CONFIGURATIONAL ENTROPY OF W A T E R

Yu. V. G u r i k o v UDC 532.12

In applying a crystal-like model to the liquid state, it is necessary to allow for intermixing between
molecules occupying lattice point sites and interstitial sites, due to the disappearance of long-range
order. With water, the mechanism by which the voids of the ice-like carcass are filled is superim-
posed on the former process. It is shown that the first process makes a contribution of about 30% to
the observed entropy of fusion of ice, while the second process contributes about 26%.

1. I n t r o d u c t i o n

The generally accepted similarity between the structures of water and ice [1-4] has given rise to numerous
models for the structure of water which emphasize its close structural relation to ice [5-7]. If, however, an absolute
significance [7-8] is ascribed to this similarity, then several very important ways in which liquid water differs from
crystalline ice may be overlooked. This difference is most clearly manifested in the calculation of the configura-
tional entropy of water, and the quasicrystalline models for the structure of water must be treated with caution.

The principal difference between the solid and Iiquid states is the absence of long-range order [9, 10] in the
latter. In a solid body, the molecules are located at the lattice points in the crystal, and that part of the eonfigu-
rational space of the crystal which corresponds to the transfer of its molecules into the interstices is practically inac-
cessible to molecules, providing that the dimensions of the voids in the crystal lattice are small. This is the case
for the overwhelming majority of substances (water, of course, is an exception to this).

Molecular exchange, which also exists in the solid state, does not reduce the differences between the lattice
point sites and the interstitial sites. On the other hand, all points of a space filled by a liquid are equivalent.
Hence, when speaking of the similarity between the structures of water and ice, it should be kept in mind that the
similarity only extends to close-range order, which expresses the spatial correlations in the arrangement of mole-
cules of the liquid in the vicinity of a certain fixed molecule [9]. Close-range order includes large regions around
the central molecule. In the case of liquid water, close range order is manifested to a greater degree, perhaps, t h a n
in other substances.
The absence of specific spatial positions means that in liquids the molecules possess greater possibilities for
the filling of the space. If a liquid is described within the framework of the quasicrystalline model, then it is abso-
lutely essential to augment this by making allowance for the peculiar intermixing between the different types of
sites. The increase in entropy which occurs with fusion is also probably connected with this phenomenon. In the
case of water an additional possible mode of filling the voids with molecules is superimposed on the process involv-
ing the intermixing of the lattice point sites and the voids of the ice-like carcass. An additional configurational en-
tropy term from the intermixing of the occupied and unoccupied cavities is associated with this. This fortuitous cir-
cumstance is not however, generally speaking, the principal distinguishing idiosyncrasy of liquid water as one of the
three fundamentaI aggregate states of matter.
2. M e l t i n g as t h e Intermixing of Lattice Point and Interstitial Sites

Let us now consider in more detail the processes involved in the fusion of a conventional molecular crystal.
We shall assume that N molecules of the liquid can be in (M + Ns) temporal positions of equilibrium. Of these we
shall call Ns crystal-like sites (s), while M are called hole vacancies (h). The two classes of equilibrium sites differ

All-Union Scientific-Research Institute of Petrochemical Processes, Leningrad. Translated from Zhurnal

Strukturnoi Khimii, Vol. 11, No. 4, pp. 590-594, July-August, 1970. Original article submitted December 14, 1967.

9 1971 Consultants Bureau, a division of Plenum P u b l i s h i n g Corporation, 227 West 17th Street, New
York, N. Y. 10011. A l l rights reserved. This article cannot be reproduced for any purpose w h a t s o e v e r
without permission o f the publisher. A copy o f this article is available from the publisher for $16.00.

552
sharply in their potential energies. The nearest environment around the crystal-like sires is the same as that about
a lattice site in a crystal. The interstices in a crystal correspond to the hole vacancies. Molecules which have
crossed over into these positions possess significantly higher potential energies than those at crystal lattice sites.
Hence a definite potential energy, s s and e h, respectively, may be ascribed to each class of equilibrium site. We
further assume that s s << s h. The difference between the solid and liquid states lies mainly in the fact that in the
crystal, the N s crystal-like sites and the M voids occupy strictly determined positions in space, while in the liquid,
any of the M + Ns equilibrium sites belong to class s for part of the time and to class h for a part of the time.

In calculating the statistical probability for the model under consideration, it is necessary to find the number,
~, of different ways of distributing Ns crystal-like sites among the total number (M + Ns) of equilibrium sites. This
number is given by [11]:

~=(M+N,)t
N~!M! (1)

The total partition function for such a systom has the form:

Q(N, V, T) = ,%~, exp { - - N , ~ , / k T I a , (2)

where r is the partition function for the vibrational and rotational motion of the molecule in an equilibrium crystal-
like site.

Since in the model taken, Ns = N, the free energy of the liquid becomes equal to

N -- e~ - k T In % ' - - k T In (v -1- t) -t- v In v (3)

where v = M/N, the number of additional equilibrium positions at one lattice point site which arise during the fu-
sion process. The state parameters in Eq. (3) have been marked with a stroke in order to emphasize that both the
density and the (quasi)lattice constant change during the fusion process.

Since ~ = 1 for a system with long-range order, we obtain for the free energy of the crystal:

FN
N
-= ~ -- kT Inr

The melting curve is determined by the condition

e~ ~ e l + kTo In%
~P/ ---- kTo { v l n v - - ( i -t- v ) l n ( t + v ) } , (4)

where T o is the melting point.

It follows from Eq. (4) that the entropy of fusion (per mole) is made up of two contributions:

a) a configurational part

ASconf ~ R { ( v -Jr- l ) in (v + 1) - - v l n v},

(5)

b) a potential part

ASpot.= R + d----ln ,
~Ps dT %

caused by the change in the force field in which the molecules are situated.
When v = 1, which corresponds to cubic close packing, Eq. (5) yields ASconf" = 2.77 eu. It is known thatthe
entropy of fusion of the majority of simple substances which crystallize with the above structure lies in the range
from 2 to 3 eu [12]. Upon fusion, the entropy of the inert gases increases by 3.4 en [13]. Hence, the configurational
contribution constitutes a large part of the entropy of fusion.

553
 3. T h e Configurational Entropy of Water

In the case of water the additional mechanism whereby some of the cavities become filled by molecules is
superimposed on the process involving the intermixing of the lattice point sites with the voids of the ice-like carcass.
If we assume that all cavity molecules are equivalent, which corresponds to the original treatment of the model due
to Samoilov [1, 2] then both mechanisms can be considered as statistically independent. In considering a carcass
with filled cavities it is convenient to employ an isothermal isobaric ensemble [7, 11], since the volume of the sys-
tem does not remain constant during this process and the expression:
M

Q (N, p, T) ~--- Z Nh! ( ~pN ~phN~exp -- . (6)

NN=0

is written for the partition function. Here Ns : N - N h, the number of lattice point sites in the carcass; Nh is the
number of cavity molecules; k s, Sh' ~s, and ~h are the energies and free volumes of the molecules at the lattice
point sites in the carcass and in the cavities; v s is the volume (per molecule) of the idealized carcass (without any
filling of the interstitial cavities). The total volume of the system is V = Nsvs and the molar volume, v = f v s,
where ~ = Ns/N, the fraction of molecules situated at la~ice point sites. In liquid water the state parameters ac-
quire new values due to the change in the intermolecular distances upon fusion

In order to allow for the absence of long-range order in water in the proper manner, it is necessary to augment
Eq. (6) by including an additional factor (1) which describes the intermixing of the lattice point sites and the voids,
independently of whether the latter are filled or not. The total partition function then becomes equal to

hi "Y..6'~-k Nhe'h +. N~pv'~I

Q(N, pT) = 2 N~! Nh! (M--N~)! kr j. (7)
Nh =0 I
The factor

= (i +Ns)!
NANh! (M -- Nh) I (s)

can be interpreted as the number of different ways of distributing Ns crystal-like molecules with energy ~ and Nh
cavity molecules with energy ~ among a total number (M + Ns) of equivalent sites. In a formal approach it
might be thought that Eq. (8) does in fact take the indistinguishabIe permutations of the carcass and cavity mole-
cules within the unchanged ice-like carcass into account. The same applies to the exchange of hhe molecular sites
together with their energy states, which is very typical of the liquid state. Such permutations lead to different con-
figurations. One can convince oneself on this point by taking, as an example, the Ising model, which was intended
to describe statistical ordering in systems of identical particles, capable of existing in two different spin states [11].
The number of ways of distributing Ns spins, which are antiparalle1 to an external magnetic field, over M + N equiv-
alent lattice points is exactly given by the expression (1) [11].

Let us now explain what has been discussed above in greater detail. Both in the solid state and in the liquid
state, systems composed of N particles can be classified in terms of the distribution of the particles (or quasiparti-
cles such as phonons) over the energy levels of the correctly chosen single particle Hamiltonian. In the Einstein
model of a crystal these could be the independent harmonic oscillations of the particles about the lattice points.
Upon transferring a molecule into an interstitial position, however, its energy state is described by a different one-
particle Hamiltonian, if only because the symmetry of the environments of molecules at lattice points and intersti-
tial positions is different. In the calculation of the number of microstates of a multiparticle system only those per-
mutations are indistinguishable which differ in a permutation of the particles between states of the one and the
same Hamiltonian. The permutation of particles between states corresponding to different single paxticle Hamil-
ionians leads to physically different configurations. In an analogous manner, in the Ising model only those permu-
tations are indistinguishable which change both the spatial positions as well as the direction of the spins. If the
spins do not change direction, the configurations are considered as distinguishable. In the liquid state, those permu-
tations of the lattice point and cavity molecules, under which each particle retains its belonging m a definite single
particle Hamiltonian, are distinguishable. In systems with long-range order such permutations are impossible. We
must take them into consideration, however, if we wish to obtain a correct description of the liquid state. The

554
TABLE I. The Entropy of Fusion of Water partition function [gq. (8)1 in which the additional possibil-
ities for distributing the equilibrium crystal-like sites in
~Sconf. as fusion, space are not taken into consideration, describes, according
[7,14, t5] eu eu
eu eu (exptl.) to what has been said above, a system with long range order
and refers to ice crystals with filled voids which do not exist
0,5 0,85 1,35 1,62 3,I I 5,2 in nature. Analogous remarks also apply to [8] in which
clathrate structures serve as the model.

Let us now return to the partition function (7). By sep-

arating out the largest term and recalling that M/N = vj~, we
obtain the thermodynamic potential of liquid water:

ft l ---~r e , ' + ( t - - l ) e h ' - - k T ] l n ~20' - - k T ( l - - J) l a , h ' + pvs"

+kr{--vllnl+ (1--I) In (1--I) + [(v + 1)I-- 1] In [(v + t)I-- tl

- (v + i ) l ] n (v + i ) } , (9)

where ~ is defined by the equation

kT,o {[. (" + l'+' I r " , ,s ."1". . t. v. l *,"

in ~h"
,
PUs" (i0)
v + t J "l'i--A-)-/J = ~h' - ---

The substitution of(10) in (9) yields the equilibrium magnitude of the thermodynamic potential

Ftl - - 8," - - k r In r + p v / + k T { v In [ ( v + t ) 1 - - t ] - - v l n J
- (v + 1) in ( v + t)}.
The thermodynamic potential of ice, in which all the cavities are vacant, has the form

~t~i-~- 8, - - k T In ~ , + pv,. (11)

Comparing (10) and (11), we obtain for the entropy of fusion of ice (per mole)

&Sfusion = ASconf" + &Spot.

' d '
where &Spot = Rln $ s + RT ~ - - In @.s , the potential part of the entropy of fusion. The configurational entropy
~s ~s
of fusion can be broken up into two contributions:

a) ASh = - R { ( 1 - f ) ln(1-jr v ] In vJ . [ ( v + 1 ) ) e - 1 ] x l n [ ( v + 1 ) j ~ - 1 ] } . This is the contribu-

tion from the distribution of the molecules over the voids.

b) ASp=Rf {(u + 1 ) l n ( u + 1 ) - u In v } . This is the contribution determined by the process of the inter-
mixing of the lattice point sites and cavities cf the ice-like carcass which takes place as the long range order is
reduced. The results of the calculation of ASh and ASp for water at 0~ are shown in Table 1.

It can be seen that the entropy change ASh associated with the distribution of a fraction of the molecules
over the voids of the ice-like carcass, only constitutes one quarter of the over-all entropy change which occurs dur-
ing the fusion of ice, while the intermixing of the lattice point sites and cavities of the carcass gives about a third
of the observed change. On the whole, the configurational entropy makes up about 60% of the total entropy of fu-
sion. The remaining part is probably associated with a change in the nature of the thermal vibrational motion of
the carcass molecules in the liquid state.

I express my deep thanks m F. M. Kuni for valuable comments.

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Hydration of Ions, Consultants Bureau, New York (1965).

555
 3. I . Z . Fisher and I. S. Andrianova, Zh. Strukt. Khim., 7, 337 (1966).
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