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Journal of Molecular Liquids 204 (2015) 176183

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Journal of Molecular Liquids


journal homepage: www.elsevier.com/locate/molliq

Hydrophobic hydration from solubilities of aliphatic hydrocarbons


in water
Amitava Bhattacharyya, Sagar Sengupta, Swapan Kumar Bhattacharya
Physical Chemistry Section, Jadavpur University, Kolkata 700032, India

a r t i c l e

i n f o

Article history:
Received 10 December 2014
Received in revised form 14 January 2015
Accepted 16 January 2015
Available online 19 January 2015
Keywords:
Hydrophobic hydration
Transfer Gibbs energies of fractions of
molecules
Additivity of different fractions
3D water structure
CH3CH2, NCH, N Cb, CH_CH2,
C`CH groups

a b s t r a c t
The internal standard transfer Gibbs energy, G0t,int is computed by subtracting corresponding standard transfer
Gibbs energy, G0t of solute hydrocarbons due to cavity and different interactions from the total G0t value as
obtained from the available experimental solubility of them in water (w). For alkanes other possible interaction
effects being negligibly small, G0t,int is a direct measure of hydrophobic hydration. The various G0t, int values of
N CH2 group evaluated from the difference of G0t,int values of two successive members of homologous alkanes, is
found to be highly precise in respect to their average, 3.95 kJ mol1, indicating additive nature of the parameter.
G0t,int values of different fractions are found to follow the order: CH3 N CH2 CH Cb. Aliphatic hydrocarbons possessing the same number of C atom follows the sequence: alkane N alkene N alkyne, according to their
reverse order of polarizability and acidity in water.
2015 Elsevier B.V. All rights reserved.

1. Introduction
The hydrophobic effect is perhaps the single most important
phenomenon in the entropy driven creation of various self-aggregated
systems like micelles, vesicles, bilayer membranes, association of
hydrocarbons (HC) and amphiphiles with proteins, etc. It also stands
for the organization of the constituent molecules of living matter into
complex structural entities such as cell membranes and organelles. In
spite of its inuences in all these systems and its long day's recognition
of having multitudinous effects, the estimation of Gibbs energy of the
involved hydrophobic interaction (HI) and particularly that of the closely related hydrophobic hydration (HbH) are still not unequivocally
made. Moreover, the direct experimental determination of these are
also not directly viable [1,2]. On the other hand it is well known [39]
that hydrophobic hydration or the hydration of the second kind arises
due to the strong attraction or afnity of water molecules for one another. The hydrophobic, amphiphalic or amphiphilic solutes with a polar
sites, not being strongly attracted by water, pushes them closer and
thus easily induce more water molecules around them with the formation of a cage in a way similar to clathrate hydrates. This results in a
signicant increase in Gibbs energy and decrease in entropy [10]. Thus
the phenomenon is signicantly guided by the water-water interaction
associated with the related structural and entropy effect [10]. But the
relative contributions of the involved interactions of different parts of
Corresponding author.
E-mail address: skbhatt7@yahoo.co.in (S.K. Bhattacharya).

http://dx.doi.org/10.1016/j.molliq.2015.01.030
0167-7322/ 2015 Elsevier B.V. All rights reserved.

the molecule, say CH3, CH2, N CH, N Cb, CH_CH2 etc. are still not
clear. Thus if anyone can subtract the transfer Gibbs energy part due
to cavity and all possible interactional effects or at least the major contributory parts of it from the total experimental Gibbs energy of solution, one can get the rest of the entropy-contributed transfer Gibbs
energy effect as designated by G0t,int and thus can understand and elucidate the possible structural change associated with the hydrophobic
effect. With this aim in mind, the phenomenon here chosen is one
that provides plausibly the simplest manifestation of the hydrophobic
effect the meager solubility of hydrocarbons in water. In fact, in
most of the previous studies [1119], as found from the literature,
HbH has been estimated and understood in association with the dispersion interaction, which is somewhat akin to hydrophobic interaction
(HI) and acted as a reversal of HbH. From statistical mechanical consideration, Arieh Ben-Naim [20,21] expressed his doubt regarding the
relative importance of the hydrophobic interaction because such interaction arises not due to unique peculiarities of liquid water but to strong
solventsolvent interaction. In some old studies [15,16,2224] efforts
made to understand HI and HbH from a set of data where effect of
all three different types of involved interactions namely, solutesolute,
solutesolvent and solventsolvent interactions are intermixed. Moreover in many previous studies, HbH were understood without the consideration of the Gibbs energy change associated with the formation
and collapsing of an appropriate cavity in water and hydrocarbon
(HC) liquid respectively i.e., the transfer Gibbs energy (G0t) due to
the so-called cavity effect, G0t, cav. In fact the application of the scaled
particle theory, which was originally devised for calculating the reversible

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

work required for a hypothetical hard sphere solute to form a cavity in a


hypothetical hard sphere liquid, into the domain of real solute and real
uid, has developed latter [18,19]. In some studies [3,25] HbH is obtained
by eliminating all the attractive interactional effects like dipoledipole
(dd), dipole-induced dipole (ind), dispersion (dis) from the experimental
energetics excluding cavity effect. However, this result seems to fail to
point out the special property of hydrophobic solute i.e., HbH, since cavity
effect would be present in all types of solutesolvent interactions, including that of hydrophilic solute. So it is thought that an effort to understand
HI and particularly HbH directly from the experimental values of solubility
of hydrophobic solute in water, without considering the above mentioned
effects, may lead to erroneous conclusions and increase confusion, both of
which still persist in spite of the importance and long day's recognition of
the phenomenon.
Moreover the initial transfer Gibbs energy of CH2 group, which
may produce hydrophobic hydration, is not found to be a unique quantity since it depends on other molecular parts with which it is attached,
in aqueous DMF solvent system as evident from our previous study [26].
This is seemingly because of the different interactions of groups like
CH3, CH2, N CH with different functional groups of the probe molecules such as carboxylate and amino groups of some lower members
of homologous series of -amino acids used in many studies [26]. It
seems that the proper value of hydrophobic hydration could be obtained under the condition where CH2 and other groups do not interact
with the functional groups of the molecules. In this regard pure saturated hydrocarbon can play a signicant role as a probe in understanding
hydrophobic hydration, since it has no functional group. In absence of
literature values of solubility of pure hydrocarbons in DMFwater solvent system, computation of hydrophobic hydration of CH2 group is
executed by using the literature values of meager solubility of hydrocarbon in water [27] in this study.
Thus in the present study, transfer Gibbs energy contributions due to
cavity formation (G0t,cav), dispersion interaction (G0t,dis), dipoledipole interaction (G0t,dd), dipoleinduced dipole interaction (G0t,ind)
have been computed for transfer of one mole of different hydrocarbon
(HC)s from the respective innitely large HC liquid system to an innitely large pure water system. The summation of all such G0t gives
rise theoretical Gibbs energy of transfer which on subtraction from the
total/experimental G0t values, evolves the internal Gibbs energy of
transfer (G0t,int), which in turn provides HbH.
Thus the total or experimental (G0t,expt) and theoretical (G0t,theo)
Gibbs energy of transfer of HC from HC liquid to water (w) are given by
Eqs. (1) and (2):

177

Table 1.1
Molar volume (V 106 m3), diameter ( 1010 m) and volume polarizability (
1030 m3) of different alkanes, alkenes and alkynes.
No. of C atoms

Alkanes

Alkenes

Alkynes

C5
C6
C7
C8
C9
C10
C11

115.2
130.7
146.5
162.6
178.7
194.9
211.2

5.78
6.07
6.34
6.59
6.83
7.05
7.27

10.01
11.85
13.69
15.53
17.37
19.14
22.04

109.5
125.0
140.8
157.0
172.9
189.4
205.7

5.67
5.97
6.24
6.50
6.74
6.98
7.20

9.85
9.88
11.71
15.58
17.12
19.04
20.88

98.7
114.8
131.2
147.7
164.1
180.6
197.0

5.45
5.77
6.08
6.35
6.61
6.85
7.08

9.17
11.00
12.85
14.68
16.52
18.35
20.19

Branch-chain alkanes

2-Methylpentane
3-Methylpentane
2,4-Dimethylpentane
2,2-Dimethylbutane
2,2,4-Trimethylpentane
2,2,5-Trimethylhexane

131.9
129.7
148.9
132.7
165.1
181.3

6.09
6.05
6.37
6.10
6.63
6.86

11.87
11.80
13.72
11.87
15.56
17.41

Thus the difference between the experimental and theoretical


0
0
values of G0t will provide w
HCG t,int which seems to contain G t for
structural (HbH) effect along with that for other possible unaccounted
interactions existing in the system.
In the case of saturated aliphatic hydrocarbons, all possible types of
solutesolute and solutesolvent interactions can be counted by considering the terms expressed in Eq. (2). Thus G0t,int is purely a composite
measure of transfer Gibbs energy associated with the entropy change of
solute and solvent i.e. (HbH) or (G0t,st) as well as that for the solvent
(w)solvent (w) interaction (G0t,ww) on such transfer of HC i.e.,
0

t;int

t;st

t;ww :

Moreover, since the successive members of any homologous series,


always possess a difference of CH2 group constitutively, it would be
interesting to see whether a xed value of G0t,int can be obtained
from the difference of group of G0t,int values of any two successive
members of the same homologous series i.e., to check whether G0t,int
or HbH is an additive property of the different fractions of a molecule.
With this view in mind, we have presented here G0t,int for all the
alkanes alkenes and alkynes possessing C atoms from 5 to 11.
2. Method of calculation

w
HC

t;expt HC G

t;theo HC G

t;int

and
w
HC

t; theo HC

t;cav

HC G

RT ln V HC =V w HC G

t; dd HC

t; dis

t;ind

where sufx t indicates the transfer process from standard state of HC to


that of water, Vi the molar volume of the ith liquid and all other quantities are as usual [1114]. Here all the terms of RHS of Eq. (2) can be the0
oretically calculated and w
HCG t,int can be obtained from Eq. (1). It seems
to be constituted by the transfer Gibbs energy due to the structural or
entropy change of the solvent (HbH) as well as G0t, for the existing interactions in the system which are not computed. One such example is
the solvent (w)solvent (w) interaction, on the said transfer of HC.
0
The total Gibbs energy of transfer w
HCG t in mole fraction scale, can
be had from the experimental solubility data [17] by using the relation

w
HC

t;expt HC

RT ln X:

The transfer Gibbs energy of hydrocarbon (HC) molecule from


HC liquid to an innitely dilute aqueous solution of HC, as represented
0
by w
HCG t (HC), may essentially be thought to consist of two steps:
(1) transfer of HC from HC liquid to vacuum the corresponding transfer Gibbs energy change is vHCG0t(HC) and then (2) transfer of HC from
vacuum to an innitely dilute solution of HC in waterthe correspond0
ing transfer Gibbs energy change is w
v G t (HC).
Thus
w
HC

t;theo HCv

G t HCHC G t HC:

Table 1.2
Dipole moment () and average dipole moment of different alkanes, alkenes and alkynes.
Hydrocarbon

(Debye)

Avg. (Debye)

Alkanes: propane
Alkenes: propene
Butene
Alkynes: pentyne
Hexyne

0.09
0.36
0.34
0.81
0.83

0.09
0.35
0.82

178

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

Table 2.1
Computed standard Gibbs energies of transfer (G0t) of various normal (n) alkanes from vacuum (v) to respective liquid alkane (HC) and water due to cavity (cav), dispersion (dis),
0
HC
0
1
dipoledipole (dd), dipoleinduced dipole (ind) and their summative interactions (w
.
v G t and v G t) in kJ mol
n-Alkanes

w
0
v G t,cav

w
0
v G t,dis

w
0
v G t,ind

w
0
v G t,dd

w
0
v G t

HC
0
v G t,cav

HC
0
v G t,dis

HC
0
v G t

C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24

61.82
65.70
69.49
73.22
76.85
80.37
83.82

53.47
57.36
60.57
63.72
65.56
67.38
72. 7

3.66
3.93
4.15
4.33
4.49
4.62
4.98

0.048
0.043
0.040
0.037
0.034
0.032
0030

4.63
4.36
4.72
5.63
6.75
8.34
6.09

45.89
47.40
48.85
50.21
51.50
52.70
53.83

23.08
24.69
25.82
26.58
27.20
27.48
30.75

22.80
22.72
23.03
23.62
24.30
25.23
23.09

Table 2.2
Theoretical (theo), experimental (expt), and internal (int) G0t of n-alkanes from alkane to water as well as G0t of CH2 and CH3 groups and their average values with standard
deviation () in kJ mol1 assuming the validity of additive rule.
n-Alkanes

0
w
HCG t,theo

w
0
HCG t,expt =

C5H12
C6H14
C7H16
C8H18
C9H20
C10H22
C11H24

18.17
18.36
18.30
18.00
17.55
16.89
17.00

28.30
32.54
35.82
39.95
44.07
48.41
53.19

RTlnX

0
w
HCG t,int

w
0
HCG t

46.47
50.90
54.12
57.95
61.62
65.30
70.19

4.43
3.21
3.83
3.67
3.68
4.89

(CH2)

0
0
HC
Since w
v G t(HC) and v G t(HC) can be calculated following Eq. (2),
0
0
HC
w
v G t,theo(HC) and hence HCG t,int(HC) can be obtained from Eq. (5)
and Eq. (1) respectively. Following Pierotti [18] we have calculated G0t
of cavity and interactional effects. We computed G0t,cav by means of

the following expressions:

t;cav

RT ln RT=V

where
G

h
i
n
o
2
2 2
2
RT ln 1Z fD=1Z g  3X D =1Z  3Y 9X D =21Z

0
c

0
Avg. w
HCG t (CH2) ()

0
w
HCG t

3.95 0.55

17.31
17.55
17.19
17.13
16.99
16.85
17.32

(CH3)

0
Avg. w
HCG t (CH3) ()

17.19 0.21

where G 0t,dis(HC) for both types of liquid, say w and HC, can be
given by
0

t;dis

8=9NA

C dis V sx

10

3
where
sx is the distance at which the attractive and repulsive interactions between the liquid (s) and solute particles (x) are equal.
In case of solutesolvent interaction sx = (s + x) / 2. In case of
solutesolute interactions x and s are same. Thus sx = s = x .
Cdis is approximately calculated after KirkwoodMuller formulation:

Cdis 5:06  10

18

s x Jm

11

7
where Z = NAa3 / 6 V, X = NAa2 / 6 V, Y = NAa / 6 V and V = M / d
where NA = Avogadro's number, M and d are the molar mass and the
density of the liquid (water or liquid HC). For solutesolvent interaction,
a is the diameter of H2O and is taken as 0.276 nm [28]. But for solute
solute interaction a = D = hard sphere diameter of the particular HC
0
is obtained from Table 1.1 w
v G t,cav represents the difference:
0

w G cav HC G cav

w Gc HC Gc RT ln V HC =V w

where s and x are the polarizabilities of the liquid (s) and HC molecule
(x) respectively. As before, in case of solutesolute interactions x and s are
same.
Similarly molar Gibbs energy of HC due to the dipoleinduce dipole
interactions in both HC liquid and water is given by
0

t;ind

4=3NA



3
2
2
1
s s x x V sx

12

8
and the corresponding transfer Gibbs energy by

where subscripts denote that the terms refer to water and hydrocarbon,
respectively. G0t values for different interactional terms are obtained
following Kim et al. by using the following appropriate formulations
as given by Marcus [28]. Consequently
0

t;dis w G t;dis HCHC G t;dis HC

w
HC

t; ind v

t;ind v

HC

t;ind :

13

Molar Gibbs energy of HC due to dipoledipole (dd) interactions


were obtained by use of Keesom orientation expression [29]
0

t;dd

8=9NA s x kT V sx

14

Table 2.3
Transfer Gibbs energies of various branch-chain alkanewater interactions in kJ mol1.
Branch-chain alkanes

w
0
v G t,cav

w
0
v G t,dis

w
0
v G t,ind

w
0
v G t,dd

w
0
v G t

2-Methylpentane
3-Methylpentane
2,4-Dimethylpentane
2,2-Dimethylpentane
2,2,4-Trimethylpentane
2,2,5-Trimethylpentane

65.99
65.45
66.18
70.06
73.80
77.41

57.01
57.47
59.90
56.78
62.56
64.95

3.91
3.94
4.10
3.89
4.29
4.45

0.043
0.044
0.039
0.043
0.036
0.034

5.03
4.00
6.01
5.47
6.91
7.97

Table 2.4
Transfer Gibbs energies of various branch-chain alkanealkane interactions in kJ mol1.
Branch-chain alkanes

HC
0
v G t,cav

HC
0
v G t,dis

HC
0
v G t,ind

HC
0
v G t,dd

HC
0
v G t

2-Methylpentane
3-Methylpentane
2,4-Dimethylpentane
2,2-Dimethylpentane

47.54
47.32
49.07
47.62

24.26
24.89
25.03
23.98

0.20
0.21
0.18
0.20

0.0023
0.0023
0.0017
0.0022

23.07
22.23
23.86
23.43

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183


Table 2.5
Theoretical (theo), experimental (expt) and internal (int) G0t of alkanes in kJ mol1.
0
w
HCG t, theo

Branch-chain alkanes
2-Methylpentane
3-Methylpentane
2,4-Dimethylpentane
2,2-Dimethylpentane
2,2,4-Trimethylpentane
2,2,5-Trimethylhexane

18.04
18.23
17.85
17.96
17.53
17.07

w
0
HCG t, expt

= RTlnX

31.60
31.80
35.01
30.89
36.60
38.75

0
w
HCG t, int

49.65
50.02
52.86
48.85
54.13
55.82

179

Table 3.1
Transfer Gibbs energies of various alkenealkene & alkenewater interactions in kJ mol1.
Alkenes
C5H10
C6H12
C7H14
C8H16
C9H18
C10H20
C11H22

w
v

w
v

w
v

w
v

w
v

HC
v

HC
v

HC
v

G0t,cav

G0t,dis

G0t,ind

G0t,dd

G0t

G0t,cav

G0t,dis

G0t

60.35
64.29
68.16
72.94
75.56
79.17
82.66

54.71
57.99
60.73
65.21
66.35
68.82
70.38

3.77
3.99
4.17
4.48
4.56
4.72
4.84

0.76
0.68
0.62
0.57
0.53
0.49
0.46

1.11
1.63
2.63
1.68
4.12
5.35
6.97

45.28
46.87
48.37
49.77
51.06
52.30
53.46

24.91
25.88
26.53
28.82
28.34
28.93
29.18

20.38
20.99
21.83
20.94
22.71
23.37
24.27

and the corresponding transfer Gibbs energy

w
HC

t;ind v

t;dd v

HC

t;dd :

15

the alkanes and some alkenes. According to this equation the total
molar polarization:


2
2
2
P i 1:05 n 1=n 2 M= 4NA =9kT 4N A =3

17

3. Selection of primary data


where n = refractive index and other terms bear usual signicance.

3.1. Choice of diameter of hydrocarbons and water


The Gibbs energy values for the cavity effect and other interactions
are particularly sensitive to the primary data chosen for the hydrocarbons and water. The radius usually taken for water is 0.276 nm.
The radii for alkanes can also be had from Farrel's modied [29] van
der Waals' radii as obtained from literature available van der Walls'
excluded volumes [30] and Farrel's separation factor [29] for aliphatic
and aromatic hydrocarbons. However, due to unavailability of van der
Waals' excluded volume for alkenes and alkynes chosen for this study,
we have used Kim's relation to calculate the hard sphere diameter of
all hydrocarbons studied. Kim's equation for relating the experimental
molar volume (Vs) of the hydrocarbon liquid with its diameter (s) is
given by:


3
1
s =nm 0:1363  0:0019 V s =cm mol 0:085  0:001: 16

3.3. Choice of dipole moment


The experimental molar volume (V 106 m3), diameter (
10
m) and volume polarizability ( 1030 m3) of various aliphatic
hydrocarbons containing different numbers of carbon atoms are presented in Table 1.1 and used for calculation of different Gibbs energy
components related with the HC solvation in water.
The dipole moments of only a few aliphatic hydrocarbons of each homologous series are available. Since values of these are low and do not
vary much from one member to another as C\H bond moment is equal
to C\CH3 group moment, an average value is taken for all the members
of each homologous series. These values are presented in Table 1.2.
0
0
HC
However the contribution of HC
v G t,dd and v G t,ind as obtained from
0
these values, to the total values G t,theo are completely negligible for
alkanes and alkenes.
10

4. Result and discussion


This relation is developed by the generalization of diameter
values of 110 liquids which are obtained on the basis of the consideration that the theoretical solubility obtained by SPT calculation of
a hypothetical hard sphere inert-gas solute of appropriate radii is
equal to the solubility of that hard sphere as found from the extrapolation of the experimental solubilities of insert gases up to that radius, where polarizability of insert gases become zero. Although the
error limit for such values is a little bit high and results in an error of
7% for values of G0t,ind of a particular hydrocarbon, we hope that
the error will be similar for all members of a particular homologous
series, so that the difference between two successive members of
the same homologous series i.e., for CH2 group and for other fraction of the molecules the error will be much less.
3.2. Choice of volume polarizability
The polarizability values for alkanes and a few alkenes were reported in the literature. For the rest of the hydrocarbons Clausius
Mossotti equation was used to calculate , since the values obtained
from this equation nearly tally with the available literature data for

Table 2.1 presents the different transfer Gibbs energy components of


alkanes from vacuum to liquid alkane/water and Table 2.2 presents
0w
0w
0
the total w
HCG t, HCG t,expt, HCG t,int for CH2 and CH3 groups. It
0
has been observed that the difference in w
HCG t,int for any two successive members of alkane is very near to their average value i.e.,
3.95 kJ mol1. This value agrees quite well with the literature [31] in
0
1
the sense that the value of w
which
octan-1-olG t (CH2) is 3.1 kJ mol
is slightly less than 3.95 kJ mol1 because of weak functional group
OH. It is well known [22] that the overall G0t of a hydrophobic solute
does not change too much on changing the initial state from pure HC
to any nonpolar organic solvent or slightly polar organic solvent containing apolar sites like octan-1-ol. A comparison of the average value
0
with the individual of w
HCG t, (CH2) as presented Table 2.2 reveals
0
that G t,int of CH2 and CH3 groups of alkanes are denite and additive. Consequently subtracting the contribution of the existing CH2
groups in a given alkane molecule, from the total G0t,int values for the alkane and dividing the result by 2, one gets the contribution for CH3.
In Table 2.3, the different free energy components of branched chain alkanes are presented. Tables 2.4 and 2.5 and 2.6 present theoretical
(theo), experimental (expt) and internal (int) of branched alkanes

Table 2.6
Internal (int) G0t of branch-chain alkanes from branch-chain alkane to water as well as G0t of NCH and NCb groups in kJ mol1 and their average values.
Branch-chain alkanes

0
w
HCG t, int

w
0
HCG t

2-Methylpentane
3-Methylpentane
2,4-Dimethylpentane

49.65
50.02
52.86

9.82
9.45
9.73

(NCH)

0
Avg. w
HCG t (NCH)

Branch-chain alkanes

0
w
HCG t int

w
0
HCG t

9.73

2,2 dimethylbutane
2,2,4 trimethylpentane
2,2,5 trimethylhexane

48.85
54.12
55.82

23.86
26.05
28.30

(NCb)

0
Avg. w
HCG t (NCb)

26.07

180

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

Table 3.2
Theoretical (theo), experimental (expt) and internal (int) G0t of alkenes from alk alkene to water as well as G0t of CH2 & CH_CH2 groups and their average values with stan standard
deviation () in kJ mol1.
Alkenes

w
0
HCG t,theo

w
0
HCG t,expt =

C5H10
C6H12
C7H14
C8H16
C9H18
C10H20
C11H22

19.36
19.36
19.21
19.26
18.59
18.03
17.30

25.22
28.36
32.36
36.50
39.92
43.78
47.46

RTInX

w
0
HCG t,int

w
0
HCG t

44.58
47.72
51.57
55.76
58.51
61.81
64.76

3.14
3.85
4.19
2.75
3.30
2.95

0
Avg. w
HCG t
(CH2) ()

(CH2)

as well as G0t,int of NCH and NC b groups, which are obtained on


the basis of the consideration that the additive rule which is applicable to CH3 and CH2 groups in n-alkanes, also holds for NCH and
NC b groups in branched alkanes.
Tables (3.1 and 3.2) and (4.1 and 4.2) for n-alkenes and n-alkynes
respectively represent similar data as these are presented in Tables 2.1
and 2.2 for alkanes. From a closer look at the different G0t,int values
of alkanes, alkenes and alkynes, one observes that, for the same number
0
0
0
w
w
of C atom: w
HCG t,int (alkane) N HCG t,int (alkene) N HCG t,int (alkyne).

w
0
HCG t

(CH_CH 2)

19.49
18.68
18.58
18.82
17.62
16.97
15.97

3.36 0.50

0
Avg. w
HCG t (CH_CH 2) ()

18.02 1.13

This can be explained on the basis of some sort of internal stability


imparted to alkenes in water which is further enhanced in alkynes.
One such property is the acidity of the hydrocarbons. It may be speculated that the electron cloud interacts with the polar water molecules in a
70
60
50
40

Table 4.1
Transfer Gibbs energies of various alkynewater interactions in kJ mol1.

C5H8
C6H10
C7H12
C8H14
C9H16
C10H18
C11H20

57.50
62.72
65.82
69.78
73.67
77.26
80.82

55.20
58.91
61.99
64.50
66.76
68.68
70.46

3.90
4.14
4.34
4.51
4.66
4.78
4.89

4.49
3.99
3.60
3.28
3.91
2.79
2.60

6.09
5.33
4.12
2.52
8.86
1.00
2.86

in kJ mol

w
0
v G t

w
0
v G t,dd

w
0
v G t,ind

Alkynes

w
0
v G t,dis

-1

30

0
w
v G t,cav

20
10
w

HC
w

-10

-30
Table 4.2
Transfer Gibbs energies of various alkynealkyne interaction in kJ mol1.

t,dis

HC

t,expt

HC

t,cav

HC

-20

t,int

-40

Alkynes

0
HC
v G t,cav

HC
0
v G t,dis

HC
0
v G t,ind

HC
0
v G t,dd

HC
0
v G t

C5H8
C6H10
C7H12
C8H14
C9H16
C10H18
C11H20

44.09
45.84
47.47
48.97
50.35
51.64
52.86

27.00
28.03
28.77
29.16
29.50
29.69
29.89

0.12
0.10
0.09
0.08
0.07
0.06
0.06

0.35
0.25
0.19
0.15
0.12
0.10
0.08

16.62
17.41
18.42
19.59
20.66
21.79
22.83

10

11

Number of C atoms in n-alkane


Fig. 2. Variation of Gibbs energy of transfer of n-alkenes due to cavity, dispersion, experimental and internal effects from water to hydrocarbon (n-alkene) with number of carbon
atoms in it.

60
70

50

60

40

50

30

in kJ mol

30
20

HC

-20
HC

t,cav

HC

-10

w
HC
w

t,dis

20
10
0

HC
w

-10
-20

t,int

-30

-30

w
HC
w
HC

t,cav

HC

t,expt

10

G t in kJ mol

-1

-1

40

t,dis

t,expt

t,int

-40

-40
5

10

11

Number of C atoms in n-alkane


Fig. 1. Variation of Gibbs energy of transfer of n-alkanes due to cavity, dispersion, experimental and internal effects from water to hydrocarbon (n-alkane) with number of carbon
atoms in it.

10

11

Number of C atoms in n-alkyne


Fig. 3. Variation of Gibbs energy of transfer of n-alkynes due to cavity, dispersion, experimental and internal effects from water to hydrocarbon (n-alkyne) with number of carbon
atoms in it.

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

181

Table 4.3
Theoretical (theo), experimental (expt) and internal (int.) G0t of alkynes from alkyne to water as well as G0t of CH2 & C`CH groups and their average values with standard deviation
() in kJ mol1.

C5H8
C6H10
C7H12
C8H14
C9H16
C10H18
C11H20

22.71
22.75
22.54
22.10
21.53
20.79
19.97

19.29
23.41
27.12
30.84
34.12.
38.04
41.50

RTlnX

w
0
HCG t,int

G0t (CH2)

42.01
46.15
49.66
52.94
55.65
58.83
61.46

4.14
3.51
3.28
2.71
3.18
2.63

manner that it has a stabilizing inuence on the system. Alkynes where


the -electron density is higher, are stabilized in water to a greater
0
extent as compared to alkenes. Similarly a closer perusal of w
HCG t,int
(CH2) values, as obtained from n-alkanes, n-alkenes and 1-alkynes re0
veals that w
HCG t, int of CH2 group varies in the order:
Alkane N 1-alkene N 1-alkyne(NOctan-1-ol).

w
0
HCG t

3.24 0.51

16.92
17.11
16.67
16.00
14.76
13.99
12.67

Table 6
Slope with their respective standard error and correlation coefcient for Figs. 13.
Figures (proles)

Transfer Gibbs
energy from HC to
water due to
various
interactions

Change in
transfer Gibbs
energy per
carbon atom
(x) (kJ mol1)

Standard
error in
x (kJ
mol1)

Linear
Correlation
coefcient
of proles

Fig. 1

0
w
HCG t(cav)
0
w
G
t(dis)
HC
0
w
HCG t(expt)
0
w
HCG t(int)
0
w
HCG t(cav)
w
0
HCG t(dis)
0
w
HCG t(expt)
0
w
HCG t(int)
0
w
G
t(cav)
HC
0
w
HCG t(dis)
0
w
HCG t(expt)
w
0
HCG t(int)

2.34
1.89
4.10
3.84
2.36
1.91
3.75
3.42
2.35
2.05
3.67
3.20

0.004
0.08
0.09
0.08
0.08
0.07
0.05
0.09
0.07
0.08
0.04
0.10

0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99
0.99

Fig. 2

Fig. 3

20

10

No. of H atoms per C atom,


exposed to water

0
w
HCG t, int
1

CH2
CH3
NCH
NCb
CH2_CH
C`CH

2
3
1
0
1.5
0.5

3.95
17.19
9.73
26.07
18.02
15.45

(kJ mol

0
w
HCG int per C atom of a
group (kJ mol1)

3.95
17.19
9.73
26.07
9.01
7.73

-10

HC
fraction

15.45 1.56

HC

Table 5
Gibbs energy of transfer (internal) of different hydrocarbon fractions from hydrocarbon to
water and the related parameters.

0
Avg. w
HCG t (C`CH) ()

(C`CH)

tertiary carbon fraction of the alkane. For N Cb group, the tertiary carbon
atom is totally blocked or buried within the molecule and cannot interact with the solvent at all under normal condition. Thus formation of
buffer bonds [6] of H-bond type or dispersion bond type with solvent
water is not possible for this fraction. On transfer of such group from
HC liquid to water, the entropy of NC b remains almost invariant. But
it denitely requires some space or cavity in water. This makes the
monomer water molecules to come together forming hydrogen bonds
between themselves and thus form a cage around the organic solute.
Since the effect of H bonding interaction between water molecules is
manifested by a large negative value of H which is possibly even greater than the corresponding entropy effect, the overall G = H TS is
here highly negative, in spite of S being also negative.

The reason behind this observation seems to be similar to that mentioned above. Because hydrogens of -C atom with respect to a double
or triple bond are acidic due to the hyperconjugation present in alkenes
and alkynes. This acidity is likely to be enhanced in aqueous solution
which has a strong dissolution capacity for H+ ion, generated from
hyperconjugation. This observation also indicated that alkene and alkyne liquids essentially provide different solvent environments for HC
0
as compared to alkane and therefore w
HCG t,int(CH3) values obtained
0
w
from alkanes, cannot be used to get HCG t,int(CH_CH2) from alkenes
0
and w
HC G t,int(C`CH) from alkynes.
0w
0
w
Figs. 13 illustrate the relative magnitudes w
HCG t,cav, HCG t,dis, HC
0
G0t,int and w
G
values
of
alkanes,
alkenes
and
alkynes
respect,expt
HC
tively. The nature of variations of these values with the number of C
atom is linear with correlation coefcient 0.99 and similar for the
three types of aliphatic hydrocarbon studied here. It can be easily observed from the three gures that all the three calculated G0t values
0w
0w
0
i.e., w
HCG t,cav, HCG t,dis, HCG t,int are all large and comparable with
one another and none can be neglected with respect to the experimental total G0t values.
w
0
0
Moreover, while G0t,cav and w
HCG t,int increase along with HCG t,expt
0
values, w
HCG t,dis decreases on increasing the number of C atom. This indicates that dispersion interaction which is somewhat akin to hydrophobic
0
interaction acts as a reversal of w
HCG t,int which perhaps is mainly constituted by HbH. Moreover the effect of HbH obtained here is more than that
expected from pure experimental values which were taken as a measure
of HbH in many earlier studies [2].
0
Table 4.3 presents w
HCG t,int of CH2 and CH`C groups of alkynes.
The number of hydrogen atom exposed to water per single NCb atom
for each fraction, is also presented in Table 5. For alkanes, unaccounted
0
solutesolute and solutesolvent interactions being absent, w
HCG t,int
represents only HbH along with Gibbs energy change due to water interaction on transfer of the respective group from HC liquid to water. From
the table it is quite apparent that the number of H atoms exposed to the
solvent water is greatest (3) for methyl group and smallest (0) for

0
Avg. w
HCG t (CH2) ()

-1

w
0
HCG t,expt =

in kJ mol

w
0
HCG t,theo

t,int

Alkynes

-20

-30
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Number of H atoms per C atom exposed to water


Fig. 4. Variation of Gibbs energy of transfer (internal) of different hydrocarbon fractions
from hydrocarbon to water with number of hydrogen atoms per carbon atom exposed
to water. Change in transfer Gibbs energy (from hydrocarbon to water) per number of H
atoms per C atom exposed to water: 14.35 kJ mol1.

182

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

The schematic representation may be: .

0
For this fraction therefore w
HCG t,int is enthalpy guided and mainly
waterwater interaction is responsible for such a large negative value
0
of w
HCG t,int.
In case of CH3, 3 atoms of H are exposed to solvent water for the
formation of buffer bonds [1114]. Thus in this case not only 3D
structuredness of water is somewhat enhanced but also due to the
formation of buffer bonds between H2O molecule and H atom,
each of the 3H atoms and attached C atom of CH3 group become
xed and unmovable, losing a large amount of entropy. Here the
buffer bonds are formed mainly by dispersion interaction between
H atom and H2 O molecule but such interaction has already been
counted. Therefore it is mainly for the loss of entropy of the solute
CH3 group due to the formation of hydrogen bonds and hydration
cage and in the process |TS| N |H| i.e., enthalpy change due to hydrogenwater and waterwater H-bonding interactions and we
0
therefore get a large positive value of w
HC G t, int for CH 3 group.
This effect is therefore said to be guided by entropy.
Now, as evident from Table 5, CH2 and C`CH groups possess
0
values of w
HCG t,int, which are almost intermediate between the values
0
of CH3 and N Cb groups. w
HCG t,int being guided by the two opposing
factors of decreased entropy effects of solute and solvent and decreased
enthalpy effect due to waterwater interaction, the magnitude of w
HC
G0t,int is positive for CH2 while that is negative for N CH group.
This means structural effects predominate for CH2 while waterwater
international effect predominates in the case of N CH since CH2 possesses more H atom to form more buffer bonds with H2O. Although
0
small, the denite positive value of w
HCG t,int for CH2 indicates that on
going to a higher member in a given homologous series of aliphatic HC,
water becomes less favorable to HC and therefore the solubility of HC
in water decreases on increasing the number of C atoms in the HC solute.
Thus for a higher member of HC in a given homologous series, the solubility of HC in water, becomes more entropy guided rather than being en0
thalpy guided. Moreover since w
HCG t,int for different fractions vary in
the order:

CH3 N CH2 CH Cb.


It reects the fact that the branched hydrocarbons possess less
hydrophobic character than the corresponding straight-chain isomer,
because branched hydrocarbons contain N C b and NCH groups with
0
negative w
HCG t,int effects.
Table 6 represents the change in transfer Gibbs energy per carbon
atom and the related statistical parameters as obtained from Figs. 13.

0
It reveals that w
HC G t,cav per carbon atom remains unchanged on
0
adding double or triple bond to the hydrocarbon system but w
HCG t,dis,
0
0
w
w
HC G t,expt and HCG t,int per carbon atom decrease on introducing
unsaturation to the same.
0
If one plots w
HCG t,int of different fractions of saturated aliphatic
hydrocarbons against the number of H atoms exposed per C atom and
hence immobilized due to the formation of buffer bonds with H2O molecules, one observes an excellent straight line with correlation coefcient
0.99 as is evident from Fig. 4. This indicates that the number of H atom attached to a sp3-hybridized C and exposed to water, is an important quantity to assess the number of buffer bonds (here dispersion bond) and the
0
amount of immobilization and thus to predict w
HCG t,int and HbH.
0
In case of CH2_CH and CH`C the observed w
HCG t,int is greater
than that expected on the basis of the straight line as illustrated in
Fig. 4. The relative values of them reect that CH`C group possesses
more acidbase type of interaction as compared to that for CH2_CH
group in water. But since the H atoms attached in these groups are differently oriented and exposed to water with respect to one another and
also differently exposed as compared to the H atoms attached to a sp3 C,
CH2_CH and CH`C group cannot be possibly analyzed with respect
to the straight line of Fig. 4. This means that the alkanes, alkenes and alkynes should be treated as separate initial states for the calculation of w
HC
G0t,int of different fractional groups of which the molecule is made.
However, as in the case for alkanes all members of a given homologous
series may be considered to provide almost the same initial state for a
given fractional group.

5. Conclusion
Thus the study concludes that
0
(1) Because of the denite positive magnitude of w
HCG t,int for CH2
group, the higher member of any type of homologous aliphatic
hydrocarbons, are successively more hydrophobic and hence
less soluble in water.
0
(2) The value w
HCG t,int(CH2) is almost independent of the primary nature of the carbon contents of the solutes whether they are
alkanes, alkenes or alkynes.
0
(3) The large negative values of w
HCG t,int for N CH and N Cb groups
indicate that branching helps solubilization of aliphatic hydrocarbons in water.
0
(4) The large negative values of w
HCG t,int for NCb groups also indicate a very strong attraction of water molecules for one another

A. Bhattacharyya et al. / Journal of Molecular Liquids 204 (2015) 176183

in comparison with which the parafnparafn or parafn


water attraction are very small.
0
(5) Magnitudes of cavity, dispersion and w
HCG t,int or HbH are
0
all comparable with the experimental total w
G
t values of the
HC
aliphatic hydrocarbons. The effect of dipoledipole and dipole
induced dipole type of interaction are either negligible or very
small owing to the very small dipole moments of aliphatic hydrocarbons.
0
(6) When initial states are same w
HCG t,int values for different fractions
are additive.
(7) Alkanes, alkenes & alkynes should be treated as different ini0
tial states for evaluating w
HCG t,int values of different fractions
constituting them.

Acknowledgment
We gratefully acknowledge Jadavpur University, India for nancial
assistance.
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