Chapter 1

Thermodynamics

What is Thermodynamics ?

The branch of physical science that deals with

the relations between heat and other forms of
energy (such as mechanical, electrical, or
chemical energy), and, by extension, of the
relationships between all forms of energy.

Properties of Substance in Thermodynamic

Temperature:Temperature is a measure of the average kinetic energy of the particles in a sample
of matter, expressed in terms of units or degrees designated on a standard scale,"
according to the American Heritage Dictionary.

Conversion between Fahrenheit and Celsius

If we know Celsius and want Fahrenheit
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C 32
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If we know Fahrenheit and want Celsius
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F 32
C
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F

Pressure

Force
Pressure
Area

Example
120 lb woman putting all her weight on 2 in2 of heals.
Pressure = 120 lb/2in2 = 60 lb/in2.
Is that a lot?
Comparison: 1 atm = 14.7 lb/in2. Thus of heals is
approximately 4 atm.
This is the pressure you would feel at a depth of
approximately 133 ft of water.
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Enthalpy :- a thermodynamic quantity equivalent to the total heat content of a system. It

is equal to the internal energy of the system plus the product of pressure and volume.
Entropy :a thermodynamic quantity representing the unavailability of a system's thermal energy
for conversion into mechanical work, often interpreted as the degree of disorder or
randomness in the system.
Mass:the property of matter that measures its resistance to acceleration.
Roughly, the mass of an object is a measure of the number of atoms in it.
The basic unit of measurement for mass is the kilogram.
Volume :The amount of space occupied by a three-dimensional object or region of space.
Volumes are expressed in cubic units.

examples of entropy
On the large scale, the ice
looks more disordered.
On the small scale, the solid
phase severely limits where the
molecules could be.
The ice crystal molecules are
much more ordered than the
free moving liquid water
molecules.
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Thermodynamic systems
To understand the laws of thermodynamics and how they work, first we need to get the
terminology right. Some of the terms may look familiar (as they are used in everyday
language as well)- but their meanings are more technical and precise, when used in TD
and hence we should not use them casually.
System is region where we focus our attention (Au block in figure).
Surrounding is the rest of the universe (the water bath at constant temperature).
Universe = System + Surrounding
More practically, we can consider the Surrounding as the immediate neighborhood of the
system (the part of the universe at large, with which the system effectively interacts).
In this scheme of things we can visualize: a system, the surrounding and the universe at
large.

In TD we usually
we do not worry
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about the universe at large!

Open, closed and isolated systems

To a thermodynamic system two things may be added/removed:
energy (heat, work) matter.
An open system is one to which you can add/remove matter (e.g. a open beaker to which
we can add water). When you add matter- you also end up adding heat (which is
contained in that matter).
A system to which you cannot add matter is called closed.
Though you cannot add/remove matter to a closed system, you can still add/remove heat
(you can cool a closed water bottle in fridge).
A system to which neither matter nor heat can be added/removed is called isolated.
A closed vacuum thermos flask can be considered as isolated.
Type of boundary

Interactions

Open

All interactions possible

Closed

Matter cannot enter or leave

Semi-permeable

Only certain species can enter or leave

Insulated

Heat cannot enter or leave

Rigid

Mechanical work cannot be done*

Isolated

No interactions are possible**

* By or on the system
** Mass, Heat or Work

Mass

Interactions possible

Work

Heat
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The Zeroth Law states that if two bodies are in thermal equilibrium with some third body,
then they are also in equilibrium with each other. This establishes temperature as a
fundamental and measurable property of matter.
The First Law states that the total increase in the energy of a system is equal to the
increase in thermal energy plus the work done on the system. This states that heat is a
form of energy and is therefore subject to the principle of conservation.
The Second Law states that heat energy cannot be transferred from a body at a lower
temperature to a body at a higher temperature without the addition of energy. This is why
it costs money to run an air conditioner.
The Third Law states that the entropy of a pure crystal at absolute zero is zero. As
explained above, entropy is sometimes called "waste energy," i.e., energy that is unable
to do work, and since there is no heat energy whatsoever at absolute zero, there can be
no waste energy. Entropy is also a measure of the disorder in a system, and while a
perfect crystal is by definition perfectly ordered, any positive value of temperature means
there is motion within the crystal, which causes disorder. For these reasons, there can
be no physical system with lower entropy, so entropy always has a positive value.
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Processes in TD
Here is a brief listing of a few kinds of processes, which we will encounter in TD:
Isothermal process the process takes place at constant temperature T=C
(e.g. freezing of water to ice at 10C)
Isobaric constant pressure P=C
(e.g. heating of water in open air under atmospheric pressure)
Isentropic process s=C
Isochoric constant volume v=C
(e.g. heating of gas in a sealed metal container)
Reversible process the system is close to equilibrium at all times (and infinitesimal
alteration of the conditions can restore the universe (system + surrounding) to the original
state.
Cyclic process the final and initial state are the same. However, q and w need not be
zero. (VCC)
Adiabatic process delta H is zero during the process (no heat is added/removed to/from
the system) Q=0

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https://www.khanacademy.org/science/phy
sics/thermodynamics

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