Electrochemical Cells
An electrochemical cell is a device where
chemical reactions either use or generate
electric current. Electrochemical cells
which generate an electric current are
called voltaic cells or galvanic cells
TWO TYPES of
ELECTROCHEMICAL CELLS
1.Voltaic (similar to a battery)
2.Electrolytic (similar to alternator in
cars)
Galvanic Cells
Chemical Energy is converted to
Electrical Energy.
A spontaneous redox reaction that is
used to generate a voltage
(Electricity)
You can separate the reactants
(oxidizing and reducing agents) and
force the electrons to travel through
a wire.
Electrolytic Cell
Reaction cannot occur spontaneously, so
electricity is used to force the reaction to
occur. In other words, electrical energy is
converted to chemical energy (opposite of
voltaic cell).
When electricity is used to force a
chemical reaction to occur, the process is
called electrolysis.
Difference b/w Galvanic cell
and Electrolytic Cell
Galvanic cell Electrolytic Cell
Chemical energy Electric energy
converted into converted into
Electric energy Chemical energy
It is based on redox
It is based on redox reaction which is non-
reaction which is spontaneous
spontaneous
i.e reaction occurs its own
Galvanic cell
Voltmeter
Salt Bridge
Galvanic cell
Anode – The electrode where oxidation
occurs
Cathode – The electrode where reduction
occurs.
Salt Bridge – prevents build up of ions on
one side of the cell and balances the
charge.
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.
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 an electrolyte
e.g KCl,NH4NO3 etc it act as bridge by
connecting two half cells
-----------Helps in
To completing the electric circuit
To prevent mixing of solution of two half cells.
To help maintain electric neutrality
Cell Diagrams
A voltaic/electrochemical cell may be
represented by the following
ANODE CATHODE
Zn(s) Zn2+ (1M) Cu2+ (1M) Cu(s)
The single lines represent phase
boundaries (e.g. solid anode to 1M liquid)
and the double lines represent the salt
bridge.
Standard conditions are 25oC,1 atm and
1M solutions.
Galvanic Cell: How it works
1. Electrons are produced at the zinc rod according to the oxidation half
reaction
Zn (s) Æ Zn2+(aq) + 2e-
Because it is oxidized, the zinc rod is the anode.
2. The electrons leave the zinc anode and pass through the wire to the
copper rod, thus creating an electrical current. The voltmeter measure the
voltage.
3. Electrons enter the copper rod and interact with copper ions in solution.
There the following reductions half reaction occurs.
Cu2+(aq) + 2e- Æ Cu(s)
Because copper ions are reduced at the copper rod, the copper rod is the
cathode.
4. The salt bridge connects the two containers. It provides a path for a flow
of ions between the two beakers in order to maintain neutrality in the
solutions. The two half reactions can be summed to show the overall
reactions:
Zn (s) Æ Zn2+(aq) + 2e-
Cu2+(aq) + 2e- Æ Cu(s)
Zn(s) + Cu2+(aq) Æ Zn2+(aq) + Cu(s)
The Cell Potential
The potential is the ability of a cell to do
electrical work. ξcell is measured in volts.
1 volt = 1 joule/ coulomb A coulomb is
the quantity of charge passing in 1 second
when the current is 1 ampere
1C = 1A•s
Standard Reduction Potentials
Most reference tables for electrochemistry are
written as reductions in a half-reaction format,
with the most negative reduction on the top and
the most positive on the bottom. By definition, all
half reductions are compared to the hydrogen half
reaction that has the standard value of 0.00 V
under standard conditions.
Standard state: 25oC, 1 atm, 1(M)
2H+ + 2 e- Æ H2 ξ0cell = 0.00
All other reduction potentials are based on this
zero point.
Standard Reduction
Potentials
Strongest
Oxidizing
Agents/
Easily
Reduced
Strongest
Reducing
Agents/
Easily
Oxidized
Rules for Using Standard Reduction
Potentials
1) Read the half reactions as written
2) The more POSITIVE the reduction potential,
the greater the tendency is for the
substance to be reduced and therefore the
better the oxidizing agent
(keep the half-reaction with the more POSITIVE
cell potential as written in the table—that is the
reduction reaction)
3) The half-cell reactions ARE reversible. IF
you need to reverse, you MUST change the
sign of the ξ0cell.
4) If you change the stoichiometric
coefficients, ξ0cell remains the same
Rules for Using Standard Reduction
Potentials
5) Under standard state conditions: any
species on the LEFT of a given half-
reaction will react spontaneously with a
species that is on the RIGHT and ABOVE
it
6) The most positive values for ξcell mean
that they are the strongest OXIDIZING
AGENTS and therefore are themselves
reduced.
7) The most negative values for ξcell mean
that they are the strongest REDUCING
AGENTS and therefore are themselves
oxidized.
The Total Cell Potential
The total cell potential is the sum of the
half-cell potentials
ξ0cell. = ξ0 ox + ξ0red
(+) ξ0cell means the reaction will happen
spontaneously
(-) ξ0cell means the reaction will not
happen.
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.
Nernst 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.
Nernst Equation
The general Nernst equation
correlates the Gibb's Free Energy DG
and the EMF of a chemical system
known as the galvanic cell.
Ecell = E 0cell - (RT/nF)lnK
Nernst Equation
Remember that
ΔG = ΔG° + RT ln K
This means
−nFE = −nFE° + RT ln K
Dividing both sides by −nF, we get the
Nernst equation: RT
E = E° − ln K
nF
2.303 RT
E = E° − logK
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 K
n
Nernst Equation
For a general reduction reaction,
M n + + n e − → M(s)
The Nernst equation can be written as
RT 1
E =E0n+ -2.303 log
Mn+ /M M /M nF [Mn+]
o 0.059 1
E n+ =E n+ - log (At 298K)
M /M M /M n ⎡Mn+⎤
⎣ ⎦
Where n = Number of electrons involved
[Mn+] = molar concentrations at 298K
Illustrative Example
Calculate the electrode potential at a copper electrode
dipped in a 0.1M solution of copper sulphate at 250C . The
standard potential of Cu2+/Cu system is 0.34 V at 298 K.
Solution:
Cu2+ + 2e- Æ Cu
0.0591
We know that E = E0 + log10 [Cu2 + ]
Cu2 + / Cu Cu2 + / Cu n
Putting the values of E0red = 0.34 V,n = 2 and [Cu+2 ] = 0.1 M
0.0591
Ered = 0.34 + log10[0.1]
2
= 0.34 + 0.02955 × (−1)
= 0.31045 volt
Calculate the EMF of the cell
Zn(s) | Zn2+ || Cu2+ | Cu(s)
The cell reaction
Zn(s) + Cu2+(aq) Æ Zn2+(aq) + Cu(s)
The EMF of the cell is the algebraic sum of the actual potential of the two
electrodes
0.0591
We know that E = E0 + log10 [Cu2 + ]
Cu2 + / Cu Cu2 + / Cu n
0.0591
and E = E0 − log10 [Zn2 + ]
Zn / Zn2 + Zn / Zn2 + n
0.0591 ⎡ Zn2 + ⎤
and E cell = E 0 + E0 − log10 ⎢ ⎥
2+
Zn / Zn Cu2 + / Cu n ⎡ Cu2 + ⎤
⎣ ⎦
Determining ξ0cell
Example:
What will be the overall reaction and the ξocell-
total if Br2 is added to a solution containing I2 at
25oC? Assume all species are in their standard
states.
Half reactions (as found in a standard table):
I2 (s) + 2 e-Æ 2I– (aq) ξocell = 0.53 V
Br2 (l) + 2e-Æ 2Br- (aq) ξored = 1.07 V
Using the standard reduction potentials, the fact that Br2
has the more positive potential indicates that the Br2
will be reduced. So, change the sign on the oxidation
reaction and reverse it so that it is written as an
oxidation.
Br2 (l) + 2e- Æ 2Br- (aq) ξored = 1.07 V
2I–(aq) Æ I2 (s) + 2 e- ξoox = -0.53 V
Add the reactions:
Br2 (l) + 2e- Æ 2Br-(aq) ξored = 1.07 V
2I– (aq) Æ I2 (s)+2 e- ξoox = -0.53 V
Br2 (l)+2I–(aq) Æ 2Br - (aq) + I2(s)
ξocell-total= +0.54 V
Sample Problem
What will be the overall reaction and the
ξocell-total if Zn(s), a 1M solution of Zn2+,
Cu(s) and a 1M solutions of Cu2+ are
reacted?
