Topic 2405

Joule-Thomson Coefficient
An important property of a given gas is its Joule-Thomson coefficient
[1-3]. These coefficients are important from two standpoints; (i)
intermolecular interaction, and (ii) liquefaction of gases.
A given closed system contains one mole of gaseous chemical
substance j at temperature T and pressure p. The molar enthalpy of the
gas Hj describes its molar enthalpy defined by equation (a).
H j = H j [T , p ] (a)

⎛ ∂H j ⎞ ⎛ ∂H j ⎞
Then, dH j = ⎜⎜ ⎟⎟ ⋅ dT + ⎜⎜ ⎟⎟ ⋅ dp (b)
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T
Hence at constant enthalpy, H,
⎛ ∂H j ⎞ ⎛ ∂H j ⎞
⎜⎜ ⎟⎟ ⋅ dT = −⎜⎜ ⎟⎟ ⋅ dp (c)
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T

⎛ ∂T ⎞ ⎛ ∂H j ⎞ ⎛ ∂T ⎞
Or, ⎜⎜ ⎟⎟ = - ⎜⎜ ⎟⎟ ⋅⎜ ⎟ (d)
⎝ ∂p ⎠ H ⎜ ∂H ⎟
⎝ ∂p ⎠ T ⎝ j ⎠p

The Joule-Thomson coefficient for gas j, μj is defined by equation (e).

⎛ ∂T ⎞
μ j = ⎜⎜ ⎟⎟ (e)
⎝ ∂p ⎠ H ( j)
For all gases (except helium and hydrogen) at 298 K and moderate
pressures μj > 0. At room temperature and ambient pressure, μj is
0.002 K Pa-1 for nitrogen and 0.025 K Pa-1 for 2,2-dimethylpropane
[3].
Further the isobaric heat capacity for chemical substance j is defined
by equation (f).
⎛ ∂H j ⎞
C pj = ⎜⎜ ⎟⎟ (f)
⎝ ∂T ⎠ p
Hence from equations (d), (e) and (f),
(∂H / ∂p) T
μj = − (g)
C pj

⎛ ∂H j ⎞
Then, ⎜⎜ ⎟⎟ = −μ j ⋅ C pj (h)
⎝ ∂p ⎠ T
Equation (h) marks an important stage in the analysis. For example, Cpj
>0. From the definition of enthalpy Hj ,
U j = H j − p ⋅ Vj (i)

Equation (i) is differentiated with respect to Vj at fixed T.

⎛ ∂U j ⎞ ⎛ ∂H j ⎞ ⎛ ⎞
Thus, ⎜ ⎟ =⎜ ⎟ − Vj ⋅ ⎜ ∂p ⎟ − p (j)
⎜ ∂V ⎟ ⎜ ∂V ⎟ ⎜ ∂V ⎟
⎝ j ⎠T ⎝ j ⎠T ⎝ j ⎠T

⎛ ∂U j ⎞ ⎛ ⎞ ⎡⎛ ∂H j ⎞ ⎛ ∂V j ⎞ ⎤
Or, ⎜ ⎟ = ⎜ ∂p ⎟ ⋅ ⎢⎜ ⎟ ⋅ ⎜⎜ ⎟⎟ − V j ⎥ − p (k)
⎜ ∂V ⎟ ⎜ ⎟ ⎢⎣⎜⎝ ∂V j ⎟⎠ T
⎝ j ⎠ T ⎝ ∂Vj ⎠ T ⎝ ∂p ⎠ T ⎥⎦

⎛ ∂U j ⎞ ⎛ ⎞ ⎡⎛ ∂H j ⎞ ⎤
Then, ⎜ ⎟ = ⎜ ∂p ⎟ ⋅ ⎢⎜⎜ ⎟⎟ − Vj ⎥ − p (l)
⎜ ∂V ⎟ ⎜ ⎟
⎝ j ⎠ T ⎝ ∂V j ⎠ T ⎢⎣⎝ ∂p ⎠ T ⎥⎦

⎛ ∂U j ⎞ ⎛ ⎞
Using equation (h), ⎜ ⎟ = −⎜ ∂p ⎟ ⋅ μ j ⋅ C pj + Vj − p
[ ] (m)
⎜ ∂V ⎟ ⎜ ∂V ⎟
⎝ j ⎠T ⎝ j ⎠T
An important application of equation (m) concerns the case where
chemical substance j is a perfect gas.
In this case, p ⋅ Vj = R ⋅ T (n)

1
Or, p = R ⋅ T ⋅ (o)
Vj

⎛ ∂p ⎞
Hence, ⎜ ⎟ = −R ⋅ T ⋅ 1 = − p (p)
⎜ ∂V ⎟ Vj2 Vj
⎝ j ⎠T
⎛ ∂U j ⎞
Then from equation (m), ⎜
⎜ ∂V ⎟
[
⎟ = p ⋅ μ j ⋅ C pj + Vj − p (q) ]
⎝ j ⎠ T Vj

⎛ ∂U j ⎞ p ⋅ μ j ⋅ C pj
Or, ⎜ ⎟ = (r)
⎜ ∂V ⎟ Vj
⎝ j ⎠T
p ⋅ μ j ⋅ C pj
But limit (p → 0) =0 (s)
Vj

⎛ ∂U j ⎞
Then limit (p → 0)⎜ ⎟ =0 (t)
⎜ ∂V ⎟
⎝ j ⎠T
⎛ ∂U j ⎞
A definition of a perfect gas is that ⎜ ⎟ is zero. Then all real
⎜ ∂V ⎟
⎝ j ⎠T
gases are perfect in the lim it (p → 0).
Footnotes
[1] James Prescott Joule(12818-1889)
William Thomson (1824-1907); Later Lord Kelvin
Some authors refer to the Joule-Thomson coefficient; e.g. E. B. Smith,
Basic Chemical Thermodynamics, Clarendon Press, Oxford, 1982, 3rd.
edn., page 119. Other authors refer to the Joule –Kelvin Effect; e.g. E.
F. Caldin, Chemical Thermodynamics, Clarendon Press, Oxford,
1958,page 81. Other authors refer to either the Joule-Thomson or
Joule-Kelvin Effect; e.g. M. H. Everdell, Introduction to Chemical
Thermodynamics, English Universities Press, London 1965, page 57.
[2] M. L. McGlashan, Chemical Thermodynamics, Academic Press,
London 1979, page 94.
[3] Benjamin Thompson (1753-1814); later Count von Rumford,
married Lavoisier’s widow.