BASIC THERMODYNAMICS

Lecture 1

Dr. Rajan Kumar

Department of Mechanical Engineering
Dr. B R Ambedkar National Institute of Technology, Jalandhar
 Definition of Thermodynamics
• Engineering Thermodynamics is the subject that deals
with the study of the science of thermodynamics and the
usefulness of this science in the design of each & every
process, device or system involving the effective
utilization of energy and matter for the benefit of
mankind.
• The name Thermodynamics stems from the Greek words
therme (Heat) and dynamics (Power).
– Clearly depicting the early efforts to convert heat into
power.
• Thermodynamics is a Greek word which means flow of
heat in physical and chemical reactions
• Thermodynamics is a branch of science which deals with
study of different forms of energy and their
interconversions
• It deals with energy changes in physical and chemical
processes
• The Trio of Thermodynamics: Heat, Work & Energy.
 Importance of thermodynamics

• Useful to predict whether any chemical reaction can occur

under specified conditions
• Used to predict the extent of chemical reaction before
equilibrium is reached
• Used to derive important laws like Law of equilibrium.
 Terms used in Thermodynamics
System
• May be defined as the part of universe selected for
thermodynamic consideration i.e. to study the effect
of temperature, pressure etc.
• It may also be defined as specified part of universe
in which energy changes are taking place
 Terms used in Thermodynamics
Surrounding
• The remaining portion of universe excluding the
system is called Surrounding

• Universe = System + Surrounding

• The System and Surrounding can be separated by

real and imaginary boundary
Terms used in Thermodynamics
 Terms used in Thermodynamics

Types of System
1. Open System: Here mass and energy can be exchanged with
surroundings eg. If some water is kept in open vessel or hot
tea in open cup
 Terms used in Thermodynamics

2. Closed System
In a closed system, there is only the exchange of energy
with surroundings, no exchange of mass takes place
For example, if water is placed in closed metallic vessel
or hot tea placed in closed tea pot.
 Terms used in Thermodynamics

3. Isolated System
There is neither exchange of mass nor energy with
surrounding.
Eg. Water placed in a vessel which is closed as
well as insulated or tea placed in a thermos flask
 Terms used in Thermodynamics
Classification of system on the basis of
nature of constituents
• Homogenous System: All the constituents are present in
the same phase and composition of system is uniform
throughout
• Heterogeneous System: It contains two or more
phases and the composition is non-uniform
throughout
 Intensive and Extensive Properties

Intensive Properties
• They do not depend on the size of the system or
quantity of matter present in it.
• They are dependent on the nature of
substance present in it.
• Example: pressure, temperature, density,
surface tension
 Intensive and Extensive Properties

Extensive Properties
• Depend on the Quantity of matter present in the
system
• Examples: volume, energy, heat capacity,
entropy
 State of system and State
Variables
State of System
• They are the condition of system which is described
in terms of certain measurable properties such as
temperature (T), pressure (P), volume (V) etc. of
the system.
 State of system and State Variables
• State Variables
The properties of system such as temperature (T),
pressure (P), volume (V) when changed ,the system
also changes. These properties are called state
variables
 State function

• It is defined as the property whose value depends

only upon the state of the system and is independent
of the path by which state has been reached
• For example: a person standing on the roof of the
building has a fixed value of potential energy and
the potential of person does not depend whether he
has reached there by stairs or lift. Ex. Potential
energy, pressure, volume, temperature, internal
energy etc.
 Process
• When state of system changes then process is said
to occur
• the first and last state of process are called initial
and final state respectively
• Process give us the
path by which system
changes from one
state to other
• There are certain
processes in which
particular state
variable is kept
constant
 Types of
Process
Isothermal Process:
• It is defined as the process in which temperature of
system remains constant.
• Heat can flow from system to surrounding and vice
versa in order to keep the temperature constant
 Types of Process

Adiabatic Process
• The system does not exchange heat with the
surrounding
• System is completely insulated from surrounding
Isochoric Process:
• Volume of system remains constant during the
process
Isobaric Process:
• Here pressure of the system remains constant during
the process
 Cyclic Process
• Here the system undergoes series of changes and
finally returns to its initial state
Reversible Process
• Such a process is carried out infintesimally slowly so that
all changes occuring in the direct process can be reversed
and the system and the surrounding remain in state of
equilibrium
• It is an ideal process and cannot be realized in actual
process
• Irreversible process
• Change is brought about rapidly and the system does not
attain equilibrium
• The force which drives the reactants towards products is
greater than opposing force which is to carry reverse
process
 Here is a brief listing of a few kinds of processes
 Isothermal process → the process takes place at constant temperature
(e.g. freezing of water to ice at –10C)
 Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
 Isochoric → constant volume
(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.
 Adiabatic process → dq is zero during the process (no heat is
added/removed to/from the system)
 A combination of the above are also possible: e.g. ‘reversible
adiabatic process’.
Spontaneous process
• It may also be defined as the process which can take place by itself
or initiation
Which take place by itself
• Evaporation of water in open vessel
• Dissolution of salt in water
• Flow of water down a hill
Which take place by initiation
• Combination of oxygen and hydrogen to form water
• Lighting of candle is initiated by ignition
Non Spontaneous Process
• It is the process which cannot take place by itself or
initiation
• Examples:
Flow of heat from cold body to hot body Flow of
water up the hill
Dissolution of sand in water
 Some Thermodynamics Quantities
Internal Energy
• Every system is associated with a definite amount of
energy, which is called its internal energy. It is donated by
E or U
• It depends upon the various factors such as temperature,
pressure and chemical nature of the substance
Change in Internal Energy
The change in internal energy in a chemical reaction is the
difference in the internal energies of the products and the
reactants
∆E= E(products)-E(reactants)
= Ep-Er
 Some Thermodynamics Quantities
• Enthalpy (H)
Enthalpy or heat content of a system may be defined
as the sum of the internal energy and the product of
its pressure and volume
H =E + PV
Where E is the internal energy
P is pressure
V is the volume of the system
 Some Thermodynamics Quantities
Change In Enthalpy
• It is the difference in the enthalpies of the
products and the reactants
• ∆H = H(products)- H(reactants)
= Hp- Hr
 Some Thermodynamics Quantities
Entropy
• I t is a measure of the randomness or disorder of the
system
• The greater the randomness, the greater the
entropy
• Entropy of a crystalline substance is minimum in the
solid state and maximum in the gaseous state
 Entropy
• Melting of ice is an example of increasing entropy
 Some Thermodynamics Quantities
Entropy
• It is represented by S
• It depends on temperature and increases with
increase in temperature
• The change in entropy is equal to heat absorbed
isothermally and reversibly during a process
divided by absolute temperature at which heat is
absorbed
• ∆ S = q rev/T
 LAWS OF THERMODYNAMICS

There are four Laws of thermodynamics:

• Zeroth law of thermodynamics
• 1st Law of thermodynamics
• 2nd Law of thermodynamics
• 3rd Law of thermodynamics
 LAWS OF THERMODYNAMICS

Zeroth Law of thermodynamics

• When two bodies A and B are separately in
thermal equilibrium with a third body, they in
turn are in equilibrium with each other
 LAWS OF THERMODYNAMICS
1st Law of thermodynamics
• Energy can neither be created nor destroyed
although it may be converted from one form to
other
• The total energy of the universe remains constant
although it may undergo transformation from one
form to other
• The energy of an isolated system remains constant
 LAWS OF THERMODYNAMICS

• 1st Law of thermodynamics

∆U= q + W
Where
∆U = change in internal
energy q = heat energy
W = work done
 LAWS OF THERMODYNAMICS
2nd Law of thermodynamics
• All spontaneous or naturally occurring processes
are irreversible
• Without the help of an external agency a
spontaneous process cannot be reversed
thermodynamically
• The entropy of an isolated system must increase if
it is to be spontaneous
 LAWS OF
THERMODYNAMICS
• 2nd Law of thermodynamics
• In an non isolated system the total energy of
both the system and surrounding must
increase or must be positive
• The total entropy of the universe must tend to
increase in a spontaneous process
• ∆S (total) = ∆S system + ∆S surrounding
 LAWS OF THERMODYNAMICS

3rd Law of thermodynamics

• The entropy of all perfectly crystalline solids
may be taken as zero at the absolute
temperature
• At absolute zero a perfectly crystalline solid
has a perfect order of its constituent particles
i.e. there is no disorder at all. Hence absolute
entropy is taken as zero
Thank
You