‫جیتنے ہیں صرف وہی لوگ جو جیتنے کی ہمت کرتے ہیں )‪Nur wer wagt , gewinnt (German proverb‬‬

Explore your imaginations and break your minds barrier

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Interdependence is of higher value SMILE – How important There is nothing Be more concerned with your character
than independence it is to smile at right to fear, it is only than with your reputation because
time and also when it to understand a character is what you really are, while
comes from the heart reputation is merely what other thinks
problem
you are

Lecture 5 – Electrochemistry; Conductometry; Potentiometry; Coulometry

& Voltametry
Physical Chemistry (2575) - BS (5th Semester)
Allama Iqbal Open University, H8 Islamabad
Tuesday 28-10-2024 (13:00 – 16:00 hrs)

Dr. (Ph.D. 1997) Shabana Waseem (PoP2019), CS (R-PAEC Sept. 2022)

Email: swans.aioue@gmail.com
Dr Shabana Waseem (POP) - 22102024
• Unit 1&2 1. Introduction; 2. Rate Laws; 3. Rate constants; 4. Reaction orders; 5. Experimental Techniques to monitor the reaction rate;; 6. Integrated rate law; 7. Derivations of
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rate expressions for zero, first order, second order, third order and pseudo order reactions; 8. Temperature dependence of reaction rate; 9. Arhenius equation; 10.
Chemical Kinetics Activation Energy; 11. Elementary reactions and reaction mechanism; 12. onsecutive elementary reactions; 13. Theories of reaction rates; 14. Steady state approximation;

• Unit 3&4
15. Lindemann – Hinshelwood mechanism

1. Fundamentals, Uses, Advantages, Scope, and applications of electrochemistry; 2.

Electrochemistry Electrochemical system; 3. Redox reactions; 4. Spontaneous reactions; 5. Liquid junction
Potential; 6. Measurements of pH and pKa, 7. Nernst’s equation, 8. Thermodynamics of redox
• Unit 5 reactions; 9. Half cell reactions and electrode; 10. Electrochemical cells; 11. The electromotive
force (EMF), 12. Standard electrode potential and its applications
Conductometry
• Unit 6 1. Ions in Solution; 2. Measurement of conductance and Kohlrausch’s law; 3. Mobility of
Potentiometry ions and transport number; 4. Conductometric titrations; 5. Debye-Huckel theory and
activity coefficient; 6. Determination of activities; 7. Application of conductance
• Unit 7 measurements

Coulometry/ 1. Basic principle; 2. Working of potentiometers; 3. Types of electrode used (Reference,

Indicator and counter electrode; 4. pH meter; 5. Working of glass membrane electrode; 6.
Voltametry Other types of electrode; 7. Potentiometric titrations
• Unit 8
Surface chemistry 1. Basic principle; 2. Faraday’s law of electrolysis; 3. Types of coulometry; 4. Controlled
• Unit 9 potential coulometry; 5. Controlled current coulometry; 6. Voltametry, its
Nuclear chemistry types and its applications

Assignment 1 (submission before mid term) Search any field of life that does not involve chemistry (directly or indirectly)
Assignment 2: (submission before final) Implementing physical chemistry on i) self cleaning materials & ii) solar energy
Dr Shabana Waseem (POP) - 22102024
a - Voltmeter

b – Salt bridge

c - Electrode

d - Electrolyte

e - Electrode

f - Electrolyte

g – conducting wire
 Conductance, or electrical conductance, measures a material’s ability to conduct electricity, essentially showing
how easily an electrical current can flow through it. It is the opposite of electrical resistance, mathematically
expressed as 1/R.
The wire
This is the simplest part of the setup. The wire
allows electrons to travel between the two half-
cells. Often it connects to a device called a
voltmeter which measures the potential.
Voltmeters are useful for monitoring the progress
of the reaction, but not required. The conductor
doesn’t HAVE to be a wire, but wires are the most
common way of connecting the cells for these
types of setups.
Salt bridge: The salt bridge is usually an
inverted U-tube filled with a concentrated
solution of inert electrolytes. It is used to
Electrolytic solutions are those that are capable of conducting an maintain the charge balance and to complete
electric current. A substance that, when added to water, renders it the circuit by allowing the flow of ions through it.
conductive, is known as an electrolyte. A common example of an e It contains a gel in which inert electrolytes like
lectrolyte is ordinary salt, sodium chloride. Solid NaCl and pure KNO3 or K2SO4 are mixed. Through the salt
water are both non- conductive, bridge, negative ion flows towards the anode
but a solution of salt in water is readily conductive. A solution of su and positive ion flows to the cathode, and the
gar in water, by contrast, is incapable of conducting a current; sugar charge balance is maintained, and the cell
is therefore a non-electrolyte. keeps on functioning.
Electrode potential: In a galvanic cell, when Zn(s) + Cu+2(aq) → Zn+2 + Cu(s) 6/15
two-electrode are dipped in their respective ion,
there is a tendency for one of the electrodes At anode (oxidation half),
(anode) to undergo oxidation, whereas the ion Zn(s) →Zn+2 + 2e–
At cathode( reduction half),
of the other electrode (cathode) has the Cu+2(aq) + 2e– → Cu(s)
tendency to gain an electron. This tendency of
losing of electrons (oxidation) or gaining of
electrons (reduction) is called electrode
potential.
Standard electrode potential (E0): Standard
electrode potential is defined as the electrode
potential of an electrode relative to a standard
hydrogen electrode under standard conditions.
The standard conditions taken are as follows:
•1 molar concentration of each ion in the
solution.
•A temperature of 298 K.
•1 bar pressure.
Dr Shabana Waseem (POP) - 22102024
Electrochemical Series
A series of the standard electrode has been established by measuring the potential of various electrodes versus 7/15
standard hydrogen electrodes (SHE). When the electrodes (metals and non-metals) in contact with their ions are
arranged on the basis of the values of their standard reduction potential or standard oxidation potentials, the resulting
series is called the electrochemical series.

Dr Shabana Waseem (POP) - 22102024

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Dr Shabana Waseem (POP) - 22102024

Cell Notation Rules
1. The anode half-cell is described first; the cathode half-cell follows.
Within a given half-cell, the reactants are specified first and the products last.
The description of the oxidation reaction is first, and the reduction reaction is
last; when you read it, your eyes move in the direction of electron flow.
2. A single vertical line ( | ) is drawn between two chemical species that are in
different phases but in physical contact with each other (e.g., solid electrode |
liquid with electrolyte ). A double vertical line ( || ) represents a salt bridge or
porous membrane separating the individual half-cells.
3. The phase of each chemical (s, l, g, aq) is shown in parentheses. If the
electrolytes in the cells are not at standard conditions, concentrations and/or
pressure, they are included in parentheses with the phase notation. If no
concentration or pressure is noted, the electrolytes in the cells are assumed to
be at standard conditions (1.00 M or 1.00 atm and 298 K).
Using these rules, the notation for the cell we put together is:
Cd (s) | Cd2+ (aq, 0.15 M) || Ag+ (aq, 0.20 M) | Ag (s)
Cell potential or emf of a cell: 10/15
In the galvanic cell, there are two half-cells, the oxidation
half-cell (anode) and the reduction half-cell (cathode). Due
to the difference in the potentials of these half-cells, the
electric current moves from the electrode of higher
potential (cathode) to the electrode of lower potential
(anode). The difference between the electrode potential of
the two half-cells is called cell potential or emf of a cell.

Eocell= ECathode– Eanode

ECathode= standard reduction potential of the cathode.

Electrode and cell potentials – Nernst equation: The
Eanode= standard reduction potential of the anode. electrode potential and the emf of the cell depend upon
the nature of the electrode, temperature and the
If Eocell is positive, then the reaction is feasible. activities (concentrations) of the ions in solution.
For the general electrochemical reaction of the type:
If Eocell is negative, then the reaction is not feasible. aA + bB → cC +dD
Ecell = Eocell – RT/ nF ln [C]c [D]d / [A]a [B]b

Ecell = Eocell – 2.0303 RT / nF log [C]c [D]d / [A]a [B]b

Ecell = Eocell – 0.0591 / n log [C]c [D]d / [A]a [B]b at 298K

Dr Shabana Waseem (POP) - 22102024
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Dr Shabana Waseem (POP) - 22102024

Conductivity
Conductivity refers to a material’s ability to transfer energy,
defining its electromagnetic properties. It measures how
much a material influences current flow when exposed to an
electric field, often linked to the current’s density created by
the field.
Conductance of a conductor also depends on factors like
shape, size, and a specific property known as its conductivity.
In electronics, conductance quantifies how much current a
device generates per unit of applied voltage. Represented by
the letter ‘G’, it is the reciprocal of resistance, ‘R’. Ohm’s law,
stated as , helps calculate this by defining R as: (1)
In metallic solids, the charge carriers are
electrons rather than ions; their mobility
is a consequence of the quantum-
mechanical uncertainty principle which
promotes the escape of the electrons fro
m the confines of their local atomic envir
onment.
In the case of electrolytic solutions, Farad
ay called the charge carrier ions (after the
Greek word for "wanderer"). His most im
portant finding was that each kind of ion (
which he regarded as an electrically-
charged atom) carries a definite amount o
f charge, most commonly in the range of
±1-3 units.
1.The matter must be composed of, or
contain, electrically charged particles.
2.These particles must be mobile; that
is, they must be free to move under t
he influence of an external applied ele
ctric field.
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Dr Shabana Waseem (POP) -

22102024
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