It is appropriate to illustrate the relationship between ΔS
and q with a consideration of the relationship between
entropy and volume. Our consideration will be the simple case
of isothermal expansion of a perfect gas, but it is possible to
apply the equations to more complicated situations.
Our starting point is the following equation, the definition
of entropy change:

Given that the expansion is isothermal, the temperature is a
constant that may be taken outside the integral, allowing us to
write

In this situation, ΔU = 0 (as there is
no temperature change, and the particles of a perfect gas do not
interact at all so are unaffected by being more widely separated)
, allowing us to use the First Law of Thermodynamics to write

so;

The work of reversible expansion is given by wrev
= - ∫
pdV . For a perfect gas, we may use the equation of state pV =
nRT to substitute for p and obtain

which integrates to

when Vf > Vi (i.e. when expansion
occurs) the ratio of volumes > 1 so the logarithmic term
and hence the overall entropy change are both positive, as we
expect. Conversely, if Vf < Vi (i.e.
contraction) the ratio of volumes < 1 so the logarithmic term
and overall entropy change are both negative.
|