2.
Molecular thermodynamics
2.3.1 Introduction
Molecular thermodynamics investigates the equilibrium
properties of matter, exploiting knowledge of molecular
structure and the forces of molecular interactions. It is a field
of study that is capable of providing answers to problems that
arise in the development of several modern technologies,
including technologies of paramount importance in the oil
and petrochemical industries. The study of thermodynamic
equilibrium in heterogeneous systems, in particular, which
requires the use of relations that allow the correlation and at
least prediction of the distribution of components among the
different phases present in a thermodynamic system, is
applied in the design and development of separation
processes, in materials characterization, and in determining
the distribution of hydrocarbons in oilfields.
The assumptions of this approach lie in statistical
mechanics, which was defined as the “art of predicting the
behaviour of a system with a high number of degrees of
freedom, once the laws determining its microscopic
behaviour are known” (Binney et al., 1992). Molecular
thermodynamics differs from statistical mechanics in the
importance given to the role of molecules in the solution of
problems taken into consideration and because it is oriented
to applications.
Three features concerning molecular structure and
behaviour are particularly important in the following
description:
• Molecular geometry, describing the spatial distribution of
the nuclei of the atoms forming the molecules.
• Dynamics, relating to the diverse molecular motions with
their associated energy values.
• Interactions, relative to the nature and the magnitude of
intermolecular forces.
If one refers to a biatomic molecule, for simplicity, it can
undergo different types of motion: translation (described by
comparing the molecule to a point mass concentrated at its
centre of mass), rotation (taking place around an axis passing
through the centre of mass and perpendicular to the axis joining
the two atoms) and finally vibration along this same axis.
Generally speaking, and neglecting reciprocal
interactions, molecular energy can be expressed as the sum of
different mutually independent contributions, each
VOLUME V / INSTRUMENTS
corresponding to the different types of motion previously
mentioned:
[1] e ⫽etr ⫹erot ⫹evib ⫹eel
where etr , erot , evib are the energies associated with
translational, rotational and vibrational motions respectively;
finally eel indicates the energy associated with the different
electronic states of the molecule itself. Each of the terms in
the equation above is quantized since it can only take on
well-defined values. As an example, the relations obtained by
using quantum mechanics to calculate the values of the energy
levels of biatomic molecules are summarized in Table 1.
The calculation of the energy values of rotational and
vibrational quantum states in a polyatomic molecule is
obviously more complex than that of the relations
summarized in Table 1. A polyatomic non-linear molecule is
characterized by three principal inertial moments referring to
three mutually orthogonal axes passing through its centre of
mass. Moreover, other degrees of freedom associated with
internal rotations around simple bonds often exist, such as
C⫺C bonds in hydrocarbons, as shown in Fig. 1.
A polyatomic molecule formed by n atoms has several
vibrational degrees of freedom, precisely 3n⫺5 if it is linear,
3n⫺6 if is non-linear. Assuming that the variation of
Table 1. Energy of the states associated with the internal
motions of a biatomic molecule A⫺B
Rotational motion h2
erot ⫽ 11 J(J ⫹1)
8p2I
J ⫽0,1,2,… quantum number
mAmB 2
I ⫽ 1131 r moment of inertia
mA⫹mB o
冢 冣
Vibrational motion 1 hn
evib⫽ hn 23 ⫹n ⫽ 223 ⫹hnn
2 2
n ⫽0,1,2,… quantum number
n ⫽frequency of vibration
63
PHYSICAL AND CHEMICAL EQUILIBRIA

Fig. 1. Internal rotations

of butane (A)
and propylbenzene (B)
molecules.

A B

intramolecular forces for small displacements could be to the behaviour of fluids and their mixtures is also discussed.
described as a linear relationship, it is possible to decompose The partition function is directly linked to the Helmholtz
the complex movements to which the different atoms are free energy function F:
subject to 3n⫺6 modes of independent harmonic vibration
1
(called normal vibration). Each normal vibration is [5] F ⫽⫺ 23 ln Z
characterized by its specific frequency, and the vibrational b
energy of the molecule is given by the sum of the energies which allows the evaluation of internal energy U, entropy S
competing in each vibration. and pressure P:
Since, in ordinary temperature conditions, the energy ⭸ln Z
difference between the fundamental electronic state and the
first excited state, for almost all molecules, is much higher
[6] 冢
U ⫽⫺ 131
⭸b 冣
V, N
than the average thermal energy, it follows that even at ⭸F U ⫺F
relatively high temperatures, it can be assumed that
molecules reside in their fundamental electronic state.
[7] S⫽⫺ 31
⭸T冢 冣 V, N
⫽ 131
T

2.3.2 Statistical thermodynamics
assumptions
In a thermodynamic system at constant temperature T, it is
possible to identify different configurations related to the
distribution of its N molecules in the space contained in a
volume V. A value Er of energy and a value Yr of a specific
observable variable correspond to each of these, the average
value of which can be obtained through the following relation:
[2] 具Y典⫽冱wrYr
r years due to the development of computer software. For
where wr represents the probability that the system lies in
the r configuration, expressed via the canonical distribution
law:
e⫺bEr
[3] wr ⫽ 11
Z stochastic chain of events, called a markovian chain,
where b⫽1/kBT, kB being the Boltzmann constant, while the
partition function Z is defined as
[4] Z(T,V,N )⫽冱e⫺bEr
r dependence on energy given by equation [3].
Equation [3], which is the fundamental law of statistical
mechanics, is not derived here, while its relationship with the
concepts of thermal equilibrium and temperature are
described, and its application to various specific cases related
⭸F
[8] 冢 冣
P ⫽⫺ 31
⭸V T, N
Therefore, once the partition function is known, it is
possible to derive the most important thermodynamic functions
and thus develop their application for the different problems.
2.3.3 Theory, simulation and experience
A direct application of equations [2] and [3] can be found in
simulation techniques that have become widespread in recent
instance, the Monte Carlo method takes into consideration
model systems composed of hundreds, if not thousands, of
objects which describe the molecules contained in a volume
V, and calculate the average of the properties associated with
several configurations, randomly built by generating a
produced by random motions of single molecules. The
calculation of the average value of thermodynamic properties
is carried out by [2], attributing to the probability a
A typical application of the Monte Carlo method is
shown in Fig. 2, which refers to a bidimensional system
composed of six particles, for simplicity. It is possible to
start from a central configuration, surrounded by ‘phantom’

64 ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 2. Example of the application of the Monte Carlo method
to a bidimensional system made up of six particles.
configurations in order to satisfy boundary conditions,
which require the conservation of the number of particles
involved in the simulation. In fact, if one particle, following
a random movement, leaves the central zone, it is made to
re-enter symmetrically at the side opposite to the one it left.
These simulation techniques make it possible to study
systems with two phases in equilibrium, proceeding for
instance according to the scheme shown in Fig. 3. This method
is called ‘statistical ensembles’, and it basically concerns
finding the minimum value of the Gibbs free energy function
Fig. 3. Scheme of application
of the Gibbs’ statistical
ensembles method
in a simulation of phase
equilibria.
vapour
liquid
initial
configuration
region I
region II
VOLUME V / INSTRUMENTS
MOLECULAR THERMODYNAMICS
at a given temperature, pressure, and the chemical potential of
the components in the two coexisting phases. The two phases
are ideally separated into two boxes which are simulated
singularly to make the calculations easier by virtue of the
absence of the interphase surface. The simulation involves
three separate types of molecular movements respectively:
internal equilibrium (by moving the molecules in each box),
mechanical equilibrium (which imposes pressure equality in
the two phases, even following small volume variation) and
finally chemical equilibrium (which imposes the equality of
chemical potential, even following molecular exchange
between the two phases). This method was successfully
applied to several one and two-component systems by using
appropriate molecular models which take specific details in
their structure into account.
These simulation methods have now reached a considerable
level of sophistication, both for their ability to describe large
systems and, above all, for the possibility to exploit molecular
models of increasing complexity and realism. The results
obtained in this way have proved to be of great importance in
clarifying some conceptual aspects on matter behaviour.
Nevertheless, the development of analytical expressions that are
easy and fast to apply still maintain great relevance. These
methods deal with the evaluation of thermodynamic properties
of pure substances and their mixtures and the determination of
equilibrium conditions between different phases, operating at
different levels and linked together, which involve experience,
theory and simulation.
Actually the solution of applicative problems often
requires the use of some effective parameters which reflect a
whole group of specific factors. In principle, they can be
T
region I
region II
volume particle
displacement variation transfer
65
PHYSICAL AND CHEMICAL EQUILIBRIA

1.5 considered simple. In this case, the intermolecular potential

u(r) is described by a curve with a shape similar to that
shown in Fig. 4 A. At short distances, repulsive forces appear,
1.0 the potential of which increases rapidly with decreasing
distance, while attraction forces prevail as distance increases.
As the distance goes to infinity the potential tends to zero
u(r)⫻1015 (erg)

0.5 compatibly with the fact that the interaction between the
molecules dies away. Repulsion occurring at short distances
is due to the overlapping of molecular electronic clouds,
while attractive interaction (according to the interpretation
0
first devised by Fritz Wolfgang London) is linked to the
instantaneous interaction between the molecules caused by
the dipoles, created by the motions of their electrons, that
⫺0.5 tend to oscillate in a synchronous or sympathetic mode. In
u0 Fig. 4A two characteristic parameters can be identified: s,
representing the distance at which the potential is equal to
⫺1.0 zero and u 0, expressing the energy corresponding to its
2.5 s 3.0 3.5 4.0 4.5 minimum. An analytical form of intermolecular potential is
°)
r (A
A given by the Lennard-Jones potential:

冤冢 冣 ⫺ 冢23sr 冣 冥
u(r) 12 6
[9] s
u(r)⫽4u0 23
r
s
0
r Attractive interaction, called ‘dispersion interaction’, is,
according to the above-mentioned London theory, inversely
proportional to the sixth power of the distance between the
centres of mass of the two molecules, and the parameters
present in equation [9] can be determined by experimental
observation on fluid behaviour. The data on state behaviour,
or P, V, T behaviour, are used in particular. In Table 2 the
B
values of these parameters for some common molecules are
Fig. 4. A, shape of the intermolecular potential. Numerical values reported, derived by using the experimentally determined
of energy (erg) and distance (Å) refer to the case of helium. values of the second virial coefficient. Obviously molecules
B, approximate shape of intermolecular potential with heteropolar bonds, and therefore with a permanent
corresponding to molecules considered similar to hard dipole electric moment, also display an electrostatic
spheres with attractive interaction. interaction between dipoles that depends on the orientation
between the molecules themselves. In these cases, the
potential has anisotropic characteristics since not only does it
obtained from knowledge of the geometric and dynamic depend on distance r, but also on the angles that describe the
characteristics of molecules but unfortunately the current mutual orientation of the two interacting molecules.
state of understanding is not at a high enough level as to give
results of an accuracy compatible with the necessary
requirements for the design of industrial units. It is therefore Table 2. Parameters of the intermolecular potential
necessary to use the information deriving from the of some substances
correlation of experimental data in order to calibrate some of
the parameters under examination semiempirically. Intermolecular parameters
In the following, some fundamental concepts of molecular Substance
s (Å) u0/kB (K)
thermodynamics will be illustrated, obviously dedicating
particular attention to its application in fluid systems, gas and He (helium) 2.576 10.2
liquid, with one or more components since, it is known that H2 (hydrogen) 2.915 38.0
they are the key players in the oil industry. The goal is to
provide the basis for calculating the thermodynamic properties N2 (nitrogen) 3.681 91.5
of hydrocarbons and their mixtures. O2 (oxygen) 3.433 113
Cl2 (chlorine) 4.115 357
2.3.4 Intermolecular forces CH4 (methane) 3.822 137

A fluid whose molecules interact with an intermolecular C2H6 (ethane) 4.418 230
potential of the central type, which depends solely on the C3H8 (propane) 5.061 254
distance between the centres of mass of the molecules, will
C2H4 (ethylene) 4.232 205
be referred to as ‘simple’. Strictly speaking, only the systems
composed of monoatomic gases belong to this category; C2H2 (acetylene) 4.221 185
nevertheless, the fluids with relatively small and compact
C6H6 (benzene) 5.270 440
molecules such as oxygen, nitrogen and methane can also be

66 ENCYCLOPAEDIA OF HYDROCARBONS

Taking this into consideration, the intermolecular
potential for a pair of molecules can be expressed in the
following form:
[10] u(1,2)⫽u0(r)⫹uelet(1,2)⫹uind (1,2)⫹udisp(1,2)
Both the relative position of two molecules, and their
mutual and internal orientation are indicated by (1,2). The
terms present in the second member of the previous
expression indicate the following contributions respectively:
a) u0(r) contribution depending only on distance; b) uelet(1,2)
electrostatic interactions; c) uind(1,2) inductive interactions
due to electronic clouds distortion; and d) udisp(1,2)
dispersive interactions.
Even though theoretical and computational chemistry has
obtained several important results in the calculation of
molecular energies in the last few years, a priori evaluation
of intermolecular forces still presents some uncertainties.
When studying equilibria between phases, effective potentials
are widely used, the parameters of which are evaluated in a
semiempirical fashion, and which are essentially related to
the Lennard-Jones potential. An important aspect concerns
the transferability of interactions between single atoms, or
atomic groups in the molecules. This issue is directly
correlated with the group contribution models, which have
achieved particular relevance in several practical applications.
In its most simple form, the potential of two molecules
can be written in the following way:
qgqd
[11] u(1,2)⫽ 冱 uab ⫹冱 11 rgd
a, b g, d
where a and b indicate the sites or groups in the molecules on
which interactions are centred, while g and d are those
involved in electrostatic interactions due to charges qg and qd.
Finally, a hydrogen atom in a molecule can act as a
bonding element (hydrogen bond) between an electronegative
atom, linked to it by a covalent bond, and another
electronegative atom, such as fluorine, oxygen and nitrogen.
The hydrogen bond has an energy content lower than covalent
bonds. The orders of magnitude of the energies involved are in
fact: non bond forces 0.2-2 kcal/mol; hydrogen bond 2-10
kcal/mol; covalent bonds 50-100 kcal/mol.
Significant examples of hydrogen bonds can be found in
hydrogen fluoride and in water. If hydrogen bonds are present,
electrostatic forces obviously take on a dominant role.
Hydrocarbon molecules have a relatively complex
structure: elongated, ramified or cyclic; in this case
decomposing the interaction in the sum of the contributions
corresponding to the different groups of atoms present in the
molecules is particularly advisable. In conclusion, in the
analysis that follows, it is reasonable to divide fluids into
simple and complex, relating to the properties of the
Table 3. Subdivision of fluids into simple and complex
simple Intermolecular forces can be described by a central potential
– Intermolecular forces are acentric, above all due to dipolar, quadripolar
Fluids interactions, and so on
complex – The molecular structure is so complex that it is advisable to decompose their
interactions in the sum of the contributions provided by the different atomic
groups present in the molecules themselves
VOLUME V / INSTRUMENTS
MOLECULAR THERMODYNAMICS
molecules of which they are composed, on the basis of the
classification shown in Table 3.
2.3.5 Calculation of the free
energy function
The determination of the most important relations that
operate in the solution of phase equilibrium problems stems
from the expression of Helmholtz free energy F(T,V,Ni ), from
which it is possible to derive the pressure of the system
through equation [8] and the chemical potential of a generic
component through the following relation:
⭸F
[12] 冢 冣
mi ⫽ 2323
⭸Ni T,V,Nj⬆i
where the different components are indicated by i and j and
their number of molecules by Nij .
In the following discussion, statistical thermodynamics
will be applied first to one-component systems, while
subsequently many-component mixtures will be taken into
consideration. Consider, then, a fluid containing N molecules
of mass m and introduce a typical length l⫽hⲐ(2pmkBT)1Ⲑ2,
proportional to the molecular de Broglie wavelength, where h
is the Planck constant. It is possible to demonstrate that the
partition function Z can be expressed as
1
[13] Z(T,V,N )⫽ 1 l3Nzint(T)NQ(T,V,N)
N!
The presence of the l term derives from the molecular
translational motion, whereas
zint ⬅zvib,rot ⫽冱 e⫺b(evib⫹erot)
[14]
vib,rot
is the molecular partition function related to internal motions
since it reflects the contribution due to vibrations and rotations
and its specific form is related to the properties of the molecule
under consideration. In general, it does not depend on volume
and therefore it does not contribute to determine the state
behaviour of the system under examination. In the following
analysis zint is not explicitly considered, since attention is
mainly focussed on the investigation of state behaviour and of
phase equilibrium; for a thorough discussion of its role see
Chapter 2.4, where the dependence of thermodynamic state
functions on temperature is specifically examined.
Finally Q is called configuration integral and it is defined
by the following relation:
[15] 冮 冮
Q (T,V,N )⬅Q ⫽ … e⫺b/(r1,r2,…,rN)dr1dr2…drN
where dr1, dr2,…,drN are elements of volume centred on the
positions of the different molecules as identified by vectors
67
PHYSICAL AND CHEMICAL EQUILIBRIA

r1,r2,…,rN , whereas / is the total potential energy due to approximation 具Q典⬇exp(baN 2ⲐV) can be given. In addition,
interactions between molecules. since molecules cannot get closer than a distance equal to s it
Introducing [13] into [5] one gets is appropriate to define a covolume b⫽1Ⲑ2(4Ⲑ3pNs 3)
representing the volume that is not accessible to molecules
l3N zint
N

冢 冣
1 1 1 Q
[16] F ⫽⫺ 23 ln 1231 ⫺ 23 ln Q ⫽Fid ⫺ 23 ln 12 due to their impenetrability caused by the ‘hard’ portion of
b N! b b VN their potential. Accounting for this, the free energy
where expression can be written as:
l3N zint
N 具Q典
冢 冣 冢 冣
1 1
[17] Fid ⫽⫺ 23 ln 1231 VN [22] F ⫽Fid⫺ 23 ln 13 ⫹ln VfN ⫽Fid⫺
b N! b VN
is the free energy of ideal gas. Introducing [16] into [8] one 1 Vf N aN
冤冢 冣 冥
2

obtains
1 ⭸ln Q
[18] P ⫽ 23 121
b ⭸V冢 冣
T,N
which is identified with the equation of state of the system. In
order for it to be valid even in proximity of the critical point,
where the free energy function displays non-analytical
behaviour, it is advisable to refer to the specific value of Q
for a single molecule, but making N and V tend to infinity,
even though the value of molecular density r⫽NⲐV is kept
fixed. This procedure is called the thermodynamic limit.
In reality, the application of equation [18] is severely
penalized by the calculation of the Q integral, which can be
performed only if appropriate approximations are introduced,
the most drastic of which being the assumption that / is zero
and that molecules are punctiform. In this case, the integral is
equal to VN and therefore one easily gets
[19] PV⫽NkBT
that is the ideal gas state equation.
The potential energy of the group of molecules is usually
evaluated by intermolecular potentials through an additive
relationship, in which the interaction energies of the different
pairs of molecules are added:
[20] / ⫽冱uij (r)
i⬍j
2.3.6 Van der Waals theory
⫺ 23 ln 13 e b V
13
b V
where the free volume, or accessible to the molecules, is
Vf ⫽V⫺b whereas parameter a, reflecting the influence of the
attractive portion of potential, is defined by [21].
By replacing the previous equation into [8], the
well-known van der Waals equation can be derived
RT ã
[23] P ⫽ 11 ⫺1
V~⫺ b~ V~ 2
whose isotherms have the typical shape shown in Fig. 5. The
previous equation refers to one mole of fluid and therefore N
is the Avogadro number which, multiplied by kB, gives the gas
~ ~
constant R, whereas V, ã, e b refer to one mole. At a high
temperature, the shape of isotherms approaches that of
equilateral hyperboles, typical of an ideal gas, whereas a
critical temperature Tc exists, at which the isotherm displays a
horizontal point of inflection. At lower temperatures,
isotherms have the shape shown in Fig. 5. The presence of a
part where pressure increases with increasing volume
corresponds to an unstable equilibrium state, since a small
alteration of the variables that identify it is sufficient to
produce a sharp spontaneous transformation towards a two-
phase system, composed of a mixture of liquid and vapour in
equilibrium. The identification of the characteristics of the
two states in equilibrium can be performed through the
graphic method proposed by Maxwell, stating that the two
areas shaded in the figure must be equal. In point A and B
the molar free energy must have the same value, and

Before tackling the problem of calculating the configuration

integral Q, in general terms, it is advisable to spend some P
time introducing a simplified approach to evaluate the
potential energy of molecules. This assumes that molecules
have a uniform distribution, and therefore each of them is
subject to an average field, and its potential energy is not
influenced by fluctuations due to molecular motions.
For simplicity, it is also assumed that the intermolecular
potential is of the central type and has the shape shown in
Fig. 4 B, in which molecules are considered similar to hard
spheres that cannot be overlapped, with a diameter equal to s,
and subject to an attraction of the ⫺u0s6Ⲑr 6 type for r⭓s.
Considering the interaction of a central molecule with those T⬎Tc
surrounding it, which are contained in a spherical shell with a Tc
4pr2dr volume, the potential energy of the fluid can be A
derived by calculating the following integral: B
T⬍Tc
2 N2 aN 2
冮
1 N
[21] / ⫽23 N u(r)4pr 2 233 dr ⫽⫺ 23 p 13 u0 s3⫽⫺ 12 V
2 V 3 V V
Fig. 5. Shape of isothermal curves in van der Waals equations.
Since the distance in which the interaction appears is The region surrounded by the dashed line (Andrews’ bell curve)
short, the integral was extended to infinity in order to avoid corresponds to the existence of a two-phase system made
the tricky problem of boundaries. Therefore, the following of liquid and vapour in equilibrium.

68 ENCYCLOPAEDIA OF HYDROCARBONS
 MOLECULAR THERMODYNAMICS

therefore its variation along the isotherm, given by the

integral of VdP, is zero only if the values of the two shaded Table 4. Diagram connecting molecules
areas are the same. In this way, a criterion to draw the
horizontal segment joining the two equilibrium states is Integrand Diagram
derived. By applying this procedure to several different
isotherms, a series of points is identified. Joined together, 1
these points define a typical curve with a bell-shape, called f12
an Andrews curve, which defines the zones of existence 1 2
between the two phases. Therefore equation [23] provides a 2
complete description of the state behaviour of a fluid. f12 f23
~
Parameters ã e b of the equation of state can be estimated
1 3
from the critical values of the state variables Pc, Vc, Tc. An
equation free from parameters specific to particular fluids is
obtained, reflecting a general law called ‘of the phenomenological and empirical bases by Heike
corresponding states’ whose validity surpasses the equation Kamerling-Onnes. The statistical approach previously
that inspired it: all fluids can be described by the same described gives a precise physical meaning to the different
equation of state, as long as it is expressed by the reduced terms of the development that express the interactions of
variables (PⲐPc, VⲐVc, TⲐTc). This only really happens with different groups of molecules. Moreover, it provides some
simple fluids, whose molecules interact with a potential that relationships that allow the calculation of the values of the
depends solely on the distance between their centres of mass. coefficients of the virial development (or virial coefficients)
The van der Waals equation therefore satisfactorily from the parameters of intermolecular potential. For example,
describes the behaviour of fluids, including the occurrence of a by using the Lennard-Jones potential [9], the following
liquid-vapour transition, and the existence of a critical point. expression of the second virial coefficient can be derived:
However, from a quantitative point of view, its application is
not so satisfactory; this is demonstrated by the fact that the
adimensional ratio PVⲐRT, evaluated at the critical point, takes
on a universal value equal to 0.378, while experimentally a contributions
value included between 0.27 and 0.29 is measured. to virial molecular clusters
coefficients

second
2.3.7 Virial development 1 2

A general method to calculate the integral of configurations 2 1 1 1

Q was proposed by Joseph Mayer and Maria Göpper Mayer third 1⫹ 2⫹ 3⫹
(Mayer and Göpper Mayer, 1940). By introducing an 3 3 2 2 3
appropriate function
2 4
[24] fij ⫽e⫺buij (r) ⫺1 ⫹ .... (12 of the same type that
differ only in numeration)
1 3
it is possible to demonstrate that Q takes on the form
2
[25] 冮 冮冱 uij (r)dr N ⫽
Q(V,T,N)⫽ … e⫺bi⬎j ⫹ 1 ⫹ .... (4 of this type)

⫽冮 …冮 冢1⫹冱 f ⫹冱冱 fij ij fkl ⫹…冣dr N 3 4

i⬎j 2
where dr N⫽dr1dr2…drN . ⫹ ⫹ .... (12 of this type)
1
The calculation of the different terms present in the fourth
previous equation is made easier by the use of appropriate 3 4
diagrams. Indeed, by indicating a molecule with • and the fij 1 4
that connects the molecules i and j with a, a diagram
corresponds to each term of development, as shown in Table 4. ⫹ ⫹ .... (3 of this type)
It is then possible to identify a sequence of groups, or 2 3
clusters, of molecules containing all possible diagrams 1 2
connecting a determined number of points directly or indirectly,
as shown in Fig. 6. It is then possible to evaluate the contribution ⫹ ⫹ .... (6 of this type)
provided by each one of them to the integral of configurations. 4 3
This approach produces an equation of state that has the 1 2
form of a power series expansion of molecular density
r⫽NⲐV: ⫹ (only this)
4 3
[26] P ⫽rkBT(1⫹Br ⫹Cr2 ⫹Dr3 ⫹…)
It is interesting to observe that the previous equation is Fig. 6. Example of diagrams representing groups
known as a virial equation of state, proposed on of interacting molecules.

VOLUME V / INSTRUMENTS 69
PHYSICAL AND CHEMICAL EQUILIBRIA
冮 冤1⫺e 冥 r* dr*
B(T*) ⫺u(r*)ⲐT*
[27] 121 ⫽3 2
b different approach, knowing that in any case van der Waals
0
where b is the covolume previously defined, r*⫽rⲐs the
reduced distance, and T*⫽TkB Ⲑu0 is the reduced temperature.
In Fig. 7, a unified comparison is reported between the
second virial coefficient, evaluated through equation [27] and
the experimental values for a series of molecules having a
compact configuration, such as rare gases, nitrogen and
methane. It is possible to observe that, by adequately
calibrating the parameters u0 and s, one can obtain an
excellent agreement between calculated and experimental
results, confirming the relevance, but also the limits, of the
corresponding states law, which is valid for molecules subject
to a central potential.
As mentioned, the different terms of development [26]
reflect the interactions among the groups that contain an
increasing number of molecules respectively, in agreement
with what is shown in Fig. 6. In principle, each one of them
can then be evaluated by the intermolecular potential;
unfortunately, though, the corresponding expressions become
increasingly complex and thus cumbersome to evaluate.
Virial development is also applied to mixtures, providing
adequate expressions of coefficients as a function of
composition given as molar fraction yi :
[28] Bmix⫽冱 yi yj Bij
i, j
Cmix⫽冱 yi yj ykCijk
i, j, k
……
where Bij , Cijk , etc. indicate a series of virial coefficients
which depend only on temperature. The previous treatment is
formally correct and elegant, but unfortunately the
development through which the state behaviour is expressed,
even though enriched by an increasingly higher number of
terms, does not converge when density approaches the high
values typical of liquids. Its application therefore does not
allow the description of condensation processes. This
circumstance pinpoints a severe limitation of the method,
which forces us to take into consideration the problem of
1
0 proposed on heuristic bases by Maxwell.
⫺1
B*⫽B/b
⫺2
argon
neon
methane
⫺3
nitrogen
⫺4
0.5 1 2 5 10 20
T*⫽⌻kB/e
Fig. 7. Comparison between calculated curves
and experimental values of the second virial coefficient
for a few simple molecules.
70
continuity between the gaseous and the liquid state by using a
theory, even though apparently simpler, is capable of giving
an answer to this problem.
2.3.8 Meaning and potentiality
of the van der Waals theory
The condensation process is the subject of many studies and
some of their features deserve to be considered in detail, even
if only at a basic level. In order to do so, it is interesting to
recall an investigation performed by Kac, Uhlenbeck and
Hemmer in 1963 (Kac et al., 1963; Uhlenbeck et al., 1963),
which goes back to the calculation for the configuration
integral Q using an approach that is different from those
considered until now. For this purpose, attention is focused on
a monodimensional fluid, in which its N molecules are
randomly arranged along a segment of length L. Moreover, it
is possible to suppose that they interact according to a
potential expressed by the following relation:
[29] u(r)⫽ 冦 ⬁⫺age⫺gr
r ⬍d
r ⭓d
repulsiva forces
attraction forces
Even though it appears hardly realistic, it is easy to verify
that by using it, a value of potential energy of the system
equal to ⫺a can be obtained, which is therefore constant and
independent from parameter g characterizing the radius of
influence of intermolecular potential. Having said this, it is
possible to demonstrate that, for a fluid whose molecules are
arranged on a segment with length L, the configuration
integral Q can be calculated exactly, even within the
thermodynamic limit. In this way, the correct equation of
state of a monodimensional fluid can be derived, showing
some interesting singularities. Indeed, by examining the
behaviour of the fluid in the g⫺0 limit, which is in the
䉴
situation where attraction forces are weak but have a radius of
influence tending to infinity, even though the potential energy
of the fluid remains unaltered, a monodimensional equation
of state in the same form as van der Waals equation [23] can
be obtained where, however, the volume must be replaced by
length L. Meanwhile, it is possible to demonstrate that a
transition of phase exists for which the zone of coexistence of
liquid and vapour is described by an isothermal horizontal
segment, without having to resort to the construction
The result obtained in this way obviously does not find
direct practical applications, since the situation taken into
consideration is not realistic, but it has an interesting
conceptual relevance since it emphasizes that the
condensation process is compatible with a physical situation
where the ratio between the radius of repulsive forces and
that of attractive forces is much less than one. In this way it is
possible to clarify the apparent paradox by which the
relatively simple van der Waals equation is capable of
describing the existence of both phases of a fluid, unlike the
more complex virial development. Moreover, the way is
50 100 shown to extend the theory adequately to more realistic and
complex molecular systems. Indeed, it includes a separation
of repulsive intermolecular forces, which determine the
structure of the fluid, and therefore its entropy, from attractive
forces that affect the value of internal energy. In other terms,
this corresponds with observing that in the description of the
ENCYCLOPAEDIA OF HYDROCARBONS

thermodynamic behaviour of fluids, it is possible to separate
the entropic effects associated with the distribution of
molecules in space from the energetic ones.
2.3.9 Perturbative methods
Perturbative techniques are used in many different fields of
physics such as, for instance, astronomy and quantum
mechanics, where some of the properties of a system are
expressed on the base of the known properties of a suitable
reference state of the system. In thermodynamics they can be
usefully applied to the calculation of the free energy function.
By taking into account the results obtained in the
previous paragraph – stating that the structure of a dense
fluid is essentially determined by the hard portion of
intermolecular potential, whereas the soft part reflecting
attractive forces exerts a correcting action of minor
importance – it is possible to divide the potential energy of
the system into the sum of two contributions
[30] / ⫽/0 ⫹/p
The first corresponds to a suitable reference state of the
system, whereas the second is a corrective term that can be
considered as a perturbation. Indicating the free energy of the
reference state with F0, it is possible to write
冮 冮
1 1
[31] F⫺F0⫽⫺ 23 ln 2333 … e⫺b(/0⫹/p)dr N ⫽
b Q0
e⫺b/0
1
b 冮 冮 Q0
1
⫽⫺ 23 ln … e⫺b/p 23133 dr N ⫽⫺ 23 具ln e⫺b/p典
b the following relation:
The last expression represents the average value of the
exp(⫺b/p) exponential of the perturbative energy, evaluated
by using the canonic distribution function [2] of the
reference state of the system. It can be written in a form that
is easier to interpret and use, by developing F with respect to
parameter b
b from which it is possible to obtain the equation of state
[32] F⫺F0 ⫽具/p典⫺ 23 [具/p2典⫺具/p典2]⫹O(b2)
2
g(r)
3 s
2
1 1
0 0
s 2s
A B
Fig. 8. Shape of the radial distribution functions g(r), for a simple fluid (A)
and for a fluid made up of diatomic molecules (B).
VOLUME V / INSTRUMENTS
MOLECULAR THERMODYNAMICS
where the third term at the second member represents the
average value of fluctuations of potential energy.
Before proceeding, it is important to observe that the
thermodynamic properties of a fluid can be evaluated by
using a suitable function g(r) called ‘radial distribution’,
which describes the average local variations of density that
are present around a molecule. As shown in Fig. 8, starting
from the centre of a molecule, there are density variations
which reflect the local structure of the system under
examination. It is possible to observe that when r increases,
the value of the radial distribution function approaches 1
since at high distances from the reference molecule the
interaction with the surrounding molecules tends to become
uniform thus reaching the average value of the density of the
fluid itself.
The radial distribution function can be experimentally
determined by sending a collimated monochromatic beam of
X rays or neutrons through a specimen, and then measuring
the intensity of the diffracted radiation with a detector. From
this, by means of a suitable normalization operation, it is
possible to derive a S(k) structure factor which depends on
the wave number k⫽2pⲐl, where l is the wavelength of the
incident radiation (in the case of neutrons it is given by h/mv).
This factor is correlated to the radial distribution function
through the following relation:
冮
[33] S(k)⫽1⫹r g(r)eik⭈rdr
where the integral at the second member is the Fourier
transform of g(r). From the radial distribution function it is
possible to calculate the potential energy of the fluid through
⬁
2pN 2
[34] / ⫽ 131
V 冮 g(r)u(r)r dr
0
2
Furthermore, it is possible to demonstrate that the pressure
of the system can be expressed in the following form:
⭸u
冮
1
[35] P ⫽ rkBT⫺ 23 r2 4pr 2g(r) 233 dr
6 ⭸r
without having to involve free energy.
g(r) l
s
r s s⫹l r
71
PHYSICAL AND CHEMICAL EQUILIBRIA
Assuming that the distribution of the molecules
corresponds to that of the reference fluid, the average
perturbative potential energy can be written in the form:
⬁ geometric structures such as disks, ellipsoids, spindles and
2pN 2
[36] 具/p典0 ⫽ 131
V 冮 g (r)u (r)r dr
0
0
p
2 so on, that simulate in an increasingly accurate way the
where g0(r) is the radial distribution function of the
reference fluid itself, whereas up is the perturbative part of
the intermolecular potential. Generally speaking, if a suitable
system, with a known distribution function, is available and
can be used as a reference, it is possible to calculate the
various thermodynamic properties, among which free
energy, which can be expressed in a first approximation by
the following relation:
[37] F ⫽F0 ⫹具/p典0
compatible with [32] if the perturbative terms of order
higher than one are neglected.
The first and more immediate choice of a system to be
elected as a reference is the hard sphere system, the
characteristics of which were already well-known thanks to
the detailed studies of simulation performed using both the
Monte Carlo method and molecular dynamics. Afterwards,
knowledge was enormously enriched when hard objects with
different shapes were taken into consideration, so that they can
simulate the core of the most common molecules, or when
objects interacting through different potentials were examined.
For some of these systems, specific and accurate
equations of state were developed, among which close
attention should be paid to the equation for a hard sphere
fluid (Carnahan and Starling, 1972):
P 1⫹h ⫹h ⫺h 2 3
[38] 1333 ⫽ 1111123 ⫽ f(h)
kBTr (1⫺h)3
where h⫽(1/6)prs3. This equation was derived heuristically
with the aim of reconciling the virial equation of state with
the results of the simulations obtained by using the Monte
Carlo method and molecular dynamics.
Obviously, the most simple hypothesis that can be
formulated on the characteristics of hard sphere systems is
that they are uniformly distributed in space, thereby
assigning to the radial distribution function a step-function
shape, equal to zero below the sphere contact distance, and
equal to one above it. By proceeding further in this
approach, it is possible to derive the van der Waals equation,
which therefore can be viewed as the first application of a
perturbative method to the study of a fluid.
If, on the other hand, one takes correctly into account the
fact that the radial distribution function cannot be
represented by a step function even in a hard sphere system,
but should be described by a function having a shape like
that shown in Fig. 8, an equation of state having the
following general form is derived
~ for polymers.
PV 1
[39] 13 ⫽f (h)⫺ 13 y(T,V~ )
RT RT
where f (h) is given by [38] while the second term at the
second member represents the perturbative contribution due
to attractive forces. The previous equation represents a
generalization of the van der Waals equation that is easily
recovered by assuming
1 proposal originally suggested by Ilya Prigogine, the fact that
[40] f (h)⫽ 121
1⫺4h
72
This method can be extended easily to different systems
which can possibly be used as reference and which, as
mentioned above, are composed of hard bodies with various
shape of the hard core of molecules.
The results obtained in this way are satisfactory in
describing many fluids. However, in order to apply the
perturbative approach previously introduced more
accurately, it is also necessary to take terms of decreasing
importance present in [32] into account. In this way, it is
possible to accurately describe the liquid-vapour equilibrium
of many-component mixtures, in particular of hydrocarbons,
as shown in Fig. 9, as a function only of the parameters of the
intermolecular potential. Actually, this research has
underlined the importance of intermolecular potential,
whose shape influences noticeably the results of the
simulation calculations and so the importance of identifying
the theoretical charcteristics intended to obtain greater
knowledge on the characteristics and form of intermolecular
potential.
The application can be extended to fluids made of polar
molecules, for which the chosen reference is represented by
a fluid made of molecules interacting through a
Lennard-Jones potential, assuming the dipole attraction as
the perturbative term.
2.3.10 Application to complex
molecules
In the previous section it was observed how the original van
der Waals approach can be improved by using appropriate
expressions describing the behaviour of the reference fluids
made of hard spheres more accurately. In this approach,
obviously, also the free volume available to molecules should
be modified. For instance, it is possible to demonstrate that a
hard sphere state equation such as [38] is compatible with
the following expression of free volume.
2
[41] Vf ⫽Ve h(3h⫺4)Ⲑ(1⫺h)
which should replace in [22] the V⫺b term present in the
original version of van der Waals theory.
Actually, molecules have been compared to interacting
objects lacking structure in the models taken into
consideration up to this point, since their rotation and
vibration movements are not influenced by the surrounding
environment, and therefore they do not have any influence
on the form of the state equation. This hypothesis is
rigorously valid for monoatomic gases as it represents a
reasonable approximation for small polyatomic molecules,
but it is inadequate for large dimension molecules such as
hydrocarbons with more than ten carbon atoms, and more so
A molecule made of n atoms has 3n degrees of freedom,
three of which are associated to their translation movements
in the volume in which the fluid is contained. The remaining
degrees of freedom are distributed between the three
rotation motions taking place around three orthogonal axes,
with their origin at the centre of mass of the molecule, and
the different vibration motions. In agreement with a
the rotations and vibrations of an extended molecule, due to
ENCYCLOPAEDIA OF HYDROCARBONS
 MOLECULAR THERMODYNAMICS

200 70 70
CH4-neo-C5H12 C3H8-C6H6 CO2-C3H8
60 60

160 50 50 37.8°C
171.1°C
liquid 40 40
P (bar)

vapour
120
30 30

20 104.4°C 20
80 4.4°C
10 10
37.8°C
0 0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
CH4 molar fraction C3H8 molar fraction CO2 molar fraction

A B C

Fig. 9. Examples of phase diagrams calculated using perturbative methods (continuous lines) compared to experimental data (circles).
A, methane-neopentane system; B, propane-benzene system; C, carbon dioxide-propane system.

its flexibility, can be influenced by the presence of molecules develop this approach starting from expression [5] of the free
close to it as a result of steric interactions, should be taken energy of a pure gas made by N molecules. In the specific
into consideration. Obviously, when the density of the fluid case of an ideal gas, the integral of configurations is equal to
tends to zero this effect disappears since the molecules are, V N; by using Stirling’s approximation
on average, very far from each other, and so the ideal gas
[43] ln N! ⬇NlnN ⫺N
behaviour is recovered. On the other hand, when the volume
of the system approaches maximum packing, all degrees of one gets
freedom associated with their external movements are 1 N 23 V
blocked. By developing this approach, the following [44] F ⫽⫺ 23 [ln(l3N zint
N )⫹N]⫺ 23 ln
b b N
expression of free energy referred to one mole was
proposed: The second term at the second member gives the
~
Vf c ⫺1 dependence of free energy from volume, so that its variations
[42] F~ ⫽F~id⫺RT ln 13 冤冢 冣 冥
~
e bãⲐV are associated to those of the configurations that the system
V~
can reach. If it is derived with respect to temperature, at
where c is a suitable parameter, equal to one constants N and V, and change of sign, it provides the
for monoatomic molecules, which reflects the amount expression of configurational entropy
by which rotations and vibrations are hindered by
V
the molecules nearby. [45] S ⫽NkB ln 23
N
The previous approach allowed the development of a
general model, called PHCT (Perturbed Hard-Chain Consider various samples of ideal gas formed by different
Theory), which provides a state equation which extends from components, each of volume Vi , where Ni molecules are
fluids made of simple molecules to fluids composed of present; if they are mixed together and the volume additivity
complex molecules, thus including a density interval that rule V⫽兺i NiVi , is assumed valid, the following expression for
goes from the ideal gas to liquids, in which maximum entropy variation associated with the mixing process can be
packing conditions are present. There are several versions of derived:
this model which depend on both the expressions used for Vf ∆S
冤 冢 N 冣 冢 N 冣冥
V Vi
and on the method adopted to evaluate the attractive [46] 13 ⫽冱Ni ln 13 ⫺ln 13 ⫽⫺冱Ni ln/i
kB
interaction between molecules. Parameter c is usually i i i i

determined on the base of experimental information; in the where /i⫽Vi ⲐV is the volume fraction of component i of the
case of hydrocarbons it is equal to 1 for methane, 1.91 for mixture. The previous relation is known as the Flory-Huggins
hexane, 2.55 for dodecane and it increases regularly with the equation which was originally, and independently, derived by
length of the molecules. these authors on the base of a lattice model. In a mixture of
ideal gases, /i corresponds to the molar fraction yi of the
different components, therefore if one refers to one mole [46]
2.3.11 Mixtures becomes:
∆S
The problem of many-component mixtures, which is [47] 13 ⫽⫺冱 y lny i i
R
obviously of primary importance in the applications of i

thermodynamics to phase equilibria, was only touched on in Actually, [46] is more general since it can also be applied
previous sections, and some important aspects will be to real gases and to liquids, the molar volume of which is
investigated in more detail in the following. It is advisable to determined by the volume of the molecules themselves, vi . In

VOLUME V / INSTRUMENTS 73
PHYSICAL AND CHEMICAL EQUILIBRIA

this case, in fact, Vi⫽Nivi and the following expression of that makes the calculation of the integrals present in [50]
entropy density can be derived: particularly cumbersome. One way to proceed consists of
∆SⲐkB / assuming that the comparison between the potential and the
[48] 113 ⫽⫺冱 1i ln/ i radial distribution functions can be performed in
V ni
i correspondence with a reduced distance given by the ratio
from which it appears that bigger molecules contribute in a between r and the molecular diameter; in other terms,
smaller part to mixture entropy. By indicating the density attributing the following expressions to the potentials and to
with ri (mass per unity volume) of the i-th component and the radial distribution:
with wi the mass fraction corresponding to a mass M, vi can
冢 冣
r
be derived by the following relation: [52] uij (r)⫽⫺u0ij f 1
sij
wi M
n ⫽ 123
g (r)⫽g 冢1冣
[49] i r
ri Ni [53] ij s ij
Obviously, for spherical molecules vi⫽(1Ⲑ6)psi3.
thereby [50] becomes:
⬁
2.3.12 Internal energy of a mixture [54] / ⫽⫺ 13 冱 Nj Ni u0ij s ij3
2p
V ij 冮 f(x)g(x)x dx
0
2

The potential energy due to interactions between molecules where x⫽r/sij . The integral at the second member of the
of many-component mixtures can be expressed by previous equation can be considered as an effective
generalizing [34] through the following relation: parameter to be determined, for instance, semiempirically. In
a rougher approximation the radial distribution function can
冮
2p
[50] / ⫽ 13 冱 Ni Nj uij (r)gij (r)r 2dr be assigned the form of a step function:
V ij
where uij (r) is the potential energy of interaction of the pair
of molecules i-j, whereas gij (r) is the corresponding radial
[55] g(r)⫽ 冦 10 r ⬍s
r ⭓s
distribution function. Obviously, in order to apply the In this case, the expression of the energy per unit volume
previous expression it is necessary to know the radial explicitly becomes
distribution functions of each pair of molecules and the
/ 2p 2p u0 s 3
corresponding potential of interaction. A reasonably [56] 13 ⫽⫺ 1343 冱 N N u0 s 3 ⫽⫺ 13 冱 / / 13233
ij ij
V 3V 2 i j ij ij 3 i j ninj
approximate method for tackling the problem consists of ij ij
assuming that each pair of molecules interacts with a where
potential compatible with a hard core, subject to an attractive V/i
interaction similar to that already used within the van der [57] Ni ⫽ 1343
ni
Waals model, that is:
⬁ r ⬍sij It is now advisable to define cohesive energy, indicated
[51] uij (r)⫽
冦 sij
⫺u0ij 13
r 冢 冣
6
r ⭓sij
by Pi* for each component, which acts as a characteristic
pressure operating internally in the fluid
2p u0ii s ii3
冢 冣
e*ii 3
where sij is the smallest approach distance of the i-j pair of [58] Pi* ⫽⫺ 13 113 ⬅ 1
molecules. 3 ni2 sii
As one can observe in Fig. 10, radial distribution This equation also defines parameters e*ii. Similarly for
functions are deeply influenced by molecular dimension, and each pair

Fig. 10. Influence of molecular

dimensions on the radial
distribution function. 1 2 1 2 2 1

1 1 1 1

1 1 2 2 1 2

g11 g12 g22

3 3 3

2 2 2

1 1 1

0 0 0
r r r

74 ENCYCLOPAEDIA OF HYDROCARBONS
 MOLECULAR THERMODYNAMICS

2p u0ij s ij3 eij* s ij By combining the expressions of internal energy

冢 冣
3
[59] Pij* ⫽⫺ 13 113 ⬅ 131 and entropy, it is possible to derive the expression of
3 ninj s ii s jj
free energy which is fundamental in the calculations of
Assuming phase equilibria. This can be obtained by assigning to
parameters j, e*, P* suitable values calibrated on the
[60] ∆Pij* ⫽Pi*⫹Pj*⫹2Pij*
basis of experimental data; for some hydrocarbons the
and substituting the previous relations into [56], it is possible values of these parameters are summarized in Table 5,
to derive the following expression of the internal potential e* and P* expressly, while j appears as the ratio
energy of the mixture: density/j.
It is to be remembered, in any case, that in a
[61]
U
1
V
⫽⫺P * ⫽⫺ 冢冱/ P ⫺冱/ / ∆P 冣
i
i i
*
i⬍j
i j
*
ij largely semiempirical treatment such expressions
represent the basis to formulating some mixture
and, consequently, the expression of parameter e⬅s(P*)1Ⲑ3. models, regarding particularly hydrocarbons, such as
One can observe that if the interaction parameters the models of regular solutions and athermal
between pairs of molecules are expressed by a geometric solutions, which today are still being used to study
average, thereby assuming phase equilibria.
241 2134
[62] eij* ⫽冪eii* ejj* sij ⫽冪siisjj
Table 5. Parameter values of e*, P*, density/j
one gets for some hydrocarbons
[63] ∆Pij* ⫽(Pi *1Ⲑ2 ⫺Pj *1Ⲑ2)⫽di ⫺dj e*/kB P* Density/j
Hydrocarbon
where di is the Hildebrand solubility parameter of (K) (MPa) (kg/m3)
component i. methane 224 248 500
ethane 315 327 640
2.3.13 Extensions and conclusions propane 371 313 690
butane 403 322 736
The analysis developed in the previous sections was intended
to offer a general view of some of the significant aspects of pentane 441 310 755
molecular thermodynamics, particularly those concerning
hexane 476 298 775
the assumptions necessary to perform the calculations on
fluid state behaviour and on phase equilibria. Without going heptane 487 309 800
into detail, for hydrocarbons and their mixtures (see octane 502 308 815
Chapters 2.6 and 2.7) methods have been illustrated that
make it possible to evaluate the most important nonane 517 307 828
thermodynamic functions, particularly internal energy and decane 530 304 837
entropy, from which it is possible to derive free energy and
chemical potentials. undecane 542 303 846
In order to provide a more general and flexible analysis dodecane 552 301 854
it is appropriate to take into consideration a volume increase
in a mixture by adding N0 moles of a zeroeth component n-C13H28 560 299 858

[64] V⫽冱ni Ni⫺V ⫹V0 䉴 n-C14H30 570 296 864

i
where V0⫽N0n0. n-C17H36 596 287 880
The expression of mixing entropy of the mixture isobutane 398 288 720
becomes
isopentane 424 308 765
∆S
[65] 12
kB 冤
⫽⫺ N0 ln(1⫺j)⫹冱Ni ln(j/i )
i
冥 neopentane 415 265 744

being 2,2-dimethylbutane 455 275 773

V 2,3-dimethylbutane 463 289 781

[66] j ⫽ 121
V0 ⫹V cyclopentane 491 388 867
Obviously, if V0 is zero, j⫽1. If the zeroeth components cyclohexane 497 383 902
were assumed to be made up of cavities, or pseudoparticles
benzene 523 444 994
of v0 dimensions, they would reflect the presence of a free
volume that would influence the value of the thermodynamic toluene 543 402 966
properties; entropy takes the form [65], which for n0⫽0, and
p-xylene 561 381 949
then j⫽1 identifies with [46], while for internal energy [61]
becomes m-xylene 560 385 952
U o-xylene 571 394 965
[67] 1 ⫽⫺j P*
V

VOLUME V / INSTRUMENTS 75
PHYSICAL AND CHEMICAL EQUILIBRIA

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F potential energy of a system
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