276 4 Thermodynamics and Statistical Physics
=(V−b)+
2 a
RT V^3
(V−b)^3
T
(
∂V
∂T
)
P
−V=
2 a
RT
−b (∴bV)
Using this in the expression for Joule–Thompson effect (Problem 4.31),
ΔT=
1
Cp
(
2 a
RT
−b
)
ΔP
4.35 The equation of state for an imperfect gas is
(
p+
a
V^2
)
(V−b)=RT
It can be shown that
ΔT=
1
Cp
(
2 a
RT
−b
)
Δp
IfT< 2 a/bR,ΔT/Δpis positive and there will be cooling.
IfT> 2 a/bR,ΔT/Δpwill be negative and the gas is heated on undergo-
ing Joule–Kelvin expansion.
IfT= 2 a/bR,ΔT/Δp=0, there is neither heating nor cooling.
The temperature given byTi=bR^2 a is called the temperature of inversion
since on passing through this temperature the Joule–Kelvin effect changes its
sign. Figure 4.3 shows the required curve.
Fig. 4.3Joule-Thompson
effect
4.36 By definition
ET=−V
(
∂P
∂V
)
T
;ES=−V
(
∂P
∂V
)
S