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Normal boiling points of pure molecular liquids: contributions of universal

and specific interactions
Vyacheslav F. Nikolaeva; Guzel I. Ismagilovaa
a
A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences,
Kazan, Russia
Online publication date: 13 June 2011

To cite this Article Nikolaev, Vyacheslav F. and Ismagilova, Guzel I.(2011) 'Normal boiling points of pure molecular

liquids: contributions of universal and specific interactions', Physics and Chemistry of Liquids, 49: 4, 470 481
To link to this Article: DOI: 10.1080/00319101003646561
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Physics and Chemistry of Liquids

Vol. 49, No. 4, JulyAugust 2011, 470481

Normal boiling points of pure molecular liquids:

contributions of universal and specific interactions
Vyacheslav F. Nikolaev* and Guzel I. Ismagilova
A.E. Arbuzov Institute of Organic and Physical Chemistry of the
Russian Academy of Sciences, Kazan, Russia

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(Received 9 November 2009; final version received 23 January 2010)

A new approach has been proposed for the analysis of normal boiling
points of pure substances that differs from the conventional additive-group
approach in using the descriptors of dispersion and electrostatic
intermolecular interactions. Dispersion interaction descriptors are calculated using the molar refraction and the molar volume of a substance, and
the calculation of electrostatic descriptor is based on the dipole moment
and the molar volume of the substance. Normal boiling points of the
organic substances of different classes have been analysed, and contributions of dispersion, electrostatic and specific interactions have been
assessed. The contribution of electrostatic intermolecular interactions
has been proved to be in the interval, the lower boundary of which has
been defined by electrostatic descriptor calculated using the square of the
molecular dipole moment and the upper one has been defined by
electrostatic descriptor calculated using the sum of squares of dipole
moments of polar bonds of the molecule.
Keywords: pure liquid; dipole moment; molar refraction; molar volume;
dispersion interaction; electrostatic interaction; specific interaction

1. Introduction
Normal boiling point is one of the most important identifying parameters of a pure
substance. This parameter is often used as a basic value for calculating the critical
temperature needed to predict the substance properties using the principle of
corresponding states. The additive-group methods for the normal boiling point
estimation, which mainly associate the boiling point with the molecular structure,
and not with the character of interaction of mutual affinity molecules, are still widely
spread [15]. These methods do not allow one to assess the contributions of different
types of the universal and specific interactions to the normal boiling point. So far
the problems concerning the boiling points of molecular liquids and the nature
of electrostatic interaction in liquids have been a point of discussion in the learned
society [6].
The main components of the intermolecular interactions include dispersion
(London), orientation (dipoledipole, dipolequadrupole), induction (dipoleinduced dipole, quadrupole-induced dipole) and specific interactions. For describing
*Corresponding author. Email: nikolaev_vf@iopc.knc.ru
ISSN 00319104 print/ISSN 10290451 online
2011 Taylor & Francis
DOI: 10.1080/00319101003646561
http://www.informaworld.com

Physics and Chemistry of Liquids

471

the main contributions of the universal interactions in the proposed model we used
data on dipole moments, molar refractions and molar volumes of the substances.
In the absence of the appropriate experimental data they may be calculated from
the molecular structure and the known scalar (for molar refraction [7] and molar
volume [8,9]) and vector (for dipole moment [10]) additive schemes.

2. Database

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The operability of the proposed model has been examined using normal boiling
point analysis of the following classes of organic substances: n-alkanes, n-alcohols,
n-carboxylic acids (Section 4.1), polar and non-polar derivatives of aromatic
hydrocarbons of benzene and naphthalene (Section 4.2) series, derivatives of cyclic
and aliphatic hydrocarbons (halogen alkanes, nitriles, ketones, nitroalkanes)
(Section 4.3). In this article, the literature data for boiling points, density, refractive
index and dipole moments have been used [1113].

3. Non-continuum model for describing the normal boiling point of

pure molecular liquids
In an earlier work [14] we have proposed a non-continuum model for predicting
molar physicochemical properties of pure liquids and for assessing the contributions
of different types of intermolecular interactions. The molar physicochemical
properties of the liquid F (molar enthalpy of evaporation, boiling point, molar
surface tension [15], vapour pressure logarithm, etc.) may be represented as a sum
of several contributions:
For substances with universal interactions
F FHHM FELST ,

and for substances with specific interactions

F FHHM FSP ,

where FHHM is a physicochemical property of a hypothetical homomorph of a

substance (dispersion contribution), that is the property of the same substance,
but with excluded electrostatic and specific interactions between their molecules;
FELST is the electrostatic contribution, which includes the contribution of orientation
(dipoledipole) interactions and the interactions of dipole-induced dipole; FSP is the
specific contribution due to the formation of hydrogen bonds between molecules.
We have proposed the following relation to describe the properties of molecular
liquids having only universal intermolecular interactions:
F FHHM FELST A B 

MR2
2
C ,
V
V

3
2

where F is the molar physicochemical property of a pure liquid, FHHM A B  MR

V
is the molar physicochemical property of a hypothetical homomorph of substance,
2
FELST C  V is the electrostatic contribution to the molar physicochemical
property (the orientation contribution together with dipole-induced
dipole interacn2 1 M
tion contribution),  is the dipole moment, MR n

2 2
d is the molar

472

V.F. Nikolaev and G.I. Ismagilova

LorentzLorenz refraction (n is the refractive index at 293.15 K for the D-line Na),
d is the density at 293.15 K, M is the molecular weight, A, B, C represent coefficients
derived from statistic data processing for substances having no specific interacting
groups, COOH, OH, CONH2, NH2, etc. For the specific interacting substances
the electrostatic contribution FELST has not been singled out separately, because
at the formation of hydrogen bonding a molecule in a liquid loses its individuality
and the dipole moment, determined in the inert solvent, practically does not reflect
the real behaviour of a molecule among others.

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3.1. Descriptors of the universal intermolecular interactions for pure liquids

3.1.1. The descriptor of electrostatic interactions
The previous analysis of evaporation enthalpies of the homologous series of polar
primary mono-substituted normal alkanes has demonstrated that besides dispersive
contribution they include a contribution proportional to the square of the dipole
moment [16]. The square of the dipole moment may be attributed to the presence
in pure liquids of two types of electrostatic intermolecular interactions namely:
dipole-induced dipole interaction and non-rotating dipoledipole interaction. In [16]
this contribution has been identified as the energy contribution of dipole-induced
dipole interactions, which is proportional to the square of the dipole moment
according to the relation: E 21 2 /2r6, where 1 is the dipole moment of molecule 1,
2 is the average polarisability of molecule 2, r is the distance between the centres
of molecules [17]. On the other hand, the proportionality of electrostatic
contributions to physicochemical properties of the pure substances to the square
of dipole moment follows from the analysis of the experiment on the magnetic
birefringence (the CottonMouton effect). This conclusion has been made on the
basis of analysis [18,19] of the solvent effect on the molar CottonMouton constants
of nitrobenzene (NB) mCNB in the process of their determination of a series of
aliphatic and aromatic solvents with different polarity and anisotropic polarisability.
The explanation has been given on the basis of the relation that describes the dipole
dipole interaction energy of two non-rotating dipoles. There has been obtained a
linear correlation (4), which confirmed the short-range order of orientational
interactions of NB with the molecules of solvent S, and a permissibility of using the
dipole approximation in describing solvent effects:
m CNB S m C0 A 

S Db S
,
3NBS

where (mCNB)S is the molar CottonMouton constant of NB in solvent S, mC0 is the

constant, equal to the value of the molar CottonMouton constant of NB in the gas
phase, S is the dipole moment, (Db)S is the polarisability anisotropy of solvent
molecule S relative to the direction of the dipole moment S, NBS is the average
distance between the molecule of NB and the solvent molecules of the first solvate
layer, calculated on the basis of the molar volumes of NB and solvent S. It is
remarkable that the molar CottonMouton constant of pure NB submits to the same
dependence. It has been shown that determinative contributions to (mCNB)S are the
orientational dipoledipole NBS and quadrupoledipole QNBS interactions
between NB and the molecules of solvent (S). The presence of solvent polarisability

Physics and Chemistry of Liquids

473

anisotropy in the relation (4) is due to the fact that only solvent effect from the
participation of anisotropic molecules S is visible in the magnetic birefringence.
The established correlation (4) was the second reason for justifying the need to use,
in the non-continuous model, the square of the dipole moment as a descriptor
of electrostatic interactions in the analysis of properties of pure liquids, with the
only difference that, in accordance with relation (5) for the energy of interaction
of two fixed dipoles requires the account of the distance between the centres of
molecules [17,20]:

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E 1  2 3 cos 1 cos 2  cos 12 =r3 ,

where 1 and 2 are the dipole moments of interacting molecules, r is the distance
between dipoles, 1 and 2 are the angles defining the orientation of dipoles in the
polar coordinate system, 12 is the angle between the directions of dipoles 1 and 2.
In the case of analysis of electrostatic contributions to the physicochemical
properties of the pure liquids, when 1 2, the proportionality E  2 =r3 should
be observed. Taking into account the proportionality of the cubed average distance
r3 between directly contacting molecules of pure liquid to its molar volume V, the
descriptor of electrostatic interactions takes the form 2 =V, where V is the molar
volume of the substance, calculated from its molar mass M and density d
(at 293.15 K). Thus, if the orientational dipoledipole interactions are considered
neither as the rotating dipole interactions as described by the Keezom relation [17],
nor as the interactions of one dipole with the continuum medium having dielectric
permeability " [21,22], but as the interactions of non-rotating dipoles of directly
contacting molecules, then in the molar physicochemical properties of pure liquids
a contribution which is proportional to 2/V should be present. This gives the
possibility for description of the contribution of induction and orientation
interactions by means of a single descriptor 2 =V. The use of electrostatic descriptor
2
V is equivalent to the recognition of the quasicrystalline mechanism of dipoledipole
interactions between immediately contacting polar molecules in a liquid. One of the
first ideas of quasicrystallinity of liquids was stated by Debye [23]. It has been
demonstrated in [24] on the basis of Monte Carlo simulations of two-dimensional
structure of dipolar liquid mixtures that the local quasicrystalline order in the
disordered equilibrium states can be strong.
The value of an electrostatic descriptor for non-associated liquids can be
indirectly calculated from the Jatkar Equation (6) [25] using data on the static
permeability " and a refractive index n (e.g. 293.15 K and D-line Na).
"  n2  V 4N0

2
,
kT

2
kT

"  n2  "  n2 :
4N0
V

6
7

3.1.2. The dispersion interaction descriptor

The mathematical form of the empirical dispersion descriptor MR2 =V offered by
us in [26] is consistent with the known correlations of the dispersion contribution
to the different physicochemical properties of a solute A with volume polarisability

474

V.F. Nikolaev and G.I. Ismagilova

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n2  1=n2 2Si of the variable solvents Si [27], and also with the linear
correlation of solvation enthalpies of the polar and non-polar solutes Ai in a constant
solvent S from the molecular refraction MRAi of the variable solute [28]. With the
aim of simplifying the use of the model, the ionisation potential J, as present in
the London equation for the dispersion interactions of two molecules [17], has been
excluded from the dispersion interaction descriptor, although in some cases the
inclusion of this parameter turns out to be quite necessary. The analysis of the
properties of pure substances can be considered as an analysis with simultaneous
change of the solute and the solvent (Ai Si). Thus the dispersion interaction
descriptor for pure liquid takes the following form: MR  n2  1=n2 2
n2  1=n2 22  M=d MR2  d=M MR2 =V [16].
The ratio of the dispersion coefficient to the electrostatic coefficient B/C in the
Equation (3) when analysing different molar physicochemical properties of a single
group of substances, whose molecules participate only in universal (Van der Waals)
interactions, has remained practically constant.

4. Results and discussion

4.1. Normal boiling points of n-alkanes, primary n-alcohols and n-carboxylic acids
In our research, owing to the wide range of substances to be analysed, and thus,
extending the interval of normal boiling points Tb (K), the new exponent of the
dispersion interaction descriptor has been empirically specified but the free term
(intercept) A, previously presented in the model (3), has been excluded. The exclusion
of the free term of the model actually means that in the absence of the forces
of universal interaction between the molecules, when MR ! 0 and  ! 0, the
boiling point Tb in an extreme case should approach the temperature of absolute zero
(0K). Thus, the modified variant of the non-continuous model for normal boiling
point takes the following form (8):

n
MR2
2
8
C  ,
Tb K B 
V
V
where B, C and n are the parameters of the model obtained from the joint statistical
2
2
data processing Tb K, MR
V , V for a series of substances without specific interacting
groups.
In order to confirm the efficiency of the dispersion descriptor, data on the normal
boiling points of the normal hydrocarbons (Figure 1) has been analysed. Figure 1
also shows points for primary n-alcohols and n-carboxylic acids, which are lying on
2
their own smooth lines, but above the line of n-alkanes. In the limit when MR
V !1
all three lines merge into one. It also follows from Figure 1 that the contributions
of hydroxyl and carboxyl groups to the boiling point are not constant and decrease
with the alkyl chain lengthening, which is only natural, the direct contacts between
two identical functional groups, as well as the formation of hydrogen bonds
becoming spatially less probable.
The dependence of Tb for n-alkanes is described by relation (9):
Tb 130:98  MR2 =V0:436934

r 0:9996, s 2:22:

475

Physics and Chemistry of Liquids

800
700
600
500

Tb, K

400
300
200

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100
0

10

15

20

25

30

35

40

45

50

55

MR 2/V

Figure 1. Normal boiling points of n-alkanes, primary n-alcohols and n-carboxylic acids
from the dispersion descriptor (notations h: n-alkanes C4C30, : 1-alcohols C1C20,
D: 1-carboxylic acid, x: water).

Table 1. Normal boiling point THHM of hypothetical homomorphs and specific contributions
DTSP for 1-alcohols and n-carboxylic acids.

Substance
Water
Methanol
Ethanol
1-Propanol
1-Butanol
1-Pentanol
1-Hexanol
1-Heptanol
1-Octanol
1-Nonanol
1-Dekanol
1-Undekanol

THHM (K)
(dispersion)

DRSP (K)

Substance

THHM (K)
(dispersion)

DRSP (K)

130
183
234
276
312
344
373
399
422
445
467
486

243
155
118
95
79
67
58
50
45
41
35
30

1-Dodekanol
1-Eykozanol
Formic acid
Acetic acid
Propanoic acid
Butyric acid
Pentanoic acid
Hexanoic acid
Heptanoic acid
Octanoic acid
Dekanoic acid
Undekanoic acid

510
635
198
238
277
311
343
371
398
422
462
478

21
7
176
153
137
125
116
107
98
90
81
75

As the ionisation potentials of n-alkanes, n-alcohols and n-carboxylic acids

are close (10.80 eV (butane), 10.19 eV (n-decane), 10.95 eV (methanol), 10.30 eV
(n-butanol), 10.66 eV (acetic acid), 10.22 eV (n-butyric acid) [29]), then using the
dependence (9), it is possible to estimate the boiling point THHM of hypothetical
homomorphs of alcohols and carboxylic acids (Table 1). In Table 1 the contributions caused by specific interactions DRSP are also given. Considering, as a first
approximation, that the probability of contact of two functional groups is

476

V.F. Nikolaev and G.I. Ismagilova

600
1-Naphtylcarbonitrile
1-Naphthylamine
Diiodobenzenes

550

Dibromobenzenes

500
Tb,exp,K

Chlorobromobenzenes

450

400

350
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Nitrobenzene
Benzonitrile
Phenol
Iodobenzene
Diethylbenzenes
Bromofluorobenzenes
Dichlorobenzenes
Bromobenzene
Xylenes
Chlorobenzene
Toluene
Trifluoromethylbenzene
Difluorobenzenes
Fluorobenzene
Benzene
Aniline

350

400

450

500

550

600

Tb,calc,K

Figure 2. Comparison of experimental boiling points Tb,exp of aromatic hydrocarbons

(Table 2) with one polar substituent (g) and the boiling points Tb,calc, calculated (straight line)
with the use of model (10). Note: The points outside the straight line correspond to ortho, meta- O and para- h substituted dihalogenbenzenes and substances with specific (f)
interactions (aniline, phenol, 1-naphthylamine).

proportional to the product of the relative parts of the areas occupied with these
groups on the molecular surfaces for calculating DRSP it is possible to use the
approximate equation DRSP /(V )4/3. Indeed, for 1-alcohols (with the inclusion
of water) the relation DRSP 50 287.2/(V 36.3032)4/3(r0.9977, s3.1) and for
carboxylic acids the relation DRSP 194 946.0/(V 155.204)4/3(r0.9991, s1.05) have
been obtained.
It is noteworthy that the boiling point of the hypothetical homomorph of water
(with excluded electrostatic and specific interactions) should be 130 K, that is,
lower by 243 than its experimental value.
4.2. Boiling points of aromatic hydrocarbons and their derivatives
Statistical data processing for a class of aromatic hydrocarbons owing to the
substantial anisometry of benzene- and naphtalene fragments, as well as the lower
ionisation potential J of molecules (benzene 9.21 eV, toluene 9.20 eV, p-chlorotoluene
7.95 eV, p-dicholorobenzene 8.95 eV, iodobenzene 9.10 eV [29]), as compared to the
class of aliphatic hydrocarbons and cycloalkanes, was performed separately.
The points departing from the dependence (Figure 2) are points corresponding
to the substances with specific interactions (aniline, phenol, 1-naphthylamine).
For benzene, its mono-substituted polar derivatives and 1-naphthalencarbnitrile
the following dependence has been obtained:
Tb 142:596  MR2 =V0:445628 487:445  2 =Vr0:998, s3:46:

10

477

Physics and Chemistry of Liquids

Table 2. Boiling points of hypothetical homomorphs THHM of mono-substituted derivatives

of benzene and naphthalene, and the contribution DTELST of electrostatic interactions.

Substance

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Benzene
Fluorobenzene
Trifluoromethylbenzene
Toluene
Chlorobenzene
Bromobenzene
Iodobenzene
Benzonitrile
Nitrobenzene
1-Naphthalencarbnitrile

 (D)

MR2/V

2/V

Tb (K)

THHM (K)
(dispersion)

DTELST (K)
(dipole)

0
1.47
2.56
0.34
1.60
1.52
1.38
3.90
3.98
4.15

7.715
7.273
7.695
9.094
9.553
10.98
13.76
9.732
10.57
17.44

0
0.023
0.0533
0.0011
0.0252
0.022
0.0171
0.1483
0.1549
0.1249

353.3
358.3
375.5
383.8
404.8
429.2
461.6
464.3
484.2
572.2

354
345
354
381.4
390
415
459
393
408
510

0
11
26.0
0.5
12
11
8
72
76
61

Table 3. Boiling points of hypothetical homomorphs THHM of mono-substituted aromatic

hydrocarbons and contributions DTSP of specific interactions.

Substance

MR2/V

Tb (K)

THHM (K)
(dispersion contribution)

DTSP (K)

Aniline
Phenol
1-Naphthylamine

10.27
9.054
17.81

457.3
455
574

403
381
515

55
74
59

Note: DTSP TbTHHM.

In obtaining correlation (10) data for substances listed in Table 2 have been used.
In Figure 2 it is seen that benzene and its mono-substituted derivatives of different
polarity are lying on the same line. Two groups of substances have been excluded
in obtaining relation (10). The first group substances with specific interactions:
aniline, phenol, 1-naphthylamine, the second group substances with substantial
quadrupole moment, which is not taken into account in the model (8), namely, para-,
meta- and ortho-di-substituted benzenes.
Using correlation (10), boiling points of hypothetical homomorphs (dispersion
contribution) and specific interaction contributions for aniline, phenol and
1-naphthylamine have been calculated (Table 3).
The deviation of the points corresponding to dihalogen-substituted benzenes
(difluorobenzenes, dichlorobenzenes, dibromobenzenes, chlorobromobenzenes,
fluorobromobenzenes) from the straight line (Figure 2) increases in the
sequence of o-isomer, m-isomer and p-isomer. This is consistent with the increase
in quadrupole moment in this series. Botcher was the first to pay attention to the
necessity of taking into account the quadrupole contributions to the boiling
points [22].
It is seen from Table 4 that the total electrostatic contribution for dihalogensubstituted benzenes, as a rule, decreases in the sequence of DTELST (ortho) 4
DTELST (para) 4 DTELST (meta). For dialkyl-substituted benzenes such regularities
have not been observed.

2.38
1.58
0
2.33
1.48
0
2.13
1.51
0
2.27
1.14
0
2.03
1.46
0
1.7
1.1
0
0.58
0.37
0
0.62
0.4
0.24

1,2-Difluorobenzene
1,3- Difluorobenzene
1,4- Difluorobenzene
1,2-Dichlorobenzene
1,3- Dichlorobenzene
1,4- Dichlorobenzene
1,2-Chlorobromobenzene
1,3-Chlorobromobenzene
1,4-Chlorobromobenzene
1,2-Bromofluorobenzene
1,3-Bromofluorobenzene
1,4-Bromofluorobenzene
1,2-Dibromobenzene
1,3-Dibromobenzene
1,4-Dibromobenzene
1,2-Diiodobenzene
1,3-Diiodobenzene
1,4-Diiodobenzene
1,2-Xylene
1,3-Xylene
1,4-Xylene
1,2-Diethylbenzene
1,3-Diethylbenzene
1,4-Diethylbenzene

6.79
6.778
6.854
11.49
11.45
11.12
12.93
12.91
12.9
9.853
9.711
9.62
14.5
14.46
14.45
20.17
20.74
20.17
10.63
10.53
10.52
13.35
13.23
13.23

MR2/V
0.0576
0.0253
0
0.0482
0.0192
0
0.039
0.0194
0
0.0502
0.0127
0
0.0347
0.0176
0
0.0223
0.0091
0
0.0028
0.0011
0
0.0025
0.001
0.0004

2/V
367.2
356.2
361.7
453.2
446.2
447.5
477.2
469
469.2
429.7
423.2
426.7
498.2
491.5
493.6
559.2
558.2
558.2
417.6
412.3
411.5
456.6
454.3
456.9

Tb (K)

Note: DTELST (quadrupole) Tb  142.596(MR2/V)0.445628  487.445 2/V.

 (D)

Substance
335
335
336
423
423
417
446
446
446
395
393
391
469
469
469
544
551
544
409
407
407
453
451
451

THHM
(K)
28
12
0
23
9
0
19
9
0
24
6
0
17
9
0
11
4
0
1
0.5
0
1.2
0.5
0.2

DTELST
(K) (dipole)
4
9
25
7
14
30
12
14
23
10
24
36
12
14
25
4
3
14
7
4.6
4.6
2.8
3.0
6.0

DTELST (K)
(quadrupole)

32
21
25
30
23
30
31
23
23
34
30
36
29
23
25
15
7
14
8
5.1
4.6
4.0
3.5
6.2

DTELST (K)
(summary)

Table 4. Boiling points THHM of hypothetical homomorph of positional isomers of di-substituted benzenes and contributions DTELST of electrostatic
dipole and quadrupole interactions.

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478
V.F. Nikolaev and G.I. Ismagilova

479

Physics and Chemistry of Liquids

800
700
600

Tb,exp,K

500
400
300
200
100

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100

200

300

400
Tb,calc,K

500

600

700

800

Figure 3. Conformance of experimental and calculated values using Equation (11) for the
boiling points of organic substances of aliphatic and cyclic series and their derivatives with
single polar bond or polar group: n-alkanes C4C30, hydrocyanic acid, nitriles C2C3, Q6, C11,
fluoroalkanes C1C6, chloroalkanes C1C10, bromoalkanes C1C12, iodoalkanes C1C10,
cycloalkanes C3C6 and their derivatives, nitroalkanes C6, C11, ketones C3C8.

4.3. Normal boiling points of aliphatic and cyclic hydrocarbon derivatives

These classes of organic substances turned out to be quite similar when subjected
to the joint analysis of boiling points using universal interaction descriptors discussed
in Section 3.1. For experiment treatment on model (8) the data for non-polar
alkanes, alkenes, alkynes, cycloalkanes, cycloalkenes, as well as for their polar
derivatives with one polar group or bond (halogen-substituted derivatives,
nitro-derivatives, nitriles, ketones) was used.
The following equation has been obtained:
Tb 129:726  MR2 =V0:436641 685:02  2 =V

r0:9938, s8:3:

11

One can see that the universal interaction contributions are well-described by the
relation (11). Although the ionisation potential in a dispersion descriptor has been
excluded by us, but as has shown the detailed analysis, deviations of points from
a line for primary monohalogenated alkanes (Figure 3) correlate with ionisation
potentials of first members of the homologous series corresponding to them
(I(fluoromethane) 13.05 eV, I(chloromethane) 11.30 eV, I(bromomethane) 10.54 eV,
I(iodomethane) 9.54 eV [29]). The electrostatic contributions calculated as
DRELST 685.022/V for a number of polar substances can attain substantial
values (nitrocyclohexane 74 , cyclohexanparbnitrile 75 , cyclohexanone 58 ,
cycloheptanone 54 ). The contributions to a boiling point of the specific
interactions calculated as DRSP RbTHHM, are equal for cyclohexanecarboxylic
acid 102 , cyclohexanol 37 , cycloheptanol 32 , cyclohexylamine 11 .

480

V.F. Nikolaev and G.I. Ismagilova

The dipole approach accepted in model (8) can be used as the description of
electrostatic contributions to boiling points of the substances having a unique
localised polar group or bond in a molecule. If a molecule includes several polar
groups (bonds) located in different parts of the molecule, the molecular dipole
moment ceases to be an effective parameter for describing the interactions of directly
contacting molecules and contributions of separate bond dipoles should be taken
into account. Thus, the electrostatic contribution can be in the interval, the lower
boundary of which is calculated based on the square of molecular dipole moment
and the upper boundary on the sum of the squares of dipoles of the most polar bonds
or groups.

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5. Conclusions
This normal boiling point correlation of non-electrolytes with parameters of polarity
and polarisability of molecules in conjunction with the observed deviations is a
conclusive evidence of short-range electrostatic (orientation and polarisation)
interactions in liquids.
The given universal interaction descriptors MR2 =V and 2 =V can be used to
describe the other molar physicochemical properties of pure liquids. In analysing
physicochemical properties determined at the room temperature, one can use the
relation (3), in which free term A is included, and the exponent of dispersion
descriptor is equal or close to 1.
An important conclusion from the mathematical form of electrostatic descriptor
is that the contribution of polar groups into normal boiling points, as well as the
contributions of specific interactions are not additive and depend on the molar
volume of the molecule. These facts should be taken into account when improving
additive-group methods of estimation of normal boiling points and other
physicochemical properties of pure liquids.

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