ELECTROCHEMISTRY

DR. ASHIMA SRIVASTAVA

DEPT OF CHEMISTRY

JSSATE, NOIDA
INTRODUCTION

Electrical energy plays a significant role in our daily life. Many of the chemical transformations are associated with
electrical energy.
There are many applications of this in every day life: Few examples of the applications of electrochemistry:
• Batteries/ Electrochemical cells (eg. redox reaction between zinc and copper sulphate results in the liberation of
electrical energy)
• Control of corrosion,
• Metallurgy and
• Electrolysis ( For example water decomposes into hydrogen and oxygen gases when electrical energy is passed through
it in the presence of small amount of acid or base.
Thus there is a definite relationship between electrical energy and chemical energy.
The branch of chemistry which deals with the study of relationship between electrical energy and chemical energy and the
interconversion of one form into another is called electrochemistry.
ELECTRODE POTENTIAL
The natural tendency of a metal to undergo oxidation (to lose electrons) or
reduction (to accept electrons) reaction when it is in contact with the
aqueous solution of its own ions is expressed in terms of electrode potential.
EXPLANATION OF THE ORIGIN OF SINGLE ELECTRODE POTENTIAL

When a metal electrode is in contact with a solution of its own ions, one of the following two chemical
reactions take place.
(i) Metal passes into the solution as metal ions leaving behind the electrons on the metal as follows
M→ Mn+ + ne- (oxidation) (Dissolution)
Thus, the metal acquires the –ve charge.
(ii) Positive metal ions from the solution deposits on the metal electrode as metal atoms as follows
Mn+ + ne- → M (reduction) (Deposition)
Thus, the metal acquires the +ve charge.
EXPLANATION OF THE ORIGIN OF SINGLE
ELECTRODE POTENTIAL

The tendency of oxidation results in the dissolution of the metal leaving the electrons to accumulate
on the solid metal thereby making the metal acquire negative charge compared to the solution.
In contrast, the tendency of reduction results in the development of positive charge on the metal
with respect to the solution as the electrons of the metal are utilized by another metal ion depositing on
it.

Consequently, as the metal acquires a negative or positive charge it attracts the oppositely charged ions
from the solution and double layer called Helmholtz electrical double layer is established at the metal-
solution interface (Fig).
EXPLANATION OF THE ORIGIN OF SINGLE
ELECTRODE POTENTIAL
If the dissolution reaction is faster than the deposition reaction, the liberated e-s accumulates on the
surface of metal making it –vely charged. This –vely charged electrode surface attracts a layer of
+vely charged ions at the interface. Thus a double layer called Helmholtz electrical double layer is
formed at the metal solution interface.
Similarly, if the deposition reaction is faster than the dissolution reaction, a layer of +ve charges
formed on the surface attracts a layer of –ve charges, develops an electrical double layer.
Across this double layer, develops a potential called single electrode potential.
HELMHOLTZ ELECTRICAL DOUBLE LAYER
EXPLANATION OF THE ORIGIN OF SINGLE
ELECTRODE POTENTIAL
Because of the formation of this layer, potential difference is set up between the metal and its solution
It prevents the further exchange of ions between the two.
At equilibrium. This difference becomes constant and is known as the Electrode potential of the metal.
It is expressed in volts. The value of electrode potential depends upon (i) the nature of metal, (ii) temperature and (iii) the
concentration of electrolyte.
The potential difference for oxidation reaction is called oxidation potential [ E(M/ Mn+)] and that of reduction is called
reduction potential [E(Mn+/M)]. According to the present convention, the half reactions are always written as reduction half
reactions and their potentials are represented by reduction potentials.

For any system its oxidation and reduction potentials are numerically same with the opposite sign, i.e. [ E(M/ M n+)] = -
[E(Mn+/M)].
STANDARD ELECTRODE POTENTIAL

Standard electrode potential: Standard electrode potential is the potential developed when the pure
metal electrode is in contact with a solution of its ions of unit concentration (1M) at 298K. It is
denoted by E°.
The reduction potential of electrode when the concentration of the ions in solution is 1 mol L-1 and
temperature 298 K is called standard reduction potential and is represented by E°red.
MEASUREMENT OF STANDARD ELECTRODE POTENTIAL

The absolute value of potential of a single electrode cannot be determined because a half cell by itself
cannot cause the movement of charges (flow of electrons; as neither oxidation nor reduction can take
place independently).
It is possible to determine the potential difference between the two electrodes with the help of
potentiometer.

It can be determined by combining the electrode with the reference electrode whose electrode
potential is exactly known or arbitrarily fixed.
The common reference electrode used for this purpose is standard hydrogen electrode (SHE) or
normal hydrogen electrode (NHE) whose electrode potential is arbitrarily taken to be zero.
STANDARD HYDROGEN ELECTRODE (SHE)

Standard hydrogen electrode (SHE) is a primary

reference electrode. It has a cylindrical glass vessel
dipped in 1M H+ ions solution. A platinum wire is fitted
inside the glass vessel. Hydrogen gas is bubbled in it at
1 atmospheric pressure.
SHE can act as anode as well as cathode as per
need and can be represented as:
Pt, ½ H2(1 atm)/ H+(1M) or
H+(1M)/ ½ H2(1 atm), Pt respectively.
At anode: H2(g) → 2H+(aq) + 2e-
At cathode: 2H+(aq)+ 2e- → H2(g)
MEASUREMENT OF STANDARD REDUCTION POTENTIAL OF COPPER BY COMBINING WITH SHE

To measure the electrode potential of

any electrode, it is connected with SHE
and the system acts as a cell. By
international agreement the standard
hydrogen electrode is arbitrarily
assigned a potential of exactly zero
volt, the EMF of the cell will be the
electrode potential of the electrode.
Let us explain it by taking an example.
Suppose we want to measure the
electrode potential of Cu2+/Cu
electrode. The electrode is connected
with the SHE as shown in the fig.
The two half reactions are represented as:
H2 (g) → 2H+ + 2e- (Oxidation at anode)
Cu2+ + 2e- → Cu(s) (Reduction at cathode)
The EMF of the cell is found to be 0.34V. therefore the reduction potential of copper electrode
is taken as 0.34V (as copper ions are being reduced) and oxidation potential as -0.34V. The
negative sign of oxidation potential indicates that the oxidation at this electrode is not a
spontaneous process.
The electrode potential of the electrode determined relative to SHE under standard conditions
(1 molar concentration of ions at 298 K temperature and 1 atmospheric pressure) is called
standard electrode potential.
ELECTROCHEMICAL CELL (GALVANIC CELL)

Electrochemical cell or galvanic cell is a device which converts free energy of a chemical
process into electrical energy.
It is made up of two half cells. One is oxidation or anodic half cell and the other is reduction or
cathodic half cell.
DANIEL CELL
Daniel cell is an example of galvanic cell having zinc and copper electrodes (Fig).
The oxidation half cell consists of zinc rod dipped in ZnSO4 solution and
the reduction half cell consists of copper rod dipped in CuSO4 solution.
Both the half cells are connected externally by metallic conductor (wire) and internally by a
bent glass tube having saturated solution of a strong electrolyte (KCl) called salt bridge (it
allows the flow of the current by completing the circuit and maintains electrical neutrality).
 DANIEL CELL

As the circuit is complete,

the flow of electrons will
be externally from anode
to cathode. The flow of
current is due to the
difference in electrode
potentials of both the
electrodes. The EMF of
the cell is measured in
volts with the help of
potentiometer
The chemical reactions taking place at both the electrodes can be written as follows:
At anode: Zn(s) → Zn2+(aq) + 2e- (oxidation)
At cathode: Cu2+(aq) + 2e-→ Cu(s) (reduction)
The overall reaction is Zn(s)+ Cu2+(aq) → Zn2+(aq) + Cu(s)
Representation of Galvanic cell
Oxidation half cell (anode) is represented as Zn/ ZnSO4(1M)
Reduction half cell (cathode) is represented as CuSO4(1M)/ Cu
Galvanic cell is represented by writing the cathode on the right hand side and anode on the left hand
side. The two vertical bars are put between the two half cells which indicate the salt bridge.
Zn-Cu galvanic cell can be represented as Zn/ ZnSO4(1M) CuSO4(1M)/ Cu
(-) (+)
DIFFERENCE BETWEEN ELECTROCHEMICAL CELL AND ELECTROLYTIC CELL
ELECTROCHEMICAL SERIES
SIGNIFICANCE OF ELECTROCHEMICAL SERIES

(i) To calculate the standard potential of the cell

The potential of the cell (EMF) formed from any two electrodes can be calculated by
electrochemical series.
E°cell = [Reduction potential of reduction half cell-Reduction potential of oxidation half cell]
or E°cell = E°cathode- E°anode
Example
Consider the following cell reaction: Cu + Ag+ → Cu2+ + Ag
From electrochemical series Cu2+ + 2e- → Cu E° = +0.34V
Ag + e → Ag
+ - E° = +0.80V

E°cell = E°cathode- E°anode = 0.80 - 0.34 = 0.46 V

(ii) Predicting the spontaneity or feasibility of the cell reaction
If the EMF of the cell as calculated above is positive, the cell reaction is spontaneous.
If E°cell is negative, the cell reaction would not be feasible.
(iii) To predict whether a metal will react with acid to give H2 gas
The metals which are placed above hydrogen in the electrochemical series like Li, Zn, Fe, etc. have
great tendency to oxidize and hence can displace hydrogen from acids.
The metals which are below hydrogen in electrochemical series like Cu, Hg, Au, Pt, etc., do not evolve
hydrogen from dilute acids.
(iv) Reducing power of metals
Reducing nature depends on the tendency of losing electron. More the negative reduction potential,
more is the tendency to lose electron. Thus, reducing nature decreases from top to bottom in the
electrochemical series. Sodium is a stronger reducing agent than zinc and zinc is a stronger reducing
agent than iron.

Element Na Zn Fe

Reduction potential -2.71 -0.76 -0.44

----------------------------------------->
Reducing nature decreases
(v) Oxidising nature of non-metals
Oxidising nature depends on the tendency to accept electron. More the value of reduction potential,
higher is the tendency to accept electron. Thus, oxidising nature increases from top to bottom in the
electrochemical series. The strength of an oxidising agent increases as the value of reduction potential
becomes more and more positive.
F2 is a stronger oxidant than Cl2, Br2 and I2.

Element I2 Br2 Cl2 F2

Reduction +0.53 +1.06 +1.36 +2.85

potential
(vi) Extraction of metals
A more electropositive metal can displace a less electropositive metal from its salt's solution. This
principle is applied for the extraction of Ag and Au by cyanide process. Silver from the solution
containing sodium argento cyanide, NaAg(CN)2, can be obtained by the addition of zinc as it is more
electro-positive than Ag.
2NaAg(CN)2 + Zn → Na2Zn(CN)4 + 2Ag
 EMF OF GALVANIC CELL
As discussed earlier that electrochemical or galvanic cell consists of two half-cells. The potentials of
these half-cells are always different. When the circuit is completed the loss of electrons occurs at the
electrode having lower reduction potential whereas the gain of electrons occurs at the electrode with
higher electrode potential.
Flow of electrons→
Anode <==============> Cathode
←Flow of current
The difference in potentials of the two half-cells is known as the electromotive force (EMF) of the cell
or cell potential. Mathematically, it can be expressed as
E°Cell = Standard Reduction potential of cathode – Standard Reduction potential of anode
= E°Cathode - E°Anode
= E°right - E°left
EMF of the cell may be defined as the potential difference between the two terminals of the cell when
no current is flowing in the circuit. It is measured with the help of potentiometer or vacuum tube
voltmeter.
NERNST EQUATION FOR ELECTRODE POTENTIAL AND CELL POTENTIAL

For Electrode Consider a general cell reaction

The electrode potential and the emf Mn+(aq) + ne- → M(s)
of the cell depend upon the nature of The decrease in the Gibbs free energy -∆G is given by the
the electrode, temperature and the equation
activities (concentrations) of the ions
in solution. The variation of electrode
and cell potentials with concentration
of ions in solution can be obtained
from thermodynamic considerations.
Where ∆Go refers to free energy change for the reaction
when the various reactants and products are present at
standard conditions, aproducts and areactants represent the
activities of the reactants and products under a given set
of conditions, R is the gas constant and T is temperature.
APPLICATIONS OF NERNST EQUATION

(i)Calculation of the EMF or potential of the Cell

Example 1:
Calculate the potential of the cell:
Cr/Cr3+(0.1M)//Fe2+(0.01)/Fe
Given: E° Cr / Cr3+ = 0.74V
E° Fe2+/Fe = -0.44V
Example 2: Calculate the e.m.f of the cell.
Mg(s)|Mg2+(0.2M)||Ag+(1×10-3M)|Ag
EoAg+/Ag = +0.8 V,
EoMg2+/Mg = -2.37 V
What will be the effect on e.m.f. if concentration of Mg2+ ion is
decreased to 0.1 M?
(i) Calculation of the Equilibrium Constant
Nernst equation can be used to find out the equilibrium constant of the given cell.
Consider a reaction at equilibrium
aA + bB → cC + dD
At equilibrium, the cell reaction is balanced, there is no potential difference between the two
electrodes and cell potential becomes zero. The Nernst equation can now be written as