1

Problem 2-7
If n moles of an ideal gas at the temperature 4 K can be pumped through a tube of diameter d, what must be the
diameter of the tube to pump the same number of moles of gas at the temperature 300 K?
Solution
We should assume that the pressure and the length of the tube is the same in two case, then from P V = nRT we
get
r
V1 d21 T2 T2
= 2 = ⇒ d2 = d1 ' 8.66d1
V2 d2 T1 T1

Problem 2-14
A vessel contains CO2 at the temperature of 137 C. The specific volume is 0.07 m3 kmol−1 .
1. Compute the pressure in Nm−2 (a) from the ideal gas equation, (b) from the van der Waals equation.
2. Calculate the ratio PTv (in J kmol−1 K−1 ), for the two pressures found above, and compare with experimental value
as read from Fig. 2-1 (p. 12 of the lecture notes) assuming that T2 =137 C.
Solution

RT N
(a) : P = = 4.87 × 107 2
v m

RT a N
(b) : P = − 2 = 5.1 × 107 2
v−b v m

PV  J PV  J
(c) : = 8.31 × 103 , = 8.7 × 103
T ideal kmolK T VdW kmolK

Problem 2-25 3
bT 2
A substance has compressibility κ = aTP 2 and expansivity β = P where a and b are constants. Find the equation of
a
state of the substance and the ratio b .
Solution #1: consider
  ln V (P2, T2 ) −ln V (P1 , T1 ).    
1 dV
Since κ = − V dP = − d dP
ln V
and β = 1
V
dV
dT = − d ln V
dT we get along the path
T T P P
P1 , T1 → P2 , T1 → P2 , T2
ln V (P2 , T2 ) − ln V (P1 , T1 ) = ln V (P2 , T2 ) − ln V (P2 , T1 ) + ln V (P2 , T1 ) − ln V (P1 , T1 )
Z T2 Z P2  Z T2 Z P2
 d ln V  d ln V  bT 2 aT13 bT23 bT 3 aT 3 aT 3
= dT + = dT − dP 2
= − 1 + 1 − 1
T1 dT P2 P1 dP T1 T1 P2 P1 P 3P2 3P2 P2 P1
On the other hand, along the path P1 , T1 → P1 , T2 → P2 , T2 we have
ln V (P2 , T2 ) − ln V (P1 , T1 ) = ln V (P2 , T2 ) − ln V (P1 , T2 ) + ln V (P1 , T2 ) − ln V (P1 , T1 )
Z P2  Z T2 Z P2 Z T2
d ln V   d ln V  aT23 bT 2 aT23 aT23 bT23 bT13
= + dT = − dP + dT = − + −
P1 dP T2 T1 ∂T P1 P1 P2 T1 P1 P2 P1 3P1 3P1
⇒
1 b 3 b 3
aT 3 aT23 1 b b
P1 b 3 b 3 b b

T2 − T1 +aT13 − 1 = −aT23 + T23 − T13 ⇔ T2 − T1 +aT13 −aT23 = aT13 −aT23 + T23 − T13


+
P2 3 3 P1 P2 P1 3 3 P2 3 3 3 3
Since P1 and P2 are arbitrary, this can be true only if
b 3 b 3 b b b
T2 − T1 + aT13 − aT23 = aT13 − aT23 + T23 − T13 = 0 ⇒ a=
3 3 3 3 3
so the equation of state is

aT23 aT 3 aT 3
ln V (P2 , T2 ) − ln V (P1 , T1 ) = − 2 ⇒ V (P, T ) = e P × const
P2 P2
 2

Solution #2: use the fact that β and κ are partial derivatives
1  dV  1 ∂V (P, T ) ∂ ln V (P, T ) aT 3
κ = − = − = − =
V dP T V ∂P ∂P P2
2
1 dV
  1 ∂V (P, T ) ∂ ln V (P, T ) bT
β = = − = =
V dT P V ∂T ∂T P
Calculating indefinite integrals, we get
∂ ln V (P, T ) aT 3 aT 3
= − 2 ⇒ ln V (T, P ) = + F1 (T )
∂P P P
∂ ln V (P, T ) bT 2 bT 3
= ⇒ ln V (T, P ) = + F2 (P )
∂T P 3P
a 1
where F1 and F2 are arbitrary functions. For both of these formulas to be correct, one needs b = 3 (and F1 =
F2 =const) so the equation of state is
aT 3
V (P, T ) = e P × const