Thermodynamics

Y Y Shan

P S

2.3. Cooling by isentropic expansion (adiabatic expansion) process:

It has been pointed out earlier that thermodynamic processes can be mathematically
described by a partial derivative under specific conditions.
isentropic above indicates no change of entropy ( dS = 0 , i.e. dQ = 0 ) happened in

the process. isentropic process is equivalent to adiabatic process (since dS = 0 means

dQ = 0 ).

expansion means when volume expands and pressure will change accordingly.
cooling means the temperature decreases.
Therefore, cooling by isentropic expansion is dealing with the T~P relationship, or is
aking how temperature changes with respect to the decrease of pressure (when volume
expands) under the isentropic condition?
Thus, the study of cooling by isentropic expansion is to answer the following
T
questions:
=?
P S

How does the temperature of a gas change when it expands?

T
:
P S

Derivation of

Entropy S is a state function, for S (T , P ) , mathematically we have

S
S
dS (T , P) =
dT + dP
T P
P T

For isentropic process (constant entropy process), dS = 0 :

S
S
0=
dT + dP
T P
P T

thus
S

T
P T

=
S
P S

T P

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Eq5-6

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----------------------------------------------------------------------------------------*Or Eq5-6 can also be obtained directly by applying the triple product rule:
For S (T , P ) :
S P T

= 1
T P S T P S

S

1
P
Therefore: T =
= T

S
P S

T P S T
T P

-------------------------------------------------------------------------------------------Applying the Maxwells relation (from dG = SdT + VdP ):

S
V
=-
,
P T
T P
Since the volume expansion coefficient:
S
CP = T
, or
T P

1 V
V

, or = V . The specific heat

T P
V T P

= CP / T is the,
T P

Therefore Eqn5-6 becomes:

S

T
P T = TV > 0
=
CP
S
P S

T P

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Eq5-7

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Thermodynamics

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Positive slope means that when pressure P decreases (volume expands), temperature T will
drop. It can be concluded that isentropic expansion always causes a decrease in temperature.
This process can be used for gas cooling.

P H

2.4. Joule-Thomson effect(Throttling process): Cooling by isenthalpic expansion

Let us perform a thermodynamic process: a high-pressure gas is forced through a

constriction, such as a partially opened valve (a throttle) or a porous wall. The throttle valve
is well thermally insulated so that no heat is transferred during the process.
The gas initially has a pressure P1, temperature T1 and volume V1. After it passes
through the valve, its final pressure is P2 and the volume is V2

The first law for this system can be written as: U = U 2 U 1 = Q + W

Since the system is thermally insulated, Q=0, so U 2 U1 = W
0

V2

V1

W = W1 + W2 = P1 dV P2 dV = P1V1 P2V2
so we obtain:

U 2 U1 = P1V1 P2V2 , i.e., U 2 + P2V2 = U1 + P1V1 ,

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Since the enthalpy is defined as H = U + PV , so we get

H 2 = H 1 or H = H 2 H 1 = 0
Thus throttling process is a constant enthalpy process (isenthalpic process).
Given a particular gas and the initial conditions P1 and T1, and final pressure P2 , we
wish to know what the final temperature T2 will be. In other words, we want to know the
change of temperature of the gas (from T1 to T2) with respect to the change of its pressure
(from P1 to P2) in this isenthalpic process:
T
=?
P H

JT =

Eqn5-8

This thermodynamic quantity JT is known as the Joule-Thomson coefficient, which is named

after James Joule and William Thomson, who together studied this process in the 1850s.
To find out

T
, we proceed by starting from the relationship:
P H

JT =

S
S
dH = T
dT + dP + VdP = T
dT + T + V dP
P T
T P
T P

P T

S
V
S
Applying the Maxwells relation: = -
, and CP = T ,
P T
T P
P P
dH becomes:

V
dH = CP dT + V T
dP
T P

For isenthalpic process (constant enthalpy process): dH = 0 , so

V
CP dT = T
V dP
T P

therefore we obtain the expression for the Joule-Thomson coefficient:

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Thermodynamics

1 V
T
=
V
T
P H C P T P

JT =

Y Y Shan

Eqn5-10

nR V
V
= , , it is straightforward to show that
For an ideal gas, PV = nRT ,
=
T P P T

JT = 0 , the temperature of an ideal gas does not change after throttling expansion.
However, when a real gas expands freely at constant enthalpy, the final temperature
( T2 ) may either decrease or increase, depending on the initial temperature ( T1 ) and
pressure( P1 ). For any given pressure, a real gas has a Joule-Thomson (Kelvin) inversion
temperature TInv . (i) When initial temperature of the gas T1 > TInv , throttling expansion

causes the temperature to rise ( T2 > T1 ).

(ii) When T1 < TInv isenthalpic expansion causes

cooling ( T2 < T1 ).
For most gases at atmospheric pressure, the inversion temperature TInv is fairly high
(above room temperature), and so isenthalpic expansion can be applied for gas cooling at
those temperature and pressure conditions.

The value of JT, representing the change of temperature with respect to a change of pressure,
depends on the specific gas, as well as the initial temperature and pressure of the gas before
expansion. For all real gases, JT will equal zero at some temperature point called the Joule-

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Thomson inversion temperature or inversion point.

It is the temperature where the

coefficient changes sign (i.e., where the coefficient equals zero).

In any gas expansion, the gas pressure decreases, meaning P is always negative
( P < 0 ). With that in mind ( JT =

T
),the following table explains when the JouleP

Thomson effect cools or heats a real gas.

If the gas temperature is

then JT is since P is thus T must be so the gas

below the inversion temperature

>0

always -

negative

cools

above the inversion temperature

<0

always -

positive

heats

Helium and hydrogen are two gases whose Joule-Thomson inversion temperatures at
one atmosphere are very low (e.g., about 222 C for helium). Thus, helium and hydrogen
will warm when expanded at constant enthalpy at typical room temperatures. So hydrogen
expansion at room temperature is very dangerous.

3. Gas cooling, liquefaction, and low temperature achievement

The Joule-Thomson effect is applied in the Linde technique as a standard process in

the petrochemical industry, where the cooling effect is used to liquefy gases (for the
production of liquid O2, N2, H2, and He), so that extremely low temperature can be achieved.
From air liquefaction to air separation: with air liquefaction, German engineer Carl
von Linde(18911934), created the conditions needed to produce pure gases using lowtemperature processes. These gases include not only oxygen and nitrogen, but also hydrogen
and inert gases - a technology for which the future has only just begun.

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Sketch of the first air liquefaction plant from 1895.

A gas must be below its inversion temperature to be cooled and liquefied. Once a gas has
been pre-cooled to a temperature lower than the maximum inversion temperature, the
optimum pressure, from which to start throttling, corresponds to a point on the inversion
curve, where the Joule-Thomson coefficient

JT = 0 . Starting at this pressure and ending at

a lower pressure (after expansion), the process produces a large temperature drop.
Consequently, the gas that has been cooled by throttling is used to cool the incoming gas,
which after throttling becomes still cooler.

After successive cooling processes, the

temperature of the gas is lowered to such a temperature that , after throttling, it becomes
partly liquefied.
Gas

Inversion temperature TInv

Liquefying temperature TLiq

At 1atm

O2

620oC

-183oC

N2

352oC

-196oC

H2

-71oC

-253oC

Ne

-239oC

-269oC

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