Thermodynamics:: It Is The Science of The Relations Between Work and The Properties of The Systems. Heat

Fundamental Concepts
and Definitions
THERMODYNAMICS:
¾ It is the science of the relations heat,
between
Work and the properties of the systems.
¾ How to adopt these interactions to our
benefit?
Thermodynamics enables us to answer this
question.
Analogy
All currencies are not equal

Eg: US$ or A$ or UK£ etc. Have a better purchasing power
than Indian Rupee or Thai Baht or Bangladesh Taka
similarly,all forms of energy are not the same.
Human civilization has always endeavoured obtain
to
¾ Shaft work
¾ Electrical energy
¾ Potential energy to make life easier
Examples
If we like to
¾ Rise the temperature of water in kettle
¾ Burn some fuel in the combustion of an aero
chamber engine to propel an aircraft.
¾ Cool our room on a hot humid day.
¾ Heat up our room on a cold winter night.
¾ Have our beer cool.
What is the smallest amount of electricity/fuel we
can get away with?
Examples (Contd…)
On the other hand we burn,

¾ Some coal/gas in a power plant to electricity.
generate
¾ Petrol in a car engine.
What is the largest energy we can get out of these efforts?
Thermodynamics allows us to answer some of these
questions
Definitions
¾ In our study of thermodynamics, we will choose a small part of
the universe to which we will apply the laws of
thermodynamics.
We call this subset a SYSTEM.
¾ The thermodynamic system is analogous to the free body
diagram to which we apply the laws of mechanics, (i.e.

Newton’s Laws of Motion).
¾ The system is a macroscopically identifiable collection of matter
on which we focus our attention (eg: the water kettle or the

aircraft engine).
¾ The rest of the universe outside the system close
enough
to the system to have some perceptible effect on the
system is called the surroundings.
¾ The surfaces which separates the system from the
surroundings are called the boundaries as shown in fig

below (eg: walls of the kettle, the housing of the
engine).
System
Boundary Surroundings
Types of System
¾ Closed system - in which no mass is permitted to cross the

system boundary i.e. we would always consider a system
of constant mass.We do permit heat and work to enter or
leave but not mass.
Boundary Heat/work
Out
system
Heat/work
in
No mass entry or exit
¾ Open system- in we permit mass to cross the system
which
boundary in either direction (from the system to surroundings
or vice versa). In analysing open systems, we typically look at
a specified region of space, and observe what happens at the
boundaries of that region.
Most of the engineering devices are open system.
Boundary
Heat/work Mass
Out out
System
Heat/work
Mass in
In
¾ Isolated System - in which is no interaction between
there
system and the surroundings. It is of fixed mass and
energy, and hence there is no mass and energy transfer
across the system boundary.
System
Surroundings
Choice of the System and
Boundaries Are at Our
Convenience
¾ We must choose the system for each and every problem
we work on, so as to obtain best possible information on
how it behaves.
¾ In some cases the choice of the system will be obvious
and in some cases not so obvious.
¾ Important: you must be clear in defining what constitutes
your system and make that choice explicit to anyone else
who may be reviewing your work. (eg: In the exam
paper or to your supervisor in the work place later)
Boundaries Are at
Our Convenience (contd…)
¾ The boundaries may be real physical or they may
surfaces be imaginary for the convenience of
analysis.
eg: If the air in this room is the system,the floor,ceiling
and walls constitutes real boundaries.the plane at the open
doorway constitutes an imaginary boundary.
Boundaries Are at Our
Convenience (contd…)
¾ The boundaries may be at rest or in
motion.
defined
eg: If we of
quantity choose
mass a(such
system
as that has a certain
gas contained in a piston
cylinder device) the boundaries must move in such
way that they always enclose that particular quantity
of mass if it changes shape or moves from one place
to another.
Macroscopic and
Microscopic
Approaches
Behavior of matter can be studied by these two
approaches.
¾ In macroscopic approach, certain quantity of
matter is considered,without a concern on the events
occurring at the molecular level. These effects can be
perceived by human senses or measured by
instruments.
¾ eg: pressure,
temperature
Microscopic Approach
¾ In microscopic approach, the effect of

molecular
motion is Considered.
eg: At microscopic level the pressure of a gas is not
constant, the temperature of a gas is a function of
the velocity of molecules.
Most microscopic properties cannot be measured with

common instruments nor can be perceived by human
senses
Property
¾It is some characteristic of the system to which some physically

meaningful numbers can be assigned without knowing the
history behind it.
¾These are macroscopic in nature.
¾Invariably the properties must enable us to identify the system.
¾eg: Anand weighs 72 kg and is 1.75 m tall. We are not
concerned how he got to that stage. We are not interested what
he ate!!.
Examples (contd...)
We must choose the most appropriate set of properties.

¾ For example: Anand weighing 72 kg and being 1.75 m
tall may be a useful way of identification for police
purposes.
¾ If he has to work in a company you would say Anand
graduated from IIT, Chennai in 1985 in mechanical
engineering.
¾ Anand hails He has a sister and his
from ---If you are looking at
Mangalore.
father is a
poet. He is
singer. him
Examples (contd…)
¾ All of them are properties of Anand. But you

pick and choose a set of his traits which describe
him best for a given situation.
¾ Similarly, among various properties which a
definition
by of a thermodynamic system is possible, a
situation might warrant giving the smallest number
of properties which describe the system best.
Categories of Properties
¾Extensive property:
whose value depends on the size or extent of the system
(upper case letters as the symbols).
eg: Volume, Mass (V,M).
If mass is increased, the value of extensive property also
increases.
¾Intensive property:
whose value is independent of the size or extent of
the system.
eg: pressure, temperature (p, T).
Property (contd..)
Specific property:
¾ It is the value of an extensive property per unit mass
of system. (lower case letters as symbols) eg: specific volume,
density (v, ρ).
¾ It is a special case of an intensive property.
¾ Most widely referred properties in thermodynamics:
¾ Pressure; Volume; Temperature; Entropy; Internal
Enthalpy;
energy
(Italicised ones to be defined later)
¾State:
It is the condition of a system as defined by the values of its
all properties.
It gives a complete description of the system.
Any operation in which one or more properties of a system
change is called a change of state.
¾Phase:
It is a quantity of mass that is homogeneous throughout
in chemical composition and physical structure.
e.g. solid, liquid, vapour, gas.
Phase consisting of more than one phase is known as
heterogenous system .
Path And Process
The succession of states passed through during a change of

state is called the path of the system. A system is said to go
through a process if it goes through a series of changes in
state. Consequently:
¾A system may undergo changes in some or all of
its properties.
¾A process can be construed to be the locus of changes
of state
Processes in thermodynamics are like streets in a city
eg: we have north to south; east to west; roundabouts;
crescents
Types of Processes
¾As a matter of rule we •Isothermal (T)

allow •Isobaric (p)
one of the properties to remain a
constant during a process. •Isochoric (v)
weConstrue
¾ can (with a different
as many property
processes as
•Isentropic (s)
kept constant during each of
them) •Isenthalpic (h)
¾Complete the cycle by
regaining the initial state •Isosteric (concentration)
•Adiabatic (no heat addition or
removal
Quasi-static Processes
The processes can be restrained or
unrestrained
We need restrained processes in practice.
A quasi-static process is one in which
¾ The deviation from thermodynamic
equilibrium is infinitesimal.
¾ All states of the system passes
through are equilibrium states.
Gas
Quasi-static Processes
(contd…)
¾ If we remove the weights slowly one by one
the
pressure of the gas will displace the piston gradually. It
is quasistatic.
¾ On the other hand if we remove all the weights
at
once the piston will be kicked up by the gas
¾ In both cases
pressure.(This the
is unrestrained have undergone
expansion) but wea change
don’t
systems
consider that the work is done - because it is not in a
of Another
¾ state. eg: if a person climbs down a ladder from
sustained manner
roof to ground, it is a quasistatic process. On the other
hand if he jumps then it is not a quasistatic process.
Equilibrium State
¾A system is said to be in an equilibrium if its properties

state
will not change without some perceivable effect in the
surroundings.
¾Equilibrium requires all properties to be uniform
generally throughout the
system.
¾There are mechanical, thermal, phase, and chemical
equilibria
Equilibrium State
(contd)
Nature has a preferred way of directing changes.
eg:
¾water flows from a higher to a lower level
¾ Electricity flows from a higher potential to a lower one
¾ Heat flows from a body at higher temperature to the one
at a lower temperature
¾ transfer occurs from a point of higher
Momentum
pressure to a lower one.
¾ Mass transfer occurs from higher concentration to a
lower one
Types of Equilibrium
Between the system and surroundings, if there is no difference in
Pressure Mechanical equilibrium

Potential Electrical equilibrium
Concentration of species Species equilibrium
Temperature Thermal equilibrium
No interactions between them occur.

They are said to be in equilibrium.
Thermodynamic equilibrium implies all those together.

A system in thermodynamic equilibrium does not deliver anything.
Definition Of Temperature and
Zeroth Law Of
Thermodynamics
¾Temperature is a property of a system determines the

which
degree of hotness.
¾Obviously, it is a relative term. than a block of
eg:
ice. A
Onhot
thecup of coffee
other is atis ahotter
hand, ice higherthan liquid hydrogen.
temperature
Thermodynamic temperature scale is under evolution. What we
have now in empirical scale.
Zeroth Law Of Thermodynamics
(Contd…)
¾Two systems are said to be equal in temperature,
when there is no change in their respective observable
properties when they are brought together. In other
words, “when two systems are at the same temperature
they are in thermal equilibrium” (They will not
exchange heat).
Note:They need not be in thermodynamic equilibrium.

Zeroth Law
¾If two systems (say A and B) are in thermal

equilibrium with a third system (say C) separately (that
is A and C are in thermal equilibrium; B and C are in
thermal equilibrium) then they are in thermal
equilibrium themselves (that is A and B will be in
thermal equilibrium
TA TB
TC
Explanation of Zeroth Law
¾ Let us say TA,TB and TC are the temperatures of A,B and C
respectively.
¾ A and c are in thermal equilibrium. Ta= tc
¾ B and C are in thermal Tb= tc
equilibrium.
Consequence of of ‘0’th law
¾ A and B will also be in thermal
equilibrium TA= TB
¾ Looks very logical
¾All temperature measurements are based on this LAW.

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Fundamental Concepts

All currencies are not equal

On the other hand we burn,

diagram to which we apply the laws of mechanics, (i.e.

on which we focus our attention (eg: the water kettle or the

surroundings are called the boundaries as shown in fig

¾ Closed system - in which no mass is permitted to cross the

Most of the engineering devices are open system.

¾ In microscopic approach, the effect of

Most microscopic properties cannot be measured with

¾It is some characteristic of the system to which some physically

We must choose the most appropriate set of properties.

¾ All of them are properties of Anand. But you

The succession of states passed through during a change of

¾As a matter of rule we •Isothermal (T)

¾A system is said to be in an equilibrium if its properties

Between the system and surroundings, if there is no difference in

Pressure Mechanical equilibrium

No interactions between them occur.

Thermodynamic equilibrium implies all those together.

¾Temperature is a property of a system determines the

Note:They need not be in thermodynamic equilibrium.

¾If two systems (say A and B) are in thermal

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