ELECTROCHEMICAL CELL

• A device is used to convert the chemical

energy produced in a redox reaction in to
Electric energy is called a electrochemical
cell or simply a chemical cell.
• These are also called as Galvanic cell or
simply a Voltaic cell.
 Redox Reactions.

Reduction Loss of oxygen

Gain of electrons
-gain of electron
-Loss of oxygen

Oxidation
- loss of electron
-Gain of oxygen
• An electrochemical cell is composed to
two compartments or half-cells, each
composed of an electrode dipped in a
solution of electrolyte. These half-cells are
designed to contain the oxidation half-
reaction and reduction half-reaction
separately as shown below.
 Voltaic Cell: How it works
• The half-cell, called the anode, is the site
at which the oxidation of zinc occurs as
shown below.
• Zn (s) ----------> Zn+2 (aq) + 2e-

• During the oxidation of zinc, the zinc

electrode will slowly dissolve to produce
zinc ions (Zn+2), which enter into the
solution containing Zn+2 (aq) and SO4-2
(aq) ions.
• The half-cell, called the cathode, is the
site at which reduction of copper occurs
as shown below.

• Cu+2 (aq) + 2e- -------> Cu (s)

• When the reduction of copper ions (Cu+2)

occurs, copper atoms accumulate on the
surface of the solid copper electrode.
How a Voltaic Cell Works

The two half-reactions can be summed to

show the overall reaction.
• Note that the electrons must cancel.
Zn(s) → Zn2+(aq) + 2e–
Cu2+(aq) + 2e– → Cu(s)
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)

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Representing Electrochemical Cells

You can represent the zinc-copper voltaic cell

by using the following shorthand form.

Zn(s) ZnSO4(aq) CuSO4(aq) Cu(s)

The half-cell that undergoes oxidation (the anode) is written first, to the left of the double vertical
lines.

• The single vertical lines indicate boundaries of

phases that are in contact.
• The double vertical lines represent the salt
bridge or porous partition that separates the
anode compartment from the cathode
compartment.
 Salt Bridge
• The reaction in each half-cell does not occur
unless the two half cells are connected to each
other.
• It is an inverted U-tube contaning aan electrolyte
e.g KCL,KNO3 etc it act as bridge by connecting
two half cells
-----------Helps in
• To completing the electric circuit
• To prevent mixing of soln of two half cell.
• To help maintain electric neutrality
 Summary of Voltaic Cells (Galvanic
•
Cell)
A device that spontaneously produces electricity by redox
• Uses chemical substances that will participate in a spontaneous redox reaction.
– The reduction half-reaction (SOA) will be above the oxidation half-reaction (SRA) in the activity
series to ensure a spontaneous reaction.
• Composed of two half-cells; which each consist of a metal rod or strip immersed in a
solution of its own ions or an inert electrolyte.
– Electrodes: solid conductors connecting the cell to an external circuit
– Anode: electrode where oxidation occurs (-)
– Cathode: electrode where reduction occurs (+)
– The electrons flow from the anode to the cathode (“a before c”) through an electrical
circuit rather than passing directly from one substance to another
– A porous boundary separates the two electrolytes while still allowing ions to flow to
maintain cell neutrality
• Often the porous boundary is a salt bridge,
containing an inert aqueous electrolyte
(such as Na2SO4(aq) or KNO3(aq)),
• Or you can use a porous cup containing one
electrolyte which sits in a container of a second
electrolyte.
 Electrolytic Cell
• It is a device to convert Electric Energy
into Chemical Energy
• An electrolytic cell is an electrochemical
cell in which the energy from an applied
voltage is used to drive an otherwise
nonspontaneous reaction. Such a cell
could be produced by applying a reverse
voltage to a voltaic cell like the Daniell cell.
 Difference b/w Electrochemical
cell and Eletrolytic Cell
Electrochemical cell Eletrolytic Cell

Chemical enrgy • Electric enrgy

converted into converted into
Electric energy Chemical energy
• It is based on redox
It is based on redox rxn rxn which is non-
which is spontaneous spontaneous
i.e rxn occurs its own
 Electrode Potential
• It is the tendency of an electrode in half
cell to lose or gain electrons when it is in
contact with solution of its own ion

• Zn (s) ----------> Zn+2 (aq) + 2e- Oxidation half rxn

• Cu+2 (aq) + 2e- -------> Cu (s) Reduction half rxn

 Electomotive force (emf)
• The two half-cells are also connected externally.
In this arrangement, electrons provided by the
oxidation reaction are forced to travel via an
external circuit to the site of the reduction
reaction. The fact that the reaction occurs
spontaneously once these half cells are
connected indicates that there is a difference in
potential energy. This difference in potential
energy is called an electomotive force (emf) and
is measured in terms of volts. The zinc/copper
cell has an emf of about 1.1 volts under standard
conditions.
 Nernst Equation
• Electrochemistry deals with cell potential
as well as energy of chemical reactions.
The energy of a chemical system drives
the charges to move, and the driving force
give rise to the cell potential of a system
called galvanic cell. The energy aspect is
also related to the chemical equilibrium. All
these relationships are tied together in the
concept of Nearnst equation.
• Walther H. Nernst (1864-1941) received
the Nobel prize in 1920 "in recognition of
his work in thermochemistry". His
contribution to chemical thermodynamics
led to the well known equation correlating
chemical energy and the electric potential
of a galvanic cell or battery.
• The general Nernst equation correlates the
Gibb's Free Energy ΔG and the EMF of a
chemical system known as the galvanic
cell.
• Ecell = E cell - (RT/nF)lnQ
0

– Here, Ecell = Electrode potential

– E0cell = Standard potential of a particular reaction
– F=Faraday constant, R=Universal Gas constant,
T=Absolute temperature
– n= number of electron involved
– Q= Amount of current flow
 Nernst Equation
• Remember that
G = G + RT ln Q
• This means
−nFE = −nFE + RT ln Q
• Dividing both sides by −nF, we get the Nernst
equation: RT
E = E − ln Q
nF
or, using base-10 logarithms,
2.303 RT
E = E − log Q
nF
 Nernst Equation
At room temperature (298 K), and
R = 8.314 J/mol K
F = 96,485 J/V-mol

2.303 RT
= 0.0592 V
F
The final form of the Nernst Equation becomes

E = E − 0.0592 log Q
n
• Primary cell
• A primary cell is a special type of
electrochemical cell in which the reaction
cannot be reversed, and the identities of
the anode and cathode are therefore fixed.
The anode is always the negative
electrode. The cell can be discharged but
not recharged.
• Secondary cell
• A secondary cell, is one in which the
chemical reactions are reversible.
• When the cell is being charged, the anode
becomes the positive (+) and the cathode
the negative (−) electrode. This is also the
case in an electrolytic cell.
• When the cell is being discharged, it
behaves like a primary cell, with the
anode as the negative and the cathode as
the positive electrode.
• For example, Rechargeable battery
 Reference Electrodes
• A reference electrode is an electrode which has a
stable and well-known electrode potential.
• There are many ways reference electrodes are
used. The simplest is when the reference
electrode is used as a half cell to build an
electrochemical cell. This allows the potential of
the other half cell to be determined.
• Common reference electrodes are
• Standard hydrogen electrode (SHE)
• Normal hydrogen electrode (NHE)
• Saturated calomel electrode (SCE)
 Potentiometric titration
• Potentiometric titration is a technique similar
to direct titration of a redox reaction. No
indicator is used. To do this, two electrodes
are used, an indicator electrode and a
reference electrode.
• The indicator electrode forms an
electrochemical half cell with the interested
ions in the test solution. The reference
electrode forms the other half cell, holding a
consistent electrical potential.
 Buffer solution
• A buffer is an aqueous solution consisting of a
mixture of a weak acid and its conjugate base or a
weak base and its conjugate acid.
• Its pH changes very little when a small amount of
strong acid or base is added to it and thus it is
used to prevent changes in the pH of a solution.
• Buffer solutions are used as a means of keeping
pH at a nearly constant value in a wide variety of
chemical application.
• One example of a buffer solution found in nature
is blood.
• Henderson–Hasselbarch equation
• In chemistry, the Henderson–Hasselbalch
equation is useful for estimating the pH of a
buffer solution and finding the equilibrium pH in
acid-base reactions.
• The equation is given by:

• Here, [HA] is the molar concentration of the

undissociated weak acid, [A⁻] is the molar
concentration of this acid's conjugate base
• And pKa= -log ka where ka is the acid dissociation
constant
 Concentration Cells
• Electrolyte concentration cell
– Where the electrodes are identical; they simply
differ in the concentration of electrolyte in the
half-cells.
• So, a concentration cell is an
electrochemical cell where the two
electrodes are the same material, the
electrolytes on the two half-cells involve the
same ions, but the electrolyte concentration
differs between the two half-cells.
• For example an electrochemical cell, where two
copper electrodes are submerged in two
copper(II) sulfate solutions, whose
concentrations are 0.05 M and 2.0 M, connected
through a salt bridge.
• This type of cell will generate a potential that can
be predicted by the Nernst equation. Both
electrodes undergo the same chemistry
(although the reaction proceeds in reverse at the
cathode)
• Cu2+(aq) + 2 e– → Cu(s) (at anode)
 Concentration Cells (II)
• Electrode concentration cells
– the electrodes themselves have
different compositions. This may be
due to.
• Different fugacity of gases involved in
electrode reactions (e.g., The H+ (aq)/H2 (g)
electrode).
• Different compositions of metal amalgams
in electrode materials.
Applications of Electrochemistry
• Measurement of activities and activity
coefficients.
• Electrochemical series.
• Equilibrium constants and
thermodynamic functions of cell
reactions
• the coating of objects with metals or metal
oxides through electrodeposition
 Cont..
• The generation of chemical energy
through photosynthesis is inherently an
electrochemical process
• production of metals like aluminum and
titanium from their ores
• Certain diabetes blood sugar meters
measure the amount of glucose in the
blood through its redox potential
 Cont..
• Electrochemistry has also important
applications in the food industry, like the
– assessment of food/package interactions,
– the analysis of milk composition,
– the characterization and the determination of
the freezing end-point of ice-cream mixes,
– the determination of free acidity in olive oil