Lets start by considering work done by
the system. We know that work = force x distance, so
if we consider a gas expanding against a constant pressure then
work = pressure x volume pushed out, or
w = - p.ΔV
The '-' sign arrives from the idea that
if the final volume is larger than the first, (ΔV greater
than zero) the gas has done work. Our definition of w is the
work done on the system. Hence the '-' sign ensures consistency.
What if the external pressure was zero? This is
called free expansion. Since
w = - p.ΔV, and p=0, therefore w=0
also.
The work done is always 0 for expansion into a
vacuum.
However, suppose the external pressure is not
constant, then we must integrate the pressure with respect to
the volume change, ie:
w = - ∫ViVf p dV∫ViVf p dV
Finally, what if the expansion took place in a
diathermic container? The temperature would have remained the
same, and if we also assume a perfect gas, we can use the equation
of state to write pV = nRT. So p = nRT/V and our integral becomes
w = - ∫ViVf nRT/V dV
since nRT is a constant, we have
w = - nRT ∫ViVf V-1 dV
 |
Boyles Law gives us this pressure - volume graph. The
work done is the area under the line.
(a) w = - p.ΔV
(b) w = - ∫ViVf p dV |
|