Statistical Thermodynamics: Molecules to Machines

Venkat Viswanathan
May 19, 2015

Module 6: Water
Learning Objectives:
Qualitatively discuss thermodynamic issues involving water.
Introduce concepts of polarizability, hydrogen bonding, and
hydropho- bicity.

Key Concepts:
Polarizability, dipole moment, electrostatic shielding, dielectric medium,
hydrogen bonding, lake turnover, melting and boiling points,
hydropho- bicity.

statistical thermodynamics: molecules to machines

Introduction
Water is the key compound for our existence on this planet and it is involved in nearly all chemical, biological and geological processes.
Access to clean water is also one of the most challenging questions for
mankind in the coming century, in particular with the prospect of
global warming. Although water is the most common molecular
substance it is also the most unusual with many peculiar properties
such as increased density upon melting, decreased viscosity under
pressure, density maximum at 4C, high surface tension and many
more. The mysterious properties of water become even more extreme
in the supercooled region below the freezing point, but they appear
also under ambient conditions. One ex- ample (Fig.1a) is the
isothermal compressibility, T , related to volume, or equivalently
density, fluctuations in the liquid, where T decreases upon cooling as
for a normal liquid, but only down to 46C where it starts to
increase again upon further cooling, indicating that density
fluctuations in the liquid increase as thermal energy is removed.
Another is the heat capacity at constant pressure, CP , which is related
to fluctu- ations in the entropy and again this property of water shows
an anoma- lous increase compared to normal liquids already at 35C
(Fig.1b). The thermal expansion coefficient, P , which is related to
the crosscorrela- tion between fluctuations in density and entropy,
becomes negative for water below the density maximum at 4C
(Fig.1c). Characteristic for all three is that they are related to
fluctuations in the liquid and that these increase upon cooling
contrary to expectation for normal, simple liquids. Importantly, while
these fluctuations and apparent divergences of thermodynamical
response functions are most evident when water is supercooled below
0C, they start to influence water properties already in the ambient,
biologically relevant regime and grow in importance in a continuous,
but rapidly increasing fashion as thermal energy is removed. One of
the most essential questions to address for a microscopic understanding of water is then: What is the structure and dynamics of the
hydrogen bonding (H-bonding) network in water that gives rise to all
these unique properties? This question has been discussed intensively
for over 100 years and has not yet been resolved. In order to gain new
unique information regarding the structure of the H-bond network in
water, it is essential to develop new techniques, both experimental
and theoretical.

Polarizability
The water molecule has a bent structure due to the structure of the sp

orbitals of the O H bonds and the unshared electrons of the oxygen

atom (Fig. 2). Since oxygen is more electronegative than hydrogen, the

Figure 1: Comparison of thermodynamical response functions for H2O

water (full line) with that of typical
liquids (dashed) showing the onset of
anomalous behavior already at ambient temperatures and pressure. The
melting point is indicated by Tm. (a)
Isothermal compressibility, T , which
shows a minimum at 46C. (b) Isobaric
heat capacity, CP , with minimum at
35C and (c) coefficient of thermal expansion, P , which becomes negative
at 4C. [Nilsson and Pettersson, 2011]

Figure 2: Structure of the

molecule.

water

statistical thermodynamics: molecules to machines

electrons in the O H bond congregate30near the oxygen atom, leading

to a dipole moment of m = ql 6 10 Cm (q is charge separation
and l is separation distance). The dipole moment of water molecules
results in electrostatic interactions that tend to order water in the
liquid phase.
The energy of interaction for two monovalent ions (same charge) in
a dielectric medium is written as:
Ecoulomb =
kB T

lB

(1)

where T is the temperature of the medium, kB is the Boltzmann constant, r is the separation of charges, and lB is the Bjerrum length, given
by:
lB =

e2
k T
B

where is the dielectric constant of the medium,

and e is the
elementary charge of electron (e = 1.602 1019C).
Consider
two dipoles with orientations u1 and u2 separated
by
a vector
z, which
is r = r1 r2 . The valance of the charge separation is
separated by a distance l.
The total energy of interaction between the dipole is:
Edd
1
1

l Bz 2k BT =|r + l (u1 u2 )| |r + l (u1 +

u2 )|
2

1
1

|r l (u1 u2 )| |r l (u1 u2 )|
For |r |

Edd
=

l, we expand Edd is powers of l, giving to order l2 .

l B z 2 k B Tl 2
r3

1
(I 3erer ) : u1 u2 =

r3

(I 3erer ) : 1 2

where 1 = ezlu1 is the dipole moment and er = r/r.

The dipole-dipole interaction energy is long-ranged (Edd r ),

thus there can be long-ranged dipole correlations in a solution. The
po- larizability of a solution can lead to dramatic consequences in the
physi- cal behavior. For example, an ion in a polarizable medium will
order the opposite charged ends of dipoles around the ion. This
effectively shields the interaction between the ions. This effect is
generally captured in the dielectric constant of the medium, thus the
polarizable medium acts as an effective medium for electrostatic
interaction (Fig. 3).
Since the polarizability leads to shielding of the charge-charge interactions, the dielectric constant increases with polarizability
of the
2

Figure 3: Schematic of ion interactions

in a polarizable medium

e
medium, thus decreasing the Bjerrum length lB
kBT . Dipole or=
dering is energetically favorable and is entropically unfavorable due to

Figure 4: Temperature dependence of

the dielectric constant of water

the loss of rotational entropy of the molecules. Therefore, the

dielectric constant is temperature dependent. Raising the temperature
prefers the molecules to engage in rotational fluctuations, thus
reducing the shielding effect, thus the dielectric constant tends to
decrease with tem- perature (Fig.4).

Phases of Liquid Water

From waters behavior, we know that it is not easily described as one
phase on the macro-scale. There could exist two separate liquid
phases, HDL and LDL, with a coexistence line in the p-T diagram deep
in the su- percooled regime and at elevated pressures (Fig. 5). This
line ends with decreasing pressure in a critical point and its
extension into the one- phase region corresponds to the Widom line.
At the Widom line the density fluctuations would reach a maximum
consistent with equal pop- ulation of molecules in HDL and LDL
related structures as also directly found in the inherent structure in
simu- lations with the TIP4P/2005 force-field. The presence of the
Widom line leads to fluctuations that ex- tend over a very large
temperature range and can be observed well above ambient
conditions. We note that the HDL is on the ambient temper- ature side
of the Widom-line whereas LDL is on the low tem- perature side. This
explains why the high density, H-bond distorted species dom- inates at
ambient conditions. The origin of the anomalous properties of water is
the increase in density fluctu- ations as water is cooled down and
approach the Widom line leading to fluctuating tetrahedral patches
growing in size as directional H-bonding becomes relatively more
impor- tant. We should also note that in the schematic picture the
boundary between the HDL and LDL regions is not sharp and the
density should vary in a continuous fashion. Furthermore, the regions
are not of one particular size and shape but should represent a
distribution, where the average changes with temperature.
The driving force to energetically allow for the formation of HDL
must be the more isotropic van der Waals interactions together with
quantum effects leading to both weaker H-bond strength and, in addition, to quantized vibrational modes which become thermally
inaccessi- ble in tetrahedral coordination. Tetrahedral ice is quite
unique among all the condensed structures with an extremely low
coordination num- ber of 4. Most other cubic and hexagonal solids
have a nearest neighbor coordination of 12. This low coordination is
the result of the direc- tional H-bonds in the tetrahedral
coordination. What makes HDL have a density significantly lower than
for the high-pressure ices is that the first shell is distorted in order to
allow thermal excitation of vibrational modes. It has been speculated
that these distortions are not symmet- rical but instead asymmetrical
in order to minimize loss of enthalpy

Figure 5: Schematic picture of a hypothetical phase diagram of liquid water

consistent with the observed enhanced
scattering at low Q and the structural
bimodality indicated by X-ray spectroscopies. Only the liquidliquid coexistence line, the LLCP and the Widom
line are shown for simplicity. [Nilsson
and Pettersson, 2011]

leading to a doubly H-bonded local structure. It turns out that the

H-bond energy is maximized when there is an equal number of donor
and acceptor bonds and a particularly favorable situation in terms of
energy per H-bond is when each molecule forms only one bond of
each kind. This would lead to a stabilization of doubly H-bonded
structures which interact with the surrounding through more isotropic
forces and gain entropy since the vibrational modes would become
thermally ac- cessible. Such a picture is supported based on
thermodynamic grounds where it has been argued that over a large
range of the liquid-vapor coexistence line the averaged water
interaction potential should resem- ble that of liquid Argon, i.e. Hbonding is not dominating resulting in mostly a doubly H-bonded
structure. Furthermore, one model suggests, also based on
thermodynamic arguments, that the H-bonding structure upon
melting of ice should mostly correspond to breaking of H-bonds
between rings in the tetrahedral ice structure while keeping the
internal ring structure intact. This would also lead to a local doubly
H-bonded picture.
The varying phases of liquid water can be studied by means of
XRD scans - they allow us to differentiate between the phases, because
of their differing average bond distance. On a given scan, for a similar
r-value, LDL has a higher-intensity peak, and HDL has a lowerintensity but wider peak (Fig.6).
The structure of liquid water is still a subject of intense debate and
the picture is one that is still evolving.

Hydrogen bonding
Another consequence of the electronegativity of oxygen is hydrogen
bond- ing, which occurs when the partial positive hydrogen on a donor
bonds with the lone pair electrons on an acceptor. Strength of the

Figure 6: Water spectra from water in

the HDL and LDL phases

Figure 7: Hydrogen bonds interactions between the Hs and the Os

of neighboring H2O molecules (see
http://www.nsf.gov/news/special_
reports/water).

hydrogen bonds in water are approximately 8kBT , thus significantly

larger than the mean thermal energy.
Hydrogen bond
F-H- - -F
O-H- - -N
O-H- - -O
N-H- - -N
N-H- - -O

Bond Energy
155 kJ /mol or 40 kcal/mol or 62 kBT (at 300K)
29 kJ /mol or 6.9 kcal/mol or 12 kBT
21 kJ /mol or 5.0 kcal/mol or 8 kBT
13 kJ /mol or 3.1 kcal/mol or 5 kBT
8 kJ /mol or 1.9 kcal/mol or 3 kBT

Since each oxygen can accept a hydrogen bond with 2 different

water molecules, liquid water tends to form hydrogen bond networks
that dra- matically influence waters physical properties. At room
temperature, each water molecule is hydrogen bonded to
approximately 3 other water molecules on average (Fig. 7).

Figure 8: Schematic of the structure of

solid water (ice).

Figure 9: Plot of specific volume v/s

temperature
showing
the
discontinuity at solid-liquid phase
transition.

Consider the structure of ice, which consists of two

interpenetrating lattice with hexagonal close packed symmetry,
resulting in four hydrogen bonds per H2O molecule (Fig. 8). The
transition from solid water to liquid water results in the molecules
having more rotational degrees of freedom that disrupt the hydrogen
bond network. Since the hydrogen bond distance no longer constrains
the molecular spacing as much in the liquid phase, the liquid phase is
denser than the solid phase. Further increase of temperature above
the solid-liquid transition leads to further densification with
temperature (up to 4C)
In Module 2, we found stability criterion for the sign of derivatives
of intensive properties w.r.t. their extensive properties. These stability
concepts, which derive from the second law of thermodynamics, say
nothing about the sign of:
.
1 .
=

Figure 10: The oxygen-oxygen pair

cor- relation function g(r) for liquid
water at 4C (dashed curve) compared
with the pair correlation function for
argon at 84.25 K and 0.71 atm (solid
curve)

(2)
p,N

since the variables are not conjugate to each other.

Hydrogen bonding in the liquid state causes water to be
substantially more ordered than the liquid-phase of other substances.
Comparing the pair correlation function of the oxygen in water
against the pair correlation function of argon (Fig. 10), we see:
The integral under the first peak shows that water molecules have
about 4.4 first-shell neighbors and argon has about 10 first-shell
neigh- bors.
However, the water molecules are more ordered than the argon
atoms, as indicated by the width of the first peak and number of
subsequent peaks.
Due to hydrogen bonding, water has a significantly higher melting
and boiling points than comparable molecules. Hydrogen bonding
also influences a number of dynamic properties of water (e.g. viscosity
and diffusivity) that make water a unique and important substance.

Hydrophobicity
A further consequence of hydrogen bonding is the hydrophobic effect,
where non-polar substances are excluded by water in order to maintain a confluent hydrogen bonded network. Hydrophobicity does not
arise due to favorable "hydrophobic interaction", rather the non-polar
molecules come together because putting water molecules next to
them would eliminate the opportunity for those molecules to hydrogen
bond with other water molecules. Essentially, the surrounding water
presses the hydrophobic groups together to maximize their contacts
with each other. Hydrophobicity is responsible for the de-mixing of oil
(nonpolar

Figure 11: The twenty amino acids divided into six categories according to
the chemical nature of their side
chains.

hydrocarbons) and water. Hydrophobic amino acids drive the collapse

of proteins in order to sequester these side chains from the
surrounding solution (Fig. 11).

References
A. Nilsson and L.G.M. Pettersson. Perspective on the structure of
liquid water. Chemical Physics, 389(1-3):134, November 2011.