Electrochemistry is the branch of chemistry that deals with the interconversion of

electrical energy and chemical energy.

Electrochemical processes are redox (oxidation-reduction) reactions in which the energy

released by a spontaneous reaction is converted to electricity or in which electrical
energy is used to cause a nonspontaneous reaction to occur.

Oxidation-Reduction Reactions
Balancing Redox Reactions

Half Reactions

Element Balance

Charge Balance
Balancing Redox Reactions
Final Balance
 In contrast to many chemical measurements, which involve homogeneous bulk
solutions, electrochemical processes take place at the electrode–solution
interface.
 Electrochemistry may be defined as the branch of chemistry that examines the
phenomena resulting from combined chemical and electrical effects.
This field covers:
Electrolytic processes:
Reactions in which chemical changes occur on the passage of an electrical current
Galvanic or Voltaic processes:
Chemical reactions that result in the production of electrical energy

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 Electrochemical cell
An electrochemical cell typically consists of:
 Two/more electronic conductors (also called electrodes)
And an ionic conductor (called an electrolyte)
 Charge transport in the electrodes occurs via the motion of
electrons (or holes) And Charge transport in the electrolyte
occurs via the motion of ions (positive and negative)
 Electrode at which the oxidation reaction occurs is called the anode
 Electrode at which the reduction reaction occurs is called the cathode
 The electrode at which the reaction of interest occurs is called the working electrode
 The electrode at which the other (coupled) reaction occurs is called the counter
electrode/reference electrode
## A third electrode, called the reference electrode may also be used
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 Reduction Involves the gain of an
electron
 Involves the transfer of electrons
from the electrode to the species
O + ne= R (2)
Reduction is also an energetic process,
and occurs when the energy of the
electrode increases above the lowest
vacant molecular orbital of the
compound–see figure part a

 Oxidation Involves the loss of an

electron
 Involves the transfer of electrons
from the species to the electrode
R = O + ne(1)
Oxidation is an energetic process, and
occurs when the energy of the electrode
dips below the highest occupied
molecular orbital of the compound–see
figure part b 6
 Reactions –half cell and overall
 At each electrode, an electrochemical reaction occurs. This reaction is called a
half cell reaction (since there are generally two electrodes in a typical cell at
which reactions occur)
 The overall chemical reaction of the cell is given by combining the two
individual half cell reactions

Half cell reaction types

There are two fundamental types of half cell reactions:
-Oxidation reactions
-Reduction reactions
A reaction is classified as oxidation or reduction depending on the direction of
electron transfer
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Voltaic Cells

Cell diagram:
Zn(s) | Zn2+(1M) || Cu2+(1M) | Cu(s)

Single line represent a denotes salt bridge

Phase boundary (separate compartment)
(solid sol) emf of Daniel cell=1.10 V
C) Salt – Bridge : Passage of ions

To complete the electrical circuit, the solutions must be connected by a conducting

medium through which the cations and anions can move from one electrode to

compartment to the other. This requirement is satisfied by the salt – Bridge –which is an

inverted U-Tube containing inert electrolyte salts like KCl or NH4NO3 .

Since ionic system must be electrically neutral , an electrochemical cell must contain

Some means for ions to pass from one side of the cell to the other . A common method

For doing this involves a salt bridge – It may be :

I. Simply a porous glass barrier.

II. Gelatinous material material like agar that contains ionic salts (KCl or NH4NO3)

In either case , salt bridge allows the passage of ions , so the system can remain electrically neutral. 9
Voltaic Cells

Cell diagram:
Zn(s) | Zn2+(1M) || Cu2+(1M) | Cu(s)

Single line represent a denotes salt bridge

Phase boundary (separate compartment)
(solid sol) emf of Daniel cell=1.10 V
 Reference electrodes
 Reference electrodes, as their name suggests, are used to give a value of potential to
which other potentials can be referred in terms of a potential difference—potentials
can only be registered as differences with respect to a chosen reference value.
 Thus, a good reference electrode needs to have a potential that is stable with time and
with temperature and which is not altered by small perturbations to the system—that
is, by the passage of a small current.
The standard (or normal) hydrogen electrode

## The standard (or normal) hydrogen

electrode is the most important reference
electrode because it is the one used to
define the standard electrode potential scale.

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# detn of the potential of Zn electrode in galvanic cell:
Cell diagram
Zn(s) Zn+2(1M) H+ (1 M) H2 (1atm) Pt (s)

Emf of the cell = 0.76V

Anode(oxidation): Zn(s) Zn+2(1M) + 2e-
Cathode(reduction): H+ (1 M) + + 2e- H2 (1atm)
Overall : Zn(s) + H+ (1 M) Zn+2(1M) + H2 (1atm)
If standard emf of the cell is Eocell , then : Eocell = Eocathod + Eoanode
Eocell = Eocathod - Eoanode (-ve sign as anode(oxidation) reaction is represented as reduction reaction)

EoH /H - EoZn
+
2
+2/Zn

0.76 = 0 - EoZn +2/Zn

EoZn+2/Zn = - 0. 76V
# detn of the potential of Cu electrode in galvanic cell:
Cell diagram
Pt (s) H2(1atm) H+ (1 M) Cu+2(1M) Cu(s)

Emf of the cell = 0.34V

Anode(oxidation):H2(1atm) H+ (1 M)+ 2e-
Cathode(reduction): Cu+2(1M)+ 2e- Cu(s)
Overall : H2(1atm) + Cu+2(1M) 2H+ (1 M) + Cu(s)
If standard emf of the cell is Eocell , then : Eocell = Eocathod + Eoanode
Eocell = Eocathod - Eoanode therefore for Daniell cell :
0.34 = EoCu /Cu
+2
- EoH /H +
2 Eocell = Eocathod - Eoanode
0.34 = EoCu +2/Cu -0 = EoCu+2/Cu - EoZn
+2/Zn

EoCu +2
/Cu = + 0.34 V = 0.34 – (-0.76V) = 1.10V
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Spontaneity of redox reaction:

∆G° K E°cell reaction under standrd state condition

-ve >1 +ve favours formation of product

0 =1 0 reactants and products are equally forced

+ve <1 -ve favours formation of reactants

Relationships among ∆G°, K and E°cell :

 0.0592𝑉𝑉
E = E˚− log 𝐾𝐾
𝑛𝑛
Battery
A series of voltaic cells that can be used as a source of direct electric current (DC) at a constant voltage.

Voltaic Cell

Primary Cell Secondary Cell

Classified based on Rechargeable cell, can be
Inefficient energy source the types of
because chemicals can re-used , requires a
electrolyte system chemical reaction that is
only be used once
rapid and readily
reversible.

Acidic or Alkaline

Organic liquid, molten salt, solid state

electrolyte
Battery Technology

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Applications using Batteries

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26
 Battery
 Convert stored chemical energy into electrical energy
 Reaction between chemicals take place
Consisting of electrochemical cells
Contains
Electrodes – cathode & anode
Electrolyte

Cathode (Positive terminal) Anode (Negative terminal)

Chemical reduction occurs (gain electrons) Chemical oxidation occurs (lose electrons)

Electrolytes allow:
Separation of ionic transport and electrical transport
Ions to move between electrodes and terminals
Current to flow out of the battery to perform work
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 Primary Cell
• One use (non-rechargeable/disposable)
• Chemical reaction used, can not be
reversed
• Used when long periods of storage are
required
• Lower discharge rate than secondary
batteries
• Use: smoke detectors, flashlights, remote
controls

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 Zinc-Carbon Battery
 A common primary battery is the
dry cell. The dry cell is a zinc-
carbon battery.
 Anode: zinc metal body (Zn). The
zinc can serves as both a container
and the negative electrode.
 Cathode: manganese dioxide
(MnO2). Actually the positive
electrode is a rod made of carbon
that is surrounded by a paste of
manganese(IV) oxide, zinc
chloride, ammonium chloride,  The half-reactions are:
carbon powder and a small Zn(s) → Zn2+(aq) + 2e- [e° = -0.763 V]
amount of water. 2NH4+(aq) + 2MnO2(s) + 2e- → Mn2O3(s) + H2O(l) + 2NH3(aq) + 2Cl-
 Electrolyte: The paste of [e° = 0.50 V]
manganese(IV) oxide, zinc  Overall reaction:
chloride and ammonium chloride Zn(s) + 2MnO2(s) + 2NH4Cl(aq) → Mn2O3(s) + Zn(NH3)2Cl2 (aq) +
dissolved in water. H2O(l) [e° = 1.3 V] 29
Secondary Cells
• Rechargeable batteries
• Reaction can be readily reversed
• Similar to primary cells except redox
reaction can be reversed
• Recharging:
• Electrodes undergo the opposite process
than discharging
• Cathode is oxidized and produces electrons
• Electrons absorbed by anode

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Lead-Acid Battery
• Anode: Porous lead
• Cathode: Lead-dioxide
• Electrolyte: Sulfuric acid, 6 molar H2SO4

• Discharging
(+) electrode: PbO2(s) + 4H+(aq) + SO42-(aq) + 2e- → PbSO4(s) + 2H2O(l)
(-) electrode: Pb(s) + SO42-(aq) → PbSO4(s) + 2e-
• During charging
(+) electrode: PbSO4(s) + 2H2O(l) → PbO2(s) + 4H+(aq) + SO42-(aq) + 2e-
(-) electrode: PbSO4(s) + 2e- → Pb(s) + SO42-(aq)

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Lithium-Ion Battery
• Ideal material
• Low density, lithium is light
• High reduction potential
• Largest energy density for weight
• Li-based cells are most compact ways of storing electrical energy
• Lower in energy density than lithium metal, lithium-ion is safe
• Energy density is twice of the standard nickel-cadmium
• No memory and no scheduled cycling is required to prolong battery
life

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 Rechargeable Li-ion batteries have gained considerable interest in recent years in
terms of highest specific energy, cell voltage, good capacity retention and
negligibly small self Discharge.

 It is desirable that the energy delivered by a battery during its discharge should be
as high as possible.

 The energy output of a battery is dependent on the equivalent weight of active

material present in it.

 Lithium metal being the third lightest element, lithium based materials with low
molecular weight can effectively produce batteries with high capacity.

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 Lithium ion battery consists of three main
components, usually, Anode: Graphite; Cathode:
Lithium metal dioxide; Electrolyte: mixture of
lithium salts
 During charge, Li+ moves from LiCoO2 to carbon
through the electrolyte which causes oxidation of
Co3+ to Co4+ and
 The reverse happens during discharge; Li+ moves
from carbon to LiCoO2.

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 Role of electrolyte is to act as a medium for the transfer of ions between the
two electrodes.

 In general, lithium salt dissolved in organic solvent is used as electrolyte in

lithium ion batteries. Main requirements for the electrolyte are, (i) it should be
a good Li-ion conductor and electronic insulator (ii) stability over the operating
voltage window (iii) chemical compatibility with cell components and
electrodes (iv) thermal stability and (v) there should not be any charge
accumulation and concentration polarisation.

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Corrosion
Corrosion is an irreversible and spontaneous deterioration of metal or alloy through chemical or
electrochemical reaction with the environment.

We can write the overall oxidation–reduction equation—

2Fe(s) + 4H+ (aq) + O2 (g) 2Fe2+ (aq) + 2H2O(l)

Prevention of Corrosion
One way to prevent corrosion is to paint the bridges, cars, and ships
with paints containing materials that seal the iron surface from H2O
and O2. But it is necessary to repaint often; a scratch in the paint
exposes the iron, which then begins to rust.

Rusting of underground iron pipes and iron

storage tanks can be prevented or greatly
reduced by connecting them to metals such as
zinc and magnesium, which oxidize more
readily than iron.

Cathodic protection of an iron storage tank

(cathode) by magnesium, a more electropositive
metal (anode). Since only the magnesium is
depleted in the electrochemical process, it is
sometimes called the sacrificial anode.
 An effective way to prevent corrosion is to place the iron in contact with a metal that substitutes for the
anode region of iron.
 Metals such as Zn, Mg, or Al lose electrons more easily than iron. When one of these metals is in contact
with iron, the metal acts as the anode instead of iron.
 For example, in a process called galvanization, an iron object is coated with zinc. The zinc becomes the
anode because zinc is more easily oxidized than Fe. As long as Fe does not act as an anode, rust cannot
form.
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