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Lecture 1

1. Robert J. Silbey, Robert A. Alberty, Moungi G. Bawendi,
Physical Chemistry, 4th Edition, John Wiley & Sons 2005.

2. Peter Atkins, Julio de Paula, Physical Chemistry, 9th edition,

W. H. Freeman and Company, New York 2010.

3. Robert M. Hanson and Susan Green, Introduction to

Molecular Thermodynamics, University Science books 2008.

4. Ken A. Dill and Sarina Bromberg, Molecular Driving Forces,

Second edition, Garland Science, New York 2011

5. Herbert B. Callen, Thermodynamics and an introduction to

thermostatistics Second edition, John Wiley & Sons 1985.
Thermodynamics is probably the most important subject in
chemistry. We need it everyday, often without realizing!

Let me ask you the following questions:

Why water flows from high to low amplitude and heat flows
from high to low temperature?
Why living things grow and decay?
Reactions in the laboratory happen, sometimes
spontaneously, sometimes by heating?
Why cant we build a machine that runs forever? Or make a
machine that takes heat from ocean and run?

Answer lies in the laws of thermodynamics.

And the answer is: entropy of the universe is behind every
phenomenon that is occurring in nature? It is unbelievable,
intriguing, but true!

Thermodynamics teaches us that we need to pay for everything

there is no free lunch and also shows us our ultimate destiny!
We have learnt how to get an estimate of energy of the matter, but
the stability of the matter lies completely in the hands of entropy.

What is thermodynamics? It is a term coined by William Thomson

in 1854. He synthesized the subject of Carnots motive power of
heat (1824), Joules mechanical equivalent of heat (1842), and
Clausius mechanical theory of heat (1850) in a subject called
thermodynamics. Broadly speaking, it is the subject on the
dynamics of heat.

In reality, thermodynamics is the subject of understanding the

enigma of entropy, which originates from the redistribution of
energy. It can be thought of also as a measure of randomness.
Precise definition will come later, but entropy depends on the
heat and temperature. So we start with these first.

Thermodynamics is a subject of equilibrium properties.

What is meant by equilibrium? A system is in equilibrium where

there is no visible change in the system during the course of
observation. (a building is in equilibrium over months, but out of
equilibrium over 100s of years).

Thermodynamics is also a subject of macroscopic systems

(a glass of water, moles of gasses, etc.), developed by several
people. Most notably by Clausius, Kelvin, Gibbs around 1840s.

Molecular thermodynamics, i.e., understanding thermodynamics

in terms of atoms and molecules proposed soon around 1870s by

In this course, we will follow both approaches to understand the

applicability and molecular origin of the thermodynamic
driving forces of nature that rule every change.

Driving force: What is then the driving force for every change?
(i.e., melting of ice, diffusion of gases, etc.)

Ans: All changes happen due to statistics of blind change, i.e., all
changes occur to go from a less probable to a more probable state,
and most probable distribution originates to maximize the

So, everything is based on probability? Yes! Including our own

existence, and possibly the existence of our universe, as well.
Timeline of Thermodynamics

Beginning of thermodynamics was probably the theory on the

denial of void

Denial of void by Parmenides' (485BC) :

A void or vacuum, in nature, cannot exist.

Torricellis barometer is based on vaccuum

theory (c.1640)

German engineer Guericke showed the power of vacuum and

created an engine with that (1650). He built Magdeburg

24 horses could not take apart the hemispheres when it was

vacuumed. It is one of the most famous experiment

Boyles pneumatical engine (1658): Based

on the theory of void, Robert Boyle built a
vacuum pump/air pump combination device
with which Boyles law was determined. It was first of the gas laws:
P is inversely proportional to V, or PV = constant
at given number of particles and temperature.
Huygens gunpowder engine (1678): Dutch scientist
Christiaan Huygens built a gunpowder engine, which
worked on the principle of vacuum.
French scientist Denis Papin (1679): Built a bone
digester. Then he built a steam engine around 1690. He
could move the piston up and down by a cycle of heating
and cooling. James Watt later (1730) modified the design
to make a proper steam engine.

Boerhaave's law: It is very obvious to us now that when

something is heated, it expands in volume (not always,
though). It is mostly true for gases. It was first
demonstrated by Boerhaave using a ball and ring

Antoine Lavoisier introduced

the concept of caloric theory. This
theory postulates that heat is composed
of a type of fluid made from
indestructible particles called
caloric. This fluid would pass from a
hot body to a cold body

Joules paddle wheel experiment: Mechanical equivalent

of heat.
Work done by the gravity on the
weight results into heat in the

This means the heat is related to

work. In fact, there is a direct
correspondence or proportionality,
1 cal = 4.2 J.

Joule also measured the temperature above and below the water
falls and the temperature of water indeed was different.