Electrochemistry

Electrochemistry

Electrochemistry is a branch of chemistry that studies chemical reactions

which take place in a solution at the interface of an electron conductor (the
electrode: a metal) and an ionic conductor (the electrolyte), and which
involve electron transfer between the electrode and the electrolyte.

It deals with the chemical reactions produced by passing electric current or
the production of electric current through chemical reactions.
Electrochemical Processes

The chemical reactions involving electricity are called electrochemical
reaction

Electrochemical reactions are redox reactions where an oxidation and a
reduction reaction go side by side and are separated in space.

The reactions are two types

1. Induced electrolytic reactions- these non spontaneous reactions are
forced by the passage of electricity through the reactants

2. spontaneous redox reaction that can produce electricity
REDOX REACTIONS

Oxidation-reduction or redox reactions take place in electrochemical cells.

The term redox comes from the two concepts of reduction and oxidation.

Oxidation describes the loss of electrons:

Zn (s)

Zn2+ (aq) + 2 e -

Reduction describes the gain of electrons

Cu2+ (aq) + 2 e -

Cu (s)

Each of the reaction is known as half- reaction or half-cell and both

must always go side by side
 The net reaction: Zn (s) + Cu 2+ (aq)

Zn 2+ (aq) + Cu (s)

Electrochemical Cells
An electrochemical cell is a device capable of either deriving electrical energy
from chemical reactions, or facilitating chemical reactions through the
introduction of electrical energy.

There are two types of electrochemical cells.

TYPES:
1. Electrochemical cell and Electrolytic Cells
2. Galvanic cell and concentration cell
3. Reversible and irreversible cell
1. Spontaneous reactions occur in galvanic (voltaic) cells;
2. Nonspontaneous reactions occur in electrolytic cells.

Both types of cells contain electrodes where the oxidation and reduction
reactions occur.
Oxidation occurs at the electrode is termed as the anode and reduction
occurs at the electrode is called as the cathode.
1. Galvanic or Voltaic cell: Produces energy by a spontaneous reaction which
produces electricity as a result of electron transfer

The cells used for the generation of electrical energy from chemical
reactions are called galvanic or voltaic cells.

The redox reaction in a galvanic cell is a spontaneous reaction.

For this reason, galvanic cells are commonly used as batteries. Galvanic
cell reactions supply energy which is used to perform work. The energy
is harnessed by situating the oxidation and reduction reactions in separate
containers, joined by an apparatus that allows electrons to flow.


Ex. A common galvanic cell is the Daniell cell, batteries, corrosion, etc
2. Electrolytic Cells The redox reaction in an electrolytic cell is non-

spontaneous. Electrical energy is required to induce the electrolysis reaction.

The cells used for electrolysis are called electrolytic cells

ex. Charging of battery, electroplating ,etc

Electrodes & Charge

The anode of a galvanic cell is negatively charged, since the spontaneous
oxidation at the anode is the source of the cell's electrons or negative charge.
The cathode of a galvanic cell is its positive terminal.
The anode of an electrolytic cell is positive (cathode is negative), since the
anode attracts anions from the solution.
In both galvanic and electrolytic cells, oxidation takes place at the anode and
electrons flow from the anode to the cathode.
An electrochemical cell is obtained by coupling two half cells
1. Anode: oxidation half-cell reaction takes place
2. Cathode: reduction half-cell reaction occurs
3. Salt bridge: A salt bridge is often employed to provide ionic contact
between two half-cells with different electrolytesto prevent the solutions
from mixing and causing unwanted side reactions.
Ex.: filter paper soaked in KNO3
Functions of salt bridge:
1. The salt bridge allows ions to move on either side and maintain the
electrical neutrality of the electrolyte on both sides.
2. It serves as a bridge to complete the electric circuit.
3. It prevents the liquid junction potential between the two electrodes.

Liquid junction potential occurs when two solutions of different

concentrations are in contact with each other. The more concentrated
solution will have a tendency to diffuse into the comparatively less
concentrated one. The rate of diffusion of each ion will be roughly
proportional to its speed in an electric field. If anion diffuses more
rapidly than the cation, it will diffuse ahead into the dilute solution
leaving the later negatively charged and the concentrated solution
positively charged. So an electrical double layer of positive and negative
charges will be produced at the junction of the two solutions. So at the
point of junction, a difference of potential will develop because of the
ionic transfer. This potential is called liquid junction potential or
diffusion potential. The magnitude of the potential depends on the
relative

speeds

of

the

ions.

4. External circuit: These two half-cells joined together by wire through

which electrons flow.
5. Electrolyte: Internal pathway that allows ions to migrate between them so
as to preserve electro neutrality.

Difference in electrolytic cell and galvanic cell

Electrolytic cell

Galvanic cell

1. Conversion of electrical energy

into chemical energy

1. Chemical energy into electrical

energy

2. The anode carries positive

charge vice versa.

2. The anode carries negative

charge Vice versa.

3. Electrons are supplied to the cell 3. Electrons are drawn from the
cell.
from the external power supply.

4. Not a spontaneous reaction. Eocell 4. Spontaneous reaction. Eocell is

is -ve, then the process is
+ve, then the process is
nonspontaneous. E.g electroplating spontaneous. eg. Corrosion
5. The extent of chemical reaction 5. The e.m.f of the cell depends
occurring at the electrode depends
on
the concentration of the
on the quantity of electricity passed
& is governed by Faradays law of electrolyte
and chemical
electrolysis.
nature of the electrode (Nernst
Equation)
6. The amount of electricity passed 6. The e.m.f produced in the cell
is measured by potentiometer.
during electrolysis is measured
by Coulometer.

ELECTRODE POTENTIAL (E)

When a metal (M) is placed in the solution of its own ion it may act as an
anode or cathode.

As an anode: Positive metal ions passing into solution (oxidation) leaving
behind e-s on the electode.

The anode attains negative charge due to accumulation of e-s which attracts
positively charged free ions (cations) from the solution. Due to the
attraction the positive ions remain close to the metal.

M

Mn+ +ne-

As a cathode: Positive ions depositing on the metal electrode (reduction)

and it attracts negatively charged ions.

Mn+ +ne- ---- M

HELMHOLTZ ELECTRICAL DOUBLE LAYER

Thus a sort of electrical double layer (positive or negative ions) is formed

all around the metal. This layer is called Helmholtz electrical double layer.

This layer prevents further passing of or deposition of metal ions on the
metal. Consequently a difference in potential (Galvanic potential) set up
between the metal and its solution.

At equilibrium, the potential difference is constant, which is known as
Electrode potential of a metal.
EMF: The diff. of potential between the two electrodes in a voltaic cell which
causes flow of current/electrons is called the electromotive force

Electrode potential of the metal shows its tendency to under go loss or gain of
electrons

Electrode potential (E):

The measure of tendency of an electrode to lose or gain electrons when it is
contact with a solution of its own ion is called electrode potential.
Standard electrode potential (Eo):
The measure of tendency of an electrode to lose or gain electrons, when it is
contact with a solution of its own salt of 1 molar concentration at 25o C is known
as standard electrode potential.
Oxidation electrode potential (Eoxid):
The measure of tendency of an electrode to lose electrons when it is contact with a
solution of its own ion is called oxidation electrode potential.
Reduction electrode potential (E red): The measure of tendency of an electrode to
gain electrons when it is contact with a solution of its own ion is called electrode
reduction potential.
Factors affecting electrode potential

1. Nature of the electrode metal

2. Temperature

3. Concentration of metal ions in solution

Measurement of Single electrode potential

Impossible to know the absolute value of single electrode potential.

To measure the ele. pot of one electrodes which is connected to reference
electrode to form a complete cell

The electrode whose electrode pot. is either exactly known or arbitrarily
fixed is called reference electrode

The pot. of one electrode is fixed arbitrarily then another electrode pot. can
be measured

EMF of the complete cell can be directly read from the potentiometer.
Ecell= E cathode - E anode

10

Potential of the single electrode can be calculated by

Nernst Equation:
The final and the most fundamental form the Nernst equation is written as:
E = Eo RT/nF ln ap /ar
where R is the universal gas constant, T is the absolute temperature in degrees
Kelvin, z is the charge number of the electrode reaction (which is the number of
moles of electrons involved in the reaction as written), and F is the Faraday
constant (96,500 C mole-1). The notation ap represents the chemical activities of
all of the species which appear on the product side of the electrode reaction and
the notation ar represents the chemical activities of all of the species which appear
on the reactant side of the electrode reaction.

Derivation
Nernst equation was derived from Vant Hoff reaction isotherm for the
2+

redox reaction, M

+ 2e- --
M

Vant Hoff Reaction Isotherm

G = - RT ln K +RT ln Q

Vant Hoff reaction isotherm is an equation for the change in free energy
during the chemical reaction.

it relates the G (free energy change)

and K (equilibrium constant) for

the redox reaction as

G = - RT ln K +RT ln Q

---------------(1)

Q (Reaction Quotient) = aC . aD / aA . aB

= [P]

/[R]

aC . aD = chemical activity of products

aA . aB

= chemical

activity of reactants

11


The activities of gases are usually taken as their partial pressures and
the activities of solutes such as ions are usually taken as their molar
concentrations.
G = - RT ln K +RT ln [P] /[R]

---------------(1)

At standard conditions of T and P, at equilibrium [P] = [R]

Go = - RT ln K
So equation 1 becomes
G = Go +RT ln [P] /[R] ---------------------(2)
Electrical energy (nFE) arises from the expense of free energy of the system
(- G).

Let n faraday charge be taken out of a electrode or cell of emf E; then

work done by the cell will be calculated as:
Work = Charge x Potential

= nFE

Work done by the cell is equal to decrease in free energy.

-G = nFE
-Go = nFEo
G

= Go + RT ln [product] / [reactant]

-nFE = -nFEO + 2.303 RT log [product] / [reactant]

Ecell = Eocell - 2.303 RT / nF log [P]/[R]
R = 8.314 J/K/mole
At 25o C, T =298 K
F= 96500 Coulombs
The oxidation potential of an electrode for the reaction
M---- Mn+ + neEoxid

= Eooxid - 0.0592/n log [Mn+] / [M]

----- half cell

[M] = 1

Eoxid

= Eooxid - 0.0592/n log [Mn+]

12

The reduction potential of an electrode for the reaction

Mn+ + ne- ---- M
Ered

= Eored - 0.0592/n log [M] /[Mn+]

----- half cell

[M] = 1

Ered

= Eored + 0.0592/n log [Mn+]

Ecell = Eocell - 0.0592/n log [P]/[R]

Ecell = Eocell - 0.0592/n log K
THE STANDARD EMF OF THE CELL: Eocell = EoR - EoL

Uses of Nernst equation:

1. To calculate electrode potential of unknoun M
2. To predict the corrosion tendency of metals
3. To calculate the emf of a cell

13

ELECTROCTREMICAL SERIES (e.m.f series): The arrangement of metals in the

increasing order of their std. reduction electrode potential

E0

Half-Reaction
Li+ + e-

Li

-3.05

Na+ + e-

Na

-2.70

Mg2+ + e-

Mg

-2.40

Al3+ + 3e-

Al

-1.66

Ti2+ + 2e-

Ti

-1.63

Mn2+ +e-

Mn

-1.18

Zn2+ + 2e-

Zn

-0.76

Fe2+ + 2e-

Fe

-0.44

Co2+ + 2e-

Co

-0.28

Ni2+ + 2e-

Ni

-0.25

Fe3+ + 3e-

Fe

-0.04

2H+ + 2e-

H2 (g)

0.00

Sn4+ + 2e-

Sn2+

+.15

Cu2+ + 2e-

Cu

+0.34

Fe3+ + e-

Fe2+

+0.77

Ag+ + e-

Ag

+0.80

Pt4+ + e-

Pt

+0.86

Mn4+ + 2e-

Mn2+

+1.23

Cr6+ + 3e-

Cr3+

+1.33

Au+ + e-

Au

+1.50

Mn7+ + 5e-

Mn2+

+1.51

Cr4+ + 1e-

Cr3+

+1.60

Au3+ + 3e-

Au

+1.69

F2 + 2e-

2F-

+2.87

14

Application of electrochemical series

1. Relative ease of oxidation or reduction can be predicted

The metals on the top with ve reduction pot. Can more easily undergo
oxidation & act as anode.

Ex. Zn = -0.76 V favours oxidation reaction

While the metals at the bottom with +ve reduction. Pot. has great
tendency to undergo reduction & act as cathode

Ex. Cu = +0.34 V favours reduction reaction.
2. Cell representation can be predicted
A galvanic cell formed by two half cells with 2 diff. metals.
From EMF series, the metal which is undergoing oxidation or reduction can
be predicted
The electrode undergoes oxidation (anode) is written at left
The electrode undergoes reduction (cathode) is written at right
Ex. For Danial cell with Zn and Cu electrodes
The cell representation
Zn / Zn2+ // Cu2+ / Cu
The cell reaction can also be written
Anodic reaction:

Zn (s)

Zn2+ (aq) + 2 e

Cathodic reaction:

Cu2+ (aq) + 2 e -

Cu (s)

The net reaction:

Zn (s) + Cu 2+ (aq)

Zn 2+ (aq) + Cu (s)

15

3. Calculation of Std emf (Eocell) of the cell

Oxidn Half cell|| Redn half cell

Eocell= Eoright - Eoleft

Or

Eocell= Eocathode (red.) Eoanode (red.)

Or Eocell= Eoref.) Eounknown

Ex.

Std e.m.f (Eocell) of (Danial cell) Zn-Cu cell

Eocell = EoCu EoZn = +0.34 (-0.76) V = +1.1 V
4. Calculation of std. free energy (Go)
Go = - nFEo
and equilibrium constant

(Keqm)

Go = - RT ln Keqm
- nFEo = - RT ln Keqm
Eo =

__RT_ 2.303 log Keqm

nF

log Keqm = nEo / 0.0592

at 25o C

5. The spontaneity or feasibility of the cell reaction can be predicted

Spontaneity of the redox reaction can be predicted from the e.m.f value of
complete cell reaction.

If the value of E cell is + ve,

(std. free energy (Go) is negative, since Go = - nFEo) the reaction is
feasible.

If E cell is -ve, Go is positive. Then the reaction is not feasible.

16

6. Hydrogen liberating tendency of the metal can be predicted

The metal with low reduction potential will displace H2 from an acid
solution.
Zn+ H2SO4

ZnSO4 + H2

The metal with +ve potential will not displace H2 from an acid solution
Ag + H2SO4

no reactn

7. Replacing tendency of a metal (M) by another M:

The metals with low reduction potential undergo oxidation and pass into the
solution and the M with high red. pot. Undergo reduction and get deposits on
electrode.
Zn, Ni undergo dissolution in CuSO4 solution and will displace Cu from solution.

8. Corrosion tendency of M:
The metals higher in the series are anodic or more active and they are more prone
to corrosion.
The metals lower in the series are noble metals and they are less prone to
corrosion.

17

Reversible and irreversible cells

Daniell cell has the emf value 1.09 volt. If an opposing emf exactly equal to
1.09 volt is applied to the cell, the cell reaction stops
Zn + Cu2+ --> Cu + Zn2+
but if it is increased infinitesimally beyond 1.09 volt, the cell reaction is
reversed.
Cu + Zn2+ --> Zn + Cu2+
Such a cell is termed a reversible cell.
Thus, the following are the main characteristics of reversible cell:
(i) The chemical reaction of the cell stops when an exactly equal opposing
emf is applied.
(ii) The chemical reaction of the cell is reversed and the current flows in
opposite direction when the opposing emf is slightly greater than that of the
cell.
(iii) The cell produces a small emf if the opposing emf is infinity smaller
than that of the cell
Any other cell which does not obey the above two conditions is termed as
irreversible. A cell consisting of zinc and copper electrodes dipped into the
solution of sulphuric acid is irreversible. Similarly, the cell
Zn|H2S04(aq)|Ag
is also irreversible because when the external emf is greater than the emf of
the cell, the cell reaction,
Zn + 2H+ --> Zn2+ + H2
is not reversed but the cell reaction becomes
2Ag + 2H+ --> 2Ag+ + H2

18

Concentration cell
A concentration cell is made up of two half cells having identical electrodes,
identical electrolyte, except that the concentration of the reactive ions at the
two electrodes are different.
The electrical energy in a concentration cell arises from the transfer of
electrons from the electrode in the lower concentration side to the electrode
in higher concentration side.
The two half - cells may be joined by a salt bridge.
When a metal (M) electrode is dipped in a solution containing its own ions
[Mn+], then the potential (E) is developed at the electrode at the electrode,
the value of which varies with conc. Of the ions in accordance with the
Nernsts equation:
E =Eo - 2.303 RT / nF log 1/ [Mn+]
E =Eo + 2.303 RT / nF log C

Let us consider a general conc. cell represented as:

M/Mn+ (C1M) II Mn+ (C2M) I M+
Where C1 and C2 are the concentrations of active metals ions (Mn+) in
contact with two electrodes respectively and C2 > C1.
THE CELL REACTIONS ARE:
At left electrode (anode): M -- Mn+ (C1.) + neAt right electrode (cathode): Mn+ (C2) + ne- - M
THE NET CELL REACTION: Mn+ (C2) --- Mn+ (C1.)
E.M.Fcell. of cell = Eright - Eleft
= [Eo + 2.303RT/nF log C2 ] [Eo + 2.303RT/nF log C1]
= 2.303RT/nF log C2/C1

19

Ecell

= 0.0592/n log C2/C1

The e.m.f so developed is due to the mere transference of metal ions from
the solution of higher conc. (C2) to lower conc. (C1.).
Applications:
i.

Determination of solubility of sparingly soluble salts:

ii.

Determination of the valency of an ion.

20

REFERENCE ELECTRODS:
The electrode with exactly known standard potential or fixed as constants or zero,
with which we can compare the potentials of other electrodes
The Characteristics of reference electrodes
1. The electrode potential should be fixed as constants or zero.
2. The temperature co-efficient should be very low.
3. It should be a reversible electrode. It can function both as an anode and a
cathode
4. It should be easy to handle and use in laboratory.

1. Primary reference electrode

Standard Hydrogen Electrode:
Construction
This is a gas electrode.
It consists of a thin rectangular platinum foil which is coated with fresh platinum
black to increase the adsorption capacity of H2 gas.
The inner tube is enclosed in an outer jacket having an inlet tube for sending in H2
gas and has a perforated wider base for the escape of excess of H2. This unit is
dipped in 1 M HCl taken in a beaker such that the metal foil remains in the
solution.
In the above system, when the H2 gas at a pressure of 1atm is bubbled through 1M
HCl, the electrode (constructed) or formed is called STANDARD HYDROGEN
ELECTRODE (SHE) or Normal H2 electrode (NHE).
Working
This is represented as Pt, H2 (1 atm) / H+ (IM) When pure and dry H2 gas is
passed through the inlet tube, a part of the gas gets adsorbed and the excess
bubbles out through the perforations.
Depends on the other half cell connected to SHE, SHE can under go either
oxidation or reduction.

21

The electrode is represented as:

Pt, H2 (1 atm); H+ (1M)
The electrod potential of SHE is fixed as zero.
The either of the reaction takeplace

H+ (aq) + e- -- H2 (g)

H2 (g) -- H+ (aq) + e
Act both as anode and cathode based on another M connected, it is a
reversible electrode.

When M electrode with lower reduction potential than H2, is coupled with
SHE, M undergoes oxidation and act as anode. Ex. Zn and SHE acts as
cathode



If the M electrode possesses higher reduction potential than H2, is coupled
with SHE, undergoes reduction and act as cathode. Ex. Cu

22

Determination of single electrode potential of a metal

1. If the single electrode Zn in ZnSO4 is connected to SHE then the emf of the
complete cell determined by means of a potentiometer. Since emf of SHE is
zero, the observed e.m.f gives directly the e.m.f of half-cell containing the
solution under test.

Zn has the tendency to under go oxidation, act as anode.

Pot. of the Zn single electrode can be obtained by

E cell = Ec. -Ea

Ecell= Ecathode (red.) Eanode (red.)

Ecell = ESHE Eunknown(Zn2+, Zn)

ESHE = 0

Eunknown(Zn2+, Zn) = 0 Ecell

Eunknown(Zn2+, Zn) = Ecell
2. If the single electrode Cu in CuSO4 is connected to SHE then the emf of the
complete cell determined by means of a potentiometer. Since emf of SHE is zero,
the observed e.m.f gives directly the e.m.f of half-cell containing the solution
under test.

Cu has the tendency to undergo reduction & act as cathode

Pot. of the Cu single electrode

Ecell = Eunknown(Cu2+, Cu) - ESHE

ESHE = 0

Ecell = Eunknown(Cu2+, Cu)

23

Zn possess lower red. Pot. than H2. Zn undergoes oxidation and act as anode.
H2 undergoes reduction.
H+ (aq) + e- --
 H2 (g) ---


act as cathode

Cu possess higher red. Pot. than H2. Cu undergoes reduction and

act as cathode. H2 undergoes oxidation,
H2 (g) --
 H+ (aq) + e- ---
 act as anode

24

It is used

1) For the determination of single electrode potential of a metal electrode
system

2) For the determination of pH of the solution.

Limitations of Hydrogen Electrode

1) It is rather difficult to regulate the pressure of the H2 gas to be at exactly 1atm
throughout the experiment.
2) Excess of H2 bubbling out carries little HCl with it and hence the H+
concentration decreases. In such a system, it is difficult to maintain the
concentration of HCl at 1M.
3) Platinum foil gets easily poisoned by the impurities present in the gas and HCl.
In fact, the attainment of equilibrium is ensured by trial and error.
4) If the solution contains any oxidizing agent, the H2 electrode cannot be used.

2.

Secondary reference electrode: Calomel and Ag, AgCl

reference electrodes
Saturated Calomel electrode:

A mercury mercurous chloride electrode

The Saturated calomel electrode (SCE) is a reference electrode based on
the reaction between elemental mercury and mercury(I) chloride. The
aqueous phase in contact with the mercury and the mercury(I) chloride
(Hg2Cl2, "calomel") is a saturated solution of potassium chloride in water.

The electrode potential of calomel electrode depends on the conc. of KCl

25


The electrode potential for decinormal 0.1 N KCl is +0.3335 V for normal
KCl solution +0.2810 V and for saturated calomel electrode (SCE) is
+0.2422 V
The electrode is represented as:

Hg, Hg2Cl2 (s), KCl (sat.solution) / Pt

The electrode potential of SCE is arbitrarily fixed as + 0.2422 V.

The electrode is based on the redox reaction

Hg22+ (s) + 2e- <--- Hg2 (l)

1. If the single electrode Zn in ZnSO4 is connected to SCE
SCE = cathode
Zn/ Zn2+ electrode = anode
The half cell reaction is
Hg2Cl2 (s) +2 e- --2Hg (l) +2 Cl- (aq)
Reduction of mercurous to mercury
The single electrode pot. can be calculated
Ecell

= ESCE - Eunknown (Zn2+, Zn)

ESCE = +0.2422 V

26

Eunknown (Zn2+, Zn) = +0.2422 Ecell

2. When Cu electrode is connected to SCE
Cu undergo reduction and act as cathode and SCE act as anode
At SCE oxidation takes place
Hg  Hg+ + e2 Hg+ + 2Cl2 - Hg2Cl2
The single electrode pot. Can be calculated
Ecell

= Eunknown(Cu2+, Cu) - ESCE

ESCE = +0.2422 V
Eounknown(Cu2+, Cu) = Ecell+ 0.2422

27