ΔS =
f
i
(3.2)
That is, to calculate the difference in entropy between any two states of a system, we
find a reversible path between them, and integrate the energy supplied as heat at each
stage of the path divided by the temperature at which heating occurs.
Example 3.1 Calculating the entropy change for the isothermal expansion of a perfect gas
Calculate the entropy change of a sample of perfect gas when it expands isothermally
from a volume Vi to a volume Vf.
Method The definition of entropy instructs us to find the energy supplied as heat
for a reversible path between the stated initial and final states regardless of the
actual manner in which the process takes place. A simplification is that the expansion
is isothermal, so the temperature is a constant and may be taken outside the
integral in eqn 3.2. The energy absorbed as heat during a reversible isothermal
expansion of a perfect gas can be calculated from ΔU = q + w and ΔU = 0, which
implies that q = −w in general and therefore that qrev = −wrev for a reversible change.
The work of reversible isothermal expansion was calculated in Section 2.3.
Answer Because the temperature is constant, eqn 3.2 becomes
ΔS =
f
i
dqrev =
From eqn 2.10, we know that
qrev = −wrev = nRT ln
It follows that
ΔS = nR ln
• A brief illustration
When the volume occupied by 1.00 mol of any perfect gas molecules is doubled at any
constant temperature, Vf/Vi = 2 and
ΔS = (1.00 mol) × (8.3145 J K−1 mol−1
) × ln 2 = +5.76 J K−1 •
Self-test 3.1 Calculate the change in entropy when the pressure of a fixed amount
of perfect gas is changed isothermally from pi to pf. What is this change due to?
[ΔS = nR ln(pi/pf
); the change in volume when the gas is compressed]
Vf
Vi
Vf
Vi
qrev
T
1
T
dqrev
T