2.
Thermodynamic properties
of hydrocarbons
2.4.1 Introduction
An extended application of thermodynamics to the
development of industrial processes was possible only
after the accumulation and organization of a great mass of
experimental data, in conjunction with the theoretical
contributions offered by statistical thermodynamics and by
quantum mechanics. A particularly significant step in this
process was the publication in 1952 of Selected values of
chemical thermodynamic properties, which was the result
of twenty years of work by Frederick D. Rossini (who at
that time was a researcher at the National Bureau of
Standards) and his co-workers. These years were mainly
spent in evaluating and organizing all thermochemical
data published up to that point in the world literature
(Rossini et al., 1952). The book also known as Circular
500, after its NBS publication designation, contains tables
with accurate values of thermodynamic properties of
organic and inorganic compounds, in a form that makes it
possible to predict the products of thousands of chemical
reactions, to forecast if a chemical reaction will take place
or not, to estimate its degree of advancement, and how
much heat is released or absorbed. In particular, the book
provided the recommended values of the heats of
formation of the various substances, of their free energies
and entropy of formation, and of their heat capacities, in
different physical states (solid, liquid, gaseous or water
solution). All values were reduced to standard conditions
at 25C temperature and 1 bar pressure. Evidently, these
data are extremely important for research and engineering.
Henry Eyring declared that the knowledge collected in
this book allowed American chemical industries, during
those years, to save enough money to pay for the entire
cost of NBS since its founding. Particularly important was
the activity dedicated to hydrocarbons, like that included
in the so-called Project 44, started in 1942 by the
American Petroleum Institute. Two circumstances
especially were of particular importance: the experience
gained in the Second World War on the fuels used by the
air force, that allowed gasoline to be obtained with high
octane numbers, and the support granted to the space
program during the 1950s for the discovery of new fuels
for rockets.
VOLUME V / INSTRUMENTS
In the years following the books publication, a great
amount of data appeared in the scientific literature,
particularly thanks to the availability of automatic
calorimeters, and it was not possible to carry out the
complete revision of the Circular 500, that was planned for
the beginning of the 1960s. However, the National Bureau
started a new project, the Chemical Thermodynamics Data
Centre, thanks to which it was possible to publish partial
revisions of Circular 500, between 1965 and 1981, in the
Technical Note 270 series. The development of computers
was of significant help in those years and greatly accelerated
the calculations for data fitting, even though a great effort
was still required in order to verify the accuracy of the
measurements reported in the literature. Finally, in 1982 the
complete revision of Circular 500 was published: The NBS
Tables of Chemical Physical and Chemical Reference Data,
which immediately became a stronghold of research. The
NBS Tables, aptly updated, were inserted in the NIST
Chemistry WebBook which can be consulted on the Internet,
and after the last update (March 2003), now contains data for
about 48.000 species. In particular, thermochemical data of
substances refer to the following properties: formation
enthalpies, combustion enthalpies, heat capacities, entropy,
phase transitions temperatures and enthalpies, vapour
tensions. Thermochemical data of chemical reactions refer to
enthalpy of reaction and free energy of reaction. Tables also
contain spectrometric data (IR, mass, UV), ionic energy
data, and thermophysical values of some fluids, that will not
be discussed in this Chapter. Below, some of the
methodologies that allow the aforementioned
thermodynamic properties to be derived will be described.
2.4.2 Heat of formation
and chemical bond energies
For a compound with the generic formula AaBbCc, the heat
of formation at constant pressure is given by the variation of
enthalpy Hf that is associated to the synthesis of a mole of
this compound from the elements
23x A
23y B
23z C A B C
a b c
[1] x y z
a b c
77
PHYSICAL AND CHEMICAL EQUILIBRIA

HR ni(products)Hi(products)
131
T
For most common substances, the values of the standard
heat of formation Hf0 are known. They correspond to a [5]  111123121 
P T i P
formation reaction where both the elements and the
n H
components are in their state of aggregation at 298 K and 1  1311114122 n C
i(reactants) i(reactants)
bar. Conventionally, a zero value of the heat of formation is T P i
i Pi

assigned to all elements in the standard state and in the state

of aggregation that corresponds to it. Furthermore, the heat the relation is known as Kirchhoffs equation. If the
of combustion Hc is defined as the heat developed in the dependency of CP from temperature is expressed through a
combustion of one mole of a substance. In Table 1, the development in a series of powers, [5] can be easily
values of Hc of some common organic molecules are integrated. One gets
shown. T2
Enthalpy is a state function (see Chapter 2.1). In 1840,
when the generalized energy conservation principle had not
[6]
H(T2) (A
BT
CT 2
)dT A(T2 T1)

T1
even been stated, Henri Hess formulated a law that
B C
represents an application of this property (the amount of heat
23 (T22 T12)
23 (T23 T13)
H(T1)
developed during the formation of a compound is constant, 2 3
regardless of whether the compound is formed directly or where
indirectly, in a series of subsequent stages). Hesss law found [7] A ni ai , B ni bi , C ni ci
extensive experimental demonstration in the following years. i i i
In terms of enthalpy, it can be defined in this way: the ai , bi e ci are the parameters used to interpolate the heat capa-
enthalpy of the reaction is the sum of the enthalpies of the cities, whereas A, B e C are their linear combinations through
various stages in which it is possible to decompose the their stoichiometric coefficients. In general, it will be:
reaction, even if this decomposition is only theoretical. An
B C
important consequence of Hesss law is that, considering a [8] H H0
AT
23 T 2
23 T 3

reaction such as: 2 3
H0 being an integration constant, the hypothetical enthalpy
[2] aA
bB
 mM
nN

variation associated to the reaction at a 0 K temperature.

it is possible to derive the corresponding enthalpy variation In a diatomic molecule AB, the bond energy corresponds
from the values of the heat of formation of the different to the energy of dissociation in the two atoms A and B, and it
species involved through the following relationship indicates the work performed to take them at infinite
distance. The potential energy of a diatomic molecule as a
[3] H R0 ni(products)Hfi(products)
0 ni(reactants)Hfi(reactants)
0
i i
function of the distance rAB between the two atoms is given
where ni indicates a generic stoichiometric coefficient. In by the function U(r); the value of the distance re that
generic conditions, different from the standard one, the corresponds to the minimum of the curve represents the
enthalpy variation associated to a reaction is given by equilibrium distance of the stable molecule. The bond energy
is therefore given by the difference between the value U0 of
[4] HR ni(products)Hi(products)ni(reactants)Hi(reactants)
i i
the potential energy at re and the value of U at an infinite
which, derived with respect to T, allows the variation of the distance between the atoms. It is actually necessary to bear
heat of reaction with temperature to be obtained: in mind that also at the thermodynamic zero, the molecule
retains a residual kinetic energy, called zero point, equal to
hn2, n being the vibration frequency of the molecule and h,
Table 1. Heats of combustion of some organic substances the Planck constant; therefore, the effective bond energy is
(values are expressed in kcal/mol and they are referred given by
to the formation of CO(g)
2 and H2O )
(l)
hn
[9] D U0
13
Hc
2
Species
The calculation of the potential energies of the
CH4(g) 212.63 molecules, and therefore the bond energies, is performed
C2H6(g) 372.68 through the methods of quantum mechanics, and is one of
the main objectives of theoretical chemistry. Performing
C2H4(g) 337.57 calculations, however, can be difficult since the bond energy
of many molecules is below 0.5% of total energy and, as
C2H2(g) 310.58
such, should be evaluated with great precision.
C6H6(l) 782.64 In order to better understand the various contributions to
bond energy in polyatomic molecules, it is necessary to refer
CH3 OH(l) 170.81 to an AaBbCc compound. Its standard heat of formation is
C2H5OH(l) 326.82
that of reaction [1]. Since the substances that take part in it
can be in their standard state, in solid, liquid or gaseous
CH3COCH3(l) 448.65 phase, Hf0 also includes the variation of energy
corresponding to cohesion forces in a crystal lattice or to
(l)
C6H12 938.64 intermolecular forces for liquids or real gases. These last two
(g)
C12H22O11 1,359.34 actually do not affect bond energy and it is appropriate to
express the enthalpy of formation by taking as a reference,

78 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

for all substances present, the hypothetical state of ideal gas,

and define as the atomization energy Ha0 of the AaBbCc Table 2. Values of dissociation energies EXY
compound the energy corresponding to the reaction of some simple and multiple bonds (kcal/mol)
[10] AaBbCc(g) aA(g)
bB(g)
cC(g)

EXY
Bond
This reaction can be calculated from the enthalpy of OO 33
formation of the substances in the hypothetical state of ideal
OH 111
gas at 1 bar pressure by using the following relationship
OF 45
[11] Ha0(298 K) aHf 0(A,g)
bHf 0(B,g)
OCl 50

cHf 0(C,g)Hf 0(AaBbCc,g) SS 63
SH 88
Since we adopted the convention stating that the heats of
formation of the elements in their standard state are zero, the SCl 66
positive terms at the second member of [11] correspond to a SBr 51
process where the elements pass from their standard physical SeSe 44
state to the hypothetical ideal gas state at 1 bar e 298 K.
NN 38
Generally speaking, the energy necessary to break a
bond in a polyatomic molecule can be considered NH 93
independent from the nature of the other atoms contained in NF 66
it. On the basis of this hypothesis, the energy of atomization NCl 48
of a molecule can be derived additively from the sum of the
PP 41
dissociation energies of the various bonds present in it that
correspond to the dissociation energies of the corresponding PH 76
diatomic molecules. This approach is actually not correct, PCl 76
since the dissociation energy of a R1R2 bond in a PBr 64
molecule represents the energy necessary to obtain its
PI 51
scission in two radicals:
HgCl 53
R1R2R1
R2

HgBr 44
where the dots indicate the unpaired electrons. However, AlCl 102
during the dissociation, radicals undergo a structure
SiF 142
variation which causes an energy effect. For example, if one
considers the ethane molecule, the dissociation of the central TiCl 103
bond CC is accompanied by variations of the distances in NF 66
the CH bonds and of the angles HCH in the two AsAs 40
radicals CH3. In other cases, for molecules of the MAn type,
AsH 61
the dissociation of each bond is accompanied by a variation
of the valence state of the M atom; therefore, subsequent AsF 115
energies of dissociation D1(AMAn1), D2(AMAn2), can AsCl 69
be significantly different among them and the bond energy is SbSb 34
thus not constant, as previously supposed. However, it is
SbCl 75
possible to assign to the different bonds some average value
that can be used to derive the atomization energies and then CC 83
the formation energies through the additivity rule. In Table 2, CO 82
a few values of these energies are shown, for simple and CH 99
multiple bonds, from which it is possible to derive the
CF 116
atomization energies by using this simple relationship:
CCl 78
[12] Ha0 nXY EXY
CBr 66
where the sum is extended to all the types of bonds present CI 57
in the molecule and nXY is the number of bonds XY.
CN 70
Saturated aliphatic hydrocarbons are a class of
compounds that make it possible to verify the approximation CC 148
limits of [12] since they involve the same types of bonds. In NN 100
fact, as the only bonds present are CH and CC, its CN 147
application gives this equation
CO 164-174
[13] Ha0 (n 1)ECC
(2n
2)ECH CS 114
where n is the number of carbon atoms. Assigning the values CC 194
ECH98.73 and ECC82.45 kcal/mol to the bond NN 225
energies, it is possible to obtain the values of the standard
CN 207-213
heats of atomization from Table 3 that also shows

VOLUME V / INSTRUMENTS 79
PHYSICAL AND CHEMICAL EQUILIBRIA

experimental values. Agreement is satisfactory, but the
equation would be inadequate if applied to branched
hydrocarbons, since it would give a situation of
thermoneutrality for isomerization reactions of linear
alkanes into their branched isomers. A more general scheme
was suggested in to order to correct this inconsistency, where
the energy of a molecule is given by the sum of terms
associated to the bonds and terms associated to the pairs of
bonds that are linked to the same atom. For example, for the
simplest n-alkanes, this approach gives the following
multiple bonds causes their delocalization in the molecule,
increasing their stability. The calculation of this energy can
be performed by applying the methods of quantum
mechanics.
2.4.3 Equilibrium law and variation
of standard free energy
Consider the usual generic reaction aA
bB
mM

expressions of the heats of atomization:
nN
. As known, the law of chemical equilibrium is
given by the following equation
[14] CH4 Ha0 4ECH
6P1
C2H6 Ha0 6ECH
ECC
6P1
6P2 [18] G 0 RT lnK

C3H8 Ha0 8ECH
2ECC
7P1
10P2
P3 that allows the equilibrium constant K of the reaction from
the standard free energy variation of the species involved in
where P1, P2 e P3 are the energies of interactions the reaction to be derived. K is given by the expression
corresponding to the pairs of bonds HCH, HCC aMm aNn
and CCC. It is now useful to introduce the following [19] K aini  11223
aAa aBb
terms expressing the effective values of the bond energies: i

3 where ai is the activity of the generic component i of the

[15] BCH ECH
23 P1 reacting system. In a reacting gaseous mixture, it is often
2
BCC ECC
3P1
6P2 advisable to choose a standard state for the different
components that corresponds to the hypothetical state of
and an interaction parameter given by GP12P2
P3. With ideal gas at 1 bar pressure and at the temperature equal to the
these notations, the set of equations [15] can be rewritten as actual temperature of system. This choice is particularly
convenient since it replaces the activities of the different
[16] CH4 Ha0 4BCH
components with the values of the fugacities. Furthermore,
C2H6 Ha0 6BCH
BCC since the standard state refers to a fixed pressure value, G 0
C3H8 Ha0 8BCH
2BCC
G and K depend only on temperature. The standard free energy
variation of a reaction is therefore a fundamental parameter
whereas for generic alkane, the following relationship holds to identify its equilibrium conditions. This explains the
[17] Ha0 (Cn H2n
2)(n 1)BCC
importance of the data tables that allow the values of G 0
for several reactions to be determined. The easiest way to

1

(2n
2)BCH
Np 6
23 Ns G proceed is to calculate G 0 from the values of the standard
2 free energies of formation of the different compounds Gfi0;
where Np e Ns are respectively the number of primary and obviously, the Gfi0 represent the free energy variations
secondary CH. By assigning the values in kcal/mol, associated to the formation of species from elements in their
BCC78.84, BCH99.29 and G2.28 to the parameters standard state. For a generic reaction, it is possible to write:
that appear in the equations, [17] makes it possible to
[20] GR0 ni(products)Gfi(products)ni(reactants)Gfi(reactants)
calculate the heats of atomization of alkanes, as well as i i
branched ones, with an average error in the order of 0.5 The tables of the National Bureau of Standards provide
kcal/mol. the values of Gfi0 for several substances, as a function of
The additivity rule of bond energies cannot be applied to temperature. A drawback is that, in many cases, Gfi0 varies
molecules containing systems of conjugated double bonds rapidly with temperature, and in order to perform accurate
such as butadiene and benzene. In these compounds, in fact, calculations, tables must contain values corresponding to
the interaction of electrons that take part in the formation of very small temperature intervals. This problem can be dealt
with by tabulating the functions of free energy (GT0G00 )T or
(GT0G298
0 )T that vary less with temperature. Once these

Table 3. Standard heats of atomization values are known, the free energy variation can be calculated
of the simplest n-paraffins (kcal/mol) as follows:
GT0 GTfiH 298
0 H 298
0

[21] 132 ni 123412441
121
fi
Values calculated Experimental
with [13] values T i
T T
As an alternative, it is possible to derive the values of
CH4 394,92 397.16 G 0 from the variations of standard enthalpy and of entropy
C2H6
of formation Hfi0 and Sfi0. Obviously, the Sfi0 represent the
674,83 674.58
entropy variations associated with the formations of species
C3H8 954,74 954.24 from elements in the standard state. From the definition of
free energy, derives:
C4H10 1.234,65 1,234.65
[22] Gfi0 Hfi TSfi0
C5H12 1.514,56 1,514.56
from which

80 ENCYCLOPAEDIA OF HYDROCARBONS

[23] G 0 ni Gfi0 ni Hfi0 T ni Sfi0 To describe vibrational states, it is also necessary to
i i i distinguish between diatomic molecules and polyatomic
2.4.4 Calculation of thermodynamic
properties in ideal gases by means
of statistical thermodynamics
The goal of statistical thermodynamics is to describe the
macroscopic properties of matter, once its structure and the
dynamic behaviour of its particles are known. In order to
evaluate the energy and entropy of gaseous molecules with
the methods of statistical thermodynamics, the energy of a
molecule of an ideal gas is considered to be composed of the
sum of the contributions of the energies of translation, et ,
rotation, erot , vibration, evib , and electronic, eel:
[24] e et
erot
evib
eel
Each one of the terms of [24] is quantized and can
therefore assume only determined values. In correspondence
to each value of energy, more molecular states can exist, the
number of which is called statistical weight or degree of
degeneration. Energy is calculated by applying quantum
mechanics. Only the results used to calculate
thermodynamic properties are reported here, without going
into details. By taking into consideration a gas contained in a
vessel with a parallelepiped form that has size a, b, c edges
and volume Vabc, the values of the energies of the
translational states of the molecules are given by the
following relationship:
h2 n 2 n 2 2
n
[25] en1,n2,n3 13 2331
2332
2333
8m a b c
Here, m represents the mass of molecules, n1, n2 e n3 are
the quantum numbers associated with the three coordinates
of the system that can assume values varying between zero
and infinity, while h is Plancks constant. As far as rotational
states are concerned, it is necessary to distinguish diatomic
molecules from polyatomic ones. In the first case, molecules
can be considered similar to a rigid rotator with a moment of
inertia
mAmB 2
[26] I  11223 r
mA
mB e
where mA and mB are the masses of the two atoms, and re is
the interatomic distance. By applying quantum mechanics, it
is possible to derive the following expression of the energies
of the rotational energetic levels:
h2
[27] erot  1223 j( j
1)
8p2I
j being 0, 1, 2, . Each one of these states is degenerate,
with a statistical weight equal to (2j
1). A non-linear
polyatomic molecule has three rotational degrees of freedom
and is therefore characterized by the main moments of
inertia Ix, Iy , e Iz , that are referred to three mutually
orthogonal axes passing through its centre of mass. In this
case, the calculation of energies of the quantum states is
more complicated, but it can be performed adopting
reasonable approximations that will not be discussed here. In
polyatomic molecules, however, there are also some further
degrees of freedom associated to internal rotation motions
around simple bonds CC, CO, etc.
VOLUME V / INSTRUMENTS
THERMODYNAMIC PROPERTIES OF HYDROCARBONS
ones. In a diatomic molecule AB, the two atoms that have an
mA and mB mass move in an intramolecular field with a
potential energy that depends on their distance. If the
average energy of vibration is not too high or, more
precisely, if it is not bigger than half of the dissociation
energy of molecules, the intramolecular potential can be
approximated by a parabolic function
1
[28] U(r)D
23 k(r re)2
2
where D is the molecule dissociation energy, while constant
k is associated with the second derivative of function U(r) in
the minimum energy point through the following
relationship
d 2U(r)
[29] k  1234421
dr re
In this approximation, it is possible to consider the
molecule similar to a harmonic oscillator with a reduced
mass
mAmB
[30] mr  11223
mA
mB
and frequency
1
m
1 1
k
[31] n 12
2p r
The energy of vibration can assume only discreet values,
related to the frequency of vibration through the expression:
1 hn
[32] evib hn 23
ni  223
hnni e vib
0
hnn
i
2 2
where ni is an integer number equal to 0, 1, 2,, and e vib0 is
the energy of the lowest level, known as vibrational
zero-point energy. A polyatomic molecule formed by n
atoms has several vibrational degrees of freedom, precisely
3n5 if the molecule is linear, 3n6 if it is non linear.
Assuming that the variations of intramolecular forces depend
only on atom displacements, it is possible to decompose the
complex atomic movements in 3n6 independent modes of
vibration, known as normal. Each normal vibration is
characterized by its own frequency ni and the vibrational
energy is the sum of the energies of the single separated
vibrations.
As far as electronic states are concerned, it is necessary
to observe that in ordinary temperature conditions, the
difference between the fundamental electronic state and the
first excited state is much higher than the average thermal
energy for almost all molecules. Up to 10,000 K, most of the
molecules therefore reside in the fundamental electronic
state.
From a microscopic point of view, the state of a system
is defined when the dynamic characteristics of the particles
composing it are known. As noted above, the energy of a gas
molecule is quantized and can take on only a series of
discreet values that will be indicated, starting from the
fundamental state, as e0,e1,,ei. Multiplicity, i.e. the number
of individual states existing at each level of energy, is given
by g0,g1,,gi . By indicating with n0 the number of
molecules residing in the fundamental state, and with ni the
number of molecules in a state with a ei energy level, the
81
PHYSICAL AND CHEMICAL EQUILIBRIA

Boltzmann distribution law states that GE0
[48] 1124 R 1lnAi
[33] ni n0 e(eie0)kBT T i

where kB is the Boltzmann constant. The number of Equations [43] and [46-48] make it possible to calculate
molecules that have a ei energy is ni gi . The total number of thermodynamic properties, once the energy levels of a given
molecules N is then: molecule are known. It is, moreover, advisable to separately
[34] N ni gi n0gi e(eie0)kBT account for the contributions due to translation, rotation,
i i vibration and electronic excitation. As far as translation is
Equations [33] and [34] make it possible to calculate the concerned, recalling [25], it is possible to derive the
number of molecules residing at the fundamental level following expression for the partition energy:
Veg
[35]
N
n0  111311244 [49] Ai (translational)(2pmkBT)32 11 0

gi e ie0)kBT
(e i
Nh3
i where g0 is the multiplicity of the fundamental state and e is
and those in a state at a ei level the base of natural logarithms. By replacing [49] into
equations [43], [46] and [47], it is possible to get:
Ne(eie0)kBT
[36] ni  111311244 3
gi e(eie0)kBT
i
[50] (EE0)(translational) 23 R
2
The total energy of the system, referred to the 3
[51] CV (translational) 23 R
fundamental level, is 2
i Ngi(ei e0) e(eie0)kBT (2pmkBT)32 Veg0

3
[52] S(translational) Rln 231311131
23 R
[37] E E0  ni gi (ei e0) 11113112112 Nh3 2
i gi e(eie0)kBT i where R is the universal constant of gases.
The following notations can be introduced: As far as rotational contribution is concerned, recalling
[27], it is possible to derive
[38] Ai gi e(eie0)kBT
1
Bi gi (ei e0)e(eie0)kBT Ai (rotational) 23s (2j
1)ej( j
1)h 8p Ik T
2 2
[39] [53] B

i j
[40] Di gi (ei e0 )2 e(eie0)kBT
where s is the symmetry number, which represents the
i Ai is also known as partition function number of identical configuration obtained by rotation
Notice that: around the symmetry centre. When h28p2IkBT1, as
occurs for a gas at a temperature that is not too high, the
B
dAi 13
[41] 12  i summation at the second member moves towards to the
dT kT 2 integral and therefore it is possible to write
dBi 13
D 8p2Ik T
[42] 12
dT
 i
kT 2
[54] Ai (rotational) 111
i
h2s
B

[37] can therefore be written as By replacing [51] into equations [43], [46] and [47], for
a linear molecule, it is possible to get:
i
Bi [55] (EE0)(rotational)RT
[43] E E0 N 1232
Aii
[56] C(rotational)R

8p2Ik1
BT
Identifying the average energy of the ensemble E with [57] S(rotational)R ln 114
h2s
U, and recalling that the specific heat at constant volume CV
is given by: A non-linear polyatomic molecule has three rotational
U degrees of freedom, and the partition function becomes
[44] CV  3441
T (8p2kBTh2)32 (Ix Iy Izp)12
V
[58] Ai (rotational) 1121111111
s
and is related to entropy S by: i

where Ix , Iy e Iz are the three main moments of inertia
[45] S  CV d lnT
defined with respect to three axes passing through the centre
one gets of mass of the molecule. By replacing [55] into equations

D A B A
N [43], [46] and [47], for non-linear molecules, one gets
[46] CV  11 i i i i
2
kBT 2 i i i i 3
and [59] (EE0)(rotational) 23 RT
2
E E
[47] S R lnAi
41344 10
i
T [60]
3
CV (rotational) 23 R
2
Recalling that GU
PVTS and that, for the ideal gas 8p2k T 32 (pI I I )12 3
law, it is PVRT, one gets: [61] S(rotational) Rln B
2311
h2 x y z
11131
s

23 R 2

82 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

The vibrational contribution can be derived by recalling necessary to add the appropriate contributions of vibrations,
[32], from which it is possible to derive: obtained through equations [63-65] summed up on all
1 vibrational degrees of freedom, in order to obtain the value
[62] Ai ehnni kBT 11114 hnkBT of a certain thermodynamic function for a given molecule;
i i
1e
M represents the molecular weight.
By posing xhnkBT and replacing into equations [43],
[46] and [47], for each vibrational degree of freedom, one
gets: 2.4.5 Calculation of free energies
[63] (EE0)(vibrational)RTx(ex 1) of formation
x 2e x1 The free energy function (GH0 )T is the thermodynamic
[64] C(vibrational)R 114
(ex 1)2 property that can be calculated more easily using a
statistical method, since it is sufficient to know the

x41
[65] S(vibrational) R 224 ln(1ex) partition function in order to calculate it. For a gas at the
e x1
standard state, it is
The total contribution of vibrations for each of these
G H0
0 0
properties is obtained by summing up all the fundamental
frequencies of vibration.
[66] 1131
T
R 1ln Ai
i

As far as the electronic contribution is concerned, it is Furthermore, for a given reaction, it is possible to
necessary to recall that molecules reside in their fundamental calculate (G 0H00)T as
electronic state at temperatures below 2,000 K. The G 0 H00 Gi0 H0i0
population is already scarce at the first energy level and the
contribution of electronic energy to thermodynamic
[67] T i

1131  12213(products)
T
Gi0 H0i0
properties is negligible.  1231 (reactants)
Table 4 (Rossini et al., 1952) shows the equations i
T
required to calculate the contributions of translation and In addition, it is
rotation to thermal contribution function (H 0H00 )T, the G 0 H00 G0 H00
free energy function (G 0H00 )T and entropy S 0, for a gas in
its standard thermodynamic state, at a fugacity equal to 1 bar
[68]
1131
T T
 11  11
T
at a given thermodynamic temperature. To this, it is Therefore, recalling [15], it is possible to obtain
G 0 H0 1322131
(G H0 ) 0 0 0
[69] 11 Rln K 131

T T T
Table 4. Equations with numerical constants to calculate
thermodynamic functions in the case of translation The value of H00 T for each reaction can be obtained
(for all molecules) and of rotation (for rigid molecules). from the values of H00 at 25C corrected at 0 K, by using
M, molecular weight (g/mol); I, moment of inertia the values of enthalpy at 25C referred at 0 K for the
(g/cm2). The values obtained are expressed in kcal/mol different molecules involved:
Translation [70] H00 H298.16
0 (H298.16
0 H00 )
(for all molecules)
where
(H 0 H00 )T Cp0 (5/ 2 )R 4.9680 [71] (H298.16
0 H00 )(H298.16i
0 H00 )(products)
(G H0 )T 6.8635 log M
7.2820 11.4392 log T
0 0 i

S 0 6.8635 log M 2.3141
11.4392T (H298.16i

0 H00 )(reactants)
i

Rotation
(for rigid molecules) 2.4.6 Tables of chemical
thermodynamics data
1) Diatomic or linear polyatomic molecules
(H 0 H00 )T R 1.9872 The tables originally published in the context of API
Research Project supplied the values of the following
a) s 1 thermodynamic properties in the gaseous state between 0
(G0 H00 )T 4.5757 log(I1039)
2.7676 4.5757 log T and 1,000 K: (H 0 H00 )T, (G0 H00 )T, S 0, H 0, H 00 , Cp0,
H f0, Gf0, log Kf .
b) s = 2
(G0 H00 )T 4.5757 log(I1039)
4.14514.5757 log T Reactions involving O2, H2, H2O, C, CO, CO2 e CH4
In Fig. 1, the values of the logarithm of the equilibrium
2) Non linear polyatomic molecules constant for the following eight reactions are shown:
(H 0H00 )T2,9808 C (solid, graphite)
CO2 (gas) 2CO (gas)

(G H0 )T 2.2878 log(Ix Iy Iz 10117)
4.5757 log s

0 0
C (solid, graphite)
H2O (gas) CO2 (gas)
H2 (gas)

3.01416.8635 log T 
CO (gas)
12 O2 (gas) CO (gas)

CO (gas)
H2O (gas) CO2 (gas)
H2 (gas)

VOLUME V / INSTRUMENTS 83
PHYSICAL AND CHEMICAL EQUILIBRIA

temperature (C) temperature (C)

273 73 127 327 527 727 927 1,127 1,327 273 73 127 327 527 727 927 1,127 1,327 1,527
10
C
2H2
CH4

20
8
CO
1/2O2
CO2

6 CH4
H2O
CO
3H2

10 m
l
4 C
CO2
2CO

i
h

G0f / T.n (cal/mol.K)

0 g
2
f
CO
H2O
CO2
H2 e
log K

0 d
CH4
2H2O
CO2
4H2
10 c
b
2
C
H2O
CO
H2


20
4

6
30
CH4
CO2
2CO
2H2
a
8

40
10
0 200 400 600 800 1,000 1,200 1,400 1,600 0 200 400 600 800 1,000 1,200 1,400 1,600 1,800
temperature (K) temperature (K)

Fig. 1. Logarithm of the equilibrium constant Fig. 2. Thermodynamic stability of n-paraffins in the gaseous
for eight reactions involving oxygen, hydrogen, state as a function of temperature: a. methane; b. ethane;
water, carbon, carbon oxide, carbon dioxide and methane c. propane; d. n-butane; e. n-pentane; f. n-hexane; g. n-heptane;
(Wagman et al., 1945a). h. n-octane; i. n-nonane; l. n-decane; m. n-hexadecane
(Prosen et al., 1945b).
CH4 (gas)
CO2 (gas)2CO (gas)
2H2 (gas)


CH4 (gas)
H2O (gas) CO (gas)
3H2 (gas)

temperature (C)
73 127 327 527 727 927 1,127 1,327 1,527 1,727
CH4 (gas)
2H2O(gas) CO2 (gas)
4H2 (gas)


28
C (solid, graphite)
2H2 (gas)
CH4 (gas)

26

Paraffin hydrocarbons 24
Fig. 2 shows the stability of a number of n-paraffins per
carbon atom compared to the solid carbon elements 22 l
Gf / T.n (cal/mol.K)

(graphite) and gaseous hydrogen as a function of i

temperature. The y axis gives the value of (1n)(Gf0T) in 20 h
cal/molK, where n is the number of carbon atoms per g
molecule, T is the thermodynamic temperature, and Gf0 is 18
f
the free energy of formation of the hydrocarbon from the
elements. The points below the zero line indicate that the 16 e
hydrocarbon in its standard state has the thermodynamic d
tendency to form from elements which are also in their 14 c
standard states. b
As far as thermodynamic stability of isomers is 12 a
concerned, it is possible to draw the following conclusions:
At 298 K (25C), among the different isomers, the 10
normal one has the lowest stability; compared to other
isomers, the stability of the normal one rises with increasing 8
200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000
temperature, and at 1,000 K, it is among the most stable temperature (K)
isomers.
At 298 K, the isomer 2,2-dimethylic is among the most Fig. 3. Thermodynamic stability of 1-alkenes in the gaseous state
stable, but its stability decreases rapidly with increasing as a function of temperature: a. ethylene; b. propylene;
temperature, and at 1,000 K, is among the least stable. c. 1-butene; d. 1-pentene; e. 1-hexene; f. 1-heptene; g. 1-octene;
Isomers with a higher degree of branching are among the h. 1-nonene; i. 1-decene; l. 1-hexadecene
least stable at high temperatures. (Kilpatrick et al., 1949).

84 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

temperature (C) temperature (C)

173 227 627 1,027 1,427 73 27 227 427 627 827
20
12
18 a
10
16 b
8
14 c
6
12 d
4
10
C2H4
H2
C2H6


2

log K
log K

8 0

6 2

4 4

2 6

0 8

2 CnH2n
H2 10
CnH2n
2; n2

4
100 500 900 1,300 1,700 300 500 700 900 1,100
temperature (K) temperature (K)

Fig. 4. Logarithm of the equilibrium constant for the dehydrogenation Fig. 6. Logarithm of the equilibrium constant for some alkylation
reaction of 1-alkenes into n-paraffins in the gaseous state reactions of paraffins with alkenes to give paraffins in the
(Kilpatrick et al., 1949). gaseous state: a. ethylene
isobutane 2,3-dimethylbutane;

b. propylene
isobutane 2,3-dimethylpentane;

c. isobutene
isobutane 2,2,4-trimethylpentane;

temperature (C) d. 2-methyl-2-butene
isobutane 2,2,5-trimethylhexane

173 27 227 427 627 827 1,027 1,227 1,427 (Kilpatrick et al., 1949).
16
temperature (C)
73 127 327 527 727 927 1,127 1,327 1,527
14 90

12
80
10 2CnH2n
C2nH4n

70
8
G0f / T.n (cal/mol.K)

60
6
log K

4 50

2 40

0 h
30
n2 g
2 f
20 e
n3
4 d
n4 c
10 b
6 n4 a
8 0
200 400 600 800 1,000 1,200 1,400 1,600 1,800
100 300 500 700 900 1,100 1,300 1,500 1,700
temperature (K) temperature (K)
Fig. 7. Thermodynamic stability of 1-alkynes in the gaseous state
Fig. 5. Logarithm of the equilibrium constant for some as a function of temperature: a. acetylene; b. propyne;
dimerization reactions of n-1-alkenes into n-1-alkenes c. 1-butyne; d. 1-pentyne; e. 1-hexyne; f. 1-octine;
in the gaseous state g. 1-tetradecine; h. 1-eicosine
(Kilpatrick et al., 1949). (Wagman et al., 1945b).

VOLUME V / INSTRUMENTS 85
PHYSICAL AND CHEMICAL EQUILIBRIA

temperature (C) temperature (C) temperature (C) temperature (C)

73 327 727 1,127 1,527 73 327 727 1,127 1,527 73 327 727 1,127 1,527 73 327 727 1,127 1,527
10 10 10 10
a a
0 0 0 a 0 a
b b
10 10 10 b 10
log K

b
20 c 20 c 20 20
c
30 30 30 30 c

40 40 40 40

200 600 1,000 1,400 1,800 200 600 1,000 1,400 1,800 200 600 1,000 1,400 1,800 200 600 1,000 1,400 1,800
temperature (K) temperature (K) temperature (K) temperature (K)
A B C D
Fig. 8. Logarithm of the equilibrium constant: A. of ethane, ethylene and acetylene formation in the gaseous state (a. ethane;
b. ethylene; c. acetylene); B. of propane, propylene, and propyne formation in the gaseous state (a. propane; b. propylene; c. propyne);
C. of n-butane, 1-butene and 1-butyne formation in the gaseous state (a. n-butane; b. 1-butene; c. 1-butyne); D. of n-pentane,
1-pentene and 1-pentyne formation in the gaseous state (a. n-pentane; b. 1-pentene; c. 1-pentyne)
(Wagman et al., 1945b).

Monolefinic hydrocarbons In Fig. 5, the values of of the following dimerization

Fig. 3 shows the thermodynamic stability as a function of reaction n-1-alkenes into n-1-alkenes in the gaseous state are
temperature of the 1-alkenes in the gaseous state, per carbon shown in the diagram as a function of temperature:
atom compared to the solid carbon elements (graphite) and
2C2H4 ( ethylene, gas) 
C4H8 (1-butene, gas)

gaseous hydrogen. In Fig. 4, the values of log10 K for the

hydrogenation reaction of a given 1-alkene into the 2C3H6 ( propylene, gas) 
C6H12 (1-hexene, gas)

corresponding n-paraffin are shown as a function of 2C4H8 (1-butene, gas) C8H16 (1-octene, gas)

temperature: 2C5H10 (1-pentene, gas) 

C10H20 (1-decene, gas)

1-alkene (gas)
H2 (gas)

n-paraffin (gas)


2CnH2n (normal 1-alkene, gas) 
C2nH4n

(normal 1-alkene, gas); n5

The curves show the variation of the value of
log10 K as the number of carbon atoms in the molecule
increase: the values calculated for propylene, 1-butene
and superior 1-alkenes all fall within the width of the
thickest curve.
The lowest curve refers to 1-pentene and to superior
1-alkenes. In Fig. 6, the values of log10 K of the following
alkylation reactions are shown as a function of temperature:
ethylene (gas)
isobutane (gas)  


2,3-dimethylbutane (gas)

temperature (C) propylene (gas)
isobutane (gas)  

73 127 327 527 727 927 1,127 1,327 

2,3-dimethylpentane (gas)

20
isobutene (gas)
isobutane (gas) 

m 
2,2,4-trimethylpentane (gas)

l
2-methyl-2-butene (gas)
isobutane (gas) 
G0f / T.n (cal/mol.K)

i 
2,2,5-trimethylhexane (gas).

h
15 g
f Acetylenic hydrocarbons
e
d Fig. 7 shows the thermodynamic stability of 1-alkynes in
c the gaseous state as a function of temperature. In Figs. 8 A, B,
C and D, the values of log10 K of the formation reactions of
b
10
the C2, C3, C4 and C5 hydrocarbons in their standard state
a starting from the elements are shown in the diagram as a
function of temperature. These reactions for the paraffin,
olefin, and acetylenic series, respectively are:
nC(solid, graphite)
(n
1)H2 (gas) 
5 CnH2n
2 (gas, n-paraffin)
200 400 600 800 1,000 1,200 1,400 1,600
nC(solid, graphite)
nH2 (gas) 
temperature (K)
CnH2n (gas, n-alkene)
Fig. 9. Thermodynamic stability of n-alkylbenzenes in the
nC(solid, graphite)
(n-1)H2 (gas) 
gaseous state as a function of temperature: a. benzene; CnH2n2 (gas, n-alkyne)
b. toluene; c. ethylbenzene; d. n-propylbenzene; e. n-butylbenzene; The differences in the values of the ordinates for each
f. n-amylbenzene; g. n-hexylbenzene; h. n-heptylbenzene; couple of curves give the value of the equilibrium constant
i. n-octylbenzene; l. n-tetradecyl benzene; m. n-eicosylbenzene of the corresponding hydrogenation or dehydrogenation
(Taylor et al., 1946). reaction.

86 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

temperature (C) temperature (C) temperature (C)

73 127 327 527 727 927 1,127 1,327 73 227 527 827 1,127 73 227 527 827 1,127
15 25 100
C6H6
1-CnH2n n-CnH2n
2 
n-CnH2n6
4H2

n-CnH2n
1C6H5

20

90

15 80
10
10 n6 70

5 n6 60
log K

5 0 50
n3
5 40

10 30 a
0
n2 15 20

20 10 b
n3
5 25 0
200 400 600 800 1.000 1,200 1,400 1,600 200 500 800 1,100 1,400 200 500 800 1,100 1,400
temperature (K) temperature (K) temperature (K)

A B C
Fig. 10. Logarithm of the equilibrium constant for: A. some alkylation reactions of benzene with 1-alkenes to give 1-alkylbenzenes in
the gaseous state; B. some cyclization reactions of n-paraffins to n-alkylbenzenes in the gaseous state; C. some trimerization reactions
of alkynes into alkylbenzenes in the gaseous state. (a. acetylene benzene; b. methylacetilene 1,3,5-trimethylbenzene)

(Taylor et al., 1946).

temperature (C) temperature (C)

0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200
25 10

n-Cm
5H2m
12 
n-CmH2m
1C5H9
H2

e d
f
20 5

m0
c b a
G0f / T.n (cal/mol.K)

15
0
log K

m0

10
5

10

0
200 400 600 800 1,000 1,200 1,400 1,600
temperature (K) 15
200 400 600 800 1,000 1,200 1,400 1,600
Fig. 11. Thermodynamic stability of n-alkylcyclopentenes in the temperature (K)
gaseous state as a function of temperature:
a. methylcyclopentane; b. cyclopentane; c. ethylcyclopentane; Fig. 12. Logarithm of the equilibrium constant
d. butylcyclopentane; e. octylcyclopentane; for the cyclization reaction of n-paraffins
f. hexadecylcyclopentane into n-alkylcyclopentanes in the gaseous state
(Kilpatrick et al., 1947). (Kilpatrick et al., 1947).

VOLUME V / INSTRUMENTS 87
PHYSICAL AND CHEMICAL EQUILIBRIA

temperature (C) temperature (C)

0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200
25 15

n-CmH2m
1C6H5
3H2
n-Cm
1H2m
3C5H9

1-Cm
5H2m
10
n-CmH2m
1C5H9

20

15 10

10 m0

5 5 m0
m1

log K
log K

5 0
m2

10 m0

15 m2 5

20

25 10
200 400 600 800 1,000 1,200 1,400 1,600 200 400 600 800 1,000 1,200 1,400 1,600
temperature (K) temperature (K)

Fig. 13. Logarithm of the equilibrium constant Fig. 14. Logarithm of the equilibrium constant
for the hydrogenation reaction of n-alkylbenzenes for the cyclization reaction of 1-alkenes
into n-alkylcyclopentanes in the gaseous state into n-alkylcyclopentanes in the gaseous state
(Kilpatrick et al., 1947). (Kilpatrick et al., 1947).

Alkylbenzenic hydrocarbons Alkylcyclopentane hydrocarbons

Fig. 9 shows the thermodynamic stability of normal-alkyl
benzenes in the gaseous state by displaying the value of
(1n)(Gf0T) in cal/molK on the y axis. In Figs. 10 A, B and
C, the values of log10 K are shown as a function of
temperature for some alkylation, cyclization and
trimerization reactions. In particular, the following reactions
are taken into consideration:
benzene (gas)
ethylene (gas)  ethylbenzene (gas)
Fig. 11 shows the thermodynamic stability of
normal-alkylcyclopentanes in the gaseous state as a function
of temperature by showing the values of (1n)(Gf0T) in
cal/molK on the y axis. Fig. 12 shows a diagram of log10 K as
a function of temperature for the following reactions of
cyclization of normal paraffins into n-alkylcyclopentanes in
the gaseous phase:

n-pentane (gas)cyclopentane (gas)
hydrogen (gas)

benzene (gas)
propylene (gas)  

n-hexane (gas)methylcyclopentane (gas)

n-propylbenzene (gas)

hydrogen (gas)
benzene (gas)
CnH2n (normal 1-alkene, gas)  

n-heptane (gas)ethylcyclopentane (gas)

n-alkylbenzene (gas); n 3

hydrogen (gas)
n-hexane (gas)  benzene (gas)
hydrogen (gas)

n-paraffin (gas)n-alkylcyclopentane (gas)

n-heptane (gas)  toluene (gas)
hydrogen (gas)



hydrogen (gas); for n-octane and
n-octane (gas) ethylbenzene (gas)
hydrogen (gas)

higher
n-nonane (gas) 
n-propylbenzene (gas)
hydrogen (gas)

The values corresponding to the hydrogenation of

n-paraffin (gas) n-alkylbenzene (gas)



n-hexane, n-heptane, and n-paraffin all fall within the width

hydrogen; for paraffins nonane of the thickest line.
acetylene (gas) benzene (gas)


Fig. 13 shows the diagram of log10 K as a function of
methylacetilene (gas)  temperature for the following hydrogenation reactions of
1,2,5-trimethylbenzene (gas)

n-alkylbenzenes into n-alkylcyclopentanes in the gaseous

In Fig. 10 B, the calculated values for n-heptane and phase:
for higher paraffins fall within the width of the thickest benzene (gas)
hydrogen (gas) 
curve. methylcyclopentane (gas)

88 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

temperature (C) temperature (C)

0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200
25 10

n-Cm
6H2m
14
n-CmH2m
1C6H11
H2

20
5

m1
G0f / T.n (cal/mol.K)

m1
15
0

log K
m0

10
5

f
5 e
d
a
c 10
b

0
200 400 600 800 1,000 1,200 1,400 1,600
temperature (K) 15
200 400 600 800 1,000 1,200 1,400 1,600
Fig. 15. Thermodynamic stability of n-cyclohexanes temperature (K)
in the gaseous state as a function of temperature: a. cyclohexane;
b. methylcyclohexane; c. ethylcyclohexane; d. butylcyclohexane; Fig. 16. Logarithm of the equilibrium constant
e. octylcyclohexane; f. hexadecylcyclohexane for the cyclization reaction of n-paraffins
(Kilpatrick et al., 1947). into n-alkylcyclohexanes in the gaseous state
(Kilpatrick et al., 1947).

toluene (gas)
hydrogen (gas) 



ethylcyclopentane (gas)


cal/molK on the y axis. Fig. 16 shows a diagram of log10 K as
ethylbenzene (gas)
hydrogen (gas) 
a function of temperature for the following reactions of
n-propylcyclopentane (gas)

cyclization of n-paraffins to n-alkylcyclohexanes in the
n-propylbenzene (gas)
hydrogen (gas) 
gaseous phase:
n-butylcyclopentane (gas)


n-hexane (gas) cyclohexane (gas)
hydrogen (gas)

n-alkylbenzene
hydrogen (gas) 

n-heptane (gas) methylcyclohexane (gas)


n-alkylcyclopentane (gas);



hydrogen (gas)
per n-butylbenzene and higher n-alkyl-benzenes
n-octane (gas) 

ethylcyclohexane

(gas)

Fig. 14 shows the diagram of as a function of temperature
hydrogen (gas)
for the following cyclization reactions of 1-alkenes into n-paraffin (gas) 
n-alkylcyclohexane (gas)

n-alkylcyclopentanes in the gaseous phase:
hydrogen (gas) for n-nonane

1-pentene (gas) 
cyclopentane ( gas)

and higher n-paraffins
1-hexene (gas) 
methylcyclopentane (gas)

The values calculated for ethylcyclohexane,

1-heptene (gas) 
ethylcyclopentane (gas)

n-propylcyclohexane and higher n-alkylcyclohexanes fall

1-alkene (gas) 
n-alkylcyclopentane (gas);

within the width of the thickest curve.

for 1-octene and higher 1-alkenes Fig. 17 shows the diagram of log10 K as a function of
The values for the formation of methylcyclopentane, temperature for the following reactions of conversion of
ethylcyclopentane and the superior alkylcyclopentanes all n-alkylcyclohexanes into n-alkylcyclopentanes in the
fall within the width of the thickest curve. gaseous phase:
cyclohexane (gas) 
methylcyclopentane (gas)

Alkylcyclohexane hydrocarbons
methylcyclohexane (gas)  ethylcyclopentane (gas)

Fig. 15 shows the thermodynamic stability of

normal-cyclohexanes in the gaseous state as a function of 
ethylcyclohexane (gas) n-propylcyclopentane (gas)

temperature by showing the values of (1n)(Gf0T) in n-propylcyclohexane (gas) 

n-butylcyclopentane (gas)

VOLUME V / INSTRUMENTS 89
PHYSICAL AND CHEMICAL EQUILIBRIA

temperature (C) temperature (C)

0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200
20 25

n-CmH2m
1C6H11
 n-Cm
1H2m
3C5H9


n-CmH2m
1C6H5
3H2
n-CmH2m
1C6H11

20

10 m0 15
m3 m3
m0
10

m2 m1
0 5 m2
m3
m1

log K
log K

10 5

10

20 15
m3

20

30 25
200 400 600 800 1,000 1,200 1,400 1,600 200 400 600 800 1,000 1,200 1,400 1,600
temperature (K) temperature (K)

Fig. 17. Logarithm of the equilibrium constant Fig. 18. Logarithm of the equilibrium constant
for the reaction of conversion of n-alkylcyclohexanes for the hydrogenation reaction of n-alkylbenzenes
into n-alkylcyclopentanes in the gaseous state into n-alkylcyclohexanes in the gaseous state
(Kilpatrick et al., 1947). (Kilpatrick et al., 1947).

n-alkylcyclohexane (gas) 
n-alkylcyclopentane (gas);


1-octene (gas) 
ethylcyclohexane (gas)

for n-butylcyclohexane and higher 1-alkene (gas) 

n-alkylcyclohexane (gas);

n-alkylcyclohexanes for 1-nonene and higher 1-alkenes

Fig. 18 shows the diagram of log10 K as a function of The values for the formation of ethylcyclohexane,
temperature for the following reactions of hydrogenation of n-propylcyclohexane and superior n-alkylcyclohexanes fall
n-alkylbenzenes to n-alkylcyclohexanes in the gaseous phase: within the width of the thickest curve.
benzene (gas)
hydrogen (gas)  cyclohexane (gas)

Olefinic Hydrocarbons
toluene (gas)
hydrogen (gas)  

 In Figs. 20 A and B, the diagram shows the values of the

methylcyclohexane (gas)

logarithm of the equilibrium constant as a function of

ethylbenzene (gas)
hydrogen (gas)  

temperature. A illustrates the dehydrogenation reactions in the

ethylcyclohexane (gas)

gaseous phase of propylene into propyldiene and each of the

n-propylbenzene (gas)
hydrogen (gas)  

four butenes into 1,3-butadiene. B illustrates the isomerization


n-propylcyclohexane (gas)

reaction, also in the gaseous phase, of propadiene into

n-alkylbenzene (gas)
hydrogen (gas)  

propyne, 1,2-butadiene into 1-butyne, 1,2-pentadiene into 1-

n-alkylcyclohexane (gas);


pentyne, 1,3-butadiene into 2-butyne, cis-1,3-pentadiene into
for n-butylbenzene and higher n-alkylbenzenes 2-pentyne and trans-1,3-pentadiene into 2-pentyne.
The upper curve in Fig. 18 is for benzene hydrogenation,
while the lower curve is for n-pentylbenzene and higher Styrene and methylstyrenes
hydrocarbons hydrogenation; curves for toluene, ethylbenzene Fig. 21 shows the values of log10 K as a function of
and n-propylbenzene fall, in this order, between the two. temperature for dehydrogenation reactions in the gaseous
Fig. 19 shows the diagram of log10 K as a function of phase of ethylbenzene into styrene, isopropylbenzene into
temperature for the following reactions of cyclization a-methylstyrene, isopropylbenzene into cis-b-methylstyrene,
of 1-alkenes into n-alckylcyclohexanes in the isopropylbenzene into trans-b-methylstyrene,
gaseous phase: 1-methyl-2-ethylbenzene to o-methylstyrene,
1-hexene (gas) 
cyclohexane (gas)


1-methyl-3-ethylbenzene to m-methylstyrene and
1-eptene (gas) 
methylcyclopentane (gas)


1-methyl-4-ethylbenzene into p-methylstyrene.

90 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

temperature (C) 2.4.7 Equations of state

0 200 400 600 800 1,000 1,200
15 and correlated properties
1-Cm
6H2m
12
n-CmH2m
1C6H11


API Research Project started its activity by collecting,
analysing and correlating the data that describe the P-V-T
behaviour and correlated properties of simple hydrocarbons.
10 For a detailed description of the equations of state most
commonly used to describe the behaviour of hydrocarbons,
m1 see Chapter 2.6.
In order to calculate the value of a thermodynamic
function in a generic state, characterized by the values of
5 pressure and temperature, compared to a reference state in
m1 which the pressure is so low that it corresponds to an ideal
behaviour of the gas, it is possible to consider a
log K

transformation divided in two stages

[72] (Pr,Tr) (Pr,T ) (P,T )

0
where the first transformation is isobaric and the second,
m0
isothermal. In order to perform the calculations for the first

Fig. 20. A. Dehydrogenation of monoolefines to diolefines in the

5
gaseous state: a. propylene
propadiene
hydrogen;

b. 1-butene 1,3-butadiene
hydrogen; c. cis-2-butene





1,3-butadiene
hydrogen; d. trans-2-butene





1,3-butadiene
hydrogen; e. isobutene

1,3-butadiene

hydrogen.
10
200 400 600 800 1,000 1,200 1,400 1,600 B. Isomerization of dioolefines aito alkynes in the gaseous state.
temperature (K) a. propadiene propyne; b. 1,2-butadiene


1-butyne;

c. 1,3-butadiene 2-butyne; d. 1,2-pentadiene

1-pentyne;

Fig. 19. Logarithm of the equilibrium constant for the cyclization e. cis-1,3-pentadiene 2-pentyne;

reaction of 1-alkenes into n-alkylcyclohexanes in the gaseous state f. trans-1,3-pentadiene2-pentyne

(Kilpatrick et al., 1947). (Kilpatrick et al., 1949).

temperature (C) temperature (C)

0 200 400 600 800 1,000 1,200 0 200 400 600 800 1,000 1,200
15
2
CnH2n
CnH2n2
H2


CnH2n2
CnH2n2

10 a
1
d
5 0
c b
1
0
c
2
5
b 3
f
log K

log K

10 e
4
e
15 5
d

a 6
20

7
25
8

30
9

35 10
200 400 600 800 1,000 1,200 1,400 1,600 200 400 600 800 1,000 1,200 1,400 1,600
temperature (K) temperature (K)
A B

VOLUME V / INSTRUMENTS 91
PHYSICAL AND CHEMICAL EQUILIBRIA

temperature (C) RT
0 200 400 600 800 1,000 1,200 [76] V  12
B(T)
10
P

In this case, the integration of [75] gives the following

expression:

dB(T)
[77] HPrP B(T) T 121 (P Pr)

5 dT
c,d
where B(T) and its derivative must be calculated at the
b temperature of the fluid. A similar approach is used for entropy:
T C p0 P S

0
a,f,g
e
T
[78] S (T, P)S (Tr ,Pr ) 12 dT 
Tr
12 dP
P T
Pr
One of Maxwells relationships states
log K

S V
d
[79]
 12  12
P T T P
5 c which, replaced in [78], gives:
T C 0 P V
T
p
[80] S (T, P)S (Tr ,Pr ) 12 dT  12 dP
T P
Tr Pr

a,e,f,g As in the previous case, the first integral can be easily

10 evaluated if the heat capacity is expressed by an equation
like [6], whereas for the calculation of the second integral,
an equation of state must be known. By using [76], it is
possible to get:
P
V P

R 211dB(T)
[81]  12 dP  23
dP 
15 T P P dT
200 400 600 800 1,000 1,200 1,400 1,600 Pr Pr
temperature (K) P dB(T)
R ln 1r  121 (P Pr)
P dT
Fig. 21. Dehydrogenation alkylbenzenes into styrenes in the
gaseous state: a. ethylbenzene
styrene
hydrogen;

b. isopropylbenzene a-methylstyrene
hydrogen;


References
c. isopropylbenzene cis-b-methylstyrene
hydrogen;

d. isopropylbenzene trans-b-methylstyrene
hydrogen;


Kilpatrick J.E. et al. (1947) Heats, equilibrium constants, and free
e. 1-methyl-2-ethylbenzene o-methylstyrene
hydrogen;


energies of formation of the alkylcyclopentanes and
f. 1-methyl-3-ethylbenzene m-methylstirene
hydrogen;


alkylcyclohexanes, Journal of Research of the National Bureau
g. 1-methyl-4-ethylbenzene p-methylstyrene
hydrogen


of Standards, 39, 523-543.
(Kilpatrick et al., 1949). Kilpatrick J.E. et al. (1949) Heats, equilibrium constants, and free
energies of formation of the C3 to C5 diolefins, styrene, and the
methylstyrenes, Journal of Research of the National Bureau of
transformation, it is possible to use the heat capacities of the Standards, 42, 225-240.
ideal gas, whereas for the second, it is necessary to have an
Prosen E.J. et al. (1945a) Free energies and equilibria of isomerization
equation of state. By applying this procedure to the enthalpy
of the 18 octanes, Journal of Research of the National Bureau of
equation, it is possible to obtain: Standards, 34, 255-261.
T P
H
12
P
Prosen E.J. et al. (1945b) Heat and free energies of formation of the
[73] H(P,T )H(Pr,T r) Cp0(T )dT
dP
paraffin hydrocarbons in the gaseous state, to 1500K, Journal
Tr Pr T
of Research of the National Bureau of Standards, 34, 403-411.
The following relationship (see Chapter 2.1)
Rossini F.D. et al. (1952) Selected values of chemical thermodynamic
H V
[74] 12
P T
V T 12
T P properties, Washington (D.C.), US Government Printing Office.
Taylor W.J. et al. (1946) Heats, equilibrium constants, and free
replaced into [73] gives energies of formation of the alkylbenzenes, Journal of Research
of the National Bureau of Standards, 37, 95-122.
T P
V
[75]
H(P,T )H(Pr ,Tr ) Cp0(T )dT

Tr
VT 1
Pr
T
2 dP
P
Wagman D.D. et al. (1945a) Heats, free energies, and equilibrium
constants of some reactions involving O2, H2, H2O, C, CO, CO2,
The first integral at the second member can be easily and CH4, Journal of Research of the National Bureau of
calculated if a polynomial expression like [4] is assigned to Standards, 34, 143-161.
the heat capacity, whereas to evaluate the second integral, an Wagman D.D. et al. (1945b) Heats, equilibrium constants, and free
equation of state is necessary. Suppose, for instance, that the energies of formation of the acetylene hydrocarbons through the
system can be described by a virial equation that is stopped pentynes, to 1500K, Journal of Research of the National Bureau
at the second term B(T): of Standards, 35, 467-496.

92 ENCYCLOPAEDIA OF HYDROCARBONS
 THERMODYNAMIC PROPERTIES OF HYDROCARBONS

List of symbols P3 energy of interaction corresponding to the pairs of

bonds CCC
ai activity of component i R universal constant of ideal gases = 8.31 J/Kmol
BCC effective value of C-C bond energy S entropy
BCH effective value of C-H bond energy T temperature
CV heat capacity at constant volume U internal energy
CP heat capacity at constant pressure U(r) potential interatomic energy
D bond energy V volume
E total energy of a system
EXY bond XY energy Greek letters
Hf heat of formation of a compound
G Gibbs free energy
H heat of combustion of a compound
h Plancks constant6.62611034 J s c
HR enthalpy of reaction
H enthalpy
H 0
a energy of atomization of a compound
I moment of inertia
G 0 standard free energy variation in a reaction
Ix, Iy, Iz moment of inertia referred respectively to the x, y
and z axes for a polyatomic molecule G f free energy variation of a compound
Sf0 entropy of formation of a compound
K equilibrium constant of a reaction
molecular energy
kB equilibrium constant for the formation reaction
el electronic molecular energy
Kf Boltzmann constant
rot rotational molecular energy
m mass of the molecule
et translational molecular energy
mA, mB, mass respectively of atom A and B in a diatomic
molecule [kg] vib vibrazional molecular energy
mr reduced mass
n1, n2, n3 quantum number associated respectively with
coordinate x, y, z n frequency of vibration of a molecule
nXY number of XY bonds ni stoichiometric coefficients of a reaction
P pressure number of symmetry
P1 energy of interaction corresponding to the pairs of
bonds HCH Stefano Carr
P2 energy of interaction corresponding to the pairs of MAPEI
bonds HCC Milano, Italy

VOLUME V / INSTRUMENTS 93