276 4 Thermodynamics and Statistical Physics
=(V−b)+2 a
RT V^3(V−b)^3T
(
∂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)=RTIt can be shown thatΔT=1
Cp(
2 a
RT−b)
ΔpIfT< 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