THERMODYNAMICS

BASIC CONCEPTS
• Thermodynamic Terms(System, Boundary, Surrounding)
• System is that part of the universe which is under
thermodynamic study and rest of universe is surroundings.
The real or imaginary surface separating the system from
surrounding is called Boundary. System and surrounding
together is called Universe
Surroundings
System Boundary
• Homogeneous System:- When a system is uniform through out, it is
called a homogeneous system. Eg Single Solid, liquid or gas, Mixtures
of gases, true solution of solid in liquid, 0.1 M NaCl solution.
Homogeneous system is made up of single phase.(Phase is defined as
homogeneous physically distinct and mechanically separable portion of
system.)

• Heterogeneous System:- Heterogeneous system is one which

consist of two or more phases. Eg. Ice in contact with liquid
water, liquid water in contact with vapour. Here ice, liquid water
and Vapour consist of separate phases.
Properties:-Properties are used to study
characteristics of system.
• Intensive property:-A Property Which does not depend on the
quantity of matter present in the system, is known as Intensive
Property. Eg. Pressure, Temperature, Density and Concentration .
• Extensive Property:-A Property that does depend on the quantity
of Matter present in System is called as an Extensive property. Eg.
Volume, No of Moles, enthalpy, entropy, Gibbs free energy.
• Extensive properties are Additive but intensive properties are
not.
State of System:-A thermodynamic System is said to be
in certain state When all its properties are fixed.
• Fundamental properties which determine state of system
• Pressure
• Temperature
• Volume
• Mass
• Composition
• (Change in magnitude of such properties alters the state of system are
referred to as State variables or State Functions or Thermodynamic
Parameters)
Equilibrium/ Non Equilibrium States
• A system in which the state variables have constant values throughout
the system is said to be in a state of thermodynamic equilibrium
• Example:-Gas confined in cylinder that has frictionless piston. If piston is
stationary, The state of the gas can be specified by giving values of
pressure and volume. The system is in state of equilibrium.
• A system in which the state variables have different values in different
part of system is said to be NON equilibrium State
• Example:-If the gas contained in a cylinder is compressed very rapidly by
moving down the piston. It passes through states P and T cannot be
specified. These properties vary throughout.
Criteria for Equilibrium

1.The temperature of system must be uniform and must be the same as

the temperature of the surroundings(Thermal Equilibrium)

2.Mechnical properties must be uniform throughout the system

(Mechanical equilibrium)

3. The chemical Composition of the system Must be uniform with no

net chemical change. (Chemical Equilibrium)
Thermodynamic Process:-When Thermodynamic system
changes from One state to Another the operation is called as
process
1.Isothermal Process-:Those processes in which the temperature remains Fixed.eg.
Placing system in thermostat.(Constant Temperature Bath) (dT=0)

2.Adiabatic Process-: Those processes in which no heat can flow ito or out of the
system.eg. Placing system in insulated container.(thermos bottle) (dQ=0)

3.Isobaric Process-:Those processes which take place at constant Pressure.eg.

Heating of Water to its boiling Point. (dP=0)o

4.Isochoric Process-:Those processes in which Volume remains constant.eg.

Heating of a substance in non expanding chamber (dV=0)

5.Cyclic Process-:When a system in given state goes through a number of different

processes and finally returns to initial state the over all process is called cyclic
process. (dE=0) (dH=0)
Reversible and Irreversible Processes
• Reversible process:-A thermodynamic reversible
process is one that take place infinitesimally slowly and
its direction at any point can be reversed by an
infinitesimal change in the state of system.

• Irreversible Process:-When a process goes from the

initial to final state in a single step and cannot be carried
in the reverse order,it is said to be an irreversible
process.
 Reversible Process Irreversible process
It takes place in infinite number of It takes place in Finite Time
infinitesimally small steps and it would
take infinite time to occur
It is imaginary as it assumes the It can be real and can be performed
presence of frictionless and weightless actually
piston
It is in equilibrium state at all stages of It is in equilibrium state only at initial
the operation. state and final state of operation
All changes are reversed when process is After this type of process has occurred
carried out in reversible direction and it all changes do not returned to initial
is extremely slow state by themselves and speedy process

Work done by reversible process is Work done by irreversible process is

greater than corresponding irreversible smaller than corresponding reversible
process process.
Units of Work and Heat
• In CGS system unit of work is erg which is defined as work done when
resistance of 1dyne is moved through a distance of 1 cm since Erg is
so small bigger unit Joule is used
• 1joule=10^7ergs
• We often use Kilojoule(KJ) for large quantities of Work
• 1KJ=1000J
• The unit of heatis calorie (Cal). Calorie is defined as the quantity of
heat required to raise the temperature of one gram of water by 1^0C
• 1Joule=0.2390 calories 1calorie=4.184J
Sign Convention of Heat and Work
• Heat flows into system q is + VE
• Heat flows out of system q is - VE

• Work is done on the system w is +VE

• Work is done by the system w is - VE
Pressure Volume Type of Work
• In elementary thermodynamics work generally considered is the work
done in expansion or compression of gas. This is known as pressure
volume type of work or PV Work
• It is important to remember that it is the External pressure Pext and
not the internal pressure of gas itself which is used in evaluating the
work.
Isothermal Reversible Expansion work of
an Ideal gas.
• Consider an ideal gas confined in a cylinder with a frictionless piston.
• It expands reversibly from volume V1 to V2 at constant temperature.
• Pressure of gas is reduced from P1 to P2
• The reversible expansion of the gas takes place in a finite number of
infinitesimal small intermediate steps. To start with the external
pressure Pext is arranged equal to internal pressure of the Pgas and
the piston remains stationary.
• If Pext is decreased by an infinitesimal amount dp the gas expands
reversibly and the piston moves through a distance dl
• Since dp is so small for all practical purpose
• Pext = Pgas = P