ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI

What are Redox Reactions?

The reaction in which oxidation and reduction takes place at a same time is called
Redox reaction.
A redox reaction can be defined as a chemical reaction in which electrons are transferred between two reactants
participating in it. This transfer of electrons can be identified by observing the changes in the oxidation states of the
reacting species. An illustration detailing the electron transfer between two reactants in a redox reaction is provided
below.In the illustration provided below, it can be observed that the reactant, an electron, was removed from reactant
A and this reactant is oxidized. Similarly, reactant B was handed an electron and was therefore reduced

The loss of electrons and the corresponding increase in the oxidation state of a given reactant is called oxidation.
The gain of electrons and the corresponding decrease in the oxidation state of a reactant is called reduction.
Electron-accepting species which tend to undergo a reduction in redox reactions are called oxidizing agents. An
electron-donating species which tends to hand over electrons can be referred to as a reducing agent. These species
tend to undergo oxidation. It can be noted that any redox reaction can be broken down into two half-reactions,
namely the oxidation half-reaction and the reduction half-reaction.
When writing these half-reactions separately, each of them must be balanced in a way that all the electrons are
accounted for.

Types of Redox Reactions

The different types of redox reactions are:

 Decomposition Reaction
 Combination Reaction
 Displacement Reaction
 Disproportionation Reactions

Decomposition Reaction
This kind of reaction involves the breakdown of a compound into different compounds. Examples of these types of
reactions are:

 2NaH → 2Na + H2
 2H2O → 2H2 + O2
 Na2CO3 → Na2O + CO2
All the above reactions result in the breakdown of smaller chemical compounds in the form of AB → A + B
But, there is a special case that confirms that all the decomposition reactions are not redox reactions.
For example CaCO3 → CaO + CO2
Types of Reactions

Combination Reaction
These reactions are the opposite of decomposition reaction and hence involve the combination of two compounds
to form a single compound in the form of A + B → AB. For example:

 H2 + Cl2 → 2HClC+O2→CO2
 4Fe+ 3O2→2Fe2O3

Displacement Reaction
In this kind of reaction, an atom or an ion in a compound is replaced by an atom or an ion of another element. It can
be represented in the form of X + YZ → XZ + Y. Further displacement reaction can be categorized into

 Metal displacement Reaction

 Non-metal displacement Reaction

Metal Displacement
In this type of reaction, a metal present in the compound is displaced by another metal. These types of reactions
find their application in metallurgical processes where pure metals are obtained from their ores.
For example CuSO4+Zn→Cu+ZnSO4

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Non-Metal Displacement
In this type of reaction, we can find a hydrogen displacement and sometimes rarely occurring reactions involving
oxygen displacement.

Disproportionation Reactions
The reactions in which a single reactant is oxidized and reduced is known as Disproportionation reactions.
For example: P4 + 3NaOH + 3H2O → 3NaH2PO2 + PH3

What are Spontaneous Reactions

Spontaneous reactions refer to the chemical reactions that occur without being driven by an outside force. The
two driving forces of a chemical reaction are enthalpy and entropy. Enthalpy is a thermodynamic property of a
system that is the sum of the internal energy added to the product of the pressure and the volume of the system.
Entropy is the other thermodynamic property that accounts for the system’s thermal energy per unit temperature.
It describes the randomness and disorder of molecules. When the occurrence of a chemical reaction decreases
the enthalpy and increases the entropy of the system, it is considered as a favourable reaction. As spontaneous
reactions fulfil the above two conditions, they occur without inside intervention.

What is an Electrochemical Cell?

An electrochemical cell is a device that can generate electrical energy from the chemical reactions occurring in it,
or use the electrical energy supplied to it to facilitate chemical reactions in it. These devices are capable of converting
chemical energy into electrical energy, or vice versa. A common example of an electrochemical cell is a standard
1.5-volt cell which is used to power many electrical appliances such as TV remotes and clocks.
Such cells capable of generating an electric current from the chemical reactions occurring in them care
called Galvanic cells or Voltaic cells. Alternatively, the cells which cause chemical reactions to occur in them when
an electric current is passed through them are called electrolytic cells.

Electrochemical cells generally consist of a cathode and an anode. The key features of the cathode and the anode
are tabulated below.

Cathode Anode

Denoted by a negative sign since electrons are liberated

Denoted by a positive sign since electrons are consumed here
here

A reduction reaction occurs in the cathode of an

An oxidation reaction occurs here
electrochemical cell

Electrons move into the cathode Electrons move out of the anode

Types of Electrochemical Cells

The two primary types of electrochemical cells are
1. Galvanic cells (also known as Voltaic cells)
2. Electrolytic cells

What is Galvanic Cell?

An electrochemical cell that converts the chemical energy of spontaneous redox reactions
into electrical energy is known as a galvanic cell or a voltaic cell.
Galvanic cell Voltaic cell is an electrochemical cell that makes use of chemical reactions to generate electrical
energy.

Table of Contents
 Principle of Galvanic (Voltaic) Cell
 Parts of Galvanic Cell
 Working of Galvanic Cell
 Example of Galvanic Cell
 Recommended Videos

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 Frequently Asked Questions – FAQs
Let us understand how a voltaic or galvanic cell is created.
In oxidation-reduction reactions, electrons are moved from one species to another species. Energy is released if the
reaction occurs spontaneously. Therefore, the released energy is used to do useful work. To tackle this energy, it is
required to split the reaction into two separate half-reactions viz. oxidation and reduction. With the help of two
different containers and wire, the reactions are put into them to drive the electrons from one end to the other end.
This creates a voltaic cell.

Principle of Galvanic (Voltaic) Cell

Electric work done by a galvanic cell is mainly due to the Gibbs energy of spontaneous redox reaction in the voltaic
cell. It generally consists of two half cells and a salt bridge. Each half cell further consists of a metallic electrode
dipped into an electrolyte. These two half-cells are connected to a voltmeter and a switch externally with the help of
metallic wires. In some cases, when both the electrodes are dipped in the same electrolyte, a salt bridge is not
required.

Galvanic Cell (Voltaic Cell) Diagram

Parts of Galvanic Cell

 Anode – Oxidation occurs at this electrode.
 Cathode – Reduction occurs at this electrode.
 Salt bridge – Contains electrolytes which are required to complete the circuit in a galvanic cell.
 Half-cells – reduction and oxidation reactions are separated into compartments.
 External circuit – Conducts the flow of electrons between electrodes
 Load – A part of the circuit utilizes the electron to flow to perform its function.

Working of Galvanic Cell

 In a galvanic cell, when an electrode is exposed to the electrolyte at the electrode-electrolyte interface, the atoms
of the metal electrode have a tendency to generate ions in the electrolyte solution leaving behind the electrons at
the electrode. Thus, making the metal electrode negatively charged.
 While at the same time metal ions in the electrolyte solution too, have a tendency to deposit on a metal electrode.
Thus, making the electrode positively charged.
 Under equilibrium condition, charge separation is observed and depending on the tendencies of two opposing
reactions, the electrode can be positively or negatively charged. Hence, a potential difference is developed between
the electrode and electrolyte.
 This potential difference is known as electrode potential.
 Out of two electrodes, the electrode at which oxidation takes place is called anode while the electrode at which
reduction takes place is called cathode.
 The anode has a negative potential with respect to the solution while the cathode has a positive potential with
respect to the solution.
 Thus, a potential difference develops between two electrodes of the galvanic cell. This potential difference is known
as cell potential.
 When no current is drawn from the galvanic cell, cell potential is known as the electromotive force of the galvanic
cell.
 When the switch is set on, due to the potential difference, electrons flow from the negative electrode to the positive
electrode.

Example of Galvanic Cell

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Electrochemical or galvanic cells were introduced as a tool for studying the thermodynamic properties of fused salts
more than a century ago. Daniel’s cell is an example of a galvanic cell that converts chemical energy into electrical
energy. In Daniel’s cell, copper ions are reduced at the cathode while zinc is oxidized at the anode.
Reactions of Daniel cell at cathode and anode are:
At cathode: Cu 2+ + 2e– → Cu
At anode: Zn → Zn2+ + 2e–

What is an Electrolytic Cell?

An electrolytic cell can be defined as an electrochemical device that uses electrical energy to facilitate a non-
spontaneous redox reaction. Electrolytic cells are electrochemical cells that can be used for the electrolysis of certain
compounds. For example, water can be subjected to electrolysis (with the help of an electrolytic cell) to form gaseous
oxygen and gaseous hydrogen. This is done by using the flow of electrons (into the reaction environment) to
overcome the activation energy barrier of the non-spontaneous redox reaction.
The three primary components of electrolytic cells are:

 Cathode (which is negatively charged for electrolytic cells)

 Anode (which is positively charged for electrolytic cells)
 Electrolyte
The electrolyte provides the medium for the exchange of electrons between the cathode and the anode. Commonly
used electrolytes in electrolytic cells include water (containing dissolved ions) and molten sodium chloride.

Diagram and Working of an Electrolytic Cell

Molten sodium chloride (NaCl) can be subjected to electrolysis with the help of an electrolytic cell, as illustrated
below.

Here, two inert electrodes are dipped into molten sodium chloride (which contains dissociated Na + cations and
Cl– anions). When an electric current is passed into the circuit, the cathode becomes rich in electrons and develops
a negative charge. The positively charged sodium cations are now attracted towards the negatively charged
cathode. This results in the formation of metallic sodium at the cathode.
Simultaneously, the chlorine atoms are attracted to the positively charged cathode. This results in the formation of
chlorine gas (Cl2) at the anode (which is accompanied by the liberation of 2 electrons, finishing the circuit). The
associated chemical equations and the overall cell reaction are provided below.

 Reaction at Cathode: [Na+ + e– → Na] x 2

 Reaction at Anode: 2Cl– → Cl2 + 2e–
 Cell Reaction: 2NaCl → 2Na + Cl2
Thus, molten sodium chloride can be subjected to electrolysis in an electrolytic cell to generate metallic sodium and
chlorine gas as the products.

Applications of Electrolytic Cells

 The primary application of electrolytic cells is for the production of oxygen gas and hydrogen gas from water.
 They are also used for the extraction of aluminium from bauxite.
 Another notable application of electrolytic cells is in electroplating, which is the process of forming a thin protective
layer of a specific metal on the surface of another metal.
 The electrorefining of many non-ferrous metals is done with the help of electrolytic cells.
 Such electrochemical cells are also used in electrowinning processes.
 It can be noted that the industrial production of high-purity copper, high-purity zinc, and high-purity aluminium is
almost always done through electrolytic cells.

. Galvanic Cells vs Electrolytic Cells

Galvanic Cells Electrolytic Cells

Spontaneous redox reactions convert the Non-spontaneous redox reactions convert

chemical energy to an electric energy the electric energy to a chemical energy

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Electric energy is generated by redox reactions Electric energy brings about the chemical
reaction with the help of an external source

The cathode is the positive electrode and anode is the The anode is the positive electrode and
negative electrode cathode is the negative electrode

The process of oxidation takes place at the Here, the oxidation process occurs at the anode
anode and the reduction process occurs at while the reduction process takes place at the
the cathode cathode

Half cells are set up in different containers Electrodes are kept in the same container in
and are connected through salt bridges a molten or solution electrolyte

Application lies in Batteries Application lies in purifying copper and

electroplating

What is Electrode Potential?

According to IUPAC electrode potential has been defined as follows-
In electrochemistry the electrode potential is the electromotive force of a cell built of two electrodes. It
is denoted by the sign E. It is not possible to measure accurately the absolute value of single electrode
potential directly. Only the difference in potential between two electrodes can be measured
experimentally. So, in an experiment to measure electrode potential, in a cell one electrode is used as
a reference electrode whose potential is already known and another electrode is used of unknown
potential. Cell potential is measured experimentally which is equal to the sum of potentials on the two
electrodes.
ECell = ECathode + EAnode
E is measured by voltameter experimentally and electrode potential of one electrode is already known
cell

so electrode potential of another (electrode with unknown electrode potential) can be calculated.
What is Standard Electrode Potential?
The potential of the half-reaction (half-cell) measured against the standard hydrogen electrode under
standard conditions is called the standard electrode potential for that half-cell or half reaction. Standard
conditions mean temperature at 298K, pressure should be 1atm, concentration of the electrolyte used
should be 1M. It is measured with respect to standard hydrogen electrodes.
Standard hydrogen electrode is a gas – ion electrode. It is used as a reference electrode for determination
of standard electrode potential of elements and other half cells. It can act as anode half - cell as well as
cathode half-cell. Value of its standard reduction potential and standard oxidation potential is always
zero at 25℃ or 298K. It is the base of the thermodynamic scale of oxidation – reduction potentials.
Standard electrode potential is denoted by E . Either Standard reduction potential or standard oxidation
0

potential can be calculated for an electrode using standard hydrogen electrode. Standard cell potential
is the difference between standard reduction potentials of two half – cells or half – reactions. It can be
represented as –
E0cell = E0cathode – E0anode

Significance of Standard Electrode Potential

 All electrochemical cells are based on redox reactions, which are made up of two half-reactions.
 The oxidation half-reaction occurs at the anode and it involves a loss of electrons.
 Reduction reaction takes place at the cathode, involving a gain of electrons. Thus, the electrons flow from the anode
to the cathode.
 The electric potential that arises between the anode and the cathode is due to the difference in the individual
potentials of each electrode (which are dipped in their respective electrolytes).
 The cell potential of an electrochemical cell can be measured with the help of a voltmeter. However, the individual
potential of a half-cell cannot be accurately measured alone.
 It is also important to note that this potential can vary with a change in pressure, temperature, or concentration.
 In order to obtain the individual reduction potential of a half-cell, the need for standard electrode potential arises.
 It is measured with the help of a reference electrode known as the standard hydrogen electrode (abbreviated to
SHE). The electrode potential of SHE is 0 Volts.

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 The standard electrode potential of an electrode can be measured by pairing it with the SHE and measuring the cell
potential of the resulting galvanic cell.
 The oxidation potential of an electrode is the negative of its reduction potential. Therefore, the standard electrode
potential of an electrode is described by its standard reduction potential.
 Good oxidizing agents have high standard reduction potentials whereas good reducing agents have low standard
reduction potentials.
 For example, the standard electrode potential of Ca2+ is -2.87 V. and that of F2 is +2.87V. This implies that F2 is a
good oxidizing agent whereas Ca is a reducing agent.
Measuring Electrode Potential
Standard Hydrogen Electrode
A Standard Hydrogen Electrode (SHE) is an electrode that scientists use as a reference on all half-cell potential reactions.
SHE is the most commonly used reference electrode since its potential is exactly equal to Zero at all temperatures. Since
the potential of SHE is zero, it forms the perfect basis to calculate cell potentials using different electrodes or different
concentrations.
Working of SHE
S.H.E. consists of a platinum wire which is connected to a square-shaped platinum electrode which is covered with finely
divided platinum black. This covering of particles of platinum black helps in increasing the surface area of the electrode,
which helps in the efficient conduction of electricity. The whole apparatus is then kept in a glass tube and is placed in a
beaker containing 1M HCl solution. Hydrogen gas is then passed through the tube and into the solution causing the
reaction
2H++2e−⇋H2(g)
During the working of S.H.E. either of the following reactions can take place at the surface of the platinum:
2H++2e−→H2(g) - Reduction
H2(g)→2H++2e− - Oxidation
Depending upon the tendency of other electrodes, S.H.E. can either act as a Cathode (Reduction reaction will take place)
or as an Anode (Oxidation reaction will take place).
If the natural tendency of the other electrode is to undergo Oxidation, S.H.E. will act as a Cathode.
If the natural tendency of the other electrode is to undergo Reduction, S.H.E. will act as an Anode.
S.H.E. is represented as: Pt(s)∣H2(g)∣H(aq)+

Liquid junction potential

Liquid junction potential occurs when two solutions of electrolytes 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, or their ion mobility. If the anions diffuse more rapidly than
the cations, they will diffuse ahead into the dilute solution, leaving the latter negatively charged and
the concentrated solution positively charged. This will result in an electrical double layer of positive
and negative charges at the junction of the two solutions. Thus at the point of junction, a potential
difference will develop because of the ionic transfer. This potential is called liquid junction potential
or diffusion potential which is non-equilibrium potential. The magnitude of the potential depends on
the relative speeds of the 'ions' movement.
Theoretical Background
i. A liquid junction potential is developed when a cell contains two electrolytic solutions of different concentration
in contact with one another (Development of potential at the junction of the two liquids).
ii. ii. The more concentrated solution possesses a tendency to diffuse into the comparatively less concentrated
one.
iii. iii. Large concentration difference between the liquid phases results in high liquid junction potential.
iv. iv. The rate of diffusion of an ion at the junction of the two solutions is proportional to its speed. The rate of
diffusion of each ion ∝ its speed (ion mobility) in an electric field
v. v. It may be regarded as a steady state where an effectively time-independent charge separation is developed. It
is non-equilibrium potential.
vi. vi. The structure of the liquid junction may hardly change as diffusion tends to be a slow process in it.
vii. vii. The dilute solution always acquires the charge of faster moving ion.
If the cations (positively charged ions) move faster from concentrated solution to diluted solution than anions
(negatively charged ions), the (+)ve ions will diffuse ahead of the (-)ve ions in the dilute solution. Thus the
dilute solution will be (+)vely charged with respect to concentrated solution. Similarly, if the anion (negatively
charged ions) moves faster, it will diffuse rapidly than (+)ve ion and the dilute solution will be (-)vely charged.
In both the cases, an electrical double layer is formed at the junction of solutions resulting potential difference.
This potential difference developed at the junction of two solutions is known as liquid junction potential (EL)
or diffusion potential, the magnitude which depends upon the relative speed of the ions. The electrical separation
and potential difference thus arises will continue to increase until the rates of diffusion of (-)ve and (+)ve ions
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are equalized by electrical forces. If two ions are moving with the same speed there will be no liquid junction
potential.

Electrochemical or activity serie When the electrodes (metals and non-metals) in contact with their ions are
arranged on the basis of the values of their standard reduction potentials or standard oxidation potentials, the resulting
series is called the electrochemical or electromotive or activity series of the elements. By measuring the potentials of
various electrodes versus standard hydrogen electrode (SHE), a series of standard electrode potentials has been
established. By international convention, the standard potentials of electrodes are tabulated for reduction half reactions,
indicating the tendencies of the electrodes to behave as cathodes towards SHE. Electrodes with positive E° values for
reduction half reactions do in fact act as cathodes versus SHE, while those with negative E° values of reduction half
reactions behave instead as anodes versus SHE. The electrochemical series is shown in the following table. A cell's standard
state potential is the potential of the cell under standard state conditions, which is approximated with concentrations of
1 mole per liter (1 M) and pressures of 1 atmosphere at 25 C. The negative sign of standard reduction potential indicates
that an electrode when joined with SHE acts as anode and oxidation occurs on this electrode. For example, standard
reduction potential of zinc is -0.76 volt. When zinc electrode is joined with SHE, it acts as anode (-ve electrode) i.e.,
oxidation occurs on this electrode. Similarly, the +ve sign of standard reduction potential indicates that the electrode
when joined with SHE acts as cathode and reduction occurs on this electrode

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Characteristics of Electrochemical Series

• The substances which are stronger reducing agents than hydrogen are placed above hydrogen in the

series

and have negative values of standard reduction potentials.

• All those substances which have positive values of reduction potentials and placed below hydrogen

in the series

are weaker reducing agents than hydrogen.

• The substances which are stronger oxidising agents than H+ ion are placed below hydrogen in the

series.

• The metals on the top (having high negative values of standard reduction potentials) have the

tendency to lose electrons readily. These are active metals.

• The non-metals on the bottom (having high positive values of standard reduction potentials)

have the tendency to accept electrons readily. These are active non-metals.

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Thermodynamics of Redox Reactions

Key Points
o Redox reactions are reactions that transfer electrons between species.
o The Nernst equation allows us to calculate the reduction potential of a redox reaction under “non-standard”
conditions.
o When the system is at equilibrium, the Nernst equation can be simplified and written in terms of the equilibrium
constant, K, which, in turn, allows for derivation of an equation to determine the change in Gibbs free energy
( ΔGΔG ) of the reaction.

Terms
 standard reduction potentialThe reduction potential of a reaction measured under standard conditions: 25 °C,
a 1 M concentration for each participating ion, a partial pressure of 1 atm for each gas, and metals in pure
states.
 Gibbs free energyA thermodynamic potential that measures the “useful” or process-initiating work obtainable
from a thermodynamic system at a constant temperature and pressure.

Reduction Potential

In order to calculate thermodynamic quantities like change in Gibbs free energy ΔGΔG for a general
redox reaction, an equation called the Nernst equation must be used. Walther Nernst was a German
chemist and physicist who developed an equation in the early 20th century to relate reduction
potential, temperature, concentration, and moles of electrons transferred.

The Nernst equation allows the reduction potential to be calculated at any temperature and
concentration of reactants and products; the standard reaction potential must be measured at 298K
and with each solution at 1M.

The Nernst equation is:

E=E0 − (RT/nF)ln Q

Where the terms are as follows:

 E is the reduction potential for the specified non-standard state
 E0 is the standard reduction potential
 R and F are the gas and Faraday constants, respectively
 n is the number of electrons transferred in the reaction
 Q is the reaction quotient CcDd /AaBb. The uppercase letters are concentrations and the lowercase letters are
stoichiometric coefficients for the reaction aA+bB→cC+dD

If T is held constant at 298K, the Nernst equation can be condensed using the values for the constants
R and F:

E=E0−(0.0257/n)ln Q

It can be further simplified if the reaction has reached equilibrium, as in that case Q is the equilibrium
constant K:

lnK=nE0/0.0257

This equation allows the equilibrium constant to be calculated just from the standard reduction
potential and the number of electrons transferred in the reaction.

Gibbs Free Energy Charge

The relationship between the Gibbs free energy change and the standard reaction potential is:

ΔG=−nFE0

In this equation:
 ΔGΔG is the change in free energy
 n is the number of moles
 E0 is the standard potential

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 F is the Faraday constant

Discussion of pH and pKa Values

The Henderson-Hasselback equation is shown below.

pH= pKa – log [A-]/[HA]

where [A-] is conjugate base and [HA] is conjugate acid This equation is often used to determine the proportion
of conjugate base [A- ] and of conjugate acid [HA] one must use to attain a particular pH value of a buffer. You
must know the pKa value for the conjugate acid you will be using. However, the above equation has additional
information that you should understand. Most chemistry students have seen the Henderson-Hassel-bach
equation and probably used it to some extent. In addition, most students probably feel comfortable calculating
the pH and the pKa values using the defined equations shown below:

pH = -log[H-] and pKa= -log[ka]

While the definition of pKa is given above, the functional definition of pKa is often not understood. What the
chemist or biochemist needs to remember is that when the pH is equal to the pKa of an acid, the concentration
of the conjugate base and of the conjugate acid are equal, meaning that there is a 50% proportion of conjugate
base, and a 50% proportion of conjugate acid. By simply entering the concentrations of conjugate base and
conjugate acid into the Henderson-Hasselbach equation, (no matter what the concentration is) are equal, their
ratio is 1:1, meaning that the log of this ratio is zero (0). No matter which acid (represented as a proton [H+]
donor) you are looking at the above relationship holds. For example, since acetic acid has a pKa value of about
4.7, when the pH is equal to that pKa, the proportion of acetate to acetic acid would be 1:1. For another acid,
such as HF, which has a pKa value of about 4.0, when the pH is equal to 4.0, the proportion of the fluoride ion
to the hydrofluoric acid would be 1:1. Ask yourself the following question, and hopefully you will come up
with the correct answer. If you add base (e.g., NaOH) to one of the conjugate acid and conjugate base
combinations above, would the proportion of conjugate base increase or decrease? Obviously (and this is the
correct answer), the proportion of the conjugate base would increase, because in the presence of base, the
conjugate acid reacts (in a neutralization reaction) to produce more of the conjugate base. Please also remember
that the conjugate base, in the presence of base stays conjugate base. Only the conjugate acid will react.

HF + NaOH  NaF + HOH

The above equation shows that the conjugate acid (HF) is converted into the conjugate base (F- ) in the present
of NaOH. This means that the amount of fluoride ion (F-) increases and the amount of HF decreases, giving a
ratio greater than 1:1. What this means, functionally, is that as you increase the pH of a solution above the pKa
value of an acid, the proportion of conjugate base increases and the proportion of the conjugate acid decreases.
For each pH unit increased, the proportion of conjugate base increases by a factor of ten. All you need to do is
to plug these values into the Henderson-Hasselbach equation. Therefore, if you increase the base composition
by the values shown below, you will see that the pH is going to rise.

Ratio of [A-]/[HA] log[A-]/[HA] Increase in pH

101:1 1.0 1.0

102:1 2.0 2.0

103:1 3.0 3.0

106:1 6.0 6.0

If the pH is at least 2.0 pH units above the pKa value, then the proportion of conjugate base is at least 99% of
the solution. This means that whenever the pH increases more than 2.0 pH units, then the major chemical in the
solution would be the conjugate base. Remember that when the pH is equal to the pKa value, the proportion of
the conjugate base and conjugate acid are equal to each other. As the pH increases, the proportion of conjugate
base increases and predominates. Conversely, for the same reason, as the pH decreases (solution becomes more
acidic), the proportion of the conjugate acid goes up, and predominates. To take two extremes, consider the
following. At pH=12, both acetic acid and hydrofluoric acid would exist as their conjugate bases (greater than
99.999999% conjugate base). Alternatively, as the pH goes down to pH=1, then their conjugate acids
predominate, with a proportion of at least 99.99%. Therefore, if you know the pH of a solution, and the pKa
value of an acid, you can quickly determine whether the conjugate base or conjugate acid predominates. If you
are at least 2.0 pH units above the pKa, then the conjugate base is at least 99% of the total. If the pH is at least
2.0 pH units below the pKa, then the conjugate acid is at least 99% of the total. Inherent to the explanation given

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above, you must know the pH of the solution containing an acid-base conjugate pair, and the pKa of that
conjugate pair.
Ways of Measuring pH
The methods for measuring pH fall roughly into the following four categories:

 Indicator methods
 Metal-electrode methods (including the hydrogen-electrode method, quinhydron-electrode method and
antimony-electrode method)
 Glass-electrode methods
 Semiconductor sensor methods
Then, each measuring method is explained briefly.

(1) Measuring pH Using an Indicator

This category basically includes two methods: One involves comparing the standard color corresponding
to a known pH with the color of an indicator immersed in the test liquid using buffer solution. The other
method involves preparing pH test paper which is soaked in the indicator, then immersing the paper in the
test liquid and comparing its color with the standard color. This method is simple, but prone to error. A
high degree of accuracy cannot be expected.
* Various errors include;
- Error due to high salt concentration in the test liquid
- Error due to the temperature of the test liquid
- Error due to organic substances in the test liquid
The indicator method cannot measure the pH of high-purity water, since the influence of the indicator itself
is too large.
(2) Hydrogen-Electrode Method
A hydrogen electrode is made by adding platinum black to platinum wire or a platinum plate. It is immersed
in the test solution and an electric charge is applied to the solution and the solution is saturated with
hydrogen gas.The electrode potential is measured between platinum black electrode and silver chloride
electrode. This potential is inversely proportional to pH of the solution.
The hydrogen-electrode method is a standard among the various methods for measuring pH. The values
derived using other methods become trustworthy only when they match those measured using hydrogen
electrode method.
However, this method is not appropriate for daily use because of the effort and expense involved, with the
inconvenience of handling hydrogen gas and great influence of highly oxidizing or reducing substances in
the test solution.

(3) Quinhydron-Electrode Method

When quinhydrone is added to a solution, it separates into hydroquinone and quinone.
Because quinone’s solubility varies depending on the pH value of the solution, pH can be determined from
the voltage between a platinum and reference electrode.
Although this method is simple, it is seldom used today, because it does not work when oxidizing or
reducing substances are involved, or when the test solution has a pH above 8 or 9.
Note: Quinhydron solution of a certain pH is sometimes used to check whether an ORP meter is operating
normally. The principle of the quinhydron electrode is applied in such a case.

(4) Antimony-Electrode Method

This method involves immersing the tip of a polished antimony rod into a test solution, also immersing a
reference electrode, and measuring pH from the difference in potential between them. This method was
once widely used because the apparatus is sturdy and easy to handle. However, its application is now quite
limited because results vary depending on the degree of polish of the electrode, and reproducibility is low.

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 ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI
Note: This method is now used only in cases where a high degree of accuracy is not required (only for
industrial use) and the test solution contains F-.
(5) Glass-Electrode Method
The glass electrode method uses two electrodes, a glass electrode and reference electrode, to determine the
pH of a solution by measuring the voltage (potential) between them.
This method is the one most commonly used for pH measurement, since the potential quickly reaches
equilibrium and shows good reproducibility, and because the method can be used on various types of
solutions, with oxidizing or reducing substances having very little impact on the result.
The glass electrode method is widely used, not only in industry but also in many other fields.
In its “Methods of pH Measurement” section, JIS states, “Since measurement using a hydrogen electrode,
as described in the definition section, is not necessarily appropriate, measurement using a glass electrode
is recommended for industrial pH measurement.”

(6)Semiconductor sensor methods

The semiconductor pH sensor, whose development started around 1970, replaces a glass electrode with a
semiconductor chip. This sensor, known as an ion sensitive field effect transistor (ISFET), is not only
resistant to damage but also easily miniaturized. Miniaturization allows the use of smaller amounts of
sample for measurement, and makes it possible to perform measurements in very small spaces and on solid
state surfaces. This sensor promises useful applications in measurement in the fields of biology and
medicine.

pH imaging
This is a measurement method in which pH is determined at multiple points and the results displayed as an
image. It has been attracting attention as a technology for visualizing pH distributions.
Historically, the method mentioned in Section (1), which combines pH indicators and microscopes, has
been used to measure the pH inside cells. However, the invention of pH-sensitive dyes and proteins as a
replacement for pH indicators has aided investigation of pH distribution in cells.

What is a Fuel Cell?

A fuel cell can be defined as an electrochemical cell that generates electrical energy from fuel via an electrochemical
reaction. These cells require a continuous input of fuel and an oxidizing agent (generally oxygen) in order to sustain
the reactions that generate the electricity. Therefore, these cells can constantly generate electricity until the supply
of fuel and oxygen is cut off.
Despite being invented in the year 1838, fuel cells began commercial use only a century later when they were used
by NASA to power space capsules and satellites. Today, these devices are used as the primary or secondary source
of power for many facilities including industries, commercial buildings, and residential buildings.
A fuel cell is similar to electrochemical cells, which consists of a cathode, an anode, and an electrolyte. In these
cells, the electrolyte enables the movement of the protons.

Working of Fuel Cell

The reaction between hydrogen and oxygen can be used to generate electricity via a fuel cell. Such a cell was used
in the Apollo space programme and it served two different purposes – It was used as a fuel source as well as a
source of drinking water (the water vapour produced from the cell, when condensed, was fit for human consumption).
The working of this fuel cell involved the passing of hydrogen and oxygen into a concentrated solution of sodium
hydroxide via carbon electrodes. The cell reaction can be written as follows:
Cathode Reaction: O2 + 2H2O + 4e– → 4OH–
Anode Reaction: 2H2 + 4OH– → 4H2O + 4e–
Net Cell Reaction: 2H2 + O2 → 2H2O
However, the reaction rate of this electrochemical reaction is quite low. This issue is overcome with the help of a
catalyst such as platinum or palladium. In order to increase the effective surface area, the catalyst is finely divided
before being incorporated into the electrodes.
A block diagram of this fuel cell is provided below.

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 ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI

The efficiency of the fuel cell described above in the generation of electricity generally approximates to 70% whereas
thermal power plants have an efficiency of 40%. This substantial difference in efficiency is because the generation
of electric current in a thermal power plant involves the conversion of water into steam, and the usage of this steam
to rotate a turbine. Fuel cells, however, offer a platform for the direct conversion of chemical energy into electrical
energy.

Types of Fuel Cells

Despite working similarly, there exist many varieties of fuel cells. Some of these types of fuel cells are discussed in
this subsection.

The Polymer Electrolyte Membrane (PEM) Fuel Cell

 These cells are also known as proton exchange membrane fuel cells (or PEMFCs).
 The temperature range that these cells operate in is between 50oC to 100o
 The electrolyte used in PEMFCs is a polymer which has the ability to conduct protons.
 A typical PEM fuel cell consists of bipolar plates, a catalyst, electrodes, and the polymer membrane.
 Despite having eco-friendly applications in transportation, PEMFCs can also be used for the stationary and portable
generation of power.

Phosphoric Acid Fuel Cell

 These fuel cells involve the use of phosphoric acid as an electrolyte in order to channel the H+
 The working temperatures of these cells lie in the range of 150oC – 200o
 Electrons are forced to travel to the cathode via an external circuit because of the non-conductive nature
of phosphoric acid.
 Due to the acidic nature of the electrolyte, the components of these cells tend to corrode or oxidize over time.

Solid Acid Fuel Cell

 A solid acid material is used as the electrolyte in these fuel cells.
 The molecular structures of these solid acids are ordered at low temperatures.
 At higher temperatures, a phase transition can occur which leads to a huge increase in conductivity.
 Examples of solid acids include CsHSO4 and CsH2PO4 (cesium hydrogen sulfate and cesium dihydrogen phosphate
respectively)

Alkaline Fuel Cell

 This was the fuel cell which was used as the primary source of electricity in the Apollo space program.
 In these cells, an aqueous alkaline solution is used to saturate a porous matrix, which is in turn used to separate
the electrodes.
 The operating temperatures of these cells are quite low (approximately 90oC).
 These cells are highly efficient. They also produce heat and water along with electricity.

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 ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI
Solid Oxide Fuel Cell
 These cells involve the use of a solid oxide or a ceramic electrolyte (such as yttria-stabilized zirconia).
 These fuel cells are highly efficient and have a relatively low cost (theoretical efficiency can even approach 85%).
 The operating temperatures of these cells are very high (lower limit of 600 oC, standard operating temperatures lie
between 800 and 1000oC).
 Solid oxide fuel cells are limited to stationary applications due to their high operating temperatures.

Molten Carbonate Fuel Cell

 The electrolyte used in these cells is lithium potassium carbonate salt. This salt becomes liquid at high temperatures,
enabling the movement of carbonate ions.
 Similar to SOFCs, these fuel cells also have a relatively high operating temperature of 650o
 The anode and the cathode of this cell are vulnerable to corrosion due to the high operating temperature and the
presence of the carbonate electrolyte.
 These cells can be powered by carbon-based fuels such as natural gas and biogas.

Applications of fuel cell

Fuel cell technology has a wide range of applications. Currently, heavy research is being conducted in order to
manufacture a cost-efficient automobile which is powered by a fuel cell. A few applications of this technology are
listed below.

 Fuel cell electric vehicles, or FCEVs, use clean fuels and are therefore more eco-friendly than internal combustion
engine-based vehicles.
 They have been used to power many space expeditions including the Appolo space program.
 Generally, the by products produced from these cells are heat and water.
 The portability of some fuel cells is extremely useful in some military applications.
 These electrochemical cells can also be used to power several electronic devices.
 Fuel cells are also used as primary or backup sources of electricity in many remote areas.
Thus, the different types of fuel cells and the working of an alkaline fuel cell are briefly discussed in this article along
with some applications of these electrochemical cells.

Corrosion
Definition
Corrosion is the deterioration of a metal, as a result of its reactions with the environment or any chemical
agent.
It is an oxidation process that occurs at the surface of the metal.

Causes of Corrosion
Corrosion may be regarded as the natural tendency of metals to return to their oxidized state. The main
causes of corrosion are as follows.

1. The atmosphere
2. Submersion in water
3. Underground Soil Attack
4. Emersion in chemicals
5. Corrosive gases
The most important of these is the atmosphere.

Examples of Corrosion
Some familiar examples of corrosion are as follows.
1. Rusting of Iron
2. Detarnishing of silver
3. Development of green coating on copper, brass and bronze.
Types of Corrosion
There are two types of corrosion.

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 ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI

1. Atmospheric Corrosion
When corrosion in metal is due to the action of atmosphere, it is known as atmospheric corrosion.

2. Corrosion in Liquid
When corrosion in metal is due to the reaction of a liquid on a metal, it is known as corrosion in liquid.

Rate of Corrosion
Corrosion is a chemical process. Different metals corrode at different rates. Gold does not corrode at all.
Iron corrodes slowly. Tin, lead, copper and silver corrode very slowly.

Mechanism of Rusting of Iron Electrochemical Theory of

Rusting
The overall rusting involves the following steps,
(i) Oxidation occurs at the anodes of each electrochemical cell. Therefore, at each anode neutral iron atoms are
oxidised to ferrous ions.

At anode :
Thus, the metal atoms in the lattice pass into the solution as ions, leaving electrons on the metal itself. These
electrons move towards the cathode region through the metal.

(ii) At the cathodes of each cell, the electrons are taken up by hydrogen ions (reduction takes place). The ions
are obtained either from water or from acidic substances (e.g. in water

or

At cathode :

The hydrogen atoms on the iron surface reduce dissolved oxygen.

Therefore, the overall reaction at cathode of different electrochemical cells may be written as,

(iii) The overall redox reaction may be written by multiplying reaction at anode by 2 and adding reaction at
cathode to equalise number of electrons lost and gained i.e.

Oxi. half reaction :

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 ELECTROCHEMISTRY BS CHEMISTRY 6TH SEMESTER BY: PROF MIRAJ MUNEER BHATTI
Red. half reaction :

Overall cell reaction :

The ferrous ions are oxidised further by atmospheric oxygen to form rust.

and

It may be noted that salt water accelerates corrosion. This is mainly due to the fact that salt water increases the
electrical conduction of electrolyte solution formed on the metal surface. Therefore, rusting becomes more
serious problem where salt water is present.

Prevention From Corrosion

Corrosion causes great damages to metallic articles such as bridges, ships and vehicles. It has been
found out that due to corrosion, one fifth of iron is lost annually. Therefore, any one of the following
methods are adopted to prevent corrosion.
1. By applying oil, grease, paint or varnish on the surface.
2. By coating/depositing a thin layer of any other metal which does not corrode. For example, iron
surface can be protected from corrosion by depositing a thin layer of zinc, nickel or chromium on it.
Copper/brass can be protected by coating it with a thin layer of tin. Tinning of brass utensils is a very
common practice in our country.
(ii) By connecting metal to a more electropositive metal: A metal can be protected from corrosion by
connecting it to a more electropositive metal. As long as the more electropositive metal is there, the given metal
does not get corroded. For example, iron can be protected from corrosion by connecting it to a block/plate of
zinc or magnesium. This method of corrosion protection is called cathodic protection.
(iii) By forming insoluble phosphate or chromate coating: Metal surfaces are treated with phosphoric acid
to form an insoluble phosphate coating on the surface. This phosphate coating protects the metal from corrosion.
Formation of a thin chromate layer also prevents the corrosion of metals

3. Protective Metallic Coating

In this method, the metal is coated with a thin layer of less oxidizing metal, which reduces the rate of
corrosion. For example, corrosion of iron is prevented by coating it with zinc, tin or chromium.

4. Non-Metallic Material Coating

In this method, the metal is coated with a thin layer of non metallic material such as paints, oils, grease,
plastic emulsion, enamels etc. For example, red lead (Pb3O4) and zinc chromate (ZnCrO4) are often used
for this purpose.

5. Alloying of Metals
Metals can be made more resistant against corrosion by making their alloys. For example, stainless steal
is an alloy of Fe, Cr and Ni.

6. Electro-Plating
Noble and bare metals are used for Electro-Plating on any desired metal.

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