Joule Thomson coefficient and inversion temperature: Interplay of

van der Walls a and b

Van der Walls has explained all these intriguing concepts for real gases with non-zero volume
and intermolecular attractions in his equation of state [P + a(n/V) ^2] [V-nb] = RT, but it is
undoubtedly challenging to interpret. P is pressure, V is volume, R is universal gas constant, T is
temperature, n is number of moles, a and b are van der Walls constants. In the van der Waals
equation, the constant 'a' represents the magnitude of attractive forces between gas
molecules, whereas 'b' represents the effective volume occupied by the gas molecules. It's also
known as excluded volume. a and b characteristic of the individual gas. The van der Waals
equation of state approaches the ideal gas law PV=nRT as the values of these constants
approach zero.
This post will attempt to explain the fundamental principles that underlie the frequently
misunderstood concepts of why and when an adiabatic process for most real gases becomes
isenthalpic, why and Joule Thomson changes sign at inversion temperature, why P-T
relationship for real gases takes U turn at inversion temperature, what happens to free energy
change at inversion temperature etc. These are all difficult concepts.
Joule-Thomson coefficient and inversion temperature can be considered confusing subjects in
thermodynamics because they involve a combination of theoretical concepts and experimental
observations.
Here are a few reasons why these concepts are challenging:

1. Complexity of the concept:

The Joule-Thomson effect involves the cooling or heating of a gas when it expands or contracts
under certain conditions. It requires an understanding of concepts like intermolecular forces,
equation of state, and the behaviour of gases at different temperatures and pressures.

2. Non-ideal behaviour of gases:

The Joule-Thomson coefficient is influenced by the non-ideal behaviour of gases, which is
typically accounted for by the van der Waals equation or other equations of state. This adds an
additional level of complexity to the calculations and understanding of the effect.

3. Inversion temperature dependence:

The inversion temperature is the temperature at which the Joule-Thomson coefficient changes
sign from positive to negative or vice versa. The behaviour of gases around this temperature
can be counterintuitive, as it involves changes in the relative significance of attractive and
repulsive forces between particles.
What is Joule Thomson effect?
The Joule-Thomson effect in thermodynamics describes how a real gas or liquid's temperature
changes when it is forced through a valve or porous plug while remaining insulated to prevent
heat from escaping into the environment. Throttling or the Joule-Thomson process is the name
of this process. All gases cool upon expansion by the Joule-Thomson process when throttled
through an orifice at room temperature with the exception of hydrogen, helium, and neon;
these three gases experience the same effect but only at lower temperatures. A change in
internal energy or the conversion between potential and kinetic internal energy are the two
things that can alter a fluid's temperature during an adiabatic expansion. Since thermal kinetic
energy (energy connected to molecular motion) is measured by temperature, a change in
temperature denotes a change in thermal kinetic energy. Thermal kinetic energy and thermal
potential energy are added to create internal energy. As a result, the temperature can change
as a result of the conversion of kinetic and potential energy, even if the internal energy does
not change.
H = U + PV
dH = 0, - U = PV, and U provides energy for PV work in the JT effect. Internal energy is denoted
by U, enthalpy by H, pressure by P, and volume by V.

What is Joule Thomson coefficient?

The Joule Thomson coefficient is the ratio of the temperature decrease to the pressure drop,
dT/dP at constant enthalpy. The temperature change produced during a Joule–Thomson
expansion is quantified by the Joule–Thomson coefficient, mu JT. This coefficient may be either
positive (corresponding to cooling) or negative (heating).
What is inversion temperature?
The inversion temperature in thermodynamics is the critical temperature below which a non-
ideal gas (all gases in reality) except H2 , He and Ne, that is expanding at constant enthalpy will
experience a temperature decrease, and above which will experience a temperature increase.
This temperature change is known as the Joule-Thomson effect and is used in the liquefaction
of gases. Inversion temperature depends on the nature of the gas. This is the temperature at
which the Joule–Thomson effect for a given gas changes sign, so that the gas is neither heated
nor cooled when allowed to expand without expending energy is the inversion temperature.
Inversion temperature is the temperature at which gas shows neither a cooling effect nor a
heating effect.
Fundamentals
Van der Walls equation
The Van der Waals equation takes into account the attractive forces between gas particles
(represented by "a") and the excluded volume of the gas particles (represented by "b"). When
a gas expands at constant enthalpy, the term P + (a/V^2) decreases since the intermolecular
forces decrease. However, the term V - (b) increases.
van der Waals enthalpy equation
For a van der Waals gas the enthalpy for a diatomic gas is expressed by the following equation
H = 5/2 n Kb T + n^2/V [b Kb T – 2a]
5 stands for the degrees of freedom for a diatomic gas, 1/2Kb T is the heat added to each
degree of freedom. [ Equipartiontheory: The original idea of equipartition was that, in thermal
equilibrium, energy is shared equally among all of its various forms; for example, the average
kinetic energy per degree of freedom in translational motion of a molecule should equal that
in rotational motion.], Kb is Boltzmann constant, T is temperature, V is volume and a and b are
van der Walls constants
From this equation, we note that if we keep enthalpy constant and increase volume,
temperature must change depending on the sign of [b Kb T – 2a].
What does it mean?
It means all these concepts that are discussing arise from the interplay of a and b and sign of [b
Kb T – 2a], a and b are van der Walls constants
How and why sign of Joule Thomson coefficient changes?

The Joule-Thomson coefficient is related to the factors (a - b) of the Van der Waals equation. a
and b are van der Walls constant

The sign change in (a - b) simply indicates a change in the dominant contribution of the
intermolecular forces and excluded volume effects.
Before the inversion temperature, (a - b) is negative, and after the inversion temperature, (a -
b) becomes positive. P -T envelope takes a U turn.
Inversion temperature
This change in sign of (a - b) is what leads to the Joule-Thomson coefficient becoming zero at
the inversion temperature. At inversion temperature [a-b] become very small. At temperatures
below the inversion temperature, the gas will experience cooling upon expansion, while at
temperatures above the inversion temperature, the gas will experience heating upon
expansion. At the inversion temperature itself, the gas neither heats nor cools upon expansion.
How a real gas becomes isenthalpic at inversion temperature?
At the inversion temperature, the process becomes isenthalpic, which means there is no
change in enthalpy. In an adiabatic expansion at constant enthalpy, the work done is zero
when there is no heating or cooling, and therefore the product PV remains constant.
At this point, for most real gases, the behavior approaches that of an ideal gas, and the Van der
Waals equation can be approximated by the ideal gas equation. The factors 'a' and 'b',
representing the attractive forces and excluded volume in the Van der Waals equation,
become negligible and can essentially be considered to disappear. Therefore, at the inversion
temperature, the Van der Waals equation reduces to the ideal gas equation.
Free energy change at inversion temperature
At the inversion temperature for a real gas, where there is no work, no change in entropy, and
no change in enthalpy, the free energy of the gas does not change. The inversion temperature
is the temperature at which the Joule-Thomson coefficient changes sign, indicating a transition
in the direction of heat exchange during expansion or compression.
Since the free energy is a measure of the system's ability to do work, and there is no work
involved at the inversion temperature, the free energy remains constant. This behavior is
specific to real gases and is a result of the intricate interplay between intermolecular forces
and the Joule-Thomson effect.