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52

Katherine Isabel T. Remulla Problem 26 Page 1 of 1

2.57a First, our goal is to calculate the work Wvdw done on the gas to the lowest relevant order
in ρ. Work is defined as
Z
W = − P dV (1)

The van der Waals equation of state is given by

N2
 

P + 2 a V − N b = N kT (2)
V
N N2
The conditions of the problem state that ρ  1 = V . Therefore the V2
term in (2) vanishes.
Isolating P and getting work via (1),
Z V2
N kT N kT
P = ⇒ W =− dV (3)
V − Nb V1 V − Nb
We may simplify (3) by making the following substitutions: u = V −N b, du = dV , u1 = V1 −N b,
and u2 = V2 − N b. The integral simplifies to
Z u2
1
W = −N kT du
u1 u
 u =V −N b
= −N kT ln u u21 =V21 −N b
 
= −N kT ln (V2 − N b) − ln (V1 − N b)
  
V1 − N b
∴ Wvdw = N kT ln (4)
V2 − N b

2.57b Next we shall calculate the work Wideal done on the gas under the same conditions assuming
that the gas is ideal. The ideal gas law is given by

P V = N kT (5)
Isolating P in (5) and applying it to (1),

Z V2
N kT
W =− dV
V1 V
V2
= N kT ln V

V1
V 
2
∴ Wideal = N kT ln (6)
V1

2.57c Lastly, let us find the difference ∆W = Wvdw − Wideal . Subtracting (4) from (6),
     
V1 − N b V 
2 V1 V1 − N b
∆W = N kT ln − N kT ln = N kT ln <0
V2 − N b V1 V2 V2 − N b
which implies that Wvdw < Wideal . By extension, the difference in temperature T is also negative.
The collisions are no longer elastic in Wvdw , the attraction and repulsion forces inhibit the movement
of the atoms and thus lower the calculated temperature of the system.

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