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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
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
t;int
t;st
t;ww :
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
w
HC
t;expt HC
RT ln X:
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
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
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
w
HC
t; ind v
t;ind v
HC
t;ind :
13
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
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
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
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
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)
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
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
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
10
11
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
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
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
182
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:
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
Acknowledgment
We gratefully acknowledge Jadavpur University, India for nancial
assistance.
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