ISSN (Print) : 0974-6846

Indian Journal of Science and Technology, Vol 10(15), DOI: 10.17485/ijst/2017/v10i15/71242, April 2017 ISSN (Online) : 0974-5645

Joule – Thomson Inversion Curves for Van Der Waals

Gas from a Mathematical Point of View
J. Venetis*
Department of Applied Mathematics and Physical Sciences, National Technical University of Athens (NTUA),
Zografou Campus 9, Iroon Polytechniou street, Zografou – 15780, Greece; johnvenetis4@gmail.com

Abstract
A continuation of our ongoing investigation into Joule – Thomson inversion curves for van der Waals gas, is performed
from a mathematical viewpoint. The methodology basis of our analysis is the quadratic polynomial theory. In this context,
focusing on the parametric equation of inversion curves in a P – V frame of reference we obtain a qualitative illustration of
variables T, V by means of two inequality relations. However, we should elucidate that these inequalities are valid only for
the intersection points between the family of Joule – Thomson inversion curves and the isothermal spinodal lines, provided
that they are both sketched in a common P – V coordinate system. The mathematical treatment of the parametric equa-
tion of these curves has been carried out in a rigorous manner and no further restriction is introduced for the variables
T, V. Thus, the proposed inequalities have a wider range of validity when compared with those that had been previously
presented by the author and therefore their possible applications to P – V – T surfaces of van der Waals gas, are also wider.

Keywords: J – T Inversion Curves, P – V System, Quadratic Polynomial, Spinodal Lines, Van Der Waals Gas

1. Introduction Where a is the thermal expansion coefficient of the gas

which arises from the following formula
The Joule – Thomson (J – T) inversion curve is deter-
mined as the set of thermodynamic states, in which the 1 Ê ∂V ˆ
a= (2)
temperature of an ideal or real gas does not vary with V ÁË ∂T ˜¯ P
isenthalpic expansion.
Moreover, the enthalpy depends on the specific heat
Yet, a direct measurement of these curves is many
capacity, along with the temperature and pressure of the
times a troublesome experimental procedure and unfor-
gas before expansion. For any real gas the coefficient
tunately may result in unreliable conclusions1. At near
μJT vanishes at some point, (inversion point). If the gas
– inversion conditions, the vanishing of Joule – Thomson
temperature is below its inversion point temperature,
coefficient implies that even very large pressure changes
this coefficient is positive and if the gas temperature
will result in small temperature differences and therefore
is above its inversion point temperature, it is negative.
extremely accurate measurements of temperature are
Furthermore, the variation of pressure is always negative
needed for the reliable determination of inversion pres-
when a gas expands. Hence, one may infer the following
sures1,2.
conclusions3,4.
Meanwhile, the Joule – Thomson coefficient which
depends on the volume, specific heat capacity, tem- i) If the gas temperature is below its inversion tempera-
perature, and thermal expansion coefficient of the gas is ture the coefficient μJT is positive and given that the
estimated as follows2,3. change of P is always negative it implies that the gas
must cool since the change of T must be negative as
V
m JT = (aT − 1) (1) well.
CP

*Author for correspondence

 Joule – Thomson Inversion Curves for Van Der Waals Gas from a Mathematical Point of View

ii) If the gas temperature is above its inversion tempera- Then, one may also report that after the necessary
ture the coefficient is now negative and given that the algebraic manipulation the following equivalent third
change of P is always negative, the gas heats since the degree polynomial equation arises4.
change of T must be positive.
Ê RT ˆ 2 a a
V3 −Áb+ ˜ V + V − b = 0 (6)
Depending on state conditions, this coefficient may be Ë P ¯ P P
positive or negative. Positive values induce a cooling of In the sequel, let us concentrate on equation (3),
the gas, since it passes through an adiabatic throttle. which can be solved for T to give
The curve linking all state points where μJT vanishes is
the Joule –Thomson inversion curve. Apparently, this is 1Ê a ˆ
T= P + 2 ˜ (V − b) (7)
an equivalent definition of this curve. R ÁË V ¯
On the other hand, it is generally accepted that the Also, a differentiation of equation (7) with respect to
prediction of the Joule – Thomson inversion curve V yields
consists in a very trustworthy test of an equation of
Ê ∂T ˆ 1 Ê 2a aˆ
state1,4. ÁË ∂V ˜¯ = R ÁË − 3 (V − b) + P + 2 ˜¯ ⇔
In the past years, a considerable amount of recent P V b
research work has been made towards the evaluation
of Joule – Thomson inversion curves for many types of Ê ∂V ˆ R
ideal or real gases. Particularly, remarkable molecular ÁË ∂T ˜¯ = 2ab a
⇔
P P+ 3 − 2
simulation analyses were presented either for pure flu- V V
ids or for mixtures in several valuable investigations5–9.
Concurrently, this family of curves was determined by 1 Ê ∂V ˆ R
=
means of other approaches in References10–13. V ÁË ∂T ˜¯ P 2ab a (8)
Finally, the influence of spinodal curve condition on J PV + 2 − 2
V V
– T inversion curves for van der Waals gas, was discussed Consequently, the thermal expansion coefficient is
in Reference14. given as
In the present work, we extend some previous results
of our ongoing research by obtaining some further quali- R
a=
tative illustration with regard to this family of curves, for 2ab a (9)
PV + 2 −
real gases of van der Waals type. V V
In this context, the Joule – Thomson coefficient μJT
can be calculated as
1.1 Towards a Qualitative Illustration of the
Variables T, V V RT
m JT = ( − 1) ⇔
CP 2ab a
The thermodynamic behavior of any van der Waals gas is PV + 2 −
V V
outlined by the following constitutive law
Ê n2 a ˆ Ê 2ab a ˆ
Á P + ˜ (V − nb) = nRT (3) V Á
RT − PV − 2 +
˜
Ë V2 ¯ m JT = V V
Á 2ab a ˜ (10)
CP Á ˜
Where the constants a,b are interconnected with the PV + 2 −
Ë V V ¯
coordinates of the critical point (P0, V0, T0) as follows:
The latter can be combined with equation (5) to yield
V0 = 3b ; 27b2 P0 = a ; 27bRT0 = 8a (4 a, b, c)
1 Ê 2aV 2 − PbV 3 − 3abV ˆ
m JT = (11)
In continuing, equation (3) when n = 1 i.e. for one CP ÁË PV 3 − aV + 2ab ˜¯
mole of the gas, is reduced to the following expression
Hence, the parametric equation of inversion curves
arises
Ê a ˆ
ÁË P + 2 ˜¯ (V − b) = RT (5) PbV 3 − 2aV 2 + 3abV = 0 ⇔
V

2 Vol 10 (15) | April 2017 | www.indjst.org Indian Journal of Science and Technology
 J. Venetis

PbV 2 − 2aV + 3ab = 0 (12) 2

x1 ≤ B x1 + C
In addition, it is known from Equilibrium ∧
Thermodynamics15 that the spinodal points of any iso- 2
x2 ≤ B x2 + C  (16 a, b)
thermal curve in a P – V coordinate system emerge from
the following formula Thus, since equation (12) is equivalently expressed as
2 2a 3a
∂P RT 2a V − V+ = 0 we can write out
=− + 3 = 0 (13) Pb P
2
∂V (V − b) V 2 2a 3a
r1 ≤ r1 +
At this point, we should emphasize that the critical Pb P
points defined by equations (3a, b, c) also satisfy equation ∧
(13), although it is not equivalent to the group of equa-
2 2a 3a
tions (3a, b, c). r2 ≤ r +
Pb 2 P  (17 a, b)
Hence, we deduce that
Ê (V − b)2 RT ˆ Hence, adding by members one finds
2a
Á − = 0 ⇔ (V − b)2 = RT V 3 ⇔
(V − b)2 Ë V 3 2a ˜¯ 2a 6a
2a 2
r1 + r2 ≤
2

Pb
(
r1 + r2 + )
P
(18)

Ê a ab ˆ Inequality (18) can be modified as

ÁË PV − Pb + V − 2 ˜¯
V
(V − b)2 = V3 ⇔ 2a 6a
(r ) ( )
2
2a 1 + r2 ≤ r1 + r2 + + 2 r1 ⋅ r2 ⇒
Pb P

2aV 2 + 2ab2 − 4abV = PV 4 − PbV 3 + aV 2 − abV ⇔

2a 6a 1 r1 ⋅ r2
r1 − r2 ≤ + +2 ⇔ (19)
Pb P r1 + r2 r1 + r2
PV 4 − PbV 3 − aV 2 + 3abV − 2ab2 = 0 (14)
Thus, referring to the isothermal spinodal points, Since r1 − r2 ≤ r1 + r2 ≤ r1 + r2 it follows
which evidently are defined as the intersection points 2a 6a 1 r1 ⋅ r2
between the inversion curves and the isothermal spinodal r1 − r2 ≤ + +2 ⇔
Pb P r1 + r2 r1 + r2
ones, one may regard the pressure P as a parameter. Also,
the same hypothesis holds for the intersection points of
the inversion curves with the family of curves arising 3a
from equation (14). In this context, one may suppose that 2 a2 − 3aPb2 2a 6a 1 P
≤ + +2
the terms in the left side of equation (12) constitute a sin- bP Pb P 2a 2a
gle – valued quadratic polynomial. bP bP (20)
Next, without violating the generality, let us assume
that equation (12) has two distinct roots r1, r2 (real or After some algebra, we obtain
complex), the values of which are nonzero.
a2 − 3aPb2 ≤ a + 3b2 P (21)
Obviously, the following expressions hold,
and therefore
2a
r1 + r2 = (15a)
Pb b2 P 2 + aP ≥ 0 (22)

3a Meanwhile, given that for one mole of a gas of van der

(15b)
r1 ⋅ r2 = RT a
P Waals type the pressure is written as P = − 2 ,
Here, we shall take into account that given a quadratic one infers V − b 3V
equation in the form x2 + Bx + C = 0 having two dis-
b2 RT ab2
tinct nonzero roots x1;x2 (real or complex) the following − +a≥0⇔
inequalities hold16,17. V − b 3V 2

Vol 10 (15) | April 2017 | www.indjst.org Indian Journal of Science and Technology 3
 Joule – Thomson Inversion Curves for Van Der Waals Gas from a Mathematical Point of View
b2 RT ab2
− + 27b2 P0 ≥ 0 ⇔
V − b 3V 2
RT a of state for P – V – T systems20.
− 2 + 27 P0 ≥ 0 (23)
V − b 3V
a2 − 3aPb2 ≤ a2
On the other hand, when the discriminant of the qua-
dratic polynomial occurring in equation (12) is strictly
negative, i.e. 4a2 –12Pb2 a < 0 the roots r1; r2 are complex
conjugates and hence it implies that r1 − r2 = 0 .
Thus inequality (18a) or inequality (20) yields
a RT a concerning the variables T, V and the parameters occur-
+ + ≥ 0 (24)
3b 2
V − b 3V 2
Here, one may point out that inequalities (23) and (24) are
valid only for the intersection points between the inver-
sion curves and the set of curves defined by equation (14).
2. Discussion
Inequalities (23) and (24) can be applied to P – V – T ther-
modynamic systems on the premise that the designation of
isothermal spinodal curves, where obviously the pressure P
may be supposed to be a parameter, was a priori executed.
Moreover, the fact that inequalities (23) and (24) hold
solely on a grid constructed by the intersection between
the isothermal spinodal lines and the family of inversion
curves indeed may constitute a solid assumption.
On the other hand, one may observe that the proposed
inequalities (23) and (24) have a very important advan-
tage when compared with those presented in Reference14,
since they performed mathematical derivation leading
to (23) and (25) was carried out without assuming that
equation (12) has real roots.
Consequently, the discriminant of the quadratic poly-
nomial appearing in the left side of equation (12) is not
supposed to be strictly positive, fact that would lead to
a further constraint between the variables T, V and the
other involved parameters.
Also, it can be claimed that the results obtained here
may be regarded as basic ones and therefore they can be
combined with theoretical formulas and experimental or
numerical results concerning more complicated thermo-
dynamic systems of practical importance appeared in the
literature18,19.
4 Vol 10 (15) | April 2017 | www.indjst.org
Οn the other hand, the performed inequalities (23)
and (24) due to their rigorous mathematical character
could be evaluated and assessed in parallel with straight-
forward approaches that shed light on issues of Equations
3. Conclusions
In this paper, the author obtained a further mathematical
analysis of some recent results of an ongoing research in
the matter of J – T inversion curves for the class of gases
described by van der Waals Eos. The objective of this work
was not to perform an analytical or numerical prediction
of this family of curves, but to derive inequality relations
ring in this constitutive law. In this context, the author
concentrated on the intersection points between the fam-
ily of J – T inversion curves and the isothermal spinodal
lines, as long as they are drawn in a common P – V coor-
dinate system. Thus, the pressure P was considered as a
parameter and then two inequalities were extracted which
could concern any grid being motivated by the possible
family of inversion curves. Obviously, these inequalities
may hold whenever the circumstantial P – V – T system
enables us to assume this variable as a parameter or as a
sequence of distinct values.
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