1.

Fundamental concepts
1.1

Thermodynamic

Studies of heat energy and its transformation into or

from other forms of energy

Normally the transformation is accompanied by change

of temperature or even phase of the system

An important aim of thermodynamic studies is to find out

ways to improve the efficiency of the process of energy
transformation

Example: Steam engine

Chemical energy Heat energy Mechanical energy

 The principles and laws of thermodynamics are

empirical
based on experience (experiment)
They are concerned with the macroscopic
properties such as temperature and pressure
The macroscopic properties are the average effect
caused by the change of the energy state of the
system
At the microscopic scale, the energy of the
particles in the system follows certain distribution
statistical consideration
Theory Kinetic

1.2

Thermodynamic systems
A thermodynamic system is a part of the
universe enclosed by a boundary
Boundary real or imaginary
Three types of system:
(a) Isolated system no interaction with other
system
(b) Closed system no material can flow into or
out of the system
(c) Open system material can flow into or out
of the system

1.3.

The state of the system

Defined by the properties of the systems
such as temperature, pressure, volume
and others
2 types of properties:
(a) Extensive property will change if the mass
of the system is changed
e.g. total volume; total energy
(b) Intensive property will not change even if
the mass of the system is changed
(also said to be Specific)
e.g. temperature; pressure; density
Total volume, V/m = 1/ = v specific volume

1.4

Pressure
Particles in a gas or fluid are moving randomly
inside the system.
They may collide with other particles or with
the wall of the container (boundary)
Collision momentum transfer force
Consider unit area inside the system
Collision occur randomly at this unit area gives rise
to force per unit area
Pressure
Unit: N/m2 ; 105 N/m2 = 1 bar ; 1 mbar = 100 N/m2
1 torr = 1 mm Hg = 133.3 N/m2 = 1.33 mbar

1.5

Thermal equilibrium - temperature

An isolated system is said to be at thermal equilibrium

The energies of the particles inside this system have a

Normal Distribution
(Maxwell-Boltzmann Distribution)
The temperature T of the system is defined by

3
E = kT
2
where E is the average energy of the particles

Consider three systems at thermal equilibrium separately :

System A at temperature TA
System B at temperature TB
System C at temperature TC
If system A is put into system B,
a new equilibrium at temperature T will be reached
If system A is at the same thermal equilibrium as system B,
then
TA = TB
Similarly, if system A is at the same thermal equilibrium as C,
then
TA = TC
Hence, system B is also at the same thermal equilibrium as C
then
TB = TC
This is the Zeroth Law of Thermodynamic

1.6

Measurement of temperature

(a) Common Thermometer

Expansion of mercury or some liquid
Length of column (volume) indicates temperature
(b) Gas thermometer
Gas Law :

PV
= m , a constant
T

If P is constant, then

V T

If V is constant, then

P T

P , V are called thermometric properties

Constant P : Level A indicates temperature

Constant V : Level B adjusted to zero level,
then level A indicates temperature

(c) Resistive thermometer

Resistance

R = Ro (1 + T + T2 )

and : temperature coefficients

Ro : resistance at T = 0 C

(d)

Thermocouple
emf produced between the two junctions of Cu-Fe,
one of which is at ice point (0C )

1.7

Reference Temperatures

To calibrate the thermometer scale,

Reference points (ultra pure water):
The steam point, Ts (at atmospheric pressure)
The ice point, Ti (at atmospheric pressure)
Using the constant volume gas thermometer,
obtain Ps and Pi
Choose Ts Ti = 100
From experiment,

Ti Pi
=
Ts Ps V
100Pi
100
Ti =
=
Ps Pi (Ps / Pi ) 1

Ps/Pi = 1.3661

Ti = 273.15, and Ts = 373.15

1.8

Units of temperature :
K

373

100

212

273

32

-273

-460

212 T 50
T = 50C
=
212 32 100
T = 50C = 122 F = 323K

1.9

Termodynamic Equilibrium

Besides Thermal Equilibrium, a system can also be at

Mechanical Equilibrium all elements in the system
have weights that balance the force acting on them due
to pressure
Chemical Equilibrium if the system consists of reactive
components, either the reactions have stopped or for
reversible reactions, reactions in both directions occur
at equal rates.
System that has achieved all three equilibrium is said to be at
Thermodynamic Equilibrium

1.10

Thermodynamic Processes

If the properties of a system is changing, the system is

said to be undergoing a certain process
* If the piston is pushed
rapidly, the process is
nonquasistatic
- equilibrium is disturbed
*If the piston is pushed very slowly so that the system
is maintained at equilibrium, the process is said to be
quasistatic
*If the quasistatic process is reversible, it is a reversible
process (if no energy is loss during the process)
*Adiabatic no loss of heat energy
*Isochoric - no change in volume
*Isothermal no change in temperature