Module 1
Module 1
Electrochemistry
In oxidation: a species loses one or more electrons resulting in an increase in its oxidation number.
M Mn+ + ne-
In reduction: the species gains one or more electrons; there is a decrease in oxidation number.
Mn+ + ne- M
A reduction process necessarily accompanies an oxidation process since electrons can be lost by a
species only when there is a counterpart to receive them. Redox reaction forms the basis of
electrochemical cells. An electrochemical cell consists of two electrodes which when connected by a
metallic wire an electric current flow as a result of a spontaneous redox reaction.
Each electrode usually consists of a metal in contact with a solution of its own ion. Since a cell is a
combination of two electrodes, each electrode is referred to as a single electrode or half- cell. A
potential called the electrode potential arises at the electrode in contact with its ionic solution. The
difference between the potentials of the two half- cells constitutes the electromotive force (emf) of
the cell.
Emf: The potential difference between the two electrodes of a galvanic cell which causes the flow of
current from one electrode (higher potential) to the other (lower potential) is called the electromotive
force of the cell or the cell potential.
Galvanic cell:
A typical egs of galvanic cell is Daniel cell, which is illustrated in the fig.
construction and working: It consists of two beakers one of which contains zinc rod immersed in
zinc sulphate solution and the other one contains copper rod in copper sulphate solution. A salt
bridge connects the solutions of two beakers. The zinc and copper rods are connected externally
through voltmeter by using a wire. On completing the circuit the following changes are observed
1. zinc rod starts dissolving.
2. copper gets deposited on copper rod
3. zinc sulphate solution becomes more concentrated with respect to Zn2+ ions
4. copper sulphate solution becomes more dilute with respect to Cu2+
5. Migration of ions takes place in solution.
The above observations are explained by the following oxidation-reduction reactions taking place at
anode and cathode respectively.
By convention, the electrode at which oxidation occurs is anode and the electrode where reduction
occurs is cathode. In a galvanic cell anode is negative and cathode is positive. The flow of electrons
is from zinc electrode to copper electrode. Hence the flow of conventional current is from copper
electrode to zinc electrode.
The net redox reaction, called electrochemical reaction, is the cause for production of electricity. The
net reaction is the sum of two electrode reactions and is called cell reaction. Each electrode reaction
is called as half-cell reaction.
Salt bridge: It is easy to construct. A thin paste of agar-agar in water is added to boiling water
containing a little of an electrolyte like KCl or KNO 3. It is then drawn preferably into U- tube and
cooled.
Function: The salt bridge not only connects the two half-cells internally. It maintains the electrical
neutrallity of both the half cells. And is used to complet the circuit.
Note: 1. When one of the solutions contains soluble silver, mercurous or thallous salt, the KCl salt
bridge cannot be employed.
2. KCl or KNO3 is used because the ions have almost same migration velocities.
i.e. Zn/Zn2+(1M)//Cu2+(1M)/Cu
Single vertical line / a phase boundary between metal and its solution.
Sign conventions:
The half cell at which oxidation (Anode) occurs is always written on the left side and The half cell
at which reduction (cathode) occurs is always written on the right side
1. The concentration of solutions, pressure of gases and physical state of the solid or liquid
involved are indicated by suitable signs within brackets.
2. If the arrow is in the forward direction ie the electrons are flowing from anode to cathode the
emf of the cell is positive. If the arrow mark is in backward direction the electrons flow from
cathode to anode the emf of the cell is negative.
3. Anode to be represented as M/Mn+and cathode in the form Mn+/M.
4. The term electrode potential refers the reduction potential. It is represented as E Mn+/M
5. The potential difference between the two electrodes, called EMF (Electro Motive Force), is
stated in volts. Ex: Ecell = Ecathode -Eanode.
= EoR - EoL
Electrochemical series: Metals are arranged in the increasing order of their standard reduction
potential with respect to hydrogen scale.
Nernst Equation
The equation for single electrode potential was derived by Nernst and is called Nernst Equation.
It is a thermodynamic equation, which gives the relationship between electrode potential and
concentration of the substance involved.
Consider a general red-ox reaction: Mn++ ne- M ----(1)
Free energy change for a reversible reaction ( Vant Hoff equation ) is given by
G = G0 + RT lnK ----(2)
Decrease in free energy represents the maximum work done
G = Wmax
Wmax = No moles electrons charge per mole electron potential
Wmax = n F E
. . G = - nEF and G0= - nE0F
.
----(3)
(where, G= free energy change, G = standard free energy change, E=electrode potential;
0
Where K is the Equilibrium constant of reaction it is equal to the concentration of the products to
the concentration of reactants, i.e.
[Products] [M ]
K= ----(4)
[Reactants] [ M n ]
by substituting Eqs.(3) and (4) in Eq.(2)
[M ]
-nEF = -nE0F+ RT ln
[ M n ]
RT [M ]
E= E ln
0
Divide by nF Then,
nF [ M n ]
RT 1
E= E ln
0
(since [M]=1)
nF [ M n ]
2.303 RT
E= E
0
log M n
nF
(R is a gas constant = 8.314 J K -1 mol-1; T= temperature in absolute scale (298K); F is Faraday
= 96,500 C mol-1)
0.0591
E= E
0
log M n at 298 K
n
The cell potential may be calculated by using the above relation
ECell = Ecathode - EAnode
ECell = {Eo cathode + 0.0591 log [Mn+]cathode } - {Eo Anode + 0.0591 log [Mn+] Anode }
n n
ECell = EoCell + 0.0591 log [Mn+]cathode
n [Mn+] Anode
2.303 RT [ M n ]cathode
Ecell = E cell
0
OR log
nF [ M n ] anode
The electrode potentials vary with temperature and the concentration of metal ions.
The term Electrode Potential (E) refers to the Reduction Potential, also depends upon the
nature of the metal.
0.0591
E= E 0
log M n at 298 K is the reduction potential
n
Types of electrodes:
Metal-metal ion electrode: This type of electrode consists of a metal in contact with a solution of its
own ions.
Egs: 1.Zinc rod in a solution of zinc sulphate.
2. Copper rod in a solution of copper sulphate.
Metal-metal salt ion electrode: Here a metal is dipped in its insoluble salt that is in contact with a
solution containing the anion of the salt
Egs 1. Calomel electrode Hg / Hg2Cl2 (s) /Cl-
2. Silver-Silver chloride electrode Ag / AgCl (s) / Cl-
Gas electrode: Here a gas is in contact with an inert metal that is dipped in an ionic solution of the
gas molecule.
Egs: SHE, Pt / H2 (1atm) / H+ (1M)
Amalgam electrode: Amalgam electrode is similar to Metal-metal ion electrode except for the fact
that in an Amalgam electrode, Metal- Amalgam is in contact with a solution containing its own metal
ions (or)
Amalgam of a metal in contact with solution containing its own metal ions. Highly active metals are
used in the form of amalgams, since the activity of metal can be varied.
Ex. Zinc in mercury in contact with zinc sulphate solution [Zn(Hg) +/ Zn2+]
Ex. Lead Amalgam electrode (Pb(Hg) / Pb2+)
Oxidation-reduction electrode: This type of electrode consists of an inert electrode (Pt or Au)
immersed in a mixed solution containing both the oxidized and reduced forms of a molecule or ion.
Egs: Pt / Fe2+: Fe3+
Pt / Sn2+: Sn4+
Ion-selective electrode: Possesses the ability to respond only to certain specific ions, thereby
developing potential w.r.t that species only in a mixture and ignoring the other ions totally. In other
words, the potential developed by an ion-selective electrode depends only on the concentration of
species or ions of interest. For egs. Glass electrode which responds to hydrogen ions
(Ag/AgCl/HCl/Glass).
Reference electrodes
Reference electrodes are the electrodes whose potential is known and with reference to those, the
electrode potential of any other electrode can be measured
There are 2 types of reference electrodes
1) Primary reference electrode
2) Secondary reference electrode
Primary reference electrode: Standard hydrogen electrode (SHE) is the primary reference electrode
and its electrode potential taken as zero at all temperature.
Secondary reference electrodes: These are the electrodes having constant electrode potential value
and their potential is known with respect to SHE, hence they are called as secondary reference
electrodes.
Eg 1. calomel electrode 2. Ag-AgCl electrode.
Calomel electrode: The calomel electrode consists of a glass vessel containing a layer of Hg over
which a paste of Hg, Hg 2Cl2 is placed. Above this there is a solution of KCl. A platinum wire is
dipped into the Hg layer provides external electrical connection. A salt bridge is used to couple with
other half-cell.
The potential of the calomel electrode depends on the concentration of KCl used.
The electrode potential decreases with increase in the concentration of chloride ions.
For 0.1N KCl E= 0.33V
1N KCl E= 0.28V
saturated KCl E = 0.24V
The potential of the Ag-AgCl electrode depends on the concentration of KCl used.
The electrode potential decreases with increase in the concentration of chloride ions.
For 0.1N KCl E= 0.290V
1N KCl E= 0.223V
Saturated KCl E = 0.199 V
Application:
1. As a secondary reference electrode in place of calomel electrode
2. In determining whether the potential distribution is uniform or not in ship hulls and old
pipelines protected by cathodic protection.
Ion-selective electrode: Possesses the ability to respond only to certain specific ions, thereby
developing potential w.r.t that species only in a mixture and ignoring the other ions totally. In other
words, the potential developed by an ion-selective electrode depends only on the concentration of
species or ions of interest. For egs. Glass membrane is only H+ ions selective.
1. Concentration of cations egs. H+ , Li+, Na+, K+, NH4+, Ag+, Pb2+, Cd2+, hardness (Ca2+, Mg2+) and
anions egs. Halide ions, NO3-, CN-, S2- etc.
Glass electrode:
Construction: A glass electrode consists of a long glass tube with a thin walled bulb at one end,
special glass of low melting point and high electrical conductance is used for the purpose [corning
glass 22% Na2O, 6% CaO and 72% SiO2]. The bulb is filled with 0.1M HCl.
A silver-silver chloride electrode dipped in the solution provides an electrical contact. The bulb of
the glass electrode is dipped into any solution containing hydrogen ions. If the hydrogen ion
concentrations of the solution inside and outside the glass membrane are different then the potential
develops across the glass membrane. Glass electrode can be represented as
Advantages
This electrode can be used to determine PH in the range 0-9, with special type of glass even up to
12 can be calculated.
It can be used even in the case of strong oxidising agents.
The equilibrium is reached quickly.
It is simple to operate, hence extensively used in various laboratories.
Limitations
The glass membrane though it is very thin, it offers high resistance. Therefore ordinary
potentiometers cannot be used, hence it is necessary to use electronic potentiometers.
Theoritically Eb= 0, when C1 = C2. However a small additional potential is developed i,e Easymmetric
Since C2 is constant, then
Eb = L + 0.0591/n log C1 Where L = -0.0591/n log C2
Overall potiential of the electrode also includes, internal reference electrode potiential
.. EG= Eb + EAg/AgCl + Easymmetric
Cell representation:-
Primary cells: In which the cell reaction is irreversible and are not rechargeable and once
discharged have no further electrical use. Ex: Dry cell
Secondary cells: In which the cell reaction is reversible and are rechargeable cells. After
discharging it is recharged to its original condition by passing current through them and we can reuse
it again Ex: Lead acid battery, Ni-Cd cells etc
Concentration Cells:
Concentration cell is a type of galvanic cell in which electrode & electrolyte present in
both the half cells are same but only the concentration of metal or electrolyte is different.
Two types of concentration cells.
Electrolyte concentration cells: It is a type of galvanic cell in which electrode & electrolyte
present in both the half cells are same but only the concentration of electrolyte is different.
Electrode concentration cells: It is a type of galvanic cell in which electrode & electrolyte
present in both the half cells are same but only the concentration of electrode is different.
Electrodes with different concentration of metal are generally obtained by dissolving different
amount of metal in liquid mercury called as amalgam electrode.
2+
For example : Pb(0.5 M) (Hg) Pb Pb (0.1 M) (Hg)
Electrode containing higher concentration of metal will have lower potential, acts as anode.
n+ -
M(C1) (Hg) M + ne
Electrode containing lower concentration of metal will have higher potential, acts as cathode.
n+ -
M + ne M (C2) (Hg)
In these cells, the potential difference is developed between two like electrodes at different
concentrations dipped in the same solution of the electrolyte.
Amalgams of the same metal Cadmium of two different concentrations are immersed in CdSO4
solution of same concentration.
Two hydrogen electrodes at different partial pressure of hydrogen in the same solution of hydrogen
ions constitute a cell of this type.
The cell reaction is spontaneous when C2> C1. As the reaction proceeds, the solution which was
originally more concentrated (C2) becomes dilute and the solution which was originally dilute (C1)
becomes more concentrated. After some times, the concentration of solution at both the half cells
becomes equal i.e., C1 = C2 and the emf of the cell becomes zero. The cell is in equilibrium. Hence in
a concentration cell, the emf depends on the ratio of concentrations of the solutions, as the ratio
changes and the ratio is 1 i.e. C2 / C1 = 1, emf is zero.
Case 3. When the ratio , C2 /C1 changes, Ecell also changes, C2 /C1 = constant then, Ecell is also
constant , Therefore Ecell C2 /C1