THERMOCHEMISTRY

The Joule-Thomson Coefficient

• The change in enthalpy, ∆𝐻, is given by
∆𝐻 = 𝐶𝑝 ∆𝑇
• By definition,
𝜕𝐻
𝐶𝑝 =
𝜕𝑇 𝑝
• From the above eqn and differential, the enthalpy, 𝐻, can be
regarded as a function of 𝑝 and 𝑇.
• 𝐻 being a function of 𝑝 and 𝑇 can mathematically be written as
𝐻 𝑝, 𝑇 .
• Thus the total differential of 𝐻 is given by
𝜕𝐻 𝜕𝐻
𝑑𝐻 = 𝑑𝑝 + 𝑑𝑇
𝜕𝑝 𝑇
𝜕𝑇 𝑝
 𝜕𝐻
• We know that = 𝐶𝑝
𝜕𝑇 𝑝
• Application of Euler’s chain relation (or cycle rule) to
𝜕𝐻
gives
𝜕𝑝 𝑇

𝜕𝐻 𝜕𝑝 𝜕𝑇
= −1
𝜕𝑝 𝑇
𝜕𝑇 𝐻
𝜕𝐻 𝑝

𝜕𝐻 1
=−
𝜕𝑝 𝜕𝑝 𝜕𝑇
𝑇
𝜕𝑇 𝐻 𝜕𝐻 𝑝

𝜕𝐻 1 1
=− ·
𝜕𝑝 𝜕𝑝 𝜕𝑇
𝑇
𝜕𝑇 𝐻 𝜕𝐻 𝑝
• Based on the reciprocal identity
1 𝜕𝑇
=
𝜕𝑝 𝜕𝑝 𝐻
𝜕𝑇 𝐻

1 𝜕𝐻
=
𝜕𝑇 𝜕𝑇 𝑝
𝜕𝐻 𝑝
• Thus
𝜕𝐻 𝜕𝑇 𝜕𝐻
=−
𝜕𝑝 𝑇
𝜕𝑝 𝐻
𝜕𝑇 𝑝
𝜕𝐻
where = 𝐶𝑝
𝜕𝑇 𝑝
𝜕𝑇
and =𝜇
𝜕𝑝 𝐻
• Thus
𝜕𝐻
= −𝜇𝐶𝑝
𝜕𝑝 𝑇
⇒ 𝑑𝐻 = −𝜇𝐶𝑝 𝑑𝑝 + 𝐶𝑝 𝑑𝑇
⇒ 𝑑𝐻 = 𝐶𝑝 𝑑𝑇 − 𝜇𝐶𝑝 𝑑𝑝
• At constant enthalpy, 𝑑𝐻 = 0.
⇒ 0 = 𝐶𝑝 𝑑𝑇 − 𝜇𝐶𝑝 𝑑𝑝
𝜇𝐶𝑝 𝑑𝑝 = 𝐶𝑝 𝑑𝑇
𝜇𝑑𝑝 = 𝑑𝑇
𝑑𝑇
𝜇=
𝑑𝑝
• Introduction of partial derivatives and the constraint
of constant enthalpy give
𝜕𝑇
𝜇=
𝜕𝑝 𝐻
where 𝜇 denotes the Joule-Thomson coefficient.
• The Joule-Thomson coefficient, 𝜇, is useful for
relating heat capacities at constant pressure and
volume and to liquefy gases.
The Joule-Thomson Experiment
• This experiment was done by Joule and Thomson to
investigate the dependence of energy and enthalpy of
real gases on volume (or alternatively pressure).
• It was done to show that the expansion resulting in
the Joule-Thomson coefficient occurs at constant
enthalpy, i.e. an isoenthalpic process.
• They allowed a gas to expand freely through a
porous plug in a system that was thermally insulated
so that the expansion occurred adiabatically,
i.e. 𝑞 = 0.
The diagram below illustrates the Joule-Thomson
experiment:

Note: The direction in which the gas expands/moves

spontaneously is upstream to downstream.
• The gas expands from a pressure 𝑝𝑖 to a pressure 𝑝𝑓
by the throttling action of the porous plug.
• The gas is allowed to flow continuously through the
porous plug, and when steady-state conditions have
been reached, the temperatures of the gas before and
after the expansion, 𝑇𝑖 and 𝑇𝑓 , respectively, are
measured directly with sensitive thermocouples.
𝑤 = 𝑤1 + 𝑤2 = 𝑝𝑖 𝑉𝑖 − 𝑝𝑓 𝑉𝑓
∆𝑈 = 𝑞 + 𝑤
𝑞 = 0 ⇒ ∆𝑈 = 0 + 𝑤 ⇒ ∆𝑈 = 𝑤 = 𝑝𝑖 𝑉𝑖 − 𝑝𝑓 𝑉𝑓
𝑈𝑓 − 𝑈𝑖 = 𝑝𝑖 𝑉𝑖 − 𝑝𝑓 𝑉𝑓
𝑈𝑓 + 𝑝𝑓 𝑉𝑓 = 𝑈𝑖 + 𝑝𝑖 𝑉𝑖
• By definition, 𝐻 = 𝑈 + 𝑝𝑉
𝐻𝑓 = 𝑈𝑓 + 𝑝𝑓 𝑉𝑓
𝐻𝑖 = 𝑈𝑖 + 𝑝𝑖 𝑉𝑖
• The last eqn on previous slide implies that
𝐻𝑓 = 𝐻𝑖 ⇒ isoenthalpic process
• Therefore the expansion occurs without a change in
enthalpy.
• The property measured in the experiment is the ratio
of the temperature change to the change in pressure:
∆𝑇
∆𝑝
• Introduction of partial differentials and the constraint of
constant enthalpy give
𝜕𝑇
𝜕𝑝 𝐻
• The above quantity is known as the Joule-Thomson
coefficient, 𝜇.
• The physical interpretation of 𝜇 is that it is the ratio of
the change in temperature to the change in pressure when
a gas expands under conditions that ensure that there is no
change in enthalpy.
• For a real gas, 𝜇 < 0 or 𝜇 > 0, i.e. 𝜇 ≠ 0.
• For a perfect gas, 𝜇 = 0.
• Hence, 𝑇 of a perfect gas is unchanged by a Joule-
Thomson expansion.
• In an expansion, 𝑑𝑝 < 0.
• Whether 𝑑𝑇 is positive or negative depends on the sign
of 𝜇.
𝜕𝑇
𝜇=
𝜕𝑝 𝐻
• We see that for 𝜇 > 0, 𝑑𝑇 < 0 (which means the gas
must go from a high 𝑇 to a low 𝑇 during the expansion,
i.e. 𝑇1 > 𝑇2 ) upon expansion so that the gas cools.
• On the other hand, for 𝜇 < 0, 𝑑𝑇 > 0 (which means the
gas must go from a low 𝑇 to a high 𝑇 during the
expansion, i.e. 𝑇1 < 𝑇2 ) so that the gas warms upon
expansion.
• In order to liquefy a gas by a Joule-Thomson (J-T)
expansion, the gas must first be cooled below the J-T
inversion temperature, 𝑇𝐼 .
• For example, the J-T inversion temperature of 𝑁2
gas is 621 K (348 ℃) and that of 𝑂2 gas is 764 K
(491 ℃).
• When 𝑁2 and 𝑂2 gases are at room temperature
(298 K or 25 ℃), they are at a temperature which is
below their 𝑇𝐼 .
• Since at rt 𝑁2 and 𝑂2 gases are below their 𝑇𝐼 , 𝑁2
and 𝑂2 gases are cooled by the Joule-Thomson effect
when expanded at constant enthalpy at typical room
temperatures.
Homework 5:
When a certain freon used in refrigeration was allowed
to expand adiabatically from an initial pressure of
32.0 𝑎𝑡𝑚 and 0 ℃ to a final pressure of 1.00 𝑎𝑡𝑚, the
temperature fell by 22.0 K.
Calculate 𝜇 at 0 ℃, assuming it remains constant over
the temperature range.
𝜕𝑇
[Hint: 𝜇 = ]
𝜕𝑝 𝐻