Relationship between cohesive energy density and hydrophobicity

Giuseppe Graziano

Citation: The Journal of Chemical Physics 121, 1878 (2004); doi: 10.1063/1.1766291
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 JOURNAL OF CHEMICAL PHYSICS VOLUME 121, NUMBER 4 22 JULY 2004

Relationship between cohesive energy density and hydrophobicity

Giuseppe Grazianoa)
Dipartimento di Scienze Biologiche ed Ambientali, Universitá del Sannio, Via Port’Arsa,
11-82100 Benevento, Italy
共Received 1 April 2004; accepted 5 May 2004兲
It has been recently claimed that the large cohesive energy density of water is the ultimate cause of
the poor solubility of nonpolar compounds in water. In order to test the validity of this idea, we
analyze the difference in solubility between light water and heavy water of several nonpolar
compounds. Even though the cohesive energy density of D2 O is larger than that of H2 O, nonpolar
compounds are slightly more soluble in D2 O than H2 O. In such case experimental data do not
support the correctness of the large cohesive energy density as the ultimate cause of hydrophobicity.
We show that D2 O is a slightly better solvent than H2 O for nonpolar compounds because it is
slightly less costly to create a cavity in the former liquid. This is because there is slightly more void
volume in heavy water than in light water. © 2004 American Institute of Physics.
关DOI: 10.1063/1.1766291兴

I. INTRODUCTION D2 O, 12,13 and v ⫽18.073 cm3 mol⫺1 for H2 O and 18.136

Hydrophobicity is the term used to indicate the poor
solubility of nonpolar compounds in water. Even though this
phenomenon is well recognized, its molecular origin is still
strongly debated in the scientific community.1– 4 In the last
few years, independently, Lazaridis5 and Kodaka,6 by means
of different arguments, proposed that the large cohesive en-
ergy density of water is the real cause of the poor solubility
of nonpolar compounds. Actually, this explanation was first
advanced by Hildebrand7 in a small note published in 1968,
and subsequently supported by Privalov and Gill,8 and by
Honig and colleagues.9 The cohesive energy density10 is de-
fined by ced⫽(⌬ vapH⫺RT)/ v , where ⌬ vapH is the molar
vaporization enthalpy change at the temperature T and v is
the molar volume of the liquid at the same temperature. The
ced of water is by far the largest among all common solvents
as a consequence of both the strength of hydrogen bonds and
the smallness of the molar volume of water. On this basis
Hildebrand stated: ‘‘The fact that octane is nearly insoluble
in water is merely the result of the fact that van der Waals
octane-water attraction is not strong enough to penetrate the
high cohesion of water.’’
In order to be considered right, this claim should be
tested in a clear-cut way. This is the aim of the present work.
We would like to show that the ced argument is not of gen-
eral validity because it fails to rationalize the well-known
experimental finding that simple nonpolar compounds are
more soluble in heavy water than in light water.11
II. RESULTS
In order to clarify the role played by ced in the hydro-
phobicity phenomenon, we compare the solubility of several
nonpolar compounds in H2 O with that in D2 O, because light
and heavy water have different values of ced. At 25 °C,
⌬ vapH⫽44.0 kJ mol⫺1 for H2 O and 45.4 kJ mol⫺1 for
FAX: ⫹39/0824/23013; Electronic mail address: graziano@unisannio.it
a兲
cm3 mol⫺1 for D2 O. 14 Thus, at 25 °C, ced(D2 O)
⫽2365 J cm⫺3 and ced(H2 O)⫽2297 J cm⫺3 . These num-
bers indicate that D2 O has a ced larger than that of H2 O:
ced(D2 O)/ced(H2 O)⫽1.0296. This is not a surprise since it
is generally recognized that the hydrogen bonds are enthal-
pically stronger in D2 O than H2 O: by 0.96 kJ mol⫺1 accord-
ing to Nemethy and Scheraga,15 0.93 kJ mol⫺1 according to
Marcus and Ben-Naim,11 and 0.84 kJ mol⫺1 according to
quantum mechanical calculations by Scheiner and Cuma.16
The larger ced of D2 O, on the basis of the claim by Hilde-
brand, Lazaridis, and Kodaka, should imply that D2 O is a
poorer solvent for nonpolar compounds than H2 O. In other
words, the solubility of a nonpolar compound should be
lower in D2 O than H2 O.
However, experimental solubility measurements state the
contrary: the solubility of simple nonpolar molecules is
larger in D2 O than H2 O. 11,17–19 The values of the
Ben-Naim20 standard Gibbs energy change associated with
the transfer from light to heavy water, ⌬G "(H2 O→D2 O),
listed in Table I, are all negative at room temperature. The
numbers are small in view of the strict similarity of the two
solvents, but the difference goes systematically into one di-
rection.
If hydrophobicity were proportional to the ced of water,
the Ben-Naim standard Gibbs energy change associated with
the transfer from the gas phase to heavy water could be cal-
culated by means of the following relationship:
⌬G "共 D2 O兲 calc⫽⌬G "共 H2 O兲关 ced共 D2 O兲 /ced共 H2 O兲兴 , 共1兲
where ⌬G "(H2 O) is the experimental Ben-Naim standard
Gibbs energy of hydration, whose values at 25 °C for the
nonpolar solutes considered are listed in the fourth column of
Table I. According to Eq. 共1兲, the values of ⌬G "(D2 O) calc are
larger than those of ⌬G "(H2 O), so that their difference is
always a positive quantity 共see the numbers listed in brackets
in the fifth column of Table I兲, in complete contrast with
experimental data 共compare the open squares with the filled

0021-9606/2004/121(4)/1878/5/$22.00 1878 © 2004 American Institute of Physics

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 J. Chem. Phys., Vol. 121, No. 4, 22 July 2004 Cohesive energy density and hydrophobicity 1879

TABLE I. Hard sphere diameter, polarizability, experimental Ben-Naim standard Gibbs energy of hydration at
25 °C, experimental Ben-Naim standard Gibbs energy of transfer from H2 O to D2 O at 25 °C for several
nonpolar compounds, and SPT estimates of ⌬G c (H2 O→D2 O). The numbers reported in brackets in the fifth
column are the ⌬G "(H2 O→D2 O) estimates obtained via Eq. 共1兲. The values of ␴ and ␣ come from Ref. 33,
except those of C3 H8 and n-C4 H10 , which come from Ref. 34. The values of ⌬G "(H2 O) and ⌬G "(H2 O
→D2 O) come from Table II of Ref. 11.

␴ ␣ ⌬G "(H2 O) ⌬G "(H2 O→D2 O) ⌬G c (H2 O→D2 O)

共Å兲 共Å3兲 共kJ mol⫺1兲 共J mol⫺1兲 共J mol⫺1兲

Ne 2.78 0.393 11 191a ⫺203a 共331兲 ⫺104

Ar 3.40 1.63 8400a ⫺245a 共248兲 ⫺145
8373b ⫺144b 共248兲 ⫺145
Kr 3.60 2.46 6922b ⫺138b 共204兲 ⫺160
CH4 3.70 2.70 8408b ⫺155b 共249兲 ⫺168
C2 H6 4.38 4.33 7682b ⫺129b 共227兲 ⫺225
C3 H8 5.06 6.29 8196c ⫺96c 共243兲 ⫺292
n-C4 H10 5.65 8.12 8715c ⫺84c 共258兲 ⫺357
O2 3.46 1.56 8639b ⫺196b 共256兲 ⫺149
N2 3.70 1.73 10 265b ⫺308b 共304兲 ⫺168
CH4 4.66 2.86 13 056b ⫺259b 共386兲 ⫺251
SF6 5.51 4.48 12 585b ⫺207b 共375兲 ⫺340
a
Reference 19.
b
Reference 18.
c
Reference 17.

ones in Fig. 1兲. Experimental ⌬G "(H2 O→D2 O) data do not
support the claim that the large ced of water is the ultimate
cause of hydrophobicity.
According to well-founded statistical mechanical
approaches,21–23 the Ben-Naim standard Gibbs energy
change associated with the transfer from light to heavy water
of a nonpolar compound is given by
⌬G "共 H2 O→D2 O兲 ⫽ 关 ⌬G c 共 D2 O兲 ⫺⌬G c 共 H2 O兲兴
⫹ 关 E a 共 D2 O兲 ⫺E a 共 H2 O兲兴 , 共2兲
where ⌬G c is the work of cavity creation and E a is the
energy of turning on solute-water van der Waals interactions.
As a first approximation, it is reliable to assume that the E a
term is nearly the same in D2 O as well as H2 O, because the
FIG. 1. Experimental Ben-Naim standard Gibbs energy of transfer from
H2 O to D2 O at 25 °C 共filled squares兲 of several nonpolar compounds 共from
left to right: Ne, Ar, O2 , Kr, CH4 , N2 , C2 H6 , CF4 , C3 H8 , SF6 , and
n-C4 H10) vs their effective diameter; SPT estimates of ⌬G c (H2 O→D2 O) at
25 °C as a function of the cavity diameter 共continuous line兲; calculated
values of the Ben-Naim standard Gibbs energy of transfer 共open squares兲,
where ⌬G(D2 O) calc has been obtained by means of Eq. 共1兲.
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two isotopic species of water have very close values of the
dielectric constant, refractive index, and molecular dipole
moment.15 Thus, one obtains
⌬G "共 H2 O→D2 O兲 ⬵⌬G c 共 D2 O兲 ⫺⌬G c 共 H2 O兲
⫽⌬G c 共 H2 O→D2 O兲 . 共3兲
Equation 共3兲 means that the different solubility of a nonpolar
compound in D2 O with respect to H2 O should be due to the
difference in the work of cavity creation. The latter quantity
can be reliably calculated by means of the analytical formula
provided by scaled particle theory, SPT.24,25 In performing
calculations we use the experimental density at 25 °C of
H2 O, 0.997 05 g cm⫺3, and D2 O, 1.104 45 g cm⫺3, as re-
ported by Kell;14 the pressure is fixed at 1 atm, as suggested
by several authors.25,26 For the size of both H2 O and D2 O
molecules, we use ␴ ⫽2.80 Å because this value is close to
the location of the first peak in the oxygen-oxygen radial
distribution function of both light and heavy water.27–29
Moreover, we30 have shown that, by assigning a diameter of
2.80 Å to water molecules, SPT is able to reproduce satis-
factorily both the cavity size distribution and the ⌬G c values
obtained from molecular dynamics simulations in TIP4P
water31 by Pohorille and Pratt.32
The calculated ⌬G c values are always large and positive
but, more importantly, prove to be slightly smaller in D2 O
than H2 O 共see the numbers listed in the last column of Table
I兲. The difference increases with the cavity size, passing from
⫺0.12 kJ mol⫺1 for a cavity of 3 Å diameter to ⫺0.40
kJ mol⫺1 for a cavity of 6 Å diameter. By plotting the experi-
mental ⌬G "(H2 O→D2 O) data versus the effective size33,34
of the nonpolar compounds listed in Table I, and the SPT
estimates of ⌬G c (H2 O→D2 O) versus the cavity diameter, it
is evident that the latter quantity more than qualitatively ac-
counts for the experimental data 共compare the filled squares
with the continuous line in Fig. 1兲.
 1880 J. Chem. Phys., Vol. 121, No. 4, 22 July 2004
The SPT formula shows that the magnitude of ⌬G c , at a
given temperature for a given cavity diameter, is determined
by two geometric properties of the solvent:35 the size of its
molecules ␴, and its volume packing density ␰
⫽ ␲␴ 3 N Av/6v , 共i.e., the ratio of the physical volume of a
mole of solvent molecules over the molar volume of the
solvent兲. The two variables work in opposite directions: for a
given ␴, ⌬G c increases on increasing ␰, and for a given ␰,
⌬G c increases on decreasing ␴. This behavior can be readily
explained. The quantity (1⫺ ␰ ) is the fraction of the total
volume not occupied by solvent molecules. Thus, when ␰
increases, the fraction of void volume diminishes and ⌬G c
increases. On the other hand, the diameter of the solvent
molecules determines the size of the pieces in which the void
volume is partitioned. Keeping fixed ␰, if the diameter of the
solvent molecules decreases, it diminishes the average size
of the pieces in which the void volume is partitioned. This
implies that the number of molecular-sized cavities, those
important for the solvation of real solutes, becomes smaller
and the corresponding ⌬G c values increase. It is the small-
ness of water molecules to render ⌬G c extremely large and
positive in water with respect to the other common liquids,
and eventually to cause hydrophobicity.22,23,35–38
For the pair H2 O-D2 O there is no difference in the size
of the molecules, but there is a small difference in the vol-
ume packing density: at 25 °C, ␰ (D2 O)⫽0.381 66 while
␰ (H2 O)⫽0.382 98, because the molar volume of D2 O is
slightly larger. As a consequence ⌬G c is smaller in D2 O than
H2 O, and the solubility of nonpolar compounds is slightly
larger in heavy water than in light water. A similar conclu-
sion emerged in previous SPT analyses39– 41 of solubility dif-
ferences between the two isotopic species of water. Since we
are interested in the difference between the work of cavity
creation in two liquids having molecules of identical size, the
SPT results have to be considered robust and reliable.
According to Fig. 1, the difference in the work of cavity
creation fully accounts for the experimental ⌬G "(H2 O
→D2 O) data in the case of solutes having a small polariz-
ability. On the other hand, Fig. 1 shows that the experimental
⌬G "(H2 O→D2 O) values become less negative on increasing
the size of the solute molecule and so its polarizability, at
odds with the trend of ⌬G c (H2 O→D2 O). This should be
reliably caused by the attractive solute-water van der Waals
interactions. The volume packing density, the polarizability,
and the dielectric constant of D2 O are slightly smaller than
those of H2 O 共i.e., ␣ ⫽1.26 Å 3 for D2 O and 1.45 Å3 for H2 O
in Ref. 42; see also Ref. 15兲, causing a reduction of the
strength of van der Waals interactions. This interpretation is
supported by the finding11 that, at 25 °C, ⌬G "(H2 O→D2 O)
⫽⫺129 J mol⫺1 for ethane ( ␣ ⫽4.3 Å 3 ), 0 for fluo-
romethane ( ␣ ⫽3.0 Å 3 and ␮ ⫽2.08 D), 70 J mol⫺1 for chlo-
romethane ( ␣ ⫽5.4 Å 3 and ␮ ⫽1.89 D), and 250 J mol⫺1 for
bromomethane ( ␣ ⫽6.0 Å 3 and ␮ ⫽1.82 D). Clearly, the
contribution of van der Waals interactions becomes more im-
portant in the Gibbs energy balance of Eq. 共2兲 on increasing
both the polarizability and the dipole moment of the solute
molecule.
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Giuseppe Graziano
III. DISCUSSION
The experimental finding that simple nonpolar com-
pounds are slightly more soluble in D2 O than H2 O cannot be
reconciled with the idea that the large ced of water is the
ultimate cause of hydrophobicity. The ced of D2 O is larger
than that of H2 O, so one should expect that the former liquid
would be a poorer solvent for nonpolar compounds than the
latter. This expectation, however, is wrong. We already
pointed out that the ced argument cannot explain the trend of
xenon solubility in n-alkanols at room temperature.43 In ad-
dition, experimental data show that the volume packing den-
sity decreases while the ced increases on passing from light
to heavy water. Therefore, Kodaka’s suggestion6 of a propor-
tionality between the volume packing density of a solvent
and its ced does not seem to hold.
A qualitative rationalization of ⌬G "(H2 O→D2 O) data is
provided by approaches that dissect the hydration process in
two consecutive steps: creation of the cavity and turning on
solute-water van der Waals interactions. The latter contribu-
tion, as a first approximation, can be considered to be the
same in light and heavy water, at least for solutes having a
small polarizability. Assuming that there is no difference in
size between D2 O and H2 O molecules, SPT calculations
show that the work of cavity creation is slightly smaller in
D2 O than H2 O because the former liquid is characterized by
a slightly smaller value of the volume packing density.
Freely speaking, there is slightly more void volume in D2 O
than H2 O and this favors the insertion of nonpolar solutes.
The assumption that there is no difference in size be-
tween H2 O and D2 O molecules is an important point. Ac-
cording to crystallographic data, the molecular dimensions
and the length of a hydrogen bond are identical in H2 O and
D2 O ice within a few thousandths of an angstrom unit.13,15
Similarly, the first peak of the oxygen-oxygen radial distri-
bution function in H2 O and D2 O occurs at the same
position.27 From a theoretical point of view a difference in
size between H2 O and D2 O could be expected,13,44 because
the amplitude of vibrations involving deuterium is smaller
than that of vibrations involving protium, as a result of the
larger mass of deuterium. However, the difference in size
caused by this effect is very small13 共i.e., it is a second order
effect affecting the vibrational fluctuation about the average
length of C-D and C-H bonds兲.
On the basis of information theory results, Pratt and
colleagues45,46 suggested the existence of a proportionality
between the work of cavity creation in water and the recip-
rocal of its isothermal compressibility, ⌬G c ⬀1/␤ T . Since it
is generally assumed that ⌬G c ⬀ ␥ , where ␥ is the surface
tension of the liquid,47 and it has been recently shown that
the product ␥␤ T is a constant for several liquids at 25 °C,
including water,48 the relationship ⌬G c ⬀1/␤ T is expected.
On this ground, Pratt and colleagues49 explained the slightly
larger solubility of nonpolar compounds in D2 O with respect
to H2 O by recognizing that the former liquid is slightly more
compressible than the latter: at 25 °C, ␤ T ⫽46.50
⫻10⫺6 bar⫺1 for D2 O, and 45.25⫻10⫺6 bar⫺1 for H2 O. 50
Clearly, ␤ T is a macroscopic thermodynamic quantity and a
microscopic interpretation of the difference between D2 O
and H2 O should be provided.
 J. Chem. Phys., Vol. 121, No. 4, 22 July 2004
Pratt and colleagues45 suggested that the small value of
␤ T for H2 O with respect to the other common solvents
should be a reflection of the stiffness of its hydrogen bonding
network 共i.e., the strength of hydrogen bonds兲. This interpre-
tation, however, does not seem to hold. Even though the
hydrogen bonds in D2 O are enthalpically stronger than those
in H2 O11,15,16 共see also Appendix A兲, ␤ T is larger for D2 O
than for H2 O.
The isothermal compressibility of a system is a measure
of the ensemble fluctuations in local number density:51 ␤ T
⫽( v /RT) 关 ( 具 ␳ 2 典 ⫺ 具 ␳ 典 2 )/ 具 ␳ 典 2 兴 , where the number density
␳ ⫽N Av / v , the angled brackets denote ensemble average val-
ues, v is the molar volume, and R is the universal gas con-
stant. The small value of ␤ T in the case of H2 O should be a
reflection of the fact that the molar volume of H2 O is signifi-
cantly smaller than that of common solvents: at 25 °C, v
(in cm3 mol⫺1 )⫽18.07 for water, 89.41 for benzene, 108.75
for c-hexane, 131.62 for n-hexane, and 97.09 for carbon
tetrachloride.14,33 The molecular origin of this is the fact that
the size of water molecules is the smallest among all other
solvents.25,33
We suggest that the isothermal compressibility of D2 O is
slightly larger than that of H2 O mainly because the molar
volume of D2 O is slightly larger than that of H2 O 共see also
Appendix B兲. Assuming that the molecular sizes of H2 O and
D2 O are the same, this means that the volume packing den-
sity of D2 O is slightly smaller than that of H2 O. In other
words, D2 O has a slightly larger void volume than H2 O and
so it proves to be more compressible. It is evident that this
explanation corresponds to that used to rationalize the find-
ing that ⌬G c is slightly smaller in D2 O than H2 O.
The present analysis, even though rudimentary in some
respects, is able to provide a rationalization of the experi-
mental ⌬G "(H2 O→D2 O) data for several nonpolar com-
pounds. The latter represent a robust test to distinguish a
physically correct interpretation of hydrophobicity from the
noncorrect ones. Since the ⌬G "(H2 O→D2 O) data cannot be
rationalized using the idea that the large ced of water is the
cause of hydrophobicity, this idea should not be considered
correct. The large unfavorable entropy change determining
hydrophobicity around room temperature has nothing to do
with the large ced of water. The process of cavity formation
provides the correct explanation: the negative entropy
change due to the excluded volume effect is exaggerated in
water by the small size of individual water molecules.
ACKNOWLEDGMENTS
This work was supported by Grant COFIN-2002 from
the Italian Ministry for Instruction, University and Research
共M.I.U.R., Rome兲.
APPENDIX A: AN ESTIMATE OF THE DIFFERENT
STRENGTH OF HYDROGEN BONDS IN D2 O AND H2 O
Dack52 proposed that, in the case of liquids characterized
by the presence of hydrogen bonds, the quantitative differ-
ence between ced and P int⫽( ⳵ U/ ⳵ V) T ⬅ ␣ T/ ␤ T , where U is
the internal energy and ␣ is the coefficient of thermal expan-
sion, should be a measure of the strength of hydrogen bonds.
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Cohesive energy density and hydrophobicity 1881
At 25 °C, P int⫽141.8 J cm⫺3 for D2 O ( ␣ ⫽0.221
⫻10⫺3 K⫺1 ), and 169.5 J cm⫺3 for H2 O ( ␣ ⫽0.257
⫻10⫺3 K⫺1 ). Thus, even though ced(D2 O)⬎ced(H2 O), it
results P int(D2 O)⬍ P int(H2 O), confirming that ced and P int
account for different properties of the liquids, especially
when hydrogen bonds are present.52 Following Dack’s pro-
posal, one obtains ced(D2 O)⫺ P int(D2 O)⫽2223.2 J cm⫺3 ,
and ced(H2 O)⫺ P int(H2 O)⫽2127.5 J cm⫺3 ; these numbers
indicate that hydrogen bonds are stronger in D2 O than H2 O
by 95.7 J cm⫺3. If the latter number is multiplied by the
mean molar volume, 18.1 cm⫺3 mol⫺1, and divided by 2, the
mean number of hydrogen bonds per water molecule, one
obtains that the difference in strength amounts to 866 J per
mole of hydrogen bond at room temperature. This estimate
agrees with those obtained by more rigorous
treatments.11,15,16 It is worth noting that, at 25 °C, a fraction
of hydrogen bonds is broken;53 this fraction should be differ-
ent in the two isotopic species of water,41,54 but such differ-
ence should be so small to be neglected in a simple calcula-
tion as the present one.
APPENDIX B: RELATIONSHIP BETWEEN MOLAR
VOLUME AND STRENGTH OF HYDROGEN BONDS
In general, the molar volume of a liquid is determined by
the size of its molecules and the strength of intermolecular
interactions. In the case of water, however, characterized by
the presence of strongly directional interactions such as the
hydrogen bonds, one has to make different considerations. A
perfect tetrahedral arrangement leads to an increase of molar
volume. The transition from liquid water to ice at 0 °C is
accompanied by an increase of molar volume,13 because
there is an increase in the number of molecules with a perfect
tetrahedral coordination. The coordination number is 4 in ice
whereas its average value in liquid water is ⬇5, due to the
presence of an ‘‘interstitial’’ molecule that is not hydrogen
bonded to the central one.27–29 On this basis, the increase in
molar volume passing from H2 O to D2 O and T2 O13 should
reflect the increase in the strength of hydrogen bonds that, in
turn, leads to an increase in the number of molecules with
perfect tetrahedral coordination. In other words, the struc-
tural arrangement of D2 O and T2 O molecules in the liquid
state is more icelike than that of H2 O molecules. Thus, the
increased strength of hydrogen bonds in D2 O with respect to
H2 O manifests itself not only in the increase of ced but also
in the increase of molar volume. Since the molecular dimen-
sions are identical for H2 O and D2 O molecules at room tem-
perature, the slightly larger molar volume of D2 O means that
there is slightly more void volume in D2 O than in H2 O. This
fact renders less costly the cavity creation in heavy water,
favoring the solubility of nonpolar compounds.
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