Ch 12.

THERMODYNAMICS
Thermodynamics, Thermodynamic system,
• Thermodynamics – It is the branch of science that deals with the
concepts of heat and temperature and their inter- conversion of heat and
other froms of energy. It mainly deals with the transformation of heat into
mechanical work vice versa.
• Thermodynamic system – An assembly of very large number of particles
having a certain value of pressure , volume and temperature is called a
thermodynamic system.
 Surroundings, Thermodynamic Variables &
Equation of state.
• Surroundings – Everything outside the system which can have a direct
effect on the system is called its surroundings.
• Thermodynamic variables – The quantities like pressure (P) , volume
(V) and temperature (T) which help us to study the behaviour of a
thermodynamic system are called thermodynamic variables.
• Equation of state – The mathematical relation between the pressure ,
volume and temperature of a thermodynamic system
• PV = n RT
 Thermal Equilibrium
• Two systems are said to be in thermal equilibrium with each other it they
have the same temperature.
 Thermodynamic Equilibrium
• A system is said to be in the state of thermodynamic equilibrium if the macroscopic variables
describing the thermodynamic state of the system do not change with time.
• A system in the state of thermodynamic equilibrium possesses the following equilibria
simultaneously
• (i) Mechanical equilibrium – There is no unbalanced force in tis interior or between the system and
the surroundings.
• (ii) Thermal equilibrium – All parts of the system and the surroundings are at the same
temperature.
• (iii) Chemical equilibrium – The system does not undergo any spontaneous change in its internal
structure due to chemical reaction, diffusion etc.
•
 Zeroth Law of thermodynamics
• It states that if two systems A & B are separately in thermal equilibrium
with a third system C, then A and B are also in thermal equilibrium with
each other.
 Internal Energy of a system
• The internal energy of a system is the sum of molecular kinetic and
potential energies in the frame of reference relative to which the center of
mass of the system is at rest.
• Internal energy of a system is a thermodynamic state variable – That
is its value depends only on the state of existence of the system and not on
the path along which that state has been brought about. Thus the internal
energy of a given mass of a gas depends only on its state described by the
specific values of pressure , volume and temperature.
 Two ways of changing internal energy of a
system
• As shown in figure, consider a fixed mass of a gas in a
Cylinder provided with a movable piston. The internal
energy of the gas can be increased in two ways:
(i)Place the cylinder over a hot body. Heat energy will flow
From the hotter body to the gas due to temperature
difference. This increases the internal energy of the system
(ii) Push the piston down by raising some weight attached to it.
Work is done on the gas. His also increases the internal energy
of the gas.
 Difference between heat and work
• (i) Heat is a mode of energy transfer due to temperature difference between the
system and the surroundings. Work is the mode of energy transfer brought about
by means that do not involve temperature difference such a s moving the piston
of a cylinder containing the gas, by raising or lowering the weight connected to it.
• (ii) When heat is supplied to a gas, its molecules move faster in all directions at
random. So heat is a mode of energy transfer that produces random motion.
When a piston compresses a gas to do work on it,it forces the molecules to move
in the direction of piston’s motion. So work may be regarded as the mode of
energy transfer that produces organized motion.
 Sign conventions used in measurement of
heat, work and internal energy.
• (i) Heat absorbed by a system is positive. Heat given out by a system is
negative.
• (ii) Work done by a system is positive . Work done on a system is
negative.
• (iii) The increase in internal energy of a system is positive . The
decrease in internal energy of a system is negative.
Indicator diagram
 Work done during cyclic process
• Any process in which the system returns to its
• Initial state after undergoing a series of changes
• Is known as cyclic process.
• Work done by gas during expansion=
• = area AXBCDA
• Work done on the gas during compression
• = area BYADCB
• The net work done = - = Area AXBYA
 First Law of Thermodynamics
• If some heat is supplied to a system which is capable of doing work, then
the quantity of heat absorbed by the system will be equal to the sum of the
increase in its internal energy and the external work done by the system
on the surroundings.

• = Force x Distance = Pressure x Area x Distance = Pressure x Volume

• =
Why does a gas not possess a unique specific
heat?
• When a gas is heated , its volume and pressure change with the increase in
temperature . So the amount of heat required to raise the temperature of 1
gram of gas through C is not fixed. That is a gas does not possess a
unique or single specific heat.
 Limits of specific heat of a gas
• (i) Suppose the gas is suddenly compressed. No heat is supplied to the gas i.e. . But the
temperature of the gas rises due to compression.
• c= = =0,
• i.e., specific heat of the gas is zero.
• (ii) Now the gas is heated and allowed to expand such that the rise in temperature of the
gas due to the heat supplied is equal to the fall in temperature due to the expansion of the
gas itself. Then the net rise in temperature is zero. i.e,
• c= == ,
• i.e., specific heat of the gas is infinite.
 Limits of specific heat of a gas …
• (iii) Again the gas is heated and allowed to expand at such a rate that the fall in
temperature due to expansion is less than the rise in temperature due to hat supplied.
The temperature of the gas will rise. i.e.,
• c = = a positive value.
• i.e specific heat of the gas is positive.
• (iv) Finally , the gas is heated and allowed to expand at such a rate that fall in
temperature due to expansion is more than the rise in temperature due to heat supplied.
i.e. ,
• i.e specific heat of the gas is negative.
 Two principal specific heats of a gas
• One when the gas is heated at constant volume and another when the gas is
heated at constant pressure.
• (i) Molar specific heat at constant volume. –
• It is defined as the amount of heat required to raise the temperature of 1
mole of a gas through C at constant volume . It is denoted by
• (ii) Molar specific heat at constant pressure. –
• It is defined as the amount of heat required to raise the temperature of 1
mole of a gas through C at constant pressure . It is denoted by
 Why > ?
• When a gas is heated at constant volume, all the heat supplied is used to
increase the temperature or internal energy of the gas.
• When a gas is heated at constant pressure, the gas expands. It does work
against external pressure. The heat supplied is used in two ways: (i) partly
to increase the internal energy and (ii) partly to do work against external
pressure. So at constant pressure, an additional amount of heat equivalent
to work done is utilized.
Mayer’s Relation - Derivation
 Thermodynamic Process & its types
• A thermodynamic process is said to occur if the thermodynamic variables of a system
undergo a change with time.
• (i) Isothermal process – It is a thermodynamic process which occurs at a constant
temperature.
• (ii) Isobaric process – It is a thermodynamic process which occurs at a constant pressure.
• (iii) Isochoric process – It is a thermodynamic process which occurs at a constant volume.
(iv) Adiabatic process – It is a thermodynamic process in which there is no exchange of
heat energy between system and surroundings.
 Quasi – static Process
• A quasi – static process is an infinitely slow process such that the system
remains in thermal and chemical equilibrium with the surroundings.
• In quasi-static process, at every stage, the temperature and pressure of the
surroundings differ only infinitesimally from those of the system.
 Work done in Isothermal Process -
Derivation

• = nRT ln (
Work done in Adiabatic Process - Derivation

• = [

• = [
 Second Law of Thermodynamics
• Kelvin – Plank statement – It is impossible to construct an engine , which
will produce no effect other than extracting heat from reservoir and
performing an equivalent amount of work
• Clausius statement - It is impossible for a sef-acting machine, unaided by
any external agency , to transfer heat from a body to another at higher
temperature.
 Reversible Process
• Reversible process – Any process which can be made to proceed in the
reverse direction by variation in its conditions such that any change
occurring in any part of the direct process is exactly reversed in the
corresponding part of reverse process is called a reversible process.
• Necessary conditions for a reversible process
• (i) The process must be a quasi – static.
• (ii) The dissipative forces such as viscosity, friction, inelasticity etc should
be absent.
 Irreversible Process
• Any process which cannot be retraced in the reverse direction exactly is
called an irreversible process. Most of the processes occurring in the
nature are irreversible processes.
• Examples : (i) Diffusion of gases
• (ii) Dissolution of salt in water.
• (iii) Rusting of Iron
• (iv) Sudden expansion or contraction of a gas.
Carnot Engine
Carnot Cycle