PROF.

RAKESH RATHI’S CHEMISTRY TUTORIALS

Pressure-volume work
The work W, that is done due to expansion or compression of a gas against an external opposing pressure is
called pressure-volume work.

Work done on irreversible expansion of a gas against a constant external pressure OR

Expression for pressure – volume work

Pex
Pex <P
V2
o
V1

Consider a certain amount of gas at pressure P, volume V1 and temperature T enclosed in a cylinder fitted with
frictionless, rigid, movable piston of area A.
As the gas expands it pushes the piston upward through a distance d against an external opposing force f.
The work done by the gas during the process is given by
W = opposing force × distance
= - f • d --------------------------------------- (1)
The negative sign signifies that when the piston moves against an opposing force, the internal energy of the
system doing the work will decrease.

The force opposing the expansion is the constant external pressure, Pex multiplied by the area A of the piston
f = Pex • A ------------------------------------------ (2)
From equations (1) and (2), we write
W = -Pex × A × d

A × d = ∆V = V2 – V1
Where V2 is the final volume of the gas
Hence, W = - Pex • ∆V = - Pex (V2 – V1)

When the gas expands, work is done by the system on the surroundings. Because V2 > V1, so work done is
negative.
When the gas is compressed, the work is done on the system by the surroundings and V2 < V1. Hence work done
is positive

Free expansion
A free expansion means expansion against zero opposing force. The expansion of this kind occurs in vacuum.
The work done by a system during expansion is given by equation.
W = -Pex • ∆V
When the gas expands in vacuum external pressure is zero. Thus, Pex = 0 and hence W = 0.

Concept of Maximum work and Reversibility : OR

Work done in reversible process is maximum. Explain.
Work done is given by, W = -Pex ∆V

For expansion of a gas, Pex < Pgas

If external pressure is zero, work done is zero.
As the value of external pressure increases, work done increases.
If the external pressure is equal to pressure of gas, then the gas does not expand.
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