Lecture 7

First Law (Contd.)

7.1 Joule-Thomson Expansion

 
In 1843 Joule tried to determine ∂U
∂V for a gas by measuring ∆T upon free expansion
T
against vacuum; see Figure 7.1. When the experiment started, the A chamber was
filled with gas, and B chamber was evacuated. Then the stopper was removed, and
the gas was allowed to reach equilibrium. Temperature change during this process was
measured by a thermometer. Due to the adiabatic walls, no heat exchange is taking
place. Thus q = 0.
As the expansion of gas against vacuum takes place on the removal of the stopper,
w = 0 as Pext = 0. Thus ∆U = 0. In other words, U is constant during the process.
From the experiment, one can compute ∆T, and one knows ∆V. Thus we can obtain
(∂T/∂V )U . Let us define µJ = (∂T/∂V )U , and is called Joule’s coefficient. Joule wanted

Thermometer

Stopper
. .
. . .
.
. . .
.
. .. .
. . . . Adiabatic
. walls
. . . .

A B

Figure 7.1: Joule’s experimental setup

1
 P1, V1, T1 porous plug P1 P2 P2, V2, T2
.
. .. . .. . ..
P1 .. . P2 P1 . .. .. P2 P1 .. . ..
. P2
P2 < P1
(c)
(a) (b)

Figure 7.2: Joule-Thomson experimental setup

   
∂U ∂T
to calculate ∂V . How is it related to ∂V ?
T U
For that, we will use identity:
     
∂T ∂U ∂V
= −1
∂U V ∂V T ∂T U
Then,
   
∂T ∂U 1
= −1 (7.1)
∂U V ∂V T µJ
   
∂U ∂U
⇒ = − µJ (7.2)
∂V T ∂T V
= −µJ CV (7.3)

Unfortunately, µ J measured by Joule in these experiments turned out to be zero. This

was mainly due to the inaccuracies in the measurements, and later more accurate mea-
surements were done by Keyes and Sears in 1924.
Joule and Thomson conducted another experiment in 1853 in which gas throttling
through a porous plug was carried out. They took an insulated pipe, and gas was made
to flow through a porous plug separating the two parts of the pipe, which are kept at
constant pressures P1 and P2 . The gas can get heated up or cooled down in this process.
This is called the Joule-Thomson expansion.
The above is an irreversible process, as P1 > P2 . The work required for pushing one
mole of gas through the porous plate is P1 V 1 (piston on the left); see Figure 7.2.
Z 0
w L = − P1 dV = P1 V1
V1

A work P2 V2 is done on the surroundings by one mole of gas (by the moment of the
piston on the right).
Z V2
w R = − P2 dV = − P2 V2
0

2
Thus the net work done on the gas is

w = w L + w R = P1 V 1 − P2 V 2

Since the pipe is insulated, q = 0. Then,

U 2 − U 1 = P1 V 1 − P2 V 2

Thus,
H2 = H1

This means there is no enthalpy change during the Joule-Thomson expansion.

The joule-Thomson coefficient is defined as
T − T1
 
∂T
µJT = = lim 2
∂P H ∆P→0 P2 − P1
µJT is zero for an ideal gas. For real gases, this can be positive at low temperatures
and negative at high temperatures. That means a cooling effect is obtained below the
inversion temperature, and a heating effect is obtained above the inversion temperature.
For gas to be cooled by expansion, µJT must be positive for a range of T and P.
Like before, one can derive that
 
∂H
= −CP µJT (7.4)
∂P H
Here the units of µJT is K atm−1 .

7.2 Reversible Adiabatic Expansion of Ideal Gas

dq = 0 (adiabatic) (7.5)

dw = − PdV (7.6)

dU = CV dT = 0 − P dV (7.7)

For ideal gas, we substitute P = nRT/V. Then,

nRT
CV dT = − dV (7.8)
V
dT dV
CV = −nR (7.9)
T V
Z 2 Z 2
CV dV
dT = −nR (7.10)
1 T 1 V

3
Taking CV constant for the temperature range T1 to T2 ,

T2 V
CV ln = −nR ln 2 (7.11)
T1 V1
T2 R V2
ln = − ln (7.12)
T1 CV V1
  R/CV
T2 V1
= (7.13)
T1 V2

When V2 > V1 , and since CV > 0 for closed systems, T2 < T1 . Adiabatic expansion of
an ideal gas leads to cooling.
We have

P1 V1 PV
= 2 2 (7.14)
T1 T2
T2 P2 V2
= (7.15)
T1 P1 V1
V1 V1 R/CV
 
P2
= (7.16)
P1 V2 V2
 1+ R/CV
V1
= (7.17)
V2

We have

C P − CV = R (7.18)

Then,

CP R
= 1+ (7.19)
CV CV
R
1−γ = (7.20)
CV
 γ
P2 V1
= (7.21)
P1 V2
γ
P1 V1 = P2 V2γ (7.22)

PV γ = constant (7.23)

For an adiabatic process, since dU = CV dT = dw.

w = ∆U = CV ( T2 − T1 )

4
 P > Isotherm

>
Adiabatic

V1 V2

Figure 7.3: P-V diagram for an isothermic expansion or adiabatic expansion.

7.3 Reversible Phase Change at Constant T and P

Heat q for the phase transition can be measured in an experiment

Z
w=− dV P = − P∆V

∆V can be calculated from change in density during the phase transition.

If one phase is gas, then we can use V = nRT/P may be used. At constant P,

q P = ∆H

∆U = q P + w