Journal of Crystal Growth 128 (1993) 1143-1149 j ........

CRYSTAL
North -Holland G ROW T H

Very large melting point depression of water in silica

J.C. van M i l t e n b u r g a n d J.P. van d e r E e r d e n
Institute of Interfaces and Thermodynamics, Padualaan 8, 3584 CH Utrecht, Netherlands

We demonstrate that even far below the melting point, thermodynamic data on water in porous systems indicate that part of the
water is in the liquid state. This gives a possibility to study some fractal properties of the pore structure, to obtain thermodynamic
data of a largely undercooled melt and also to obtain estimates of interfacial energies. The latter data indicate that ice in pores is
covered by a quasi-liquid layer at temperatures down to 100 K.

1. Introduction capacity of water in small pores and that of bulk

The behaviour of water and other compounds
confined to porous materials like silica has been
the subject of many studies. The interest in water
in porous systems is triggered by theoretical rea-
sons like interface theories and nucleation as well
as by practical aspects like catalysis, preventing
frost damage and the change in properties when
it is enclosed in biological systems.
Due to the large curvature and the strong
adhesion of the water/silica surfaces, there is a
large melting point depression AT in narrow
pores. In section 2 we shall give an expression for
AT, on the basis of the Gibbs-Thomson equa-
tion.
In the literature several results on the system
porous silica/water have been obtained:
(1) Several investigators [1-3] reported that the
melting enthalpy of water in a porous medium is
lower than that of the bulk phase. Often a non-
freezing layer of about 1 nm on the surface of the
porous material is assumed. Other authors [4]
assume that this layer becomes a glass when the
temperature is further lowered. These assump-
tions are not backed by experimental evidence as
no measurements were performed below 160 K.
(2) Etzler and Connors [5] reported structural
transitions in the confined water phase between 0
and 50°C. This can be of special relevance for the
study of biological systems. They also reported
large differences of up to 25% between the heat
water.
(3) All measurements of the melting behaviour of
water in small pores have been performed with
DSC or D T A techniques. Small effects with slowly
changing heat capacity are hard to detect with
these techniques and thus far the lowest melting
point of water is about -40°C.
In this paper we report on accurate thermody-
namic measurements in a large temperature range
of 15-300 K. We shall see that the data suggest
that in the narrowest pores the melting tempera-
ture is as low as 100 K.
Also our data allow us to estimate the interfa-
cial free energies of the water/silica and the
ice/silica interfaces in this temperature range.
The values obtained support the idea that in the
pore the solid ice is separated by a quasi-liquid
layer from the silica surface.
Finally, we show that our data also support
that the pore structure has a fractal nature, and
we can obtain the Hausdorff dimension of the
porous system.
2. Theory
Starting point of our discussion is the Gibbs-
Thomson effect. In its most common form [6] it
states that inside a finite body which is in chemi-
cal and mechanical contact with its environment
the pressure is higher than the ambient pressure.

0022-0248/93/$06.00 © 1993 - Elsevier Science Publishers B.V. All rights reserved

1144 Z C. van Miltenburg, ZP. van der Eerden / Very large melting point depression of water in Si
For isotropic systems, mechanical equilibrium im-
plies that the pressure difference is 6 P = K o ' ,
where K is the surface curvature and o- the
interface tension. We shall neglect the orienta-
tion and stress dependence of o-.
Furthermore, chemical equilibrium (i.e. the
possibility to exchange particles) between the fi-
nite solid body and the liquid environment im-
plies that the chemical potentials in both phases
are equal, i.e. /zs(P,T) =/~L(P + 3P, T). Apply-
ing this to a small ice crystal in equilibrium with
molten water, we see that they are in equilibrium
at a temperature T below the normal melting
point Tm = 0°C of ice at 1 bar:
~'~K°r = /£L(T) - / Z s ( T )
= f~m[Se(r' ) - Ss(T')] dT'.
Here /-1 is the molar volume (in m3/mol) of the
solid phase, /z s and /z e are the chemical poten-
tials (in J / m o l ) of the solid and the liquid phase,
respectively, both at ambient pressure, and S s
and S e the entropies (in J / K . mol).
When the surface tension and the entropies
are independent of temperature, then the melting
point depression is found to be
Tm -- T = AT = KOo'Tm/AHf,
where AHf is the molar heat of fusion (in J / m o l )
at the melting point.
Let us apply this to water and ice in porous
silica. At every temperature T < Tin, one could
expect that there is a certain pore diameter dm(T)
such that water in thicker pores, d > din(T), is
frozen but in thinner pores, d < dm(T), water is
still liquid.
A simple method to estimate dm(T) is to as-
sume [7] that solid/liquid interfaces in pores with
d = d m ( T ) are hemispherical with radius d/2.
Then dm(T) is found by substituting 4 / d m for the
curvature K and the i c e / w a t e r interfacial tension
CrSL for o- in eq. (2). This model can be justified if
there is complete wetting. Indeed it is necessary
that Crse + o-Lw < CrSW, where O-sw and ~rLw are
the interfacial tension of the ice/silica and the
water/silica interface respectively. A more gen-
eral method to obtain d m is given below.
Experimentally we are interested in the en-
thalpy of the solid and liquid water in the pores.
In the present picture we have:
H ( T ) = hLV L + hsV s + ~rLwAew + CrswAsw
+ OvSLA SL, (3)
where h L and h s are the specific enthalpy ( J / m 3)
of the liquid and the solid phase, Aew and Asw
are the silica area in contact with liquid and with
solid water. The last term is the i c e / w a t e r contri-
bution, which will often be negligible. As only
pores with d > dm(T) contain solid water, we see
that VL and Vs and likewise ALW and Asw are
temperature dependent, and we shall need some
model for the pore structure to be able to inter-
pret H(T) data.
(1) To make contact with the pore structure, let
Vp(d) and Ap(d) be the pore volume and the
pore area of all pores with a diameter less than d.
Then we have VL(T) = Vp(dm(T)) and ALw(T) =
Ap(dm(T)).
The value of d m corresponds to the minimum
of the Gibbs free energy:
G( T) = gL VL + g s V s + O'swAsw + OVLwALw,
(4)
(2) where gL and gs are the Gibbs free energy per
unit volume. Note that there is no term related to
the solid-liquid interface in this expression for
G, since that term compensates the contribution
due to the pressure difference of the solid and
the liquid water. Since Vmax = Ve + Vs and Amax
= A s w +ALw are constant we find that the mini-
mum G is reached if
( g L - - g s ) Vp(dm) + (O'Lw-- O'SW) A ' p ( d m ) = 0 .
(5)
This is the generalization of eq. (2) which we
need. Indeed, if we introduce the dimensionless
shape factor
~( d) =- dA'p( d) / V ; ( d), (6)
then it follows that
O'LW-- O'SW
dm = (7)
gL -- gs
 Z C. van Miltenburg, J.P. van der Eerden / Very large melting point depression of water in Si
For several pore models /3 is independent of the
pore diameter, e.g. /3 = 4 for cylindrical pores.
We can also rewrite the expression for H(T) as
follows:
H ( T ) = Vmaxhs +AmaxO-sw
(8)
+ VL[hL-- h s - Y ( g L - - g s ) ] ,
where
A p ( d ) Vp(d)
y(d) = A,o(d) Vp(d) (9)
is another p a r a m e t e r which depends on the pore
model, e.g. if the pore structure is fractal (Vp(d)
~ d ~, A p ( d ) ~ d ~ - l ) , then y = o l / ( a - 1 ) . This
expression is the basis to interpret our thermody-
namic data. Note that from H(T) we could get
direct information about VL(T), i.e. about the
pore structure, if the dependencies of the en-
thalpy and the entropy on t e m p e r a t u r e are known
for both the solid and the liquid phase. Con-
versely, if the pore structure is precisely known,
then eq. (8) can be used to obtain accurate ther-
modynamic data on (highly) undercooled melts.
3. Experimental procedure
The adiabatic calorimeter has been described
extensively [8]; it consists of a small vessel of 12
ml, surrounded by t e m p e r a t u r e regulated shields.
The whole system is evacuated in order to dimin-
ish the heat transfer and can be cooled with
liquid nitrogen or liquid helium. Measurements
are made in an interrupted mode; heat is sup-
plied to the sample for a certain time (between 80
and 330 K for 900 s), resulting in a temperature
Table 1
Fit parameters for the heat capacity of dry silica in the form Cpgram(T)=[a 0 + a l ( T / K ) + a2(T2/K2)+ a3(T3/K3)] J K 1 g 1
Temperature range A0 A1
(K)
15-40 -0.038884 4.05936741x10 -3
30-330 -0.05927 4.10822731 X 10 3
1145
rise of about 2 K, and the t e m p e r a t u r e drift of
the sample is followed for about 1500 s. This
procedure is repeated until the desired end tem-
perature is reached. The silica was dried for at
least 24 h under vacuum at 125°C. Filling with
water was done by placing a known amount of
silica spread out in a thin layer over a petridish
with water in a vacuum exicator. The silica was
kept in the exicator for 48 h to achieve a com-
plete filling of the mesopores. After filling, the
excess water was removed from the exicator and
the silica with the absorbed water was kept under
vacuum for 24 h to allow it to come to an internal
equilibrium.
We did not perform any adiabatic calorimetry
experiments with samples filled with more water
than the pore volume. As water expands during
freezing, this would have damaged the calorime-
ter vessel. The internal inaccuracy of a set of heat
capacity data can be as low as 0.02%. In this case
we conventionally estimate the absolute error to
be about 1%.
4. Materials
The silica used was from Janssen Chimica
(article No. 24.038.79) consisting of 0.2-0.5 m m
particles and a mean pore diameter of 6 nm. The
specific pore volume as determined by nitrogen
absorption (the B E T method) was 0.855 cm 3 g-1,
the specific surface measured by this method was
395 m 2 g 1. Dry silica was measured once and
the heat capacities were compared with an earlier
m e a s u r e m e n t of chromatografic column material
(LiCrosorb, Merck) published in 1983 [9]. No
significant differences were found and we con-
clude that all dry silica's do have the same heat
A2 Number Standard deviation
of points ( j - 1 K-1 g - l )
-1.1510565×10 s 29 1.58×10 3
- 3.9357939 × 10 -6 83 3.80× 10 -3
1146 J.C. van Miltenburg, J.P. van der Eerden / Very large rnelting point depression of water in Si

0.16
capacity curve. Between 5 and 15 K no reliable
measurement of the dry silica could be made. In
this temperature region the heat exchange gas
+
(helium, about 2000 Pa at room temperature), ÷
++ +

which is added to the sample before closing the + + +

+

vessel is absorbed in the pores, resulting in a very

o
"L ÷+ + +
+ +

poor heat contact of the sample with the sample H.-relaxation

container. For this work we fitted the heat capac-
ity curve of dry silica in two parts, one between 0.15 ~ i
15 and 50 K and the second between 40 and 330 90 100 110 120 130

K. The results of these fits are given in table 1. In T/K

the measurements reported in this article, 4.20375
Fig. 2. Detailed structure of ( ~ S / ~ T ) p = C p / T in the region
g of silica filled with 3.22802 g of water were
where melting starts. The effect of proton relaxation in solid
placed into the calorimeter vessel. This corre- ice (discontinuity) and of the onset of pore melting (positive
sponds to 0.768 g of water in a gram silica. In the contribution to -(~S/6T)p
- - at about 100 K are visible.
terminology of section 2 this means the maximum
pore volume and area are Amax = 9000 mZ/mol
and Vmax = 6 X 10 - 6 m3/mol. bulk ice. Therefore we conclude that all water is
frozen below 100 K. In view of eq. (8) with
VL = 0, we interpret the (almost constant) differ-
5. Results and interpretation ence in heat capacity of 0.29 J / m o l . K as the
temperature derivative of the i c e / p o r e surface
Specific heat measurements were made be- energy. With Amax=9000 m 2 / m o l this gives
tween 15 and 330 K. The experimental molar 3O'sw/ST= 32 × 10 - 6 J / m o l • m 2" K.
heat capacities of the water in the pores (after Next we consider the temperature range from
subtracting the heat capacity of dry silica) are 90 to 130 K. The heat capacity is given in fig. 2.
given in fig. 1. We will discuss this large tempera- We compared our data with the adiabatic mea-
ture interval in parts and mention specific obser- surements of Haida et al. [10]. They measured an
vations. enthalpy relaxation between 95 and 100 K which
Between 15 and 100 K, the molar heat capacity
of the water in the pores is close to that of the

100
1050 ~ "

+ 360 , J
"l-
E
v: 50
--j o ."
._J ,'~ Y-- 10.98 + 1.344"x
85
TIK
.... • -". •. • . . . . ' " ' " ' "
25
.......'" 218 K 253K
~...,.........,......-'~ .... 4
// ,y L~
-5 -4 -3 -2
0 '~" ' ' ' ' '
0 50 100 150 200 250 300
Ln (1/(273.15-T))
T/K Fig. 3. Double logarithmic plot of the excess enthalpy AH of
Fig. 1. Overview of heat capacity data. Plotted is the heat the molar water in the pores versus undercooling. The data fit
capacity of the water in the silica, i.e., the contributions of the well to the straight line in the temperature interval from
dry silica and of the apparatus have been subtracted. about 120 to 260 K.
 J.C.vanMiltenburg,J.P.vanderEerden / Verylargemeltingpointdepressionof waterin Si
is related to the ordering of the proton configura-
tion. This small effect depends on the thermal
treatment of the sample, shifting to lower tem-
peratures after longer annealing periods. In the
pore water we also detect this effect, starting at
about 100 K.
Immediately after this effect, the curve of
Cp/T against T shows, however, an upward trend
and apparently the melting of the ice in the pores
starts. The heat capacity curve rises very slowly to
its maximum at 264 K and then drops to the value
corresponding to undercooled water (fig. 1). Inci-
dentally, at about 130 K there is a slight b u m p in
the curve suggesting a glass transition [11].
The total enthalpy increment between 90 and
280 K for the water in the pores is 10640 J / m o l
and for bulk water 11302 J / m o l . This difference
can be ascribed to the difference in interfacial
free energy of the ice/silica interface at 90 K and
the water/silica interface at 280 K. Taking for
the area of these interfaces again A max = 9000
m2/mol, we conclude that ~rsw(T=90 K ) -
~Lw(T = 280 K) ~ 0.07 J / m 2. It can be noted that
this value is remarkably close to the interfacial
energy O-so(T= Tm) ~-0.04 J / m 2 of the equilib-
rium i c e / w a t e r interface. The latter value would
be obtained if a liquid layer were separating the
ice from the silica surface.
The interfacial energy ~rcw between liquid wa-
ter and the silica surface can be obtained from
the heat of immersion; we measured that 1640
J / m o l are released when the silica is filled with
water at 298 K. We find ~rLw-~ - 0 . 1 8 J / m 2 at
T = 280 K. Now we also have an estimate O-sw(T
= 9 0 K ) - - 0 . 1 1 J / m 2 for the ice/silica inter-
face energy at low temperature.
In the range 100 < T < 270 K, we assume that
the water in the narrowest pores is already melted.
In order to interpret these data we define the
excess enthalpy AH as
A H ( T ) -- H ( T ) - H ( T o ) - [rOHS dT'
.IT~ OT'
-(T- To) 6Cp. (10)
This definition is used for T > To, and we chose
T 0 = 100 K. The first contribution H ( T ) - H(T o)
is obtained from integration of our experimental
1147
heat capacity data. The next term can be found
with the data of bulk ice, as published by Haida
et al. [10]. The last contribution is our estimate of
the ice-wall surface energy; we take ~Co(T)=
6Cp(T o) --- 0.29 J / m o l • K. It should be noted that
this method to define an excess enthalpy is some-
what different from the base line construction
described in ref. [11].
Our assumption is that the excess enthalpy, as
defined in this way represents the partial melting
effect:
A H ( T ) = VL(T ) [ h L ( r ) - h s ( T ) - 7(gL(T)
-gs(T)]. (11)
It turns out (see fig. 3) that the data for A H can
be well fitted to
with H 0 = 60 J / m o l and a = 1.34, over the tem-
perature interval 120 < T < 260 K.
When we compare eqs. (11) and (12), and we
assume that far enough below the melting point
the specific enthalpy difference h L - h s is almost
independent of temperature and that 7 ( g c - gs)
is a small correction term, then it follows that the
dependence A H ~ AT -~ is characteristic for the
pore structure. Indeed, if we make the further
assumption that gL - gs ~ ~IT, then eq. (7) shows
that d m ~ 1~AT and finally that Vp(d) ~ d ~.
To make the correspondence a bit more pre-
cise, we propose the following interpretation of
our data. Below T = 100 K all water is present in
solid form. Above that temperature, melting starts
in the narrowest pores, following the law
VL(T ) Vmax(dm(T°) )a[( dm(T) ) c~ ]
dmax am(T0)
(13)
Consistent with V m a x = 6 × 10 -6 m 3 / m o l , Areax =
9000 m 2 / m o l and a = 1.34 are the value 7 --- 3.94
and dmax = 10 nm for the pore structure factor
and the maximum pore diameter in the fractal
regime.
1148 J.C. van Miltenburg, J.P. van der Eerden / Very large melting point depression of water in Si
The value of H 0 can be used to check if our
interpretation is consistent. Indeed, it follows
from eqs. (11)-(13) that
1-10 = V m a x [ d m ( T o ) / d m a x ] a ( A h - T A g ) ,
where H 0 = 60 J / m o l , Vm~ = 6 × 10 -6 m 3 / m o l ,
dma x ~ 10 nm and a = 1.34. H e r e Ah and Ag are
effective (average) values of h L - h s and gL -- gs
in the t e m p e r a t u r e range of the fit. If we assume
that the pores are cylindrical (/3 = 4) and we use
the estimate o-Lw- O-SW-------0.07 J / m 2, then eq.
(7) allows us to express dm(T0) in terms of gL(To)
- g s ( T 0 ) = Ag. Thus, eq. (14) can be considered
as a relation between Ah and Ag. With the
present experimental results we obtain:
Ah = 3.94 Ag + 1.05 × 10 -3 A g 1"34,
where Ah and Ag are expressed in J / m 3. It
should be noted that eq. (15) has been obtained
without the assumption of constant enthalpy and
entropy over the whole temperature interval from
T o to Tm. It has been used that the factor in
square brackets in eq. (11) is almost constant over
the interval where the fit by eq. (12) is accurate.
Of course, the numerical values of the parame-
ters in eq. (15) have a fair uncertainty; we judge
an uncertainty level of 20% for H0, 10% for a
and y, 20% for ~rLw- ~rsw and 5% for Vmax. A
more accurate determination becomes possible if
the pore structure can be described more pre-
cisely.
Nevertheless, we can draw the following con-
clusions. First, dm(T0) should be less than dmax in
order for the model to have any relevance. This
implies that a g > 28 X 106 J / m 3, and hence a h
>__120 X 106 J / m 3. Second, the maximal value of
Ah is the heat of fusion at the melting point
(334 x 106 j / m 3 ) , and this leads to Ag < 75 X 106
J / m 3 and dm(T0) > 3.5 nm.
Third, from the use of the data we also have
u p p e r and lower bounds to the entropy difference
of the liquid and the solid phase. Using an aver-
age t e m p e r a t u r e of 150 K for the relevant inter-
val, we have that 0.6 x 10 6 _~ A S ~ 1.7 x 10 6
J / K " m 3.
6. Summary
We have shown that accurate thermodynamic
data on a solid/liquid system in porous silica
(14)
contain interesting information both on the pore
structure and on the properties of a largely un-
dercooled melt.
In order to separate the two types of informa-
tion, it is desirable to obtain structural informa-
tion on the pore system independently, or by
comparing data of different liquids in the same
silica. Once piece of such information is avail-
able: porous silica may be an excellent system to
investigate properties of undercooled melts. Good
knowledge of these properties is also essential for
an accurate description of rapid crystal growth
from the melt.
The values of several parameters suggest the
(15) following physical picture of the water in the
pores. For every pore diameter, there is a tem-
perature below which the water freezes. In that
case the value of surface energies makes it plausi-
ble that the ice is separated by a thin quasi-liquid
layer from the pore walls. Above that tempera-
ture the water in the pore is not solid, from our
data alone it could be a metastable liquid (without
first order phase transition connected to liquid
water at T > Tm) or amorphous solid. A nice
account of the difference is given by Speedy [11].
The values Ah ~ 77 × 10 6 J / m 3 and As ~ 0.35 X
106 J / K . m 3 which he reports for " w a t e r I I " are
less than the lower bounds we find here. This
suggests that the liquid water which is present in
the narrow pores is the metastable continuation
of normal liquid water, rather than "water II".
The driving force for the melting point depres-
sion is the stronger adhesion of liquid water to
silica than of ice to silica.
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