Introduction to

Thermodynamics
Introduction
 Thermodynamics is the science of the relations between heat, work and
the properties of systems.
 Thermodynamics is the science of energy transfer and its effects on the
physical properties of substances.
 Thermodynamics is primarily based upon the observations of common
experience formulated into laws, which govern energy conversion.
Thermodynamic System

In the study of any special branch of physics we usually start with a separation
of a restricted region of space or a finite portion of matter from its surroundings.
The portion that is set aside and on which attention is focused is called the system.

System is a fixed and identifiable collection of matter enclosed by a real or imaginary

surface which is impermeable to matter but which may change its shape or volume.
The surface is called the boundary.

 Surroundings or environment: Everything outside the system which has a direct bearing
on the system's behavior.
Classes of Systems
• Closed system:
Fixed mass. No mass transfer across the system boundary;
energy transfer into or out of the system may occur
• Open system:
Matter crosses the boundary of the system; energy transfer
may also exist
• Isolated system:
There is no interaction between the system and the surrounding
Macroscopic Vs Microscopic
When a system has been chosen, the next step is to describe it in
terms of quantities related to the behavior of the system or its
interactions with the surrounding or both. Two points of view may
be adopted: macroscopic or microscopic

Microscopic approach considers the behavior of every molecule

by using statistical methods. The study based on this approach is
generally called “Molecular thermodynamics”

In Macroscopic approach we are concerned with the gross or

average effects of many molecules' interactions. These effects,
such as pressure and temperature, can be perceived by our senses
and can be measured with instruments. This approach greatly
reduces the complexity of the problem and we use this approach in
this course. This is known as "Classical Thermodynamics".
Property
The conditions of the system, and the substance within it, is defined
by the properties of a system.

A Property is any observable characteristic of a system.

Properties can be defined only when they are uniform throughout a
system

• Examples:
– Length,
– volume,
– pressure,
– density,
– refractive index, etc.
 Property: Pressure

Pressure: A property which is quite important in thermodynamics.

A fluid exerts forces on its boundaries, due to the change in

momentum of molecules when they collide with the boundary.
These forces are not concentrated at one point, due to
random motion of molecules but are distributed.
Therefore, we can define pressure as the normal force exerted on a
surface, divided by the area of the surface.
The unit of pressure is the force 1 Newton acting on a square metre
area, which is called a Pascal.
Property: Pressure
In most thermodynamics investigations we are concerned with the
absolute pressure. However, most pressure gauges measure the
difference between the absolute pressure and the atmospheric
pressure which is known as gauge pressure.
Extensive & Intensive Properties
In general, one can make distinction between two types of properties.
(i) Extensive: Extensive properties are those whose value is the sum of the
values for each subdivision of the system, eg mass, volume.
(ii) Intensive Properties are those which have a finite value as the size of the
system approaches zero, eg pressure, temperature, etc.

Extensive properties may be made intensive by dividing them by

the system mass. For example:
system volume = 12 m3, mass = 4 kg
system specific volume = 12/4 = m3/kg
State
The state of a system is fixed by defining all its properties or
sufficient properties so that all others may be described. The state
of a system changes if any property changes. In most of the simple
systems that we shall consider a small number of properties will be
enough to completely define the state of a system.

Equilibrium
A system is in thermodynamic equilibrium if no tendency towards
spontaneous change exists within the system. Energy transfers across
the system disturb the equilibrium state of the system but may not shift
the system significantly from its equilibrium state if carried out at low
rates of change.

Note: to define the properties of a system, they have to be uniform

throughout the system. Therefor to define the state of a system, the
system must be in equilibrium. (Inequilibrium of course implies nonuniformity
of one or more properties).
Process (1/2)
A process is the description of what happens when a system
changes its state by going through a succession of equilibrium
states.

Property Diagram and Path

Consider a system which we are monitoring and assume that properties X
(pressure) and Y (eg. volume), which are being measured, are enough to define
the state of the system. Then if we plot X versus Y, we get a Property diagram.
Process (2/2)
A point, such as 1, on the diagram represents the properties of the system at a particular instant and is known
as a state point. Three different hypothetical processes have been drawn:
Process 1 - 2:
is relatively undefined. We cannot guess what happens between the two equilibrium states 1 and 2.
Process 3 - 4
In this case the properties have been measured at points a, b, c, d, ..., etc, and so we can draw a dotted line
through the points.
Process 5 - 6:
– In this case the properties have been measured continuously and we have obtained an infinity of
equilibrium
states between 5 and 6. We are now justified in drawing a full line. This line is called the path of the
process. Note: to fully define the process we need to monitor the system - surrounding interactions as well.
identical.
Interactions Between Systems (Work & Heat)
• What happens when we bring two systems into contact?
•
• The configuration or states of (A) and (B) may be altered until after a certain time
when the systems reach equilibrium, and there is no change. Systems (A) and
(B) can interact even at a distance, eg. earth and moon (tide). But in
Thermodynamics, we are concerned with only two kinds of interactions, work and
heat.
Thermodynamic Definition of Heat and Work
• In mechanics work is defined as a force acting through a displacement x, the
displacement being in the direction of the force. That is:
W=Fxx
or in the case in which F is varying
• Unit of work - 1 Nm = 1 Joule
• But this definition of work is very restrictive and not adequate in
Thermodynamics. (Example a system consisting of a battery!)
Work - Interactions Between Systems I
• "Positive work is done by a system,
during a process, when the ONLY
effect external to the system could
be reduced to the rise of a weight".
• Definition seems arbitrary! But partly
is forced on us since we have to
make distinctions between work and
heat as a result of the Second Law
of Thermodynamics.
• A simple way to visualise this:
– The system boundary moves in such a way as
to push the lever system to a new dotted
position. The work done as in mechanics is
(WxL) Nm.
Work - Interactions Between Systems I
• This does not show the width of the application of Thermodynamic
definition. So consider a battery which we take as our system. The
battery terminals are connected to a resistor through a switch:
• When the switch is shut for a time, current flows through the resistor
and it becomes "Warmer". Is this a work interaction? Of course from
mechanics we would say NO! (since no force has moved its point of
application).
Work - Interactions Between Systems I
• "Positive work is done by a system,
during a process, when the ONLY
effect external to the system could
be reduced to the rise of a weight".
• Definition seems arbitrary! But partly
is forced on us since we have to
make distinctions between work and
heat as a result of the Second Law
of Thermodynamics.
• A simple way to visualise this:
– The system boundary moves in such a way as
to push the lever system to a new dotted
position. The work done as in mechanics is
(WxL) Nm.
Interactions Between Systems (Work & Heat)
• What happens when we bring two systems into contact?
•
• The configuration or states of (A) and (B) may be altered until after a certain time
when the systems reach equilibrium, and there is no change. Systems (A) and
(B) can interact even at a distance, eg. earth and moon (tide). But in
Thermodynamics, we are concerned with only two kinds of interactions, work and
heat.
Thermodynamic Definition of Heat and Work
• In mechanics work is defined as a force acting through a displacement x, the
displacement being in the direction of the force. That is:
W=Fxx
or in the case in which F is varying
• Unit of work - 1 Nm = 1 Joule
• But this definition of work is very restrictive and not adequate in
Thermodynamics. (Example a system consisting of a battery!)
Property: Pressure
• A property which is quite important in thermodynamics is the
pressure.

• A fluid exerts forces on its boundaries, due to the change in

momentum of molecules when they collide with the boundary.
These forces are not concentrated at one particular point, due to
random motion of molecules, but are distributed. Therefore, we can
define pressure as the normal force exerted on a surface, divided by
the area of the surface.

• The unit of pressure is the force 1 Newton acting on a square metre

area, which is called a Pascal.
1 Pa = 1 N/m2 and 1 bar = 105 Pa
Work - Interactions Between
Systems I
• This does not show the width of the application of
Thermodynamic
definition. So consider a battery which we take as our
system. The
battery terminals are connected to a resistor through a
switch:
• When the switch is shut for a time, current flows
through the resistor
and it becomes "Warmer". Is this a work interaction? Of
course from
mechanics we would say NO! (since no force has moved
its point of
application).
Some Notes:
• (i) The "ONLY effect", is necessary since, an interaction
in the form of heat transfer could result in the rise of a
weight as a part of its effect.
• (ii) External to the system - Work is defined with respect
to a system boundary. If you choose a different system
and hence boundary, then work may be changed.
• (iii) "Could be reduced to" - This means that a weight does
not actually have to be raised, but we must be able to
visualise a real physical method of raising the weight by
hypothetical changes in the surroundings!
• (iv) "Positive Work"; also implies negative work!
Negative Work
• "If a system does positive work, then obviously the surrounding do an equal amount of
negative work and vice versa. In symbols:
W system+ Wsurroundings = 0

• Important to know:
Work is a Transient. It is present during the interaction but does not exist either before or
after the interaction. It is something which happens to a system but it is not a
characteristic of a system ie not a property!