CH 18 Electrochemistry

Electrochemistry
• Daily life applications: Starting your car, calculators, smartphones,

listening to radio in a remote area Dependent on electrochemical
reactions.
• Electrochemistry is best defined as the study of interchange of
chemical and electrical energies.
• It is primarily concerned with two processes that involve oxidation-
reduction reactions:
1. The generation of electrical current from a spontaneous chemical
reaction
2. The use of current to produce a chemical change.
• Overall this is a very complicated thing in aqueous solutions. To make
it more simple, we go for half-cell reactions.
Balancing the redox reactions for acidic solutions
• Electrode at which oxidation occurs is called anode (produces
electrons)
• Electrode at which reduction occurs is called cathode (consumes
electrons)
• This is the Galvanic cell: It is the
device in which chemical energy
is converted into electrical energy
(Opposite is called Electrolysis)
• Galvanic cell consists of an oxidizing agent (which itself gets reduced)
in one compartment which pulls the electrons from a reducing agent
(which gets oxidized) via a wire.
• This “pull” or the driving force on the electrons is called the cell
potential or the electromotive force (emf)
• The unit of electric potential is “Volts” abbreviated as V.
• This can be measured using a voltmeter.
• The reaction in a galvanic cell is always a redox (oxidation-reduction)
reaction which can be broken down into two half cell reactions.
• To understand the concept of standard reduction
potential, let’s start with the following redox reaction.
• Thus for anode (oxidation half reaction)
• For cathode (reduction half reaction)
STANDARD HYDROGEN ELECTRODE: Pt, H2 1 atm, 1M H+ sol

• What is the potential of individual
electrode process?
• We can determine that!
• If we want potential for each half
reactions, (half cells), we must
arbitrarily divide the total cell
potential, e.g. if we assign exactly
zero Volts to standard Hydrogen
electrode
• Then, the reaction
• Convenient to assign potential to each half-cell reaction: so that when
we construct a cell from a given pair of half-reactions, we can obtain
the cell potential by summing the half-cell potentials.
Line notations
• Anode components are listed on left hand side
• Cathode components are listed on right hand side
• The two half cell reactions are separated by double vertical lines
(which indicates the salt bridge or porous disk between the two
compartments)
• Phase boundary is indicated by a single vertical line
• When the dissolved ions cannot act as solid electrode, then inert
electrode such as Pt is used.
• Let’s explore a more theoretical approach towards galvanic cells (i.e.,
the relationship between thermodynamics and electrochemistry
• The work can be extracted for some application when the electrons
move in the wire.
• The electron transportation through the wire depends on the driving
force which gives the push to the electrons in the desired direction.
This thermodynamic driving force (the emf) is the potential difference
between the two points in the circuit.
• Volt represents a joule of work per coulomb of charge.
• The work of 1 Joule is produced (or required) when 1 Coulomb of
charge is transferred between two points in the circuit which differ y
1 Volt.
• The work is viewed as a point of view of the system. I.e. work flowing
out of the system has negative sign, while work entering or being
done on the system has positive sign.
• When a galvanic cell produces a current, the cell potential is positive
and thus, the current can be utilized to do some kind of work e.g.
powering a motor or so.
• But there is a problem. To obtain electrical work, the current must
flow. When the current flows, some electrical energy is wasted or
dissipated in the form of lost heat for instance. So you cannot obtain
the maximum work from it.
• So there is a general principle that in any real spontaneous process,
some energy is always wasted, the actual electrical work is always less
than the calculated maximum.
• Recall from thermodynamics, that the maximum work can only be
realized in case of hypothetical reversible process
• We can never extract maximum work from a given galvanic cell but
we can still measure the maximum potential. There is always a
negligible amount of current flow when the potential between the
two electrodes of a galvanic cell is measured using an efficient digital
voltmeter. No current flow implies no waste of energy and thus, the
maximum potential can be measured.
• This can be used to calculate the efficiency of the galvanic cell,
though, max work can never be realized practically
• The actual work is
• Under standard conditions, all concentrations are 1M
• Under standard conditions, the following reaction has the potential of
1.36V
• Higher conc of Ce4+ will take the reaction in forward direction and cell
potential will be higher than when in standard conditions
• What if the molarities are different in two
different compartments
Since the Ag+ ions conc is different in two

Half cells, their potentials will not be
Identical and the cell will exhibit a positive potential
• If the cell with two compartments have same components but at
different concentrations, we call it a concentration cell
• Fuel cell is the galvanic cell in which the reactants
are continuously supplied
• The galvanic cell produces electricity when a redox reaction proceeds
spontaneously.
• The electrolytic cell (or electrolysis) uses electrical energy to produce
a chemical change
• Electrolysis involves forcing a current through a cell to produce a
chemical change for which the cell potential is negative (i.e., the
reaction is non-spontaneous)
• E.g. charging a battery, industrial prep of Al metal, Chrome plating an
object.
A potential greater than cell potential is
required to reverse the process i.e., for
electrolytic process
• Haul-Heroult Process: In which, the cryolite is used as solvent
• Water cannot be used as solvent due to the following reason:
• To create ion mobility, bauxite (Al2O3) must be melted which is not

possible below 2050 degrees C

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Electrochemistry

• Daily life applications: Starting your car, calculators, smartphones,

• Thus for anode (oxidation half reaction)

• For cathode (reduction half reaction)

STANDARD HYDROGEN ELECTRODE: Pt, H2 1 atm, 1M H+ sol

Since the Ag+ ions conc is different in two

• To create ion mobility, bauxite (Al2O3) must be melted which is not

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