Scheme)
M.Sc. Course Pattern and Scheme of Examination under
CBCS approved by
PG-BOS in Chemistry held on 25-01-2019
UNIT-IV: ELECTROCHEMISTRY
16 hrs
Electrolytic solutions, Activity and activity
coefficients, mean ionic activity coefficient,
dependence of activity coefficients on ionic
strength (Debye - Huckel limiting law), Debye -
Huckel equation for appreciable concentration
[Debye - Huckel - Bronsted equation].
Thermodynamics of electrolytic cells,
polarization and over voltage, decomposition
potential. Half cell reactions, reversible electrodes,
single electrode potential, standard electrode
potentials, electrochemical series, Nernst
equation. Electrochemical energy systems -
introduction, fundamentals of batteries, dry cell,
alkaline MnO2 batteries and other secondary
batteries, Lead acid and alkaline storage batteries.
Battery charging-theory and practice. Energy
economics, Fuel cells – types, electrochemistry of
fuel cells.
drsenata@gmail.com
which in dissolved state capable of carrying
electricity through them. When dissolved they
produce ions which carry electricity. Electrolytes
can be classified into STRONG and WEAK
ELECTROLYTES.
Weak electrolytes dissociate slowly in a
solvent there by produce very few numbers of
ions. But strong electrolyte produce very large
number of ions in short time. Thus properties of
these two are different. Strong electrolyte-solution
behaves completely different.
Debye-Huckel-Onsagar theory of strong
electrolyte
In order to explain the abnormal behaviour
of strong electrolytes, Debye and Huckel in 1923,
and Onsagar in 1926 put forward the modern
theory of strong electrolytes known as Debye-
Huckel- Onsagar theory of strong electrolyte.
Non-electrolyte solutions (like urea, sugar) are
considered as ideal solution because the
intermolecular forces are very weak and hence
they obey Colligative properties (properties
depends on concentration or number of particles;
but at very low concentration electrolyte solutions
tend to behave like ideal solution-Rauolt‟s law),
but, this is not true for electrolyte or ionic
solutions especially strong electrolyte. In these
solution, there are significant electrostatic
interactions between solute-solvent as well as
solute-solute molecules. The interactions are
stronger at higher concentrations. Consequently,
the behavior of an electrolyte solution deviates
considerably from that an ideal solution.
Each ion is surrounded by the oppositely
charged ions. This is called the ionic atmosphere
of that ion. This is spherical as depicted bellow.
Page 1
All these facts are governed by Debye–Hückel
theory which is based on the following
assumptions.
 The dissolved electrolyte is completely
dissociated.
 Ions are spherical and are not polarized by
the surrounding electric field.
 Salvation of ions is ignored. (The process
of each ion surrounded by solvent
molecules is salvation). That means
solvent just provides a medium.
 Each cation is surrounded by a spherically
symmetric cloud of negative ions and vice
verssa. This cloud has SYMMETRICAL
charge density. The cloud has a net
negative charge. Similarly each anion is
surrounded by a cloud with net positive
charge.
Asymmetry, or Relaxation effect
Each ion is surrounded by the oppositely
charged ions. Imagine cation is surrounded by
anions. This is called the ionic atmosphere of
cation. See figure:
When an EMF is applied, the negative ions
migrate towards the anode leaving behind the
ionic atmosphere of positive ions. The ionic
atmosphere and the charge density do not remain
symmetrical. This is known as „asymmetric or
relaxation effect‟. This can be shown as follows;
drsenata@gmail.com
This resists and decreases the speed or mobility of
the ion. Higher the concentration of solution; more
is the decrease in mobility.
As the ion keep moving towards the
electrode, the ionic atmosphere is left behind and
a new ionic atmosphere begins to form. The rate
of formation of new ionic atmosphere is not the
same as disperse of old ionic atmosphere. The
time gap between the formation of the new and
disperse of the old is called „relaxation time‟.
Electrophoretic effect
The solvent molecules (polar) attach
themselves to ionic atmosphere. The central ion
has to drag the solvent molecules with it. This
reduces the mobility of the ion. This effect is
called the electrophoretic effect.
Relaxation and electrophoretic effect
together, considerably reduce the speed of the ion.
Activity and activity coefficients, Mean ionic
activity coefficient
In order to answer these effects,
thermodynamics introduced the concept of
activity , denoted by symbol “a”. The properties
of strong electrolyte depends on activity which is
proportional to concentration, c. The
proportionality constant is known as an activity
coefficient, .
For non-electrolyte/very dilute, ideal
electrolyte solution the activity coefficients of all
the ions are equal to one. Thus activity is equal to
concentration.
But, non-ideality arises principally because
ions of opposite charge attract each other due
to electrostatic forces, while ions of the same
charge repel each other. In consequence ions are
not randomly distributed throughout the solution,
as they would be in an ideal solution. Instead they
get concentrated at few positions.
Activity coefficients of single ions cannot
be measured experimentally. Instead, a mean
activity coefficient, is defined. For example,
for electrolyte NaCl
Page 2
 The mean activity coefficient, in general is
as follows: (derivation ignored)

For Na2CO3

where I is the ionic strength.

Dependence of activity coefficients on ionic

strength (Debye - Huckel limiting law)
Mean activity coefficient depends on ionic
strength not on electrolyte concentration.
Depending on the range of ionic strength,
following Debye-Huckel laws are suggested
Debye-Hückel Limiting Law that is
generally good for concentrations smaller than
10-2m and
Extended Debye-Hückel Law which is
reasonable up to about 0.10 m.

The significance of this result is that for

very low values of the ionic strength (dilute
solutions of about 0.01m) the value of
denominator becomes one. Thus mean activity
coefficient is proportional to the square root of the
ionic strength. This is known as the Debye–
Hückel limiting law.
Limitations and extensions
The equation for gives satisfactory
agreement with experimental measurements for
low electrolyte concentrations. Deviations from
the theory occur at higher concentrations and with

drsenata@gmail.com Page 3
electrolytes that produce ions of higher charges,
particularly unsymmetrical electrolytes.
Essentially limitations are.
* Complete dissociation. Ion-association may take
place, particularly with ions of higher charge.
* we assume ions are spherical, point charges and
are not polarized. But many ions such as
the nitrate ion, NO3−, are manifestly not spherical,
polarizable.
* Role of the solvent was not considered. The
water molecules in aqueous solution are
both dipolar and polarizable. Ion-solvent
interactions are significant.
Debye-Huckel equation for appreciable
* We assume that the ionic radius is negligible,
concentration [Debye - Huckel - Bronsted
but at higher concentrations, the ionic radius
equation]
becomes comparable to the radius of the ionic
Earlier to the Debye- Huckel theory, Brønsted had
cloud.
independently proposed empirical equations for
activity and osmotic coefficients where the
Debye-Huckel- Onsagar (DHO) Equation
activity coefficient depended not only on ionic
Debye and Hückel modified their
strength, but also on the concentration, m, of the
theory in 1926 and their theory was further
specific ion through the parameter β.
modified by Lars Onsager in 1927. All the
Activity Coefficient: lnγ = −αm1/2 – 2βm
postulates of the original theory were retained. In
Osmotic Coefficient: 1 –φ = (α/3) m 1/2 + βm
addition it was assumed that the electric field
This is the basis of SIT theory, used to estimate
causes the charge cloud to be distorted away from
single- ion activity coefficients in electrolyte
spherical symmetry- ie., electrophoretic
solutions at relatively high concentrations, by
effect. After taking this into
taking into consideration interaction coefficients
account,viscosity and electrophoretic effects, and
between the various ions present in solution.
brownian movement of ions, Onsager modified
Interaction coefficients are determined from
the debye-huckel theory - known as DHO
equilibrium constant values obtained with
equation which is as follows:
solutions at various ionic strengths. The
determination of SIT interaction coefficients also
λC = λ∞ – [A(Z+ +Z–) + Bλ∞]√(Z+ + Z–) C yields the value of the equilibrium constant at
where λC = Conductance at concentration C infinite dilution
λ∞ = Equivalent conductance at infinite
concentration
C = concentration
A & B = constants
Z+ & Z– = ionic charges
For uni valent ions Z+=1 & Z– =1, thus above
equation becomes
λC = λ∞ – [A+ Bλ∞]√C
Above two equations are called DHO equations.

drsenata@gmail.com Page 4
Electrochemical cells:
Noble; less active

Daniel cell
Reversible cell

More active

Electrochemical cell;
The standard electrode potentials at 298 K In general electrochemical cell is assembly
(25 Celsius) of few elements in a particular consisting of two electrodes immersed in different
sequence suitable electrolytes. A cell consists of
Anode: electrode where oxidation takes Place
Inactive (Process of removal of electron & the released
electrons are send to the circuit) [it need not be +
Cl2(g) + 2e– → 2Cl– E° = +1.36 all the time]
+ –
O2 (g) +4H + 4e → 2H2O E° = +1.23 Cathode: electrode where reduction takes place
Au3+ + 3e– → Au(s) E° = +1.40 (Addition of electron & electrons are consumed
Ag+ + e– → Ag(s) E° = +0.80 from the circuit) [it need not be − all the time]
2+ –
Cu + 2e → Cu(s) E° = +0.34
Electrolyte: one or mix of substances in the form
2H+ + 2e– → H2(g) E° = 0.00
of solution or in fused state responsible for the
Ni2+ + 2e– → Ni(s) E° = –0.25 conduction the current
Fe2+ + 2e- → Fe (s) E° = –0.44 Electrodes: metals (active or inert) in contact
2+ –
Zn + 2e → Zn(s) E° = –0.76 with the electrolyte responsible for the transfer of
+ –
Na + e → Na(s) E° = –2.71 electrons (electricity).

Reactive Electrochemical cell is broadly classified into

Electrochemical series;
Is the series in which elements are
arranged in an order in the form of reduction
reaction according to their standard potential (Eo).
it is shown bellow.
Galvanic cell or voltaic cell: which produces
electricity as a result of chemical reaction taking
place in the device.
For example; dry cell; lead acid battery; etc
Electrolytic cell: this is an electrochemical
cell which consumes electricity to bring chemical
reaction/change.
For example; electrolysis of CuSO4 solution

drsenata@gmail.com Page 5
Fuel cell: It is a device in which energy from the In other words, for galvanic cells, decrease in free
combustion of fuel is directly converted into energy is equal to emf of the cell. For electrolytic
electrical energy cell free energy increases to the extent exactly
For example; H2-O2 fuel cell
equal to the decrease when the cell is made as
Common example of fuel cell is H2-O2 fuel cell
galvanic.
Thermodynamics of the cell potentials. For example; Daniel cell, a reversible cell; works
The E.M.F or cell potential of an as both galvanic and electrolytic;
electrochemical cell can be calculated from Zn(s) | Zn+2( aq) || Cu+2 (aq) | Cu(s)
thermodynamics and Nernst equation. The e.m.f
of a cell is dependent on the activities of the when it is working as galvanic cell
reactants and products. Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s);
Activity of a species is the product of E = +1.1V & ∆G = –21.22 kJ mol–1
activity coefficient and the molar concentration of when it is working as electrolytic cell
that species. E = −1.1V & ∆G= +21.22 kJ mol–1
a. = ν . M Cu (s) + Zn 2+ (aq) → Cu 2+ (aq) + Zn (s);
Where ν = activity coefficient & M = molar E = −1.1V means, external voltage of 1.1 V needs
concentration. (If the activity coefficient is one, to be applied to bring about electrolysis. This is
then activity is equal to molar concentration). true only when the cell is truly reversible (ideal).
Generally, activity is assumed to be molar Pictorially;
concentration.
For cell reaction of type,
Zn(s) | Zn+2( 0.1M) || Cu+2 (0.1M) | Cu(s)
The cell reaction is
Zn + Cu+2 ↔ Zn+2 + Cu
The equilibrium constant in terms of
activities is
2 2
Cu q Zn +2
q
Equilirium Const. Q = 2 2
Zn q Cu +2
q

The subscript q represents that it is activity of the

∆𝐺
species. WKT, the activity of solids or pure Eq. 3 can be written as E = − nF
substance is unity. Where ∆G is Gibbs free energy, n is
2
Zn +2
q number of electrons involved in
Thus Q = 2 ---------------- (1)
Cu +2
q Oxidation/reduction, F is Faraday constant and E
This Q can be related to Gibbs free energy is e.m.f of the cell
as follows Substitute, (2) in (3) , then
− 𝑅𝑇 𝑙𝑛 𝑄 + 𝑅𝑇 𝑙𝑛 𝐾
∆G = − RT ln Q + RT ln K -------- (2) E= nF
−𝑅𝑇 𝑅𝑇
= ln Q + 𝑛𝐹 ln K
Where, Q is equilibrium constant in terms 𝑛𝐹

of activities, K is the equilibrium constant when But we know,

𝑅𝑇
substances are in standard state, R is gas constant Standard electrode potential, E° = 𝑛𝐹 ln K
& T absolute temp 𝑅𝑇
Thus, E = − 𝑛𝐹 ln Q + E°
According to Gibbs-Helmoltz law the 𝑅𝑇
decrease in free energy of a process is equal to the E = E° + − 𝑛𝐹 ln Q ----------------- (4)
electrical energy (emf) of a cell. Mathematically it Then substitute (1) in (4)
is 𝑹𝑻 𝐙𝐧+𝟐
E = E° − 𝒏𝑭 ln 𝐂𝐮+𝟐
∆G = − nFE ----------------- (3)
By converting the natural logarithm in to
the base 10 (multiply by 2.303) and substituting

drsenata@gmail.com Page 6
the values of R (8.314JK–1 mol–1), F (96487 C But, WKT equilibrium constant Kc is given
mol–1), T = 298 K, it reduces to Cu 2 Zn +2
2
1 2 Zn +2
2
Zn +2
2
by Kc = = =
𝟎.𝟎𝟓𝟗 𝐙𝐧+𝟐 Zn 2 Cu +2 2 1 2 Cu +2 2 Cu +2 2
E = E° − log
𝒏 𝐂𝐮+𝟐
This is the equation used to determine the 0.059
E° = log Kc
e.m.f of a cell theoretically or from the 2
1.1 ×2
thermodynamics. Log Kc = = 37.228
0.059
Further, in general for any reaction
0.059 oxidised species
E = E° − log Kc = 2×1037 at 298 K
𝑛 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑝𝑒𝑐𝑖𝑒𝑠
Thus, equilibrium constants of the reaction,
difficult to measure otherwise, can be calculated
For the following cell;
from the corresponding E° value of the cell.
Ni(s)| Ni2+(aq) ǁ Ag+(aq)| Ag
The cell reaction is
Question: The standard electrode potential for
Ni(s) + 2Ag+(aq)→Ni2+(aq) + 2Ag(s)
Daniell cell is 1.1V. Calculate the standard Gibbs
The Nernst equation can be written as
𝟎.𝟎𝟓𝟗 𝐍𝐢+𝟐
energy for the reaction:
E = E° − log [𝐀𝐠+ ]𝟐 Zn(s) + Cu2+(aq) ⎯→ Zn2+(aq) + Cu(s)
𝒏
Question: Represent the cell in which the
following reaction takes place and Calculate its Answer:
E(cell) if E°(cell) is = 3.17 V. WKT, ΔG = – nFE or ΔG° = – nFE°
Mg(s) + 2Ag+(0.0001M) → n in the above equation is 2, F = 96487 C mol–1
Mg2+(0.130M) + 2Ag(s) and E° = 1.1 V

Answer: The cell can be written as Therefore, ΔG° = – 2 × 1.1V × 96487 C mol–1
Mg⎥ Mg2+(0.130M)⎥⎥ Ag+(0.0001M)⎥ Ag = –21227 J mol–1
= –21.227 kJ mol–1
0.059 Mg +2
E = E° − log [Ag +]2
𝑛 Problem: The Eocell is 0.48 V for the galvanic
0.059 0.130
E = 3.17 − log [0.0001 ]2 cell based on the reaction 2Al(s) + 3Mn2+(aq) →
2
2Al3+ + 3Mn(s); Consider a cell in which [Mn2+] =
= 3.17 – 0.21 = 2.96 V. 0.50M and [Al3+] = 1.50M; calculate the cell
Equilibrium Constant from Nernst Equation potential ?
For cell reaction of type,
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s) Answer;
Zn(s) | Zn+2( aq) || Cu+2 (aq) | Cu(s) 2Al(s) | 3Mn2+(aq) ǁ 2Al3+ | 3Mn(s)
As time passes, the concentration of Zn2+
0.059 [Al +3 ]2
keeps on increasing while the concentration of E = E° − log [Mn +2 ]3
𝑛
Cu2+ keeps on decreasing. At the same time
voltage of the cell as read on the voltmeter keeps 0.059 [1.50]2
on decreasing. After some time, we shall note that E = 0.48 − log
𝑛 [0.50]3
there is no change in the concentration of Cu2+
and Zn2+ ions and at the same time, voltmeter n= ?
gives zero reading. This indicates that equilibrium
has been attained. In this situation the Nernst
equation may be written as:
0.059 Zn +2
E = 0 = E° − log
𝑛 Cu +2

drsenata@gmail.com Page 7
Spontaneity of Redox Reactions = 0.34 – (−0.76) = 1.1 V

Calculate the cell potential for the following system:

Write the half-reactions with the half-cell

potentials:

Question; What is the equilibrium constant for

the following reaction at 250 C?
Multiply the reactions to get the lowest common
Fe2+ (aq) + 2Ag (s) →Fe (s) + 2Ag+ (aq)
multiple of electrons:

Answer;
𝟎.𝟎𝟓𝟗
Equation to be used is E=0 = E° − log Kc
𝟐
To find Eo
Oxidation: 2Ag → 2Ag+ + 2e-
- 2+
Reduction: 2e + Fe → Fe
Here n = 2
and Kc is to be determined Nernst Equation Example
E°= E°Fe /Fe +2 (reduction) − E°Ag /Ag+ (oxidation) A zinc electrode is submerged in an acidic
0.80 M Zn 2+ solution which is connected by a salt
E° = −0.44 − 0.80 = −1.24 V bridge to a 1.30 M Ag + solution containing a
0.059 silver electrode. Determine the initial voltage of
0= −1.24 − log Kc the cell at 298K.
2
0.059 E0red: Zn2+aq + 2e- → Zns = −0.76 V
−1.24 = log Kc
2
E0red: Ag+aq + e- → Ags = +0.80 V
Kc = 1.23 x 10−42
Ecell = E0cell - (0.0591 V/n)log Q
Question; What is the standard emf of an And Q = [Zn2+]/[Ag+]2
electrochemical cell made of a Cd electrode in a the balanced chemical equation for the cell
1.0 M Cd(NO3)2 solution and a Cr electrode in a reaction and can calculate E0:
1.0 M Cr(NO3)3 solution?
Zns → Zn2+aq + 2e- and E0ox = +0.76 V
Answer;
Cd2+ (aq) + 2e-→ Cd (s) E° = −0.40 V 2Ag+aq + 2e- → 2Ags and E0red = +0.80 V
Cr3+ (aq) + 3e-→ Cr (s) E° = −0.74 V
Cd is the stronger oxidizer; it will oxidize Cr Zns + 2Ag+aq → Zn2+a + 2Ags with E0 = 1.56 V
Anode (oxidation): Cr (s) → Cr3+ (1 M) + 3e−
Cathode (reduction):2e− + Cd2+(1 M) → Cd (s) Now, applying the Nernst equation:
2Cr (s) + 3Cd2+ (1 M) ↔ 3Cd (s) + 2Cr3+ (1 M) Q = (0.80)/(1.30)2
Q = (0.80)/(1.69)
E° = Ecathode − Eanode
Q = 0.47
E° = −0.40 − (−0.74) cell E = 1.56 V - (0.0591 / 2)log(0.47)
E° = 0.34 V cell E = 1.57 V

Illustration: finding the E° of following cell;

Zn (s) + Cu2+ (aq) →Cu (s) + Zn2+ (aq)
[Cu2+] = 1 M & [Zn2+] = 1 M
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
Anode cathode
E° = E°cathode − E°anode

drsenata@gmail.com Page 8
Polarization;
Polarisation can be defined in many ways
“Polarisation is the variation in the electrode
potential from its equilibrium or theoretical
potential”. This may be due to;
First;
 Slow movement of ions from the bulk to
the electrode or vice verssa.
 Adsorption, desorption and crystallization
of species
 Slow rate of transfer of electrons from
electrode to reducible species or vice
verssa
 Deviation from ideality (imaginary)
 supplied/transported by external means like
Second;
“Deviation from the ohms law”
Ohms law is E= IR or V = IR. E or V is
emf or voltage or potential; I is current and R is
resistance. A graph of current of cell against e.m.f
should be a straight line as shown in the figure.
It means that I is directly proportional to E
or V means that when E or V increases I also
increase. It is found that for small currents up to 5
mA, the plot/increase is linear and for more
currents the plot starts to deviate from the
linearity.
This deviation of the electrode potential
from this linearity (Nernst equation) is called or is
due to polarization.
The extent of deviation in terms of Volts is
called over voltage or over potential. This is
denoted by symbol π.
Because of the polarization,
The emf of a Galvanic cell is found to be less than
the theoretical emf
And the Applied emf of Electrolytic cell is more
than the theoretical emf
i.e., Eapplied > Etheoretical & Eactual < Etheoretical
Polarization can affect one or both the
electrodes. The extent of polarization can be very
small to very large. Sometimes, polarization can
be too large that it may become independent of the
potential.
The polarization is mainly because of two reasons.
Namely
drsenata@gmail.com
1. Concentration polarisation
Concentration polarisation is because of the
insufficient supply/transport of the reactants to or
from the electrode surface, as required by the cell
to produce the current & emf in accordance with
thermodynamics or theory. To understand this,
take the following example.
For Daniel cell Zn | Zn+2 ǁ Cu+2 |Cu
Cell reaction Cu + Zn+2 ↔ Cu+2 + Zn
As Zn+2 ions are reduced to Zn atoms at the
– ve electrode surface, the concentration of the
Zn+2 ion at the electrode surface decreases
compared to the bulk. So Zn+2 ions from the bulk,
has to move to electrode surface or to be
stirring, etc. otherwise, the concentration of Zn+2 ,
near to the electrode surface decreases to zero and
finally no current will flow.
Similarly at the other electrode Cu(s) is oxidized
to Cu+2 ions which are released at the surface of
the +ve electrode. The concentration of the Cu+2
ions at the surface increases compared to the bulk.
So Cu+2 ions have to be removed/transported out
of the electrode surface.
Otherwise, there is +ve charge builds up
near the surface which oppose the flow of the
current.
Concentration polarisation can affect,
reduction electrode, oxidation electrode or both.
The effect of polarisation on reduction electrode is
given by Nernst equation.
M+n + ne− → M (s)
0.059 1
E = E° − log 𝑟𝑒𝑑𝑢𝑐𝑒𝑑
𝑛 𝑠𝑝𝑒𝑐𝑖𝑒𝑠
0.059 1 0.059
E = E° − log = E° + log M +
𝑛 𝑀+ 𝑛
The ions or spicies are transported to and
from the electrode surface by three methods
namely
a) Diffusion:
Diffusion is the movement of ions due the
concentration gradient (difference in
concentration). Here ions move/diffuse from high
concentrated region to the low concentrated
region. The diffusion continues until the gradient
becomes zero. Gradient decreases gradually and
finally becomes zero. When concentration
Page 9
gradient or difference is zero, a small amount of 1) Forced convection such as agitation.
current flows in the circuit which is called 2) Using higher surface area of electrode.
limiting current. 3) Less concentration of electrolyte decreases
The potential of the electrode can be calculated the polarisation.
from the following relationship. 4) Bigger electrodes or electrodes with large
b) Migration: surface area decrease the polarisation.
The movement or transportation of ion due to
electrostatic forces of attraction of the applied Overvoltage or potential (η)
electric field is called Migration. This ionic The effect of polarisation is seen as
movement constitutes current. overvoltage or potential. It is the difference
[In case analyte species have less mobility a third between actual cell or electrode potential and
substance, an inert electrolyte, called supporting theoretical cell or electrode potential.
electrolyte, is added. This electrolyte releases its Mathematically,
ions having high mobility, thereby reduce the η = Eactual - Etheoritical
resistance of the cell and IR drop. Supporting In a galvanic cell over potential means less
electrolyte does not reduce concentration energy is obtained than thermodynamics or Nernst
polarisation]. equation would predict. And in an electrolytic
c) Convection: cell, more emf is needed to be applied than theory
The movement of ions due to temperature, would expect. In one case there is some loss of
density difference and mechanical means (stirring) energy and in another, use of extra energy.
is termed as convection.
Varieties of overpotential
2. Kinetic polarisation (KP) Overpotential can be divided into many
We know that as a result of oxidation and different subcategories; they are named after the
reduction there is exchange/transfer of electron effect from which they exist. However these
between electrodes and reactants. If the speed or varieties are not always well defined.
rate of transfer is slow when compared to the Factors which affect overvoltage:
theory to produce theoretical emf leads to kinetic 1. Nature and physical state of an electrode
polarisation. This may be due to slow oxidation 2. Nature of the material reduced and oxidized
and reduction at one or both electrode. This is also 3. Nature of electrolyte
called as charge – transfer polarisation. 4. Temperature
KP is more intense/significant if the
products/reactants of the cell are gases (the
kinetics of gas). it reduces the effective area of the Overpotential for the evolution of selected gases on various electrode
materials at 25 °C
electrode and increases the local current density
Material of the electrode Hydrogen Oxygen Chlorine
This is also significant which involves the
Platinum (platinized) −0.07 V +0.77 V +0.08 V
participation of transition metals such as Fe, Cr,
Palladium −0.07 V +0.93 V
Ni, Co etc wherein the rate of ox/red is slow. This
Gold −0.09 V +1.02 V
polarisation also depends on the composition of −0.15 V
Iron +0.75 V
the electrode. For e.g., KP more pronounced in Platinum (shiny) −0.16 V +0.95 V +0.10 V
cells which involve soft metals such as tin, lead, Silver −0.22 V +0.91 V
zinc and particularly mercury. KP is negligible in Nickel −0.28 V +0.56 V
cell involving metals like Cu, Zn, Ag, Cd, etc Graphite −0.62 V +0.95 V +0.12 V
Kinetic polarisation usually decreases Lead −0.71 V +0.81 V
with the increase of the temperature and current Zinc −0.77 V

density. [Mobility of ions increase with Mercury −0.85 V

temperature].
Polarisation can be kept low by

drsenata@gmail.com Page 10
 Bubble overpotential is due to the
evolution of gas at either the anode or cathode.
This reduces the effective area for current and
increases the local current density.
Hydrogen overvoltage (ηH2)
Almost every electrochemical cell used in
industry contains water or dil. Acid solution
which furnish H+ ions. Thus, at cathode,
reduction of H+ takes place as follows
4H+ + 4e → 2H2 (g) E° = ?.... = 1.23
Electrochemically H+ are formed from
O2 (g) +4H+ + 4e– → 2H2O E° =1.23 V
Theoretical production of water from H2 and O2
should occur at 1.23 V. that is Etheoritical = 1.23 V.
but Eactual is 1.68 V. The difference 0.45 V is the
Hydrogen overvoltage.
Oxygen overvoltage (ηO2)
Take the example of industrial production
of chlorine gas and sodium hydroxide by
electrolysis of an aqueous sodium chloride
solution between Platinised Platinum electrodes
(platinum black- Pt powder deposited on Pt metal;
high surface area).
Na+, Cl−,
H+, O2−,
Anode; Cl2(g) + 2e– → 2Cl– E° =1.36 V
+ –
Anode; O2 (g) +4H + 4e → 2H2O E° =1.23 V
Cathode; Na+ + e− → Na (s) E°= −2.71 V
Platinum (platinized) +0.77 V +0.08 V
Platinum (shiny) +0.95 V +0.10 V
Graphite +0.95 V +0.12 V
For the electrolysis Na+Cl−;
E°cell = E°cathode – E°anode (for electrolytic
cell)
1.36 – (− 2.71) = 4.07 V
For the electrolysis Na+O2−;
1.23 – (− 2.71) = 3.94 V
Theoretically, electrolysis Na+O2−, liberating O2
evolution should takes place earlier to the
evolution of Cl2. Practically its not so. Reason is
drsenata@gmail.com
Eactual is different from E°cell It would be, Say
using Platinised Platinum electrodes,
For the electrolysis Na+Cl−;
E°cell = E°cathode – E°anode
1.36+0.08 – (− 2.71) = 4.07 V
1.44 – (− 2.71) = 4.15 V
For the electrolysis Na+O2−;
1.23+0.77– (− 2.71) = 3.94 V
2.00 – (− 2.71) = 4.71 V
Now, in reality, evolution of Cl2 takes
place before O2. Thus, because of existance of
polarisation and hence overvoltage, electrolysis of
NaCl possible (production of sodium metal).
Significance of Hydrogen overvoltage;
Hydrogen overvoltage due to the evolution
of Hydrogen gas in an electrochemical cell. ηH2
has great use/significance compared to the η of
other gases. Since most of the electrolysis and
electroplating is being done using aqueous or
dilute acid solutions, wherein evolution of H2 is
theoretically expected to begin, before the
deposition of the metal. This is because it requires
a small potential of 1.23 V, compared to the
deposition of other metal (Al=1.66,
Na=2.71,Ca=2.87). But, in reality evolution of H2
doesn‟t happen at 1.23 V. Thanks to H2
overvoltage. It needs higher potential. Thus
metals having lower deposition potential than that
of Eactual of H2, can be deposited comfortably. If
there were no hydrogen overvoltage, many
metal deposition would not have been possible.
Page 11
Example: Consider the electrolysis of a solution −0.23 V. {cell voltage = –0.23–(–0.76) = 0.43 V}.
that is 1.00 M in each of CuSO4(aq) and Thus, reduction in over potential with respect to
NaCl(aq); hydrogen accelerates the corrosion rate of the
Ans; Essentially the electrodes are inert; say metal].
platinum or graphite; ions/species present/ to be
−
considered are Cu+, SO2−
4 , Na+, Cl , H2O,
At Anode(+); Oxidation possibilities follow.
2Cl–(aq) → Cl2(g) + 2e– E° = –1.358 V
2SO42–(aq) → S2O82–(aq) + 2e– E° = –2.01 V
2H2O = 4H+(aq) + O2(g) + 4e– E° = –1.229 V
(Oxidizing species must have small negative E°)

At cathode (-); Reduction possibilities follow:

Na+(aq) + e– = Na(s) E° = –2.713 V
Cu2+(aq) + 2e– = Cu(s) E° = +0.337 V
2H2O + 2e– = H2(g) + 2OH–(aq) E° = +0.828 V
(Reducing species must have small positive E°)

Thus production of O2 (g) and Cu (s) are expected.

But the over-voltage for producing O2 (g) (+ 0.77
V on PP) from solution is considerably higher
than the standard potential. The voltage for this
half cell seems to be closer to –1.5 V (1.229 +
0.77 [confusion]) in reality. The result then is the
production of Cl2(g) and Cu(s).
Anode, oxidation:
2Cl–(aq) = Cl2(g) + 2e– E° = –1.358 V
Cathode, reduction:
Cu2+(aq) + 2e–=Cu(s) E° = +0.337 V

Overall: CuCl2(aq) : Cu(s) + Cl2(g) E = –1.021 V

E° = Ecathode − Eanode
E° = 0.337 − (−1.358)
E° = 1.695 V

We must apply a voltage of more than +1.021 V

to cause this reaction to occur.

[Overvoltage
When a metal, which occupies a high position in
galvanic series, say zinc, is placed in 1N H2SO4, it
undergoes corrosion with the evolution hydrogen
gas. The initial rate of reaction is quite slow,
because of small cell voltage {–0.77– (–0.76) =
0.01 V}. the value –0.77 V is the hydrogen over
voltage on zinc. However, if a few drops of copper
sulphate (CuSO4) are added, the corrosion rate of
zinc is accelerated, because some copper gets
deposited on the zinc metal, forming minute
cathodes, where the hydrogen overvoltage is only

drsenata@gmail.com Page 12
Decomposition potential. alkaline-manganese,
It is defined as the potential or voltage mercury- zinc, silver-zinc, and
required to bring about continuous electrolysis of lithium cells (e.g., lithium-manganese dioxide,
a electrolyte. lithium-sulfur dioxide, and lithium-thionyl
The graph of current flown (amps) versus the chloride).
voltage applied (V), is shown below: 2. Secondary or reversible cells
Secondary cells are rechargeable and require a DC
charging source to restore reactants to their fully
charged state.
Examples of secondary cells include
Lead-lead dioxide (lead-acid),
Nickel-cadmium, nickel-iron, nickel-hydrogen,
nickel-metal hydride,
silver-zinc, silver-cadmium, and
lithium-ion
Initially current increases slowly with the
Components of a cell or battery
increase of applied voltage. After a certain point,
1. Anode (negative electrode)
the amount of current flown rapidly increases.
Where oxidation reaction takes place and
Thus two straight lines are obtained. The point of
thus releases electrons to the circuit.
intersection of these two lines corresponds to the
M(s) → M+n + ne−
decomposition potential of that electrolyte.
A good anodic material should have
Should be a good reducing agent (E°
Electrochemical energy systems or battery or
value)
galvanic cell.
Good conductivity
Introduction, fundamentals of batteries,
Stable in contact with electrolyte
WKT, a spontaneous chemical reaction
Low price,
involves the decreases of free energy. This
Easy for handling, fabrication, disposing
thermodynamic aspect has become the basis for a
off, etc.
electrochemical energy source or simply, battery.
2. Cathode (positive electrode)
This spontaneous reaction, creates a redox couple
Where reduction reaction
involving lose or gain of electrons. The tendency
takes place and consume electros from the circuit.
to lose or gain electrons is nothing but the
M+n + ne− → M (s)
electrical energy given out by that cell.
A good cathodic material should have
Battery: A system which converts chemical
Should be a good oxidising agent (E°
energy into electrical energy. More correctly, a
value)
battery is an electrochemical cell: Galvanic Cells
Good conductivity
convert the energy from spontaneous chemical
Stable in contact with electrolyte
reactions into electricity.
Low price and easy fabrication
There are mainly two types of energy
3. Electrolyte
sources, namely;
Electrolyte provides a medium for the
1. Primary or irreversible cells
transfer of ions between anode and cathode. It
Primary cells are not rechargeable and must be
should have high ionic conductivity. Electrolyte
discarded or replaced once the reactants are
need not have to be all the time a liquid. It can be
depleted. The free energy change of active
even a paste, solid. An electrolyte must be
materials involved in a redox reaction is used as
compatible to these properties
electrical energy.
Examples of primary cells include
carbon-zinc (Leclanche or dry cell),

drsenata@gmail.com Page 13
Battery characteristics/specifications
1. Capacity or Amp-hour or Ah rating of a
battery: a battery rated at 100 A·h can deliver
100 A of current continuously for a period of 1
hour, or 50 A for 2 hr, or 5 A over a 20-hour
Period. [temperature dependent, at nominal
voltage].
For eg., Anode: Zn (s) → Zn2+(aq) + 2e−
Cathode:
2NH4 (aq) + 2MnO2(s) + 2e−→ Mn2O3 (s) + 2NH3 (aq) + H2O (l)

Zn (s) + 2NH4 (aq) + 2MnO2 (s) →

Zn2+ (aq) + 2NH3 (aq) + H2O (l) + Mn2O3 (s)

1.2 V 600 mAh Alkaline MnO2 batteries;

2. Voltage: mid-point voltage MPV is the
nominal voltage of the cell, and is the voltage that
is measured when the battery has discharged 50%
of its total energy. Normally voltage range is 1.5
V to 2 V and rarely > 3 V. Lead acid is 12 V.
3. C- rating/ Current rating/peak
current/discharge current/recharge current:
This is amount of current [A or mA] per unit time.
WKT E = I R. higher voltage means higher
Current. But depending on the materials used for
making battery, Ampere range from 200 mAh to
8000 mAh [ voltage range remains 1 to 2 V].
Peak current is maximum current that a battery is
able to deliver
Alkaline batteries the reaction between zinc and
manganese dioxide (Zn/MnO2).
The alkaline battery gets its name because it has
an alkaline electrolyte of potassium hydroxide, (in
zinc-carbon batteries there is acidic ammonium
chloride or zinc chloride electrolyte).
Compared with zinc-carbon batteries of the
Leclanché or zinc chloride types, alkaline batteries
have a higher energy density and longer shelf-life,
with the same voltage.
Anode; positive electrode manganese dioxide
Cathode;. negative electrode is zinc
Electrolyte; alkaline electrolyte of KOH; only the
zinc and mangenese dioxide are consumed during
discharge, not KOH.

Dry cell (Leclanché cell or Zn-MnO2 cell)

Cathode; A carbon or Graphite rod (with a metal

cap at the out side top) at the centre
The half-reactions are:
Electrolyte; thin layer of MnO2 surrounding the Zn(s) + 2OH−(aq) → ZnO(s) + H2O(l) + 2e− [E° = -1.28 V]
cathode and a paste of ZnCl2-NH4Cl.
Anode; thin cylinder enclosing the whole 2MnO2(s) + H2O(l) + 2e− → Mn2O3(s) + 2OH−(aq)
[E° = +0.15 V]
assembly of anode, cathode and electrolyte. Overall reaction:
The cell can be represented as Zn(s) + 2MnO2(s) ZnO(s) Mn2O3[E° = 1.43 V]
Zn | Zn+2 | | MnO2.NH4Cl | C
Dry cell has an emf of 1.5 V Cell has an emf of 1.45 V
It is diagrammatically shown as follows.

drsenata@gmail.com Page 14
Advantages;
1. Superior compared to dry cell
2. Capacity of an alkaline battery is greater (3-5
times greater) than an equal size Leclanché cell
3. Effective capacity 700 mAh to 3000 mAh
which is common for digital cameras,
4. Good shelf life;
Disadvantage that
1. They are costlier.
2. The voltage of the battery declines steadily
during use.
3. On a heavy load, capacity is reduced on
continuous discharge compared with intermittent
discharge,
Mercury Battery (Button cell);
Mercury oxide-Zinc battery;
Anode; Amalgamated zinc (paste of zinc in
mercury)
Electrolyte : KOH containing a paste of Zn(OH)2
and HgO
Cathode; Mixture of Graphite poeder and HgO,
pressed into a pallet.
Anodic and cathodic compartments are separated
by a suitable membrane allowing the movement of
only ions (parchment paper).
The whole cell is sealed by plastic insulation.
Cell has a voltage of 1.34-1.45 V
Cell may be represented as
Zn(s) | Zn(Hg) ǁ KOH HgO |C(s) |Steel
Anode:
Zn(Hg) + 2OH− (aq) →ZnO (s) + H2O (l) + 2e−
Cathode:
HgO (s) + H2O (l) + 2e− → Hg (l) + 2OH− (aq)
Zn(Hg) + HgO (s) → ZnO (s) + Hg (l)
Advantages;
1. Long storage life (2 Years)
drsenata@gmail.com
2. High capacity; provide more current
3. Perform well even at 60 – 90 Celsius
4. Yield a constant Voltage. Thus can be used a
reference cell
5. Allow high discharge. Large amount of current
can be drawn rapidly
Disadvantage;
1. High cost;
2. Bad at low temp.
Magnesium dry cell
Represanted by Mg | MgBr2 ǁ MnO2 |C
Anode is magnesium alloy,
Cathode is mix of MnO2 + BaCrO4 + acetylene
black
Electrolyte is MgBr2 gel inhibited with lithium
chromate
Cell voltage is 1.9 V
Anode reaction is Mg → Mg+2 + 2e−
Cathode reaction is
2MnO2(s) + H2O(l) + 2e− → Mn2O3(s) + 2OH−(aq
Magnesium dry cells made similar to the
conventional Leclanché cell
Advantages;
1. Very high capacity,
2. Successfully stored two years, retaining more
than 85 per cent of their initial capacity.
3. Low temperature discharge properties are
highly promising and tropical storage properties
are outstanding.
Secondary batteries
Rechargeable battery or charge accumulator
The characteristics of secondary battery are
It is a cell or combination of several cells
The reactions are highly reversible
The reaction can be reverted by allowing DC
current flow into the battery. This is called
charging process.
The process of drawing current from the charged
battery is called discharging process.
The charging and discharging can be done several
times; the best example is the lead acid battery.
Lead acid batteries;
They have a relatively large power-to-weight ratio
and low cost, make them attractive for use in
Page 15
motor vehicles to provide the high current While, as the battery is charged, the lead sulfate
required by automobile starter motors. coating on the electrodes is removed, and the acid
electrolyte becomes stronger

Fully Completely
Charged Discharged

State of charge: 100% 0%

Electrolyte ~6 ~2 molar
concentration: molar
Electrolyte specific ~1.3 ~1.1
gravity
Lead and lead-dioxide are good electrical No-load voltage: 12.7 V 11.7 V
conductors.
Anode is rectangular plates of spongy lead
Cathode id pead antimony alloy coated with
PbO2. Electrodes are dipped in 27-39% by weight
Nickel-Cadmium Batteries
sulphuric acid (6 M). entire assembly is enclosed Positive electrode:
in corrosion resistant material. 𝑑𝑖𝑠𝑐 ℎ𝑎𝑟𝑔𝑒
2NiOOH + 2H2O + 2e− < > 2Ni(OH)2 + 2(OH) −
𝐶ℎ𝑎𝑟𝑔𝑒

Anode reaction: oxidation Negative electrode:

Pb (s) + 𝑺𝑶𝟐−
𝟒 (aq) → PbSO4 (s) + 2e
−
Eo= 0.356 eV Cd + 2(OH) − < 𝑑𝑖𝑠𝑐 ℎ𝑎𝑟𝑔𝑒
𝐶ℎ𝑎𝑟𝑔𝑒
> Cd(OH)2 + 2e
−

Cathode reaction: reduction

PbO2 (s) + 4H+ (aq) + 𝑆𝑂42− (aq) + 2e− → 𝑑𝑖𝑠𝑐 ℎ𝑎𝑟𝑔𝑒
E0 = 1.685 eV
2NiOOH + Cd +2H2O < >
PbSO4 (s) + 2H2O (l) 𝐶ℎ𝑎𝑟𝑔𝑒
2Ni(OH)2 + Cd(OH)2
+
Pb (s) + PbO2 (s) + 4H (aq) + 2 𝑺𝑶𝟐−
𝟒 (aq)
→2PbSO4 (s) + 2H2O (l) Capacity of acid batteries;
Or Depends on the concentration of the active
Pb(s) + PbO2(s) + 2H2SO4 (aq) material present in the battrery
→2PbSO4(s) + 2H2O(l) WKT, anodic and cathodic reaction form
PbSO4, which is a non conducting material. Thus
Total voltage (at T = 298˚K and 1molar acid during discharging and charging, internal
electrolyte) is Ebatt = 0.356 + 1.685 = 2.041 V resistance increases. Over discharging and
The Nernst equation relates the chemical reaction charging needs to be avoided. For this reason 3-4
energy to electrolyte energy: times of active material is taken as that of
𝟐.𝟑𝟎𝟑𝑹𝑻 [𝑯𝟐𝑶 ]𝟐 theoretical.
E = E° − log [𝑯𝟐𝑺𝑶𝟒]𝟐
𝒏𝑭
Lower temperature decreases the
° 𝟐.𝟑𝟎𝟑𝑹𝑻
E=E + log [H2SO4]2 capacity of the battery. Low temperature decrease
𝒏𝑭
E = energy at a given concentration diffusion, mobility, conductivity and increase the
E0 = energy at standard 1 molar concentration viscosity of the electrolyte.
Lead sulphate is formed due to both anodic and The efficiency of lead acid battery is about
cathodic reactions. 80%. This decrease is due to the generation of
Thus, as the battery is discharged, both the heat and vaporization (fuming).
electrodes become coated with lead sulfate and the
acid electrolyte becomes weaker Alkaline storage batteries (Edison battery).
The nickel–iron battery (Ni-Fe battery) is
a rechargeable battery having a nickel(III) oxide-

drsenata@gmail.com Page 16
hydroxide cathode and an iron anode, with an Where E, constant voltage of charging;
electrolyte of potassium hydroxide. It is a very Ec, cell voltage
robust/heavy duty/rough battery which is tolerant Rc, resistance of cell/battery
of overcharge, over discharge, and short-circuiting Here E should be greater than Ec; i.e., charging
and can have very long life. It is often used in voltage should be higher than battery voltage.
backup situations where it can be continuously The charging current I and the rating in
charged and can last for more than 20 years. hours at the beginning and end of a charging
Due to its low specific energy, poor charge process can be calculated as follows. For a battery
retention, and high cost of manufacture, other of 4 Ah capacity. At time t = 0 , Rc = 0.1, Ec =
types of rechargeable batteries have displaced the 1.25 V and E =1.45 V; means when battery
nickel–iron battery in most applications. potential is 1.25 V, charging potential is 1.45 V.
Nickel-iron batteries have long been used Therefore
in European mining operations, London 𝑑𝐸 0.25
I= = = 2 A = Charging Current
𝑅𝑐 0.1
underground electric locomotives, New York City 4 𝐴ℎ
Subway car, etc. Rating at the beginning is = 2 ℎ𝑜𝑢𝑟𝑠
2𝐴
At the anode: After charging, say Ec = 1.43 V and E =1.45 V.
Fe + 2 OH− ↔ Fe(OH)2 + 2e− this means that the battery is charged to a voltage
At cathode, of 1.43 V.
Ni2O3 + 2e−→ 2NiO Then I =
𝑑𝐸
=
0.02
= 0.2 A
𝑅𝑐 0.1
Over all is
Fe + Ni2O3 ↔ Fe(OH)2 + 2NiO Eo = 1.33 V 4 𝐴ℎ
Rating is = 20 ℎ𝑜𝑢𝑟𝑠h battery charged to
0.2 𝐴
Advantage; 1,43 V, can give an output of 0.2 A current for 20
Long Storage life even in idling hours.
Over charging and discharging does damage
Low maintenance cost. 2. Constant current–charging
Environment friendly; no lead, cadmium The circuit diagram is as follows;

Battery charging-theory and practice.

There are basically three methods of
charging
1. Constant Voltage−charging
The circuit diagram is as follows;

Its expression is
𝐸 − 𝐸𝑐 𝑑𝐸
ICh = =
𝑅𝑐 + 𝑅𝑠 𝑅𝑐 + 𝑅𝑠
The charging current can be controlled by
using a variable resistance (Rs) present in line
The charging current is given by expression with the circuit. In this method of charging, the
𝐸 − 𝐸𝑐 𝑑𝐸 change the charging current Ich is negligible.
ICh = =
𝑅𝑐 𝑅𝑐

drsenata@gmail.com Page 17
 Example; consider a battery with
internal resistance of 0.1 ohm. The required
variable resistance to charge a battery with a
constant current of 0.4 A from a charger of 10
V, is calculated as follows (ell potential Ec =
1.25 V).
𝐸 − 𝐸𝑐 10 − 1.25
𝑅𝑠 = − 𝑅𝑐 = − 0.1
𝐼𝑐ℎ 0.4
= 21.775 ≈ 21.8 𝑜ℎ𝑚
After charging, if cell is charged to 1.43 V, then
10 − 1.43
ICh = = 0.39 𝐴
21.8 + 0.1
In constant current charging, the change in
charging current is negligible;
3. Taper−charging
In thismethod the charging current is high
in the beginning and tepered (made to decrease) to
low at the end of charging. This is made by using
a constant voltage charging source and variablr
risistance for varying current. In the beginning of
charging process, high current is employed and
reset to lower current when gasing is observed
(formation of gases, especially due to the
decomposition of water) (towards the end).
Energy economics,
ED
Efficiency =
EC
EC = Total energy during charging
ED = Total energy during discharging
Energy efficiency =
= voltage efficiency × coulomb efficiency
discharge A−hrs
Coulomb efficiency =
charge A−hrs
discharge voltage
Voltage efficiency =
charge voltage
Energy is lost during charging when
reactions other than reversal of sulfation occur. At
beginning of charge cycle, coulomb efficiency is
near 100%. Near end of charge cycle, electrolysis
of water reduces coulomb efficiency. This can be
avoided by reducing charge rate (taper charging)
Typical net coulomb efficiency: 90%
≈ Voltage efficiency: (2V)/(2.3V) = 87%
Energy efficiency = (87%)(90%) = 78%
drsenata@gmail.com
Commonly quoted estimate: 75%
Over-discharge leads to “sulfation” and the
battery is ruined. The reaction becomes
irreversible when the size of the lead-sulfate
formations become too large
Overcharging causes other undesirable reactions
to occur. Electrolysis of water and generation of
hydrogen gas. Electrolysis of other compounds in
electrodes and electrolyte, which can generate
poisonous gasses. Bulging and deformation of
cases of sealed batteries
Battery charge management to extend life of
battery:
Limit depth of discharge
When charged but not used, employ “float” mode
to prevent leakage currents from discharging
battery
“Absorption” or “taper charging” Trickle charging
/ float mode Equalizes the charge on series-
connected cells without significant gassing
Prevents discharging of battery by leakage
currents Occasional pulsing helps reverse
sulfation of electrodes
Lead-acid batteries always should be stored in
the charged state. If allowed to remain in the
discharged state for a prolonged time period, the
battery becomes damaged by “sulfation.”
Sulfation occurs when lead sulfate forms into
large, hard crystals, blocking the pores in the
active material. The sulfation creates a high
impedance condition that makes it difficult for the
battery to accept recharge. The sulfation may or
may not be reversible, depending on the discharge
conditions and specific cell design. The ability to
recovery from deep discharge has been improved
in recent years by electrolyte additives, such as
sodium sulfate.
For vented-cell batteries, electrolyte
topping must be performed on a regular basis to
replenish the water loss that occurs during
charging. Maintenance intervals are typically 2 to
4 months. For sealed-cell batteries, water
replenishment obviously is unnecessary,
Memory effect (Practice or Habit effect)
If a battery is repeatedly discharged to
only 30% of it's capacity during normal operation
Page 18
and then recharged, the battery will only accept a Types of fuel cells
charge to 30% of it's capacity. Assume a battery On the basis of temperature, into
could last a full 8 hour shift - this means the radio 1. Low temperature fuel cell [< 100 C]
user only utilized 30% or 2 hours and 40 minutes 2. Moderate temperature fuel cell [100-250 C]
of the available operation time. As a result, that 3. High temperature fuel cell [> 100 C]
user can only operate that battery for 2 hours and In order to achieve better performance of
40 minutes, even though it received a full charge! a fuel cell, suitable electrolyte and electrode
Pollution caused by the spent battery is material are selected. On this basis fuel cells are
also to be considered while designing a battery. 1. Alkaline Fuel cell [AFC]
2. Phosphoric acid fuel cell [PAFC]
Reserve battery; 3. Molten carbonate [MCFC]
A reserve battery, also called stand-by 4. Polymer electrolyte membrane
battery, is a primary battery where a part of the it, [PEMFC]
is isolated until the battery needs to be used. When 5. Solid oxide [SOFC]
long storage is required, reserve batteries are often 6. Bio-chemical [BCFC]
used, since the active chemicals of the cell are
kept separated until needed, thus reducing self-
discharge. Common example of fuel cell is H2-O2 fuel cell
These batteries are used in missiles, This cell is also known as Bacon cell
projectile and bomb fuzes, and various weapon The reactions taking place at electrodes are:
systems. Reserve batteries may be activated by At anode
addition of water, by adding electrolyte, by {H2 + 2OH− (aq) → 2H2O (l) +2e− }×2
introducing a gas into the cell or by heating a solid At cathode
electrolyte to a temperature at which is becomes O2 + H2O (l) +4 e− → 4 OH− (aq)
conductive. 2H2(g) + 4OH− →4H20 + 4e− Ecell =1.12 V
Reserve batteries remain uncommon in
civilian applications because of their higher cost
and relatively short life after activation.
Example is zinc-air batteries where the
cell is sealed until use: a tab is removed to admit
air and activate the cell.

Fuel cells –types, electrochemistry of fuel cells.

Fuel cell is a device in which energy from
the combustion of fuel is directly converted into
electrical energy. It is much different from
primary and secondary cell. Composition
In primary cell, chemical energy active 1. Fuel H2 (gas or liquid)
material is converted in to electrical energy. In 2. Oxidant O2 (gas or liquid)
fuel cell, the active material is continuously fed 3. Electrolyte 70-80% KOH
sot that electricity is continuously drawn. Alkaline electrolyte is more used; because alkalis
Secondary is rechargeable, but fuel cell is not. less corrosive to acid; reduction of O2 is more
Usually fuel is oxidized releasing electrons. The reversible in alkaline than in acid;
oxidant is reduced by consuming electros. The 4. Anode Ni
chemical energy of the redox reaction is converted 5. Cathode Nio/ Ni
to electrical energy. 6. Temperature 200 C

drsenata@gmail.com Page 19
Advantages of a fuel cell
1. It works continuously as long as gases are
supplied
2. High efficiency (high conversion of free energy
of active material)
3. Pollution free (harm less products).
4. Low noise pollution
5. Less attention is needed

drsenata@gmail.com Page 20