Electrochemistry

Dr. Bhaskar Devu Mukri

Assistant Professor
Department of Chemistry
Motilal Nehru National Institute of Technology Allahabad,
Prayagraj – 211004, India
Introduction:
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical
potential difference and identifiable chemical change.
 Lithium ion battery Glucose sensor Corrosion
Charge
Enzyme - Glucose oxidase

Discharge
Separator
Cu Al

At anode: 4Fe → 4Fe2+ + 8e−

At cathode: 2O2 + 4H2O + 8e− → 8OH−
4Fe2+ + 8OH− → 4Fe(OH)2
Fuel cell 4Fe(OH)2 + O2 → 2Fe2O3 + 4H2O
Overall, 4Fe + 3O2 + 2H2O → 2Fe2O3∙H2O

Electrolyte solution:
Energy conversion
Ethylene carbonate + Dimethyl carbonate / LiPF6
TiO2 Dye Catalyst
Industrial electrolysis
Working Counter
Organic electrosynthesis electrode electrode
hv

Dye Sensitized Solar Cell

Electrolyte: It is a medium containing ions that is electrically conducting through the movement of those ions.
• This includes most soluble salts, acids, and bases dissolved in a polar solvent, such as water. Some
solid-state electrolytes are also exist.
• This substance dissociates into ions (cations and anions) in the solution or in the molten state that
acquires the capacity to conduct electricity.
• Electrolytes are one of the main components of electrochemical cells

Arrhenius theory of electrolyte dissociation:

‘In aqueous solution, the molecules of an electrolyte undergo spontaneous dissociation to form positive and
negative ions.’
Ex: NaCl(aq) Na+(aq) + Cl−(aq)

• Strong electrolytes: The substances that dissociate completely into their respective ions in the aqueous
solutions even at moderate conditions.
Ex: Strong acids (HCl, H2SO4, HNO3, etc), strong bases (NaOH, KOH, etc), and salts (NaCl, KCl, CaCl2, etc)

• Weak electrolytes: The substances that partially dissociate into their respective ions in the aqueous solutions.
Ex: Acids (acetic acid, formic acid, etc), bases (NH4OH, Cu(OH)2, etc), and salts (ammonium acetate, silver
acetate, etc)
Limitations:
• This theory is applicable to aqueous solution, but not to non-aqueous solutions.
• The solvent is not deciding the strength of an electrolyte. Ex: HCl is a strong acid in water, but
it is a weak acid in benzene.
• This theory is effective only for weak electrolytes.
 Electrical Conductivity
Ohm’s law:
It expresses the current, I through a medium of resistance, R in the presence of a potential difference, V with
the relation,
V = IR
Here, the current is expressed in amperes (A), the resistance is in ohms (Ω), and the potential difference is in
volts (V).
V
Ohm’s law may be rearranged into I= =GV
R
where G is the conductance, which expressed in siemens, S (1 S = 1 Ω−1, mho)

Other than temperature and pressure, the conductance of a sample depends on its dimensions. If a sample has
length L and area cross-section A, then the conductance is
A
G=
L
where  (kappa) is the conductivity, with units siemens per meter (S m-1).

The conductivity can be determined from the dimensions of the sample and current flowing for a given
potential difference from
L I L
=G =
A V A
 Conductivity cell

Conductivity cell
R1
Rx Detector P

R3 R2

AC source
Pt electrode Pt electrode

 The conductivities of solutions are determined by calibration using a solution of known conductivity.
 An alternating current (AC) is used to avoid the formation of decomposition products at the electrodes.
 Molar conductivity (Λm)
• As number of ions per unit volume increases with increasing in the electrolyte concentration, electrical
conductivity, κ usually increases.
• To get a measure of current carrying ability of a given amount of electrolyte, molar conductivity (Λm) is
introduced.
• It is defined as the conductivity of an electrolyte divided by its molar concentration.

c
where ‘c’ is the molar concentration of an electrolyte.
The SI unit of molar conductivity is siemens meters squared per mole (S m2 mol−1). However, these values
are often quoted in S cm2 mol−1.
Molar conductivity varies with concentration of the electrolyte solution
 The number of ions in the solution might not be proportional to the concentration of the electrolyte.
 For strong electrolytes, the molar conductivity depends only weakly on concentration.
 On dilution, there is a regular increase in the molar conductivity of strong electrolyte due to the
decrease in solute–solute interaction.
 For weak electrolytes, the molar conductivity strongly depends on concentration.
 More dilute a solution, the greater its molar conductivity due to increased ionic dissociation.
Ex: acetic acid has a higher molar conductivity in dilute aqueous acetic acid than in concentrated acetic
acid.
The concentration dependence of molar conductivities indicates that there
are two classes of electrolyte.
• Strong Electrolyte: Molar conductivity depends only slightly on the molar
concentration. In general, molar conductivity increases slightly as the
concentration is decreased.

• Weak Electrolyte: Molar conductivity is normal at concentrations close to

zero but raises sharply to high values as the concentration decreases.
Strong Electrolytes:
Kohlrausch’s law
• Based on experimental data, Friedrich Kohlrausch proposed the non-linear law for strong electrolytes.

where
Λm is the molar conductivity of the electrolyte, c is the concentration of the electrolyte
Λ∘m is the molar conductivity at infinite dilution, i.e. limiting molar conductivity, which can be
determined by extrapolation of Λm as a function of √c
K is the Kohlrausch coefficient, which depends mainly on the stoichiometry of the specific salt
in solution
• This law is valid for low electrolyte concentrations only.
Kohlrausch's law of independent migration of ions
• Friedrich Kohlrausch established that to a high accuracy in dilute solutions, molar conductivity can be
decomposed into contributions of the individual ions. This is known as Kohlrausch's law of independent ionic
migration.
• Limiting molar conductivity of an electrolyte is the sum of individual limit molar conductivities of its cations
and anions.
• If the limiting molar conductivity of the cations is denoted as λ+ and that of the anions is λ−, then this law states
that
Λ∘m = v+λ+ + v−λ−
where v+ and v− are the numbers of cations and anions per formula unit of electrolyte, respectively
Ex: v+ = v− = 1 for HCl, NaCl and CuSO4, v+ =1 and v−= 2 for MgCl2
Applications of Kohlrausch’s law of independent migration of ions:

1. Calculation of limiting conductivities of weak electrolytes:

2. Determination of degree of ionization (α) of weak electrolyte:
• Weak electrolytes are not fully ionized in solution. This partially ionization is described in terms of the
degree of ionization (α).
• In solution, the ions are in dynamic equilibrium with the unionized molecules. Such an equilibrium can be
described by a constant called ionization constant, K
For a weak electrolyte, HA i.e. weak acid, the ionization equilibrium is

And ionization constant or acidity constant, Ka is

Ka =

If c is the initial concentration of the weak electrolyte HA in solution, then the equilibrium concentrations of
various species are
[H3O+] = αc, [A−] = αc, and [HA] = (1−α)c

Then, acidity constant, Ka becomes

Ka =

Ka = ………. (1)
At infinite dilution, a weak electrolyte is almost completely ionized because a fraction α is actually present as
ions in the solution and the limiting molar conductivity is Λ°m.
Then, the measured molar conductivity,
Λm = α Λ°m

α=

Rearrange equation (1) and put this α value,

=
Ka =

Ka (1− α) = α2c
=
=

= =

If 1/Λm is plotted against Λmc, then the intercept at c = 0 will be 1/Λ°m. From Λm
and Λ°m values, the degree of ionization or ionization constant of the electrolyte
at any concentration can be determined.
 The mobility of ions
• The ability of an ion to conduct electricity depends on its ability to move through the solution.
• When an eclectic field, E is applied, the ions in the solution are accelerated and the cations are moved
towards the negative electrode and the anions are accelerated towards the positive electrode.
• However, the faster travelling of ions in the solution experiences the greater the retarding force from the
viscosity of the medium.
• Hence, ions settle down into the limiting average speed, which is called a drift speed, s. It is proportional to
the strength of the applied electric field.
s = μE

where μ is called mobility of the ions, i.e. the ability of ions to move through a
medium in response to an electric field.

• Stokes’ law:
Retarding force due to the viscosity, F = 6πηas
where, η is the viscosity of the medium, ‘a’ is the radius of an ion, and s is the speed.
When an ion with charge ‘ze’ is subjected in an electric field, E, it accelerates with a force of magnitude
│z│eE.
When the ion has reached its drift speed, the accelerating and viscous retarding forces are equal. So,

│z│eE = 6πηas

s=
 Then, μE =

Mobility of the ions, μ =

• The mobility of an ion determines the rate at which it can transport charge through a solution. Therefore,
the result is its molar conductivity.

λ+ = │z│μ+F and λ− = │z│μ−F

Where μ+ and μ− are the mobilities of the cation and anion , z is the charge number,
and F is Faraday’s constant (F = 96485 C mol-1).

Cations μ Cations μ Anions μ Anions μ

H+(H3O+) 36.23 Mg2+ 5.50 OH− 20.64 NO3− 7.41
Li+ 4.01 Ca2+ 6.17 F− 5.74 SO42− 8.29
Na+ 5.19 Sr2+ 6.16 Cl− 7.92
K+ 7.62 NH4+ 7.62 Br− 8.09 μ, 10−8 m2s-1V-1 at 298.15 K
Rb+ 8.06 N(CH3)4+ 4.65 I− 7.96
Cs+ 8.00 N(CH2CH3)4+ 3.38 CO32− 7.18
• When an ion migrates in the water medium, it carries its hydrating water molecules with it.
• Small ions are most more extensively hydrated than large ions, because they give rise to a stronger electric
field in their vicinity. Hence, an ion of smaller radius has a large hydrodynamic radius.
• Thus, the hydrodynamic radius decreases with increasing in ionic radius (Group I).

High mobility of H+ ion in water (Grotthuss mechanism):

• The proton (H+ ion) on one H2O molecule migrates to its neighbour, then that H2O molecule releases its proton
to the next neighbour H2O molecule, and so on along a chain.
• This motion is an effective motion of a proton, not the actual motion of an individual proton.
 Electrolysis
It is a technique uses for the decomposition or ionic compounds into their elements formation by passing direct
current through the solution.
• Electrolysis is commercially important as a stage in the separation of elements from naturally occurring
sources such as ores using an electrolytic cell.
• The key process of electrolysis is the interchange of atoms and ions by the removal or addition of electrons
due to the applied current.
• Each electrode attracts ions that are of the opposite charge. The cations (positive charge) move towards the
electron-providing (negative) cathode. Anions (negatively charged) move towards the electron-extracting
(positive) anode.
• When neutral atoms or molecules, which those on the surface of an electrode gain or lose electrons, they
become ions and may dissolve in the electrolyte. Also, they react with other ions.
• When the ions gain or lose electrons and become neutral, they will form compounds that separate from the
electrolyte.
• When an ion gains or loses electrons without becoming neutral, its electronic charge is altered in the process.
Electrolysis of brine (chloralkali process ):

Saturated brine is passed into the first chamber of the cell where the chloride ions are oxidized at the anode, losing
electrons to become chlorine gas.
2Cl− → Cl2↑ + 2e−
At the cathode, positive hydrogen ions pulled from water molecules are reduced to hydrogen gas by the electrons
provided by the electrolytic current and also, releasing hydroxide ions into the solution.
2H2O + 2e− → H2↑ + 2OH−
The ion-permeable ion-exchange membrane at the center of the cell allows Na+ ion to pass to the second chamber
where they react with OH− ion to produce caustic soda (NaOH).

Overall reaction, 2NaCl + 2H2O → Cl2↑ + H2↑ + 2NaOH

 Uses of electrolysis in industry
• Extraction of Metal from their Ores
The metal ore is treated with strong acid or is melted and then a DC current is passed through the
resulting solution, the solution is decomposed and pure metal is deposited on the cathode.

• Refining of Metals
The anode of impure metal is placed in a suitable electrolytic solution and when DC current is passed
through the solution, pure metal is deposited on the cathode.

• Manufacturing of Chemicals
When an electric current is passed through the solution, the compound presence in the solution gets
breakdown into its constituent components which are liberated at the anode and cathode,

• Electro-Deposition and Electroplating

Both are the electrolytic processes, in which a metal is deposited on any metallic or nonmetallic surface.

• Production of perfluorinated organic compounds such as trifluoroacetic acid by the process of

electrofluorination.

• Rust removal and cleaning of old coins and other metallic objects.
 Research trends
 Electrolysis of carbon dioxide
The electrolysis of carbon dioxide gives formate or carbon monoxide, but sometimes more elaborate
organic compounds such as ethylene.
CO2 + H2 → HCOOH
CO2 + H2 → CO + H2O
CO2 + 4H2 → CH4 + 2H2O
2CO2 + 6H2 → C2H4 + 4H2O
2CO2 + 6H2 → C2H5OH + 3H2O

 Electrolysis of acidified water

Electrolysis of water produces hydrogen and oxygen.
2H2O → 2H2 + O2, E° = +1.23 V
 Carbon/hydrocarbon assisted water electrolysis (CAWE)
This process utilizes solid coal/carbon particles or powder as fuels dispersed in acid/alkaline electrolyte in
the form of slurry and the carbon contained source co-assist in the electrolysis process as following,
Carbon/Coal slurry (C + 2H2O) → CO2 + 2H2, E′ = 0.21 V
Or Carbon/Coal slurry (C + H2O) → CO + H2, E′ = 0.52 V
Thus, this CAWE approach is that the actual cell overpotential can be significantly reduced to below 1.0 V
as compared to 1.5 V for conventional water electrolysis.