Electro chemistry is that branch of chemistry which

deals with the inter-relationship between electrical

energy and chemical energy.
 Electrochemistry refers to the conversion of
chemical energy to electrical energy and vice
versa. It is basically the study of Production of
electricity from energy released during
spontaneous reaction and use of electrical
energy to bring about non-spontaneous
chemical transformation.
Electrochemical cell:- The device in which chemical energy is converted into electric
energy

Galvanic cell Voltaic cell is an electrochemical cell that makes use of chemical
reactions to generate electrical energy.
A galvanic cell is an electrochemical cell that converts the chemical energy of spontaneous
redox reactions into electrical energy. It is also known as a voltaic cell.
A Daniell cell is the best example of a galvanic cell which converts chemical
energy into electrical energy.

Electrolytic cell:- The chemical reaction occuring due to the passge of electric
current is called electrolysis and the device to carry out electrolysis is called an
electrolytic cell. In this cell electrical energy converted into chemical energy.
  The chemical reaction responsible for
 Daniel Cell-The cell that converts the chemical production of electric current is redox
energy liberated as a result of redox reaction to reaction
electrical energy is called a Daniel cell.  At the anode:
Oxidation ---------------- loss of electrons.
Zn --> Zn2+ + 2e-
At cathode,
Reduction -------------gain of electrons.
Cu2+ + 2e- --> Cu
o The net reaction of this cell is the sum of two half-cell
reactions.
Zn(s) + Cu2+ (aq) --> Zn2+ (aq) + Cu(s)

*It consists of two half cells contains a Zinc electrode

dipping in a molar solution of Zinc sulphate- Oxidation o The electrons in this cell moves from zinc anode to copper
takes place. It is known as anode(negative electrode). cathode through the wire connecting the two electrodes in
the external circuit and current flow from Cu to Zn rod
Copper electrode dipping in a molar solution of copper o A bulb placed within this circuit will glow and a voltmeter
sulphate solution-Reduction takes place. Known as connected within this circuit will show deflection.
cathode(+ve electrode). A salt bridge is placed between
the two beakers
 Salt bridge
In a Daniel cell a salt bridge is placed between the two beakers containing a solution of zinc sulfate
(ZnSO4) and a solution of copper (II) sulfate respectively. This provides a path for the movement of ions
from one beaker to the other in order to maintain electrical neutrality.
 The main advantage of suing this bridge is that it
prevents the arousal of potential difference (also called
liquid junction potential) when two solutions are in
contact with each other.
 It completes the electrical circuit as it connects the
 Salt bridge is an inverted U-tube like structure. electrolytes in the two half cells.

  It avoids the chances of diffusion of solutions between

The tube is filled with concentrated solution of an inert
electrolyte. the half cells.

  It maintains electrical neutrality by providing a path for

The electrolyte does not undergo any sort of chemical
reaction nor does it reacts with concentrated solution the movement of ions
in the two half cells.
 Most of the time salts like KCl, KNO3, NH4NO3 are
used as electrolyte.
 Salt bridge is constructed by filing the U-tube with a
mixture prepared by mixing agar-agar or gelatin with a
hot concentrated solution of the electrolyte.
How to Represent a Galvanic Cell?
1. An oxidation and reduction half-cells are represented by putting a single vertical
line between the symbols of metal acting as an electrode and the symbol of ion
present in the electrolyte in contact with metal. The vertical line represents the
phase boundary.
2. In the oxidation half cell, the reduced half is written on the left, whereas in the
reduction half cell, the reduced state is written on the right.
3. The molar concentration of the solution is written in the parenthesis after the
formula of the ion.

o Refer pg 136&137
Electrode potential:- A potential difference develop in between the electrode
and electrolyte is called electrode potential.

Loss electron - oxidation potential.

Gain electron - reduction potential.
*Oxidation potential and reduction potential are equal but opposite in sign.
*The reduction potential alone is called electrode potential.

Standard electrode potential:- The electrode potential under standard

conditions (298k, 1 atm pressure and 1M conc.) is called standard electrode
potential E0.
Standard Hydrogen electrode: It is a reference electrode
against which the electrode potentials of all
electrodes are measured. When Hydrogen gas at 1 atm-
pressure is adsorbed over platinum electrode dipped in
1M HCl at 25oC, it is standard hydrogen electrode and its
potential is, E0=±0 volt.
This apparatus consists of beaker having 1 molar HCL solution. In it, a sealed tube having
platinum wire is dipped. This platinum wire is further attached to platinum foil. This
complete cell is connected to the cell. Then continuously hydrogen gas maintained at 1
atm is bubbled. Platinum foil here acts as a site of reaction.
The Standard electrode potential of SHE is zero volt. This SHE can act as anode or cathode,
depending upon the half cell that is attached to it.
If it acts as cathode then following reaction occurs:
2H+ + 2e- --> H2 (Reduction Occurs)
Hydrogen Ion Hydrogen Gas
If it acts as anode then following reaction occur:
2H - 2e- --> 2H+ (Oxidation occurs)
Hydrogen Gas Hydrogen Ions
Applications:
•This is used to calculate the electrode potentials of various half cells.
electrode potential of Cu half-cell
Let us calculate the electrode potential of Zn half-cell.

We known Zinc is more reactive than hydrogen, that is it

has more tendency to loose electrons. Therefore, the
following reactions occur:
Refer Text book for electro chemical series
Electrochemical Series Important Points
Here are some important points to remember from this lesson.
•In the electrochemical series, the reduction potential of an element is
taken in reference to the hydrogen scale where Eo = zero. As per the
definition, the standard reduction potential of an element is described
as the measure of the tendency of an element to undergo reduction.
•The greater the reduction potential of an element the more easily it will
be reduced. Meanwhile, elements that have low reduction potential will
get oxidized much quickly and easily.
•Alternatively, elements who give up electrons without any difficulty
have negative or lower reduction potential. Elements that do not give
up electrons easily rather they accept electrons effortlessly have
positive) or higher reduction potential.
•Stronger reducing agents that have negative standard reduction
potential are usually situated above the hydrogen in the
electrochemical series. On the other hand, weaker reducing agents
with positive standard reduction potential are found below the hydrogen
in the series.
•As we move down in the group the reducing agent’s strength decreases
while the oxidizing agents’ strength increases.
•Lower reduction potential of an element implies that the element gets oxidized easily.
Oxidizing and Reducing Strengths
Electrochemical series helps us to identify a good
oxidizing agent or reducing agent. All the substance appearing
on the bottom of the electrochemical series are a good
oxidizing agent i.e., they have positive Value of standard
reduction potential whereas those appearing on the top of the
electrochemical series are a good reducing agent i.e., they
have a negative value of standard reduction potential. For
Example, F2 electrode with the standard reduction potential
value of +2.87 is a strong oxidizing agent and Li+ with
standard reduction potential value of -3.05 volts is a strong
reducing agent.
 Application of Electrochemical Series

2. Calculation of Standard emf Eo of

Electrochemical Cell
Eocell = Eocathode – Eoanode
Example:
For a reaction, 2Ag+ (aq) + Cd → 2Ag + Cd+2(aq)
The standard reduction potential given are: Ag+/ Ag =0.80 volt,
Cd+2/ Cd = -0.40 volt
From the reaction, we can see that Cd losses electron and Ag+
gains. Hence, oxidation half cell or anode is Cd.
Using the formula,
Eocell = Eocathode – Eoanode
=0.80 -(-0.40)
= 1.20 volt
3.Reactivity of metals –The metal having a lower value of standard reduction
potential is more reactive
4. Predicting the Feasibility of Redox Reaction
Any redox reaction would occur spontaneously if the free energy change (ΔG0) is
negative. The free energy is related to cell emf in the following manner:
ΔGo = -nFEo
Where n is the number of electrons involved, F is the Faraday constant and E o is the
cell emf.
•ΔGo can be negative if Eo is positive.
•When Eo is positive, the cell reaction is spontaneous and serves as a source of electrical
energy.
For example, let us find out whether we can store copper sulphate solution in a nickel vessel or not.
Given: Ni+2/ Ni = -0.25 volt, Cu+2/Cu = 0.34 volt
Ni + CuSO4 → NiSO4 + Cu
We want to see whether Ni metal will displace copper from copper sulphate solution to give NiSO4 by
undergoing oxidation reaction.
Ni(s) + Cu+2(aq) → Ni+2(aq) + Cu(s)
From the above reaction, it is clear the oxidation terminal will be Ni electrode.
Eocell = Eocathode – Eoanode
= 0.34 – (-0.25)
= 0.59 volt
As the emf comes out to be positive, it implies copper sulphate reacts when placed in a nickel vessel and hence
cannot be stored in it.
4.Displacement of metals from salt solution:

5Displacement of hydrogen by metals from dil acids

6.Predicting the Product of Electrolysis

In case, two or more types of positive and negative ions are present in solution,
during electrolysis certain metal ions are discharged or liberated at the electrodes in
preference to others. In general, in such competition, the ion which is a stronger
oxidizing agent (high value of standard reduction potential) is discharged first at the
cathode.
Thus, when an aqueous solution of NaCl containing Na+, Cl-, H+ and OH- ions is
electrolysed, H+ ion is preferentially deposited at cathode (reduction) instead of Na+
being reduced, this is because reduction potential of hydrogen (0.00 volt) is higher
than the reduction potential of sodium (-2.71 volt). At the anode where oxidation takes
place, the anion that has lower reduction potential will be oxidized. Therefore, OH- with
standard reduction potential 0.40 volt will be oxidized in preference to Cl- with
standard reduction potential of 1.36 volt.
Factors on which electrode potential
depends:
Concentration of ions in solution.
Nature of metal and its ions.
Temperature

Copy down up to slide 22

 Nernst Equation

Nernst gave a relationship between electrode potentials and the concentration of

electrolyte solutions known as Nernst equation.
For a general electrode reaction,
Mn+(aq) + ne¯ ——-> M(s)
the Nernst equation is

Where E (Mn+|M) = Electrode potential

Eø (Mn+|M) = Standard Electrode potential
R= Gas constant
T =Temperature
F = Faraday of electricity
n= Number of electrons gained during the electrode reaction.
[Mn+ (aq)] = Molar concentration of ions
[M] = Molar concentration of metal
Substituting the values of R (8.314 JK-1 mol-1), T
(298 K) and F (96500 coulombs), the Nernst
equation at 25°C becomes

The concentration of the solid phase, [M(s)] is

taken to be unity.
The above equation may also be written as:
Question 5. The standard electrode potential for
Daniell cell is 1.1 V. Calculate the standard Gibbs
Energy for the reaction:
Question 1. Represent the cell in which the following reaction takes
place: