CHAPTER 4

PRELIMINARY ASPECTS OF
THERMODYNAMICS
&
THE ZEROTH LAW OF
THERMODYNAMICS
 Lecture outlined:

Thermodynamics
Thermodynamic System, Boundaries & Surrounding
Macroscopic & Microscopy Approaches
State, Property, and Process
Extensive & Intensive Properties
The Zeroth Law of Thermodynamics
Thermometry
 Thermodynamics

Thermodynamics is a physical science concerned with the

transfer of heat and the appearance or disappearance of
work attending various conceivable chemical and physical
processes.
Thermodynamic methods do not make any assumptions as
to the atoms and molecule; the only quantities and concepts
in the thermodynamics are the experimental properties of
matter such as pressure, volume, temperature and composition.
Such properties of matter are in bulk rather than isolated
individual and therefore are called macroscopic properties.
Applying the laws and principles of thermodynamics, we
are possible to predict the type of chemical process taking place
and changes that due to the processes undergo.
Thermodynamic System, Boundaries & Surrounding

System is the part of universe that we are interested to

observe its change – we study physical and/or chemical
changes of substances inside the system.
Surrounding is the part of universe that interact with the
system – systems interact with surrounding by exchanging
energy (heat, work), and matter.
Boundary is a divider/separator between the system and
the surrounding – it may be real or imaginary.
Four types of thermodynamic system:
An open system can exchange both energy and matter
with its surrounding.
A closed system can exchange energy but no transfer of
matter with its surrounding.
 A thermally isolate system has no exchange of energy
(heat) with it surrounding.
A mechanically isolate system has no work is done on
the system or by the system.

(a) (b)
Figure 4.1: (a) System is separated from surrounding by a
boundary, (b) Three different types of systems.
Figure 4.2: Closed system – a gas
in a piston – cylinder assembly
Figure 4.3: Example of a control volume (open
system) – an automobile engine
 Macroscopic & Microscopy Approaches

A macroscopic approach is concerned with the gross or

overall behaviour of matter – no model of the structure of
matter at the molecular, atomic, and subatomic levels is
directly used.

A microscopic approach is concerned directly with the

structure of matter – the objective is to characterize by
statistical means the average behaviour of the particles
making up a system.
 State, Property, and Process

State (also called physical state) is the condition of the

system or surrounding before or after the change (or
reaction).
The state of a system (as well as surrounding) can be
defined by four observable macroscopic properties of
matter known as the variable of state, namely pressure,
volume, number of mole and temperature.
The physical state of a sample of a substance, its physical
condition, is defined by its physical properties.
Two samples of a substance that have the same physical
properties are in the same state.
When any if the properties of a system change, the state
changes and the system is said to have undergone a
process.
Reversible process: In order that a process be thermodynamically
reversible it must be carried out very slowly (infinitesimally
change) so that the system remains in temperature and pressure
equilibrium with its surroundings. A system undergoing such a
change can be completely restored to its initial state.

Irreversible process: In such a process a property of the system

differs by a finite amount from one instant to another and the
system cannot return to its origin state. Such process are real or
natural processes.

Spontaneous process: A spontaneous process is one which takes

place under a given set of conditions without application of any
force. Such processes are also irreversible processes.
Isothermal process: When a reversible process occurs at a
constant temperature (i.e. no change in temperature
occurs), it is said to be an isothermal process. An exchange
of heat between the system and its surroundings occurs to
maintain the temperature constant.

Adiabatic process: An adiabatic process is thermally isolated

so that no heat can enter or leave the system. The system
does external work but, because it is thermally insulated,
the necessary energy comes from the kinetic energy of the
gas molecules.
Isentropic process: A reversible adiabatic process is called
an isentropic process.
Isobaric process: Iso means “same” and baros means
“weight” and hence an isobaric process is a constant
weight/force process, i.e. a process carried out at a
constant pressure.
Isochoric process: The Greek word chora means “place”. So
an isochoric process is one where the space remains
constant throughout the process, or in other words the
process is carried out at constant volume.
Cyclic process: If initial state is designated by 1 and the
final state by 2, and if states 1 and 2 coincide, then the
process is called a cyclic process.
If the state of the system shows no tendency to change, we
say that the system is at equilibrium with the
surroundings.
The understanding of how the energy of a system relates
to its other measurable is called thermodynamics (heat
movement).
Thermochemistry is the branch of thermodynamics that
deals with the heat involved in chemical reaction.
State function is any thermodynamic property whose
value for the process is independent of the path – it
depends only on the state of the system, in term of
state variables like p, V, T, and n.
Internal energy is an example of state function,
whereas work and heat are not.
Therefore, we use lower case letters to represent non–
state functions (like work w and heat q) while capital
letter for the state functions (like internal energy U).
 Processes and Cycles
• Process
– Change that a system undergoes from one
equilibrium state to another

• Path
– Series of states through which a system passes
during a process
State 2

• Quasi-equilibrium process
State 1 Process Path

– Slow process that allows the entire system to adjust

so the entire system remains close to equilibrium
 Thermodynamic process

p
State 1

State 2

T
Thermodynamic Processes/Cycles

• Isothermal P

– Temperature remains constant T

• Isobaric P

– Pressure remains constant

• Isometric T

– Volume remains constant P

• Cycle V

– System reaches initial state at the end of the

process P

V
Thermodynamic process
Process 1
p
State 1
State 2

Process 2 V

T
 The Zeroth Law of Thermodynamics

Q: What occurs if a beaker of water containing a

thermometer is heated over a flame?
– the rapidly moving gas particles in the flame collide more
energetically with the atom of beaker, transferring some of
their kinetic energy to the molecule of water, which move
faster and transfer kinetic energy to the atoms in the
thermometer bulb. These, in turn, transfer kinetic energy to
the atoms of mercury.
Temperature is a measure of how much average kinetic
energy the particles of a system have.
In the macroscopic word, we see this as a temperature
increase; in molecular world, it is a sequence of kinetic
energy transfers from higher to lower energy particles.
The zeroth law of thermodynamic stated that:
two systems (of any size) are in thermal equilibrium with
each other and a third system is in thermal equilibrium with
one of them, then it is in thermal equilibrium with the other
also
Consider 3 blocks labelled A, B, and C:

A B C

TA TB TC

where TA ≠ TB ≠ TC before thermal equilibrium

If three blocks are arranged as follow, after a while and
at the moment of thermal equilibrium, the blocks will
have the same temperature

A B C

TA = TB = TC = TEq

where the average kinetic energy:

EkA  EkB  EkC  EkEq

What is temperature ?
 Temperature Units and Conversions

There are two temperature scales in common use in

the chemical and biological industries – degrees
Fahrenheit (oF) and Celsius (oC)
Temperatures are often expressed as Kelvin (K) or
degree Rankine (oR) instead

o
C o
F K o
R

Boiling Point 100 212 373.15 671.67

Melting Point 0 32 273.15 491.67
Absolute zero –273.15 –459.67 0 0
The following equation can be used to convert from
the temperature from one to another:

o
F = 32 + 1.8(oC)
o
C = (1/1.8)(oF – 32)
o
R = o
F + 459.67
K = o
C + 273.15
Questions?