Electrochemistr

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This chapter, "Electrochemistry," delves into the fascinating
interdisciplinary field that studies the relationship between electrical
energy and chemical reactions. It covers both the generation of
electricity from spontaneous chemical reactions and the use of electrical
energy to drive non-spontaneous chemical transformations. This subject is
crucial for both theoretical understanding and practical applications,
including the production of various chemicals and metals, the functioning
of batteries and fuel cells, and even the transmission of sensory signals in
the human body.

Here's an in-depth explanation of the key concepts presented in the

sources:

1. Electrochemical Cells

Electrochemical cells are devices that facilitate the interconversion of

chemical and electrical energy. There are two main types:

 Galvanic (or Voltaic) Cells: These cells convert the chemical

energy liberated during a spontaneous redox reaction into
electrical energy. A prime example is the Daniell cell, which uses
the spontaneous reaction between zinc and copper ions to produce
electricity. In a galvanic cell, the half-cell where oxidation occurs
is called the anode, and it has a negative potential relative to the
solution. The other half-cell, where reduction occurs, is called
the cathode, and it has a positive potential relative to the solution.
Electrons flow from the negative electrode (anode) to the positive
electrode (cathode), and the current flows in the opposite direction.
The chemical energy is converted into electrical work, which can
power motors or other electrical devices.

 Electrolytic Cells: These devices use electrical energy to carry

out non-spontaneous chemical reactions. An example is when
an external potential greater than the cell potential of a Daniell cell
is applied, reversing the reaction and making it function as an
electrolytic cell. In an electrolytic cell, the application of a DC
voltage causes ions to discharge at the electrodes, leading to
 changes in composition due to electrochemical reactions. Many
metals like sodium, magnesium, and aluminium are produced on a
large scale using electrochemical reduction in electrolytic cells.

2. Electrode Potential and Standard Electrode Potential

At the interface between a metal electrode and an electrolyte solution,

there is a tendency for metal ions to deposit on the electrode,
making it positively charged, and simultaneously, metal atoms from the
electrode tend to go into solution as ions, leaving electrons behind
and making the electrode negatively charged. At equilibrium, a potential
difference develops, known as electrode potential.

 When the concentrations of all species involved in a half-cell

are unity, the electrode potential is called the standard electrode
potential.

 According to IUPAC convention, standard reduction potentials

are now called standard electrode potentials.

 The potential of an individual half-cell cannot be measured

directly; only the difference between two half-cell potentials (the
cell emf) can be measured.

 The Standard Hydrogen Electrode (SHE) is arbitrarily assigned a

zero potential at all temperatures and is used as a reference to
determine other electrode potentials. The SHE consists of a platinum
electrode coated with platinum black, dipped in an acidic solution,
with pure hydrogen gas bubbled through it, all maintained at
standard conditions (1 bar H2 gas, 1 M H+ ions).

 A positive standard electrode potential indicates that the

species (oxidised form) is more easily reduced than H+ ions,
while a negative standard electrode potential means that H+
ions can oxidise the reduced form of the species.

 Inert electrodes like platinum or gold do not participate in the

reaction but provide a surface for electron transfer.

3. Cell Potential (Electromotive Force, emf)

The potential difference between the two electrodes of a galvanic

cell is called the cell potential, measured in volts. When no current is
drawn from the cell, this potential difference is specifically referred to as
the electromotive force (emf) of the cell.

 By convention, the anode is kept on the left and the cathode

on the right when representing a galvanic cell.
  The emf of the cell is given by the difference between the
reduction potentials of the cathode and the anode: Ecell =
Eright – Eleft

 For the Daniell cell, the standard cell emf (E°cell) is 1.1 V when
concentrations are unity.

4. Nernst Equation

The Nernst equation is used to calculate the electrode potential or cell

potential when the concentrations of species are not at unity.

 For an electrode reaction Mn+(aq) + ne– → M(s), the electrode

potential (E) at any concentration, measured with respect to SHE, is
given by: E = E° – (RT/nF) ln(1/[Mn+]) Where:

o E° is the standard electrode potential

o R is the gas constant (8.314 J K–1 mol–1)

o F is the Faraday constant (96487 C mol–1)

o T is the temperature in Kelvin

o n is the number of electrons involved in the reaction

o [Mn+] is the concentration of the species

 For a general electrochemical reaction aA + bB → cC + dD, the cell

potential is: E(cell) = E°(cell) – (RT/nF) ln Q Where Q = ([C]^c
[D]^d) / ([A]^a [B]^b) is the reaction quotient.

 At 298 K, by converting natural logarithm to base 10, the equation

simplifies to: E(cell) = E°(cell) – (0.059/n) log Q

5. Equilibrium Constant and Gibbs Energy from Nernst Equation

The Nernst equation allows for the calculation of the equilibrium

constant (Kc) and the standard Gibbs energy (ΔrG°) of a cell
reaction.

 At equilibrium, the cell potential E(cell) becomes zero.

 In this state, the reaction quotient Q becomes the equilibrium

constant Kc.

 The relation between E°(cell) and Kc at 298K is: E°(cell) =

(0.059/n) log Kc

 Electrical work done by a galvanic cell is equal to the decrease

in its Gibbs energy.
  The relationship between Gibbs energy (ΔrG) and cell potential
(E(cell)) is: ΔrG = – nFE(cell)

 For standard conditions (ΔrG° and E°(cell)): ΔrG° = – nFE°(cell)

 From ΔrG°, the equilibrium constant can also be calculated using:

ΔrG° = – RT ln K

6. Conductance of Electrolytic Solutions

This section covers how electricity is conducted through solutions,

distinguishing it from metallic conduction.

 Resistance (R): Measured in ohm (Ω). It is directly proportional to

length (l) and inversely proportional to the area of cross-section (A).
R = ρ (l/A)

 Resistivity (ρ): The constant of proportionality in the resistance

equation, measured in ohm metre (Ω m) or ohm centimetre (Ω cm).
It is the resistance of a substance that is one metre long and has an
area of cross-section of one m².

 Conductance (G): The inverse of resistance, measured in

siemens (S) or ohm–1 (mho). G = 1/R

 Conductivity (κ): The inverse of resistivity, also known as

specific conductance, measured in S m–1 or S cm–1. It is the
conductance of a material that is 1 m long and has an area of cross-
section of 1 m².

 Electronic (Metallic) Conductance: Due to the movement of

electrons, common in metals and some non-metals like graphite. It
decreases with an increase in temperature.

 Electrolytic (Ionic) Conductance: Due to the movement of ions

present in solutions. It increases with an increase in
temperature.

 Factors affecting electrolytic conductivity: Nature of

electrolyte, size and solvation of ions, nature and viscosity of
solvent, concentration of electrolyte, and temperature.

7. Measurement of Conductivity

Measuring the resistance of an ionic solution requires special techniques

because direct current changes solution composition and solutions cannot
be connected like solid wires.

 Alternating Current (AC) Source: Used to prevent changes in

solution composition.
  Conductivity Cell: A specially designed vessel with two platinum
electrodes coated with platinum black, with a defined area (A) and
separation distance (l).

 Cell Constant (G): A characteristic of the conductivity cell, defined

as l/A. It is typically determined by measuring the resistance of a
standard KCl solution whose conductivity is known. G = Rκ

 Wheatstone Bridge: Used to measure the resistance of the

solution in the conductivity cell.

 Once the cell constant and solution resistance are known,

conductivity (κ) = G/R*.

8. Molar Conductivity (Λm)

Molar conductivity is a more physically meaningful quantity than

conductivity, as it relates conductivity to the concentration of the
electrolyte.

 Definition: The conductance of the volume of solution containing

one mole of electrolyte kept between two electrodes at a unit
distance. Λm = κ/c (where c is concentration in mol m–3, and κ in S
m–1)

 Units: S m2 mol–1 or S cm2 mol–1.

 Variation with Concentration:

o Conductivity (κ) always decreases with dilution

(decrease in concentration) because the number of ions per
unit volume decreases.

o Molar conductivity (Λm) increases with dilution because

the total volume containing one mole of electrolyte (V)
increases, compensating for the decrease in κ.

 Limiting Molar Conductivity (Λ°m): The molar conductivity when

the concentration approaches zero (infinite dilution).

o Strong Electrolytes: Λm increases slowly with dilution and

can be represented by the equation: Λm = Λ°m – A√c. Λ°m
can be obtained by extrapolation of a Λm vs. √c plot to
zero concentration.

o Weak Electrolytes: Λm increases steeply with dilution,

especially at lower concentrations, due to an increase in the
degree of dissociation (α). Λ°m cannot be obtained by
simple extrapolation for weak electrolytes.
9. Kohlrausch Law of Independent Migration of Ions

This law helps determine the limiting molar conductivity of electrolytes,

especially weak ones.

 Statement: The limiting molar conductivity of an electrolyte

can be represented as the sum of the individual
contributions of the anion and cation of the electrolyte.

 Equation: For an electrolyte that dissociates into n+ cations and n–

anions: Λ°m = n+λ°+ + n–λ°– Where λ°+ and λ°– are the limiting
molar conductivities of the cation and anion, respectively.

 Applications: Used to calculate Λ°m for any electrolyte from

individual ion conductivities. For weak electrolytes, it helps
determine Λ°m (which cannot be found by extrapolation) and
subsequently the degree of dissociation (α) and dissociation
constant (Kc).

o α = Λm / Λ°m

o For a weak electrolyte like acetic acid, Kc = (cα²) / (1–α).

10. Quantitative Aspects of Electrolysis (Faraday's Laws)

Michael Faraday established two laws governing the quantitative aspects

of electrolysis:

 Faraday's First Law: The amount of chemical reaction at any

electrode is proportional to the quantity of electricity
passed through the electrolyte.

 Faraday's Second Law: The amounts of different substances

liberated by the same quantity of electricity are proportional
to their chemical equivalent weights (Atomic Mass ÷ Number of
electrons required for reduction).

 Quantity of Electricity (Q): Calculated as Q = It (current in

amperes × time in seconds).

 Faraday Constant (F): The charge on one mole of electrons

(approximately 96487 C mol–1 or 96500 C mol–1 for calculations).

 The amount of charge required for oxidation or reduction depends

on the stoichiometry of the electrode reaction (e.g., 1 mole of
Ag+ requires 1F, 1 mole of Mg2+ requires 2F).

11. Products of Electrolysis

The products formed during electrolysis depend on the nature of the

material being electrolysed, the type of electrodes used (inert or reactive),
and the standard electrode potentials of the species present. Sometimes,
overpotential (extra potential) might be needed for a reaction to occur,
making it more difficult. For example, in the electrolysis of aqueous NaCl,
H2 and Cl2 gases are produced along with NaOH, not Na metal, due to the
relative ease of reduction of H+ over Na+ and the overpotential of oxygen
formation.

12. Batteries

Batteries are practical galvanic cells that convert chemical energy into
electrical energy. They are designed to be light, compact, and maintain a
relatively constant voltage.

 Primary Batteries: Reactions occur only once; they cannot be

recharged and become dead after use.

o Dry Cell (Leclanche cell): Used in transistors and clocks.

Consists of a zinc container (anode) and a carbon rod
(cathode) surrounded by MnO2 and carbon paste, with NH4Cl
and ZnCl2 paste as electrolyte. Potential is approx. 1.5 V.

o Mercury Cell: Suitable for low-current devices (hearing aids,

watches). Uses zinc-mercury amalgam (anode) and HgO-
carbon paste (cathode) with KOH and ZnO electrolyte.
Potential is approx. 1.35 V and remains constant.

 Secondary Batteries: Rechargeable by passing current in the

opposite direction, allowing for multiple discharge-charge cycles.

o Lead Storage Battery: Commonly used in automobiles and

inverters. Consists of a lead anode and a lead dioxide cathode,
with 38% sulphuric acid as electrolyte. Reactions are reversed
upon charging.

o Nickel-Cadmium Cell: Has a longer life than lead storage

cells but is more expensive.

13. Fuel Cells

Fuel cells are galvanic cells designed to continuously convert the

energy of combustion of fuels (like hydrogen, methane, methanol)
directly into electrical energy.

 They are highly efficient (around 70%) compared to thermal power

plants (around 40%) and are pollution-free.

 A common example uses the reaction of hydrogen with oxygen

to form water. This cell was used in the Apollo space programme,
 providing drinking water for astronauts from the produced water
vapour.

 Reactants are fed continuously, and products are removed

continuously.

 Catalysts like platinum or palladium are often incorporated into

electrodes to increase reaction rates.

14. Corrosion

Corrosion is an electrochemical process where a metal is oxidised by

losing electrons to oxygen, forming oxides or other salts of the metal.

 Rusting of iron is a common example, occurring in the presence of

water and air.

 The process is essentially an electrochemical phenomenon

where a spot on the iron acts as an anode (iron oxidation: Fe →
Fe2+ + 2e–), and another spot acts as a cathode (oxygen
reduction: O2 + 4H+ + 4e– → 2H2O).

 The resulting ferrous ions (Fe2+) are further oxidised by

atmospheric oxygen to ferric ions, forming hydrated ferric oxide
(rust).

 Prevention of corrosion is critical and can be achieved by:

o Preventing contact with the atmosphere (e.g., painting).

o Covering the surface with other inert or sacrificial metals (e.g.,

galvanising with zinc).

o Using a sacrificial electrode of a more reactive metal (e.g.,

Mg, Zn) that corrodes instead of the protected object.

Formulas

Here is a comprehensive list of formulas from the sources:

1. Resistance: R = ρ (l/A)

2. Conductance: G = 1/R

3. Conductivity: κ = 1/ρ = G (l/A)

4. Cell Constant: G* = l/A = Rκ

5. Unknown Resistance (Wheatstone Bridge): R2 = (R1 * R4) / R3

6. Molar Conductivity: Λm = κ/c

 o If κ in S cm–1 and c in mol L–1: Λm (S cm2 mol–1) = (κ ×
1000) / molarity (mol/L)

7. Relation between S m2mol–1 and S cm2mol–1:

o 1 S m2mol–1 = 104 S cm2mol–1

o 1 S cm2mol–1 = 10–4 S m2mol–1

8. Molar Conductivity (alternative definition): Λm = κV (where V

is volume containing 1 mole of electrolyte)

9. Strong Electrolytes (Molar Conductivity variation): Λm = Λ°m

– A√c

10. Kohlrausch's Law: Λ°m = n+λ°+ + n–λ°–

11. Degree of Dissociation (α) for weak electrolytes: α = Λm

/ Λ°m

12. Dissociation Constant (Kc) for weak electrolytes: Kc =

(cα²) / (1–α)

13. Quantity of Electricity: Q = It (current × time)

14. Faraday Constant (Charge on 1 mole of electrons): F =

96487 C mol–1 (approx. 96500 C mol–1)

15. Electrode Potential (Nernst Equation): E = E° – (RT/nF)

ln(1/[Mn+])

o At 298 K: E = E° – (0.059/n) log(1/[Mn+]) [derived from 29]

16. Cell Potential (Nernst Equation): E(cell) = E°(cell) – (RT/nF)

ln Q

o At 298 K: E(cell) = E°(cell) – (0.059/n) log Q

17. Standard Cell Potential: E°(cell) = E°cathode – E°anode or

E°(cell) = E°right – E°left

18. Relationship between Standard Cell Potential and

Equilibrium Constant: E°(cell) = (2.303RT/nF) log Kc

o At 298 K: E°(cell) = (0.059/n) log Kc

19. Gibbs Energy and Cell Potential: ΔrG = – nFE(cell)

20. Standard Gibbs Energy and Standard Cell Potential:

ΔrG° = – nFE°(cell)

21. Standard Gibbs Energy and Equilibrium Constant: ΔrG°

= – RT ln K
Tips on How to Solve Questions

Based on the examples and in-text questions provided, here are some tips
for tackling problems in electrochemistry:

1. Understand the Type of Cell:

o First, identify if the cell is galvanic (spontaneous) or

electrolytic (non-spontaneous). This determines whether
you're converting chemical to electrical energy or vice versa.

2. Identify Anode and Cathode:

o In a galvanic cell, oxidation occurs at the anode

(negative electrode) and reduction at the cathode
(positive electrode).

o Write down the half-reactions for oxidation and reduction.

o Combine them to get the overall cell reaction.

3. Determine Standard Electrode Potentials (E°):

o Use the provided Table 2.1 (Standard Electrode

Potentials) to find the E° values for the half-reactions
involved. Remember these are usually given as standard
reduction potentials.

o To calculate E°(cell), use the formula: E°(cell) = E°cathode

– E°anode. Ensure you use reduction potentials for both
cathode and anode.

4. Apply Nernst Equation for Non-Standard Conditions:

o If concentrations are not unity, use the Nernst equation.

o Crucially, identify 'n', the number of electrons transferred in

the balanced overall reaction. This is often the most common
mistake.

o Correctly set up the reaction quotient (Q) with products

over reactants, raised to their stoichiometric coefficients.
Remember that concentrations of solids are taken as unity.

5. Calculate Gibbs Energy and Equilibrium Constant:

o Use the standard cell potential (E°(cell)) and the number of

electrons (n) to find standard Gibbs energy (ΔrG° = –
nFE°(cell)). Ensure units are consistent (J or kJ).
 o Then, use ΔrG° to find the equilibrium constant (K), or
directly use E°(cell) with the simplified Nernst equation at
equilibrium (E(cell) = 0).

6. Conductivity and Molar Conductivity Problems:

o Cell Constant (G)*: If not given, calculate it using a standard

solution (e.g., KCl) whose conductivity is known (G* = Rκ).

o Units: Pay close attention to units (S cm–1 vs S m–1, mol L–1

vs mol m–3) and convert as necessary.

o Molar Conductivity (Λm): Apply Λm = κ/c, ensuring correct

units for κ and c.

o Variation with Concentration: Remember that κ decreases

with dilution, while Λm increases.

o Kohlrausch Law: Use it to find Λ°m for weak electrolytes or

for complex strong electrolytes from individual ionic
contributions (Λ°m = n+λ°+ + n–λ°–).

o Weak Electrolyte Dissociation: Calculate degree of

dissociation (α = Λm / Λ°m) and then the dissociation constant
(Kc = cα² / (1–α)).

7. Faraday's Laws and Electrolysis Calculations:

o Charge (Q): Calculate Q = It if current and time are given.

o Moles of Electrons: Relate charge to moles of electrons

using the Faraday constant (1 F = 96487 C mol–1).

o Stoichiometry: Use the balanced half-reaction to relate

moles of electrons to moles (and then mass) of substance
deposited or consumed. For instance, Cu2+ + 2e– → Cu
means 2 moles of electrons deposit 1 mole of copper.

o Products of Electrolysis: When dealing with aqueous

solutions, consider the competitive reactions at both anode
and cathode. Use standard reduction potentials to predict
which species will be preferentially reduced or oxidised,
keeping in mind overpotential effects for gas evolution
reactions (like O2).

8. Feasibility of Reactions:

o Calculate E°(cell) for the given reaction. If E°(cell) > 0, the

reaction is spontaneous/feasible under standard conditions.
If E°(cell) < 0, it is non-spontaneous.
 o Alternatively, calculate ΔrG°. If ΔrG° < 0, the reaction is
spontaneous.

Complete and Simple Summary

Electrochemistry is the study of how chemical reactions produce

electricity (in galvanic cells) and how electricity drives non-spontaneous
chemical reactions (in electrolytic cells).

In galvanic cells, like the Daniell cell, a spontaneous redox reaction

occurs, converting chemical energy into electrical energy. The anode is
where oxidation happens (negative), and the cathode is where reduction
happens (positive). The potential difference between these electrodes is
the cell potential or emf. The Standard Hydrogen Electrode (SHE)
serves as a reference with zero potential.

For reactions not under standard conditions (i.e., concentrations not

unity), the Nernst equation is used to calculate electrode and cell
potentials. This equation also links the cell's standard potential (E°cell)
to the equilibrium constant (Kc) and the Gibbs energy (ΔrG°) of the
reaction.

Conductance in solutions is due to ion movement. Conductivity (κ)

measures how well a solution conducts electricity per unit volume, while
molar conductivity (Λm) accounts for the concentration of the
electrolyte. As a solution is diluted, κ decreases, but Λm generally
increases. Kohlrausch's Law states that at infinite dilution, the molar
conductivity of an electrolyte is the sum of the individual contributions of
its ions. This law is crucial for determining the dissociation constant of
weak electrolytes.

Electrolysis is quantified by Faraday's Laws, which relate the amount of

substance produced to the quantity of electricity passed through the cell.
The Faraday constant (F) represents the charge of one mole of
electrons. The specific products of electrolysis depend on the species
present and their standard potentials, sometimes requiring extra voltage
due to overpotential.

Practical applications of electrochemistry include batteries, which are

galvanic cells. Primary batteries (like dry cells and mercury cells) are
non-rechargeable, while secondary batteries (like lead-acid and nickel-
cadmium) are rechargeable. Fuel cells are highly efficient galvanic cells
that continuously convert the chemical energy of fuels (like hydrogen)
directly into electricity, producing minimal pollution.

Finally, corrosion, such as the rusting of iron, is an electrochemical

process involving oxidation of the metal and reduction of oxygen. It
causes significant damage but can be prevented by protecting the metal
surface or using sacrificial electrodes.