PROF.

RAKESH RATHI’S CHEMISTRY TUTORIALS

Thermodynamic equilibrium
A system is said to be in thermodynamic equilibrium when the state functions (macroscopic properties like
temperature, pressure etc) of the system do not change with time.

Suppose, for example a gas is enclosed in a cylinder having a frictionless movable piston. The gas has a definite
temperature, pressure and volume. These properties remain constant as long as piston is motionless. This is an
equilibrium state. However, this thermodynamic equilibrium will be disturbed as soon as the piston is moved.
During the motion of the piston, the macroscopic properties like pressure, temperature and volume cannot be
specified as these properties will change, continuously as long as the piston is in motion. This state in which the
piston is moving is a non-equilibrium state. When the movement of the piston is stopped, the thermodynamic
property will remain constant and the system will be in a new equilibrium state.

A system under thermodynamic consideration should exist in three types of equilibria simultaneously.
Mechanical equilibrium: Pressure in all parts of system remains constant.
Thermal equilibrium: Temperature in all parts of system remains constant.
Chemical equilibrium: When chemical composition (concentration of reactant and product) does not change
with time.

Types of processes
The path followed by system to change state from one state to another is called process.

The different types of processes that are common in the study of thermodynamics are as follows:
Isothermal process:
A process carried out at constant temperature is called an isothermal process

In such a process, heat can flow from the system to the surroundings or vice versa in order to keep the
temperature constant. For example, if the process is exothermic, heat will be released to the surrounding and if it
is endothermic, heat will be absorbed from the surrounding in order to maintain the temperature of the system
constant.

For gaseous system, heat is absorbed by system from surroundings in expansion of gas (q = -w) and in
compression of gas, heat is evolved by system into surroundings (-q = w)

It is carried out in thermostat

Adiabatic process:
A process in which there is no exchange of heat between the system and its surroundings is called an
adiabatic process (q = 0).

In such a process, the system is completely insulated from the surroundings.

Work done on the system is equal to increase in internal energy of the system (∆U = W) or work done by the
system is at the cost of the internal energy (-∆U = - W)

If reaction is exothermic, the heat evolved remains in the system and hence temperature of system increases.
If reaction is endothermic, the heat required is taken from the system and temperature of system decreases.

For gaseous system, heat from the system itself is used in expansion of gas, causing decrease in temperature of
system (-∆U = -W). While heat released in compression of gas remain inside the system, causes increase in
temperature of the system (∆U = W).

It is carried out in thermosflask