The Joule-Thomson Effect

Ka Ho YUEN
Department of Physics
Hong Kong Baptist University

Abstract

When a gas undergoes a pressure decrease while going through an adiabatic expansion, a
thermodynamic process known as the Joule-Thomson effect takes place. Depending on the
initial temperature and the kind of gas being used, the gas may either cool down or heat up
throughout this expansion. In refrigeration and gas liquefaction systems, this effect is crucial.
This term paper is providing a comprehensive understanding of the Joule-Thomson effect,
including its underlying principles, practical applications, and potential limitations.

1. Introduction

In the field of thermodynamics, the Joule-Thomson effect (also known as the Joule-
Kelvin effect) refers to the temperature change experienced by a real gas or liquid (except for
ideal gas) when it is forced through a valve or porous plug while being insulated to prevent
heat exchange with the surroundings. This process is termed throttling or the Joule-Thomson
process. At room temperature, all gases, except for hydrogen, helium, and neon, cool during
the Joule-Thomson process when they expand through an orifice. These three gases exhibit
the same effect, but only at lower temperatures. Most liquids, such as hydraulic oils,
experience warming during the Joule-Thomson throttling process.

Fig. 1 Throttling process

The cooling effect observed in gases during the throttling process is widely utilized in
refrigeration systems, including liquefiers in air separation industrial processes. In hydraulics,
the warming effect resulting from Joule-Thomson throttling can help identify internally
leaking valves, as they generate heat that can be detected using a thermocouple or a thermal-
imaging camera. Throttling is fundamentally an irreversible process, and the flow resistance
caused by throttling in supply lines, heat exchangers, regenerators, and other components of
thermal machines contributes to losses that limit their overall performance.
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2. Historical Background

The Joule-Thomson effect has its origins in the middle of the 19th century, when two
well-known scientists, James Prescott Joule and William Thomson (after known as Lord
Kelvin), made substantial contributions to the discipline of thermodynamics. Their combined
efforts resulted in the discovery of the temperature change that a real gas or liquid
experiences when it is driven through a valve or porous plug while being insulated to avoid
heat exchange with the surroundings.

In 1852, Joule and Thomson conducted a series of experiments known as the porous plug
experiments, which formed the foundation of the Joule-Thomson effect. They were
investigating the behavior of real gases under various conditions, specifically focusing on the
relationship between pressure, volume, and temperature changes in gases undergoing
adiabatic expansion. The experimental setup involved forcing a highly compressed gas
through a porous material, such as cotton-wool or silk, which acted as a throttling device. The
plug was surrounded by a nonconducting jacket to ensure adiabatic conditions, meaning no
heat was exchanged with the surroundings.

The findings of the experiments showed that a real gas experiences a temperature change
when it is pushed to expand through a throttling device from a region of high pressure to a
region of low pressure. The initial temperature, initial pressure, and properties of gas were
discovered to be correlated with this temperature change, which became known as the Joule-
Thomson effect.

3. Theoretical Explanation

To illustrate the thermodynamic principles of the Joule-Thomson effect, the design of the
porous experiment should be demonstrated first. Then, the quantitative analysis, including the
Joule-Thomson coefficient, and the qualitative analysis of the effect would also be discussed.

3.1 Experimental Design

As shown in Fig. 2(a), at the initial state, there is a fixed porous plug between two pistons
in an insulated container. On the left side of the plug, the piston traps a real gas of volume V1
and the pressure outside the piston isP1 . On the right side of the plug, the piston traps nothing
and the pressure outside the piston is P2. Note thatP1 is greater thanP2 .

After pushing the left side piston towards the plug until all the real gas flows to the right
side of the plug, the final state is reached. As shown in Fig. 2(b), at the final state, the left
piston traps nothing and the right piston traps the flowed real gas of volume V2.

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 piston porous
plug
P2 P1

Fig. 2(a) At beginning of experiment Fig. 2(b) After finishing the experiment

3.2 Isenthalpic Process

In order to study the effect in depth, it is essential to first prove that the Joule-Thomson
expansion is isenthalpic. Let’s begin with the total work done on the gas in the expansion.
The total work done is
0 V2

W=−∫ P1 dV−∫ P2 dV = P1 V 1−P2 V 2 . (1)

V1 0

By the first law of thermodynamics, we know

ΔE = Q + W
E2−E1 = P1 V1−P 2 V2
E 1 + P1 V 1 = E 2 + P2 V 2 . (2)
By the definition of enthalpy: H = E + PV
∴ H1 = H2 (3)
From that, we proved that the enthalpy of the gas in the expansion is conserved, therefore this
is an isenthalpic process.

3.3 The Joule-Thomson Coefficient

Since we are interested in the temperature change of the gas when we reduce its pressure
at constant enthalpy, we can define a coefficient to describe the temperature change, which is
called the Joule-Thomson coefficient (μJT). Mathematically speaking, it is defined as
μJT=( eq \f( ∂ T,∂ P) )H
(4)
To further transform the equation to an expression that can be computed easier, we can start
with the definition of enthalpy:
H = E + PV
dH = dE + PdV + VdP. (5)
By the first law of thermodynamics, dE = δQ + δW = TdS – PdV. Therefore,
dH = TdS + VdP (6)

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Then, we can derive an equation of TdS to replace the term in equation (6).
Let the entropy S be a function of T and P: S = S(T, P)

dS= ( ∂S∂T ) dT+(∂S∂P ) dP

P T
(7)

TdS=T (∂S∂T ) dT+T (∂S∂P ) dP

P T
(8)

Since T(∂S/∂T)P = CP, which is the definition of heat capacity under constant pressure, and by
2nd Maxwell’s relation, (∂S/∂P)T = – (∂V/∂T)P. Hence,

TdS=CP dT−T (∂V

∂T )P
dP. (9)

Substitute equation (9) into equation (6), we get

dH=CP dT− T
[( ) ] ∂V
∂T P
−V dP.
(10)

Since it is an isenthalpic process, i.e. dH = 0. Therefore

[( ) ]
CP dT= T
∂V
∂T P
−V dP.

Thus, we found the expression of the Joule-Thomson coefficient, which is

μJT=( eq \f(∂T,∂P) )H=

1
CP [( ) ]
T
∂V
∂T P
−V . (11)

3.4 Interpretation of the Joule-Thomson Coefficient

After getting the expression of the Joule-Thomson coefficient, we can now think about
the physical meaning of it. Let’s consider the sign of the coefficient:

Temperature Sign of ∂P Sign ofμJT Sign of ∂T Effect

Below Ti – + – Cooling
Above Ti – – + Heating
Fig. 3 Sign of temperature change

First, as we are forcing the gas flow from high pressure region to low pressure region, the
pressure of the gas must be decreased, therefore the sign of ∂P must be negative. If the sign
of the coefficient is positive, then by its definition, the sign of ∂T must be negative. That
means the temperature decreases hence cooling effect would be occurred during the

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expansion. In contrast, if the sign of the coefficient is negative, then the sign of ∂T must be
positive. That means the temperature increases hence heating effect would occur during the
expansion. As a result, the temperature change depends on the sign of the coefficient, and the
sign of it depends on the initial temperature and the inversion temperature Ti.
The inversion temperature Ti of a real gas at an initial pressure depends on the specific
heat capacity, molar mass, and the interactions between the molecules of the gas. If the initial
temperature is higher than the inversion temperature at a certain initial pressure, the Joule-
Thomson coefficient would be negative and a heating effect would be occurred. If the initial
case is reversed, the coefficient would be positive and a cooling effect would be occurred. In
particular, if the initial temperature equals the inversion temperature, the gas would neither be
heated nor be cooled.

For deeper study, we can discuss the graphs ofμJT against T and T against P as shown in
Fig.3. Fig.3(a) indicates the relationship between μJTand initial temperature T for different
real gases at 1 atm of pressure. We can observe that their μJTbecome negative once their T are
greater than their critical temperatures. Thus, we can conclude that the inversion temperature
Ti of gases is equal to the initial temperature T at μJT= 0. Also, Fig.3(b) illustrates the so-
called inversion curve of nitrogen gas in a T against P graph, and the initial conditions on the
curve result inμJT= 0. From that, we can observe if the initial temperature is in the bound
region of the curve,μJTwould become positive. Otherwise,μJTwould become negative.

Fig. 3(a)μJTvs T for different gases at 1 atm Fig. 3(b) T vs P for nitrogen gas

3.5 The Joule-Thomson Coefficient for Ideal Gases and Real Gases

In the introduction of the paper, it was mentioned that the Joule-Thomson effect works
for real gases but not ideal gases. We can verify that by computing the Joule-Thomson
coefficient of ideal gases. The equation of state of 1 mole of ideal gases is
PV = RT. (12)
So, we get

(13)
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 (∂V
∂T ) R V
= = .
P T
P

Plugging equation (13) into equation (11), we can obtain

μJT=
1 V
[
T −V =0 .
CP T ] (14)

Since the Joule-Thomson coefficient of ideal gases is zero, there will be no temperature
change during the expansion. Hence, there is no Joule-Thomson effect for ideal gases.

For real gases, such as van der Waals gases, we can get a different result from the ideal
gases. Since there is a cubic term of V in the equation of state of van der Waals gases, we
cannot solve the van der Waals equation for V explicitly. So we have to use an approximation.
This can be written as

Z=1+
1
RT
b−
a
RT(P+… ) (15)

which is the first two terms of the virial equation approximation for 1 mole of van der Waals
gases, where Z is called the compressibility factor. Since by definition, Z = PV/RT, we can
solve equation (15) for V to get

V=
RT
P
+ b−
a
RT(+… . ) (16)

From that, we can get

(∂V
∂T ) P R T
R a
= +
P
+…. 2 (17)

Using equation (16) and (17) to solve equation (11), it would be

μJT=
1
CP{(R a
T +
P RT 2
+… −
RT
P
+ b−
a
RT)[ (
+… . ) ]} (18)

And finally we can get

μJT ≈
1 2a
CP RT (
−b . ) (19)

From equation (19), we can observe some relationships between the initial temperature T and
the coefficient. First, if 2a/RT – b = 0, i.e. T = 2a/Rb, thenμJT= 0. Therefore, the inversion
temperature Ti = 2a/Rb. Based on the inversion temperature, if T > Ti, thenμJTwould be
negative and thus heating effect will occur. If T < Ti, then μJT would be positive and thus

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cooling effect will occur. This result matches the experiment that real gases can be heated,
cooled, or neither heated nor cooled during the expansion.

3.6 Physical Mechanism of The Joule-Thomson Effect

Despite the quantitative analysis of the Joule-Thomson effect above, it is also essential to
understand the effect more qualitatively. We can begin with the consideration of differences
between ideal gases and real gases. As we know, the only difference between ideal gases and
real gases is there are molecular interactions in real gases but not in ideal gases (i.e. potential
energy). Thus, we can deduce that the interactions between molecules, including attractions
and repulsions, are the main factor in the occurrence of the Joule-Thomson effect.
According to Gans (1992), at low temperatures attractive forces between molecules
predominate in a real gas, while at high temperatures the repulsive forces between molecules
predominate in a real gas. So, we can explain the Joule-Thomson effect in these ways:
1. If T < Ti, the intermolecular attraction is the most important interaction. When the real
gas is expanded, the molecular potential energy will gain extra energy from internal
energy to pull the molecules apart (since the expansion is adiabatic, the only source of
energy is the internal energy of the gas). It will lead to a decrease in internal energy and
hence the molecular kinetic energy will also decrease. As a result, the temperature of the
gas will decrease and the gas cools.
2. If T > Ti, the intermolecular repulsion is the most important interaction. When the real
gas is expanded, the molecular potential energy will release energy to internal energy as
the molecules tend to separate. It will lead to an increase in internal energy and hence the
molecular kinetic energy will also increase. As a result, the temperature of the gas will
increase and the gas heats.

4. Applications

The Joule-Thomson effect plays a crucial role in refrigeration and air conditioning, and
cryogenics. Here, I will focus on how the Joule-Thomson effect applies to these applications.

4.1 Refrigeration and Air Conditioning

The Joule-Thomson effect is the working principle in refrigeration and air conditioning
systems, which are designed to cool objects and the environment. When a compressed gas is
expanded through a Joule-Thomson valve or an expansion valve in these systems, it will be
cooled due to the Joule-Thomson effect. The typical working fluid of a refrigeration system is
usually ammonia, freon, or carbon dioxide. This working fluid is compressed to a high
pressure and then expanded to a lower pressure through the expansion device. The rapid

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expansion causes the Joule-Thomson effect, resulting in a decrease in the refrigerant's
temperature.

The cooled refrigerant raises the cooling capacity of the system as it will then flow
through an evaporator and absorb heat from the surrounding environment such as a room or
refrigerated space. This heat absorption causes the refrigerant to evaporate and effectively
reduces the temperature of the space.

The heated gas is then compressed again, and the cycle starts over. By continuously
cycling the refrigerant through compression, expansion, and heat exchange processes,
refrigeration and air conditioning systems exploit the Joule-Thomson effect to maintain the
desired low temperature in the enclosed space.

Fig. 4 Simple structure of a refrigerator

4.2 Cryogenics

Cryogenics is the branch of engineering that study the production and behavior of
materials at very low temperatures (i.e. below 123 K). In cryogenic applications, the Joule-
Thomson effect is applied to achieve extremely low temperatures and gas liquefaction. The
process typically involves compressing and cooling a gas before allowing it to expand
through a Joule-Thomson valve or other throttling devices, such as expansion valves or
capillary tubes.

Due to the Joule-Thomson effect, the expansion causes a considerable reduction in gas
temperature. The gas may be liquefied by repeating this cooling process several times until it
reaches a sufficiently low temperature, which can be used in a variety of industries including
industrial, scientific, and medicinal.

The production of liquid nitrogen is one of the most often used cryogenic applications.
Numerous scientific, medicinal, and industrial uses are possible. By expanding nitrogen gas
through a Joule-Thomson valve, liquid nitrogen is created by chilling and liquefying the gas.
The expansion can reduce the temperature to the boiling point of liquid nitrogen (i.e. -196°C).

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 Other cryogenic utilizes of the Joule-Thomson effect include the generation of liquid
helium or hydrogen and the cooling of superconducting magnets used in particle accelerators
and MRI machines. In addition, the Joule-Thomson effect is used in a variety of scientific
studies, including those in low-temperature physics, material science, and chemistry, to cool
down samples.

5. Discussions

Although the Joule-Thomson effect can be utilized in different aspects, there are some
limitations to its applications. First, there is an issue of energy consumption. The Joule-
Thomson effect can consume a significant amount of energy. Since most common real gases
have negative Joule-Thomson coefficients at room temperature and 1 atm, the gas must be
compressed to high pressure before expansion, which requires more energy than other
appliances. This can limit its efficiency and increase operating costs.

Second, there are equipment requirements. The Joule-Thomson effect requires

specialized equipment, such as Joule-Thomson valves or other expansion devices. The
equipment must also be designed to handle the specific gas or gas mixture being used.
Furthermore, when a large pressure drop occurs through a valve, it may freeze. This can
occur either through the seizure of components within the valve or the valve becoming
inoperable because ice has formed on the outside of the valve. As a result, using this
equipment can be expensive and require maintenance.

6. Conclusion

To conclude, the Joule-Thomson effect occurs when real gases or liquid are forced
through a valve or porous plug and are expanded from a high pressure region to a low
pressure region, given that the expansion is adiabatic and isenthalpic. The result of the
expansion can be the gas is heated, cooled, or neither heated nor cooled. It depends on the
initial temperature and the inversion temperature of the gas at a certain pressure. In addition,
there is no Joule-Thomson effect for ideal gases as there are no molecular interactions in ideal
gases. We have also talked about the equation and meaning of the Joule-Thomson coefficient.
If the coefficient is positive, there will be a cooling effect. If the coefficient is negative, there
will be a heating effect.

There are two applications of the Joule-Thomson effect we have discussed, that are
refrigeration and air conditioning, and cryogenics. Both are applying the cooling effect of the
Joule-Thomson expansion. Refrigeration and air conditioning use the cooled gas to absorb
heat from an enclosed space, and cryogenics utilize the effect to produce liquefied gas and
apply it in the fields like industrial, scientific, and medical.
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 We have also discussed the limitations of the Joule-Thomson effect, such as energy
consumption, and specialized equipment requirements. Despite these challenges, the Joule-
Thomson effect remains an essential mechanism in many industries and scientific fields. Its
ongoing research and knowledge may result in creative ideas, enhanced system layouts, and
more effective cooling technologies.

In summary, the Joule-Thomson effect provides important information on how gases

behave under varying pressure circumstances and forms the framework for many cooling
system designs and operations. Further investigation into the Joule-Thomson effect and its
applications is essential for the continuous development of these vital technologies as the
need for more effective and environmentally friendly cooling solutions rises.

7. References

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Blundell, S. J., & Blundell, K. M. (2006). Concepts in Thermal Physics. Oxford University
Press.

de Waele, A. T. A. M. (2017). Basics of Joule–Thomson Liquefaction and JT Cooling.

Journal of Low Temperature Physics. https://doi.org/10.1007/s10909-016-1733-3

Gans, P. J. (1992). Joule-Thomson Expansion. New York University.

Kittel, C., & Kroemer, H. (1980). Thermal Physics. W. H. Freeman.

Koltz, I. M., & Rosenberg, R. M. (1991). Chemical Thermodynamics. Benjamin, Meno Park,
California.

Mandl, F. (1971). Statistical Physics. John Wiley & Sons Ltd.

Pippard, A. B. (1957). Elements of Classical Thermodynamics. Cambridge University Press,

Cambridge, U.K.

Schroeder, D. V. (2000). An Introduction to Thermal Physics. Addison Wesley Longman.

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Zemansky, M. W. (1968). Heat and Thermodynamics; An Intermediate Textbook. McGraw-
Hill.

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