Molecular-level description of temperature and pressure effects on the viscosity of

water
C. H. Cho, J. Urquidi, and G. Wilse Robinson

Citation: The Journal of Chemical Physics 111, 10171 (1999); doi: 10.1063/1.480367
View online: http://dx.doi.org/10.1063/1.480367
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 JOURNAL OF CHEMICAL PHYSICS VOLUME 111, NUMBER 22 8 DECEMBER 1999

Molecular-level description of temperature and pressure effects

on the viscosity of water
C. H. Cho and J. Urquidi
SubPicosecond and Quantum Radiation Laboratory, Department of Chemistry and Biochemistry, Texas
Tech University, Lubbock, Texas 79409-1061
G. Wilse Robinsona)
SubPicosecond and Quantum Radiation Laboratory, Department of Chemistry and Biochemistry and
Department of Physics, Texas Tech University, Lubbock, Texas 79409-1061
Received 9 July 1999; accepted 15 September 1999
The steep non-Arrhenius temperature dependence at low temperatures of the shear viscosity of
water and its backwards-sounding increased fluidity under pressure for temperatures below 33 C
are two of the anomalies of this liquid that have been known for a very long time. The purpose of
the present paper is to show how these two important characteristics of water emerge quantitatively
from an explicit two-state outer-neighbor mixture model that we have used to explain many other
properties of this substance. It will be shown here that both of these viscosity anomalies are directly
related to the steep variations with temperature and pressure of the fractional compositions of
ice-Ih-type bonding and ice-II-type bonding in the two-state mixture. This compositional
dependence has already been obtained in earlier work from the variations of the density and the
isothermal compressibility of water with temperature. The viscosity analysis presented here thus
helps to unify further all the properties of this liquid under a single, very simple structural
characteristic. 1999 American Institute of Physics. S0021-96069951246-4

I. INTRODUCTION
The importance of the viscosity for understanding the
structure and anomalies of water and its isotopic modifi-
cations cannot be overemphasized.1,2 From a practical point
of view, the importance of the viscosity of water to biology3
and the environment,4 to engineering and reactor
technology,5 to other technologies,6 and as a reference mate-
rial in viscometry,79 has been discussed widely in past
work. This importance is further evidenced by the continuing
activity, since the time of Bingham,7 for whom a viscometer
was named, in the measurement, refinement and analysis by
national and international organizations of the viscosity data
for ordinary and heavy water.418 The search for an under-
standing of the peculiarities of the viscosity of water with
changing temperature and pressure and a possible simple re-
lationship between the viscosities of the isotopic modifica-
tions of water have been of greatest interest. Yet, following
much past activity, these problems have remained unsolved.
We believe that the main difficulty with past attempts to
create an understanding of liquid water, or to develop valid
relationships for its viscosity, is the failure to recognize the
intrinsic differences between this liquid and others.19 Though
suggested long ago by Tammann20 and later more explicitly
by Kamb,21 the consideration of temperature- and pressure-
dependent outer-neighbor structural changes in water has
been absent in all but our own work.2225 These structural
effects now seem well established experimentally.2527 Ex-
cept for bending21,24 of the regular tetrahedral OOO
angle of 109.5, the inner structure in the liquid remains
a
Electronic mail: gwrob@ttacs.ttu.edu
intact with respect to the number of neighbors, four, and the
OO distances, 2.8 . However, on increasing the tem-
perature or the pressure, a transformation takes place in the
outer-neighbor region from a stiff Ih-type OO structure at
4.5 to a less rigid, more dense II-type bent hydrogen-
bonded OO structure near 3.5 . This model should be
carefully distinguished from all the many other mixture mod-
els for water, two-state or otherwise, where this explicit
outer-neighbor characteristic is not considered. The purpose
of the present paper is to illustrate in a quantitative fashion
how this extremely lucid idea can be used to gain a more
correct molecular-level understanding of the viscosity of liq-
uid water under temperature and pressure changes.
II. ANOMALOUS BEHAVIOR
For a long time it has been known that the thermal varia-
tions of the viscosity, as well as other dynamic properties of
water, do not obey the Arrhenius equation. Attempts to take
this into account go all the way from T-dependent apparent
activation energies with five adjustable parameters28 to two-
parameter power law fits.29 In 1971, Eicher and Zwolinski,11
on the basis of the analysis of their viscosity data from
8.28 C to 40 C, concluded that the then common prac-
tice of fitting an Arrhenius equation to the higher tempera-
ture data and a Vogel-type equation to the lower temperature
data may not be justified. They introduced a four-parameter
equation for the T-dependent viscosity that was a generaliza-
tion of other equations in common use for Newtonian liq-
uids, where the viscosity itself is independent of the external
force acting on a molecule. They then claimed that, The
necessity of defining two temperature regions for shear vis-

0021-9606/99/111(22)/10171/6/$15.00 10171 1999 American Institute of Physics

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 10172 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999
cosities remains an issue, and that their data for water in the
supercooled state, does not support the view of distinct
temperature regions in which glasslike transitions at lower
temperatures influence the viscosity. However, in 1974,
Kingham et al.4 returned to the VogelArrhenius-type fitting
procedure, claiming that the EicherZwolinski equation did
not fit their data well. The two-temperature theme was also
followed by Hindman30 in his analysis of relaxation times in
water.
Coming up to more recent times, in the Introduction of a
1991 Walrafen and Chu paper,31 it was stated that, the
strong temperature dependence of the activation energy of
the shear viscosity of liquid water at 1 atm, and especially
below 0 C, has been a longstanding problem, and that, an
explanation in terms of known mechanisms is particularly
troubling. They then state that, the corresponding Arrhen-
ius activation energies and their temperature dependencies
may thus lack true, or complete meaning, and that, ln s
vs T 1 plots fail to provide complete insights into the
mechanism of the shear viscosity.
III. STRUCTURAL ASPECTS
When explicit structural properties in liquid water are
discussed, they continue to deal with nearest-neighbor bond-
ing considerationsthe formation of rings, the presence of
clathrate structures, random networks of hydrogen bonds
HB and the breaking of them. For example, in a more re-
cent Walrafen and Chu paper32 stressing structure, emphasis
is placed on the presence of small and large holes in the
liquid, giving two energetic steps with high and low activa-
tion energies. Water molecules can either squeeze through
hydrogen-bonded pentagonal rings or move through larger
voids in bulky clathratelike polyhedra. This mixed high-
viscosity/low-viscosity type description was said to explain
the high activation energies and large negative activation
volumes for the viscosity in supercooled water. In partial
qualitative agreement with the views to be expressed here,
two things take place as the temperature is lowered; a normal
stiffening of structure occurs, but on top of this, not easily
penetrable structure grows in to further increase the viscos-
ity. However, the fact that the higher viscosity component in
this Walrafen/Chu model corresponds to one of higher den-
sity makes it difficult to understand the pressure anomaly.
In the Krone paper,2 emphasis does seem to shift some-
what towards bent hydrogen bonds and the possible impor-
tance of bonding in the various ice forms. It is said that
structures in water can be derived from its viscosity, and that
there is compelling evidence of structure in liquid water.
It is then stated that a recently developed viscosity
temperature relation has led to a description of liquid water
in terms of a continuous succession of structural transitions
as the bonding diminishes with rising temperature. However,
the extended structures in the liquid described by Krone2
seem far too icelike, though missing any clearly formulated
connection with outer-neighbor structural characteristics re-
lated to the dense ice polymorphs.21
In past work,24 we have summarized how the bending of
the OOO structure from normal ice-Ih-like 4.5 OO
outer distances to more compact ice-II-like 3.5 OO
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Cho, Urquidi, and Robinson
distances can account for the density variations, the isother-
mal compressibility and other structural properties of wa-
ter. However, these OO transformations, while clearly the
centerpiece for the description of the density, may have only
a secondary effect on the viscosity by helping to promote a
softening of some of the OHO structure. Distortions
of the linear OHO assembly and the OOO bending
may have to be considered as separate steps in the continu-
ous succession of structural transitions.2 On the other hand,
an increased fluidity could be produced by the overall
temperature-dependent transformation of Ih-type bonding to
more fluid but more dense II-type bonding, accompanied by
an inherent softening of the OHO structure. This would
complement the ordinary temperature-dependent softening
effects as the temperature rises, leading to the steeper than
expected increase of fluidity with increasing temperature.
The pressure effect18,33 on the viscosity of water, which con-
tradicts the case met for ordinary liquids where pressure
squeezes the molecules together and increases the viscosity,
can also be understood in this way.
IV. EXPERIMENTAL VISCOSITY DATA
There exist many experimental papers concerned with
the viscosity of liquid H2O over normal to high temperature
ranges for atmospheric and elevated pres-
sures.4,6,814,1618,3335 However, fewer data are available for
D2O1,10,12,15,17,3641 or for normal and elevated pressures in
the supercooled region.9,11,41,42 Since any explicit mixture
model would be expected to break down at high
temperatures,23 the present paper will concentrate mainly on
temperatures below 100 C.
In 1978, Kestin et al.9 reanalyzed the then existing vis-
cosity data for H2O, using four- or five-parameter empirical
relationships to represent the ratio of the viscosity at tem-
perature t C and the viscosity at some standard temperature,
t * , taken to be 20 C, where the viscosity of H2O has been
fixed as an international standard, 201.002 centipoise
cP.43 A useful summary of the Kestin et al. smoothed vis-
cosities for 5 C increments is presented in Table VII of Ref.
9, and some of those values are reproduced here in Table I.
These data are from two different equations, a low-
temperature equation 8 to 40 C and one used in an
earlier paper,35 best for higher temperatures 40 to
150 C, having an additional parameter but with less over-
all precision for this extended temperature range.
The raw experimental data of Eicher and Zwolinski11
match those of Kestin et al. very well from perhaps 5 C to
nearly 40 C, though for t0 C and for t30 C the un-
certainties are larger see Table I. For example, at 8.28 C,
the Eicher/Zwolinski viscosity is about 0.009 cP higher than
the Kestin et al.9 value from their low-temperature equation.
Another useful set of viscosity data for H2O was published
by Korosi and Fabuss6 in 1968. The temperatures of these
data ranged from 20 to 150 C. From about 110 to 140 C,
the Korosi/Fabuss viscosities are a modest 0.0005 cP
higher than those of Kestin et al.9 For the data from 80 to
95 C, however, the situation is reversed. An even earlier
paper by Hardy and Cottington10 covered the broad tempera-
ture range of 5 to 125 C. When compared with other com-
 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 Viscosity of water 10173

TABLE I. Smoothed experimental viscosity data from Eq. 1 and two-state fit.a

t C 20 10 0 10 20 30 40 50 60 80 100

Ref. 18 1.792 1.307 1.002 0.7977 0.6532 0.5470 0.4665 0.3544 0.2818
Ref. 9 4.242 2.628 1.792 1.307 1.002 0.7973 0.6527 0.5471 0.4670 0.3551 0.2821
Refs. 10, 11 4.372 2.642 1.792 1.307 1.002 0.7973 0.6528 0.5467 0.4665 0.3548 0.2822
Ref. 10 4.381 2.642 1.791 1.306 1.002 0.7975 0.6530 0.5469 0.4666 0.3547 0.2821
Ref. 11 4.373 2.642 1.792 1.307 1.002 0.7972 0.6527 0.5467 0.4666 0.3553 0.2834
Ref. 6 4.473 2.668 1.798 1.308 1.002 0.7972 0.6528 0.5468 0.4666 0.3548 0.2821

Two-state 4.353 2.647 1.792 1.306 1.002 0.7973 0.6530 0.5469 0.4665 0.3547 0.2823
a
The first two rows of data are standard values from the literature, while the third row gives our smoothed experimental data from Refs. 10 and 11. Boldface
represents smoothed data for temperatures covered in the original experiments, while italics are data extended by Eq. 1 beyond the temperatures of the
original experiments, except for Ref. 9, where their Eq. 15 was used to extend the data below 0 C. The two-state values at the bottom of this table will be
discussed in Sec. VI of this paper. All viscosity data are in units of cP.

pilations and using various methods of smoothing, the Even though our smoothed viscosities differ from the
Hardy/Cottington results seem very good indeed. best experimental viscosities by less than 0.0005 cP for all
Since, at higher temperatures, smoothing gives some- temperatures from 0 up to 150 C, included in Table I are
what better agreement with the Hardy/Cottington data10 also data only up to 100 C. Above even 70 C, the reliability of
the Korosi/Fabuss data6 than from the Kestin et al. the simple mixture model idea begins to depreciate as seen
equations,9 we have combined the data from Ref. 10 for from Table III of Ref. 23, so, for the purposes here, inclusion
temperatures 40 C with the Eicher/Zwolinski data11 from of the higher temperature data are not relevant. It should be
6.647 to 30 C to create a best set of experimental H2O noted from Table I that the uncertainties among all the data
viscosities. The most recent internationally recognized vis- sets increase below 0 C. Because of the lack of the most
cosity compilations for 0 t100 C can be found in reliable experimental data in the supercooled region, the
Table C.II of Ref. 18. This compilation over a more limited probable errors in the smoothed viscosity values from Eq. 1
temperature range gives viscosities fairly close to our could very well climb towards 0.05 cP for temperatures be-
smoothed values and will merely be used here as a reference low 20 C. The resulting best fit parameters for the data
for other values in Table I. sets of Table I are given in Table II, along with root-mean-
The usual empirical method for expressing the viscosity square deviations with respect to the actual experimental
of water is through the use of a T-dependent series expansion points obtained by the original authors.
of its logarithm. The Kestin et al. equations9,35 have this
form. However, this equation, with its usual four or five ad- V. VISCOSITIES OF D2O AND T2O
justable parameters, is not so well equipped for reproducing
the steeply rising viscosity of water at very low temperatures Since a paper on thermal offset viscosities has been
and at the same time the flatter dependence at higher tem- published in another journal,45 only a brief discussion of D2O
peratures. The viscosities at low temperatures are forced to and T2O viscosities will be presented here. This thermal off-
too low a value, as seen in Table I. An empirical smoothing set effect is a purely structural effect caused by the differ-
equation, related to the logarithmic equations, but which has ences in intermolecular vibrational zero-point energies be-
a curvature more suitable for fitting the viscosities of water tween the isotopic forms for the mixed structures in the
over a wide temperature range, is a five parameter extended liquid. The existence of such an effect in liquid water, as
power-law equation, previously also obtained from an analysis of the densities46
of H2O and D2O, helps further to confirm the two-state mix-
T A TaT 2 bT 3 cT 4 , 1
ture model picture for this substance.
where A, a, b, c, and are adjustable constants and The remarkable results of our thermal offset paper45 can
TTT 0 , with T 0 225.334 K being the limiting tem- be briefly summarized here. By merely shifting the tempera-
perature at which intermolecular bonding in the liquid be- ture of H2O viscosity data upwards by 6.498 C,44 excellent
comes purely Ih-type or low-density-amorph-type. This T 0 agreement with the expected47 M D2 O /M H2 O isotopic ratio
temperature has already been determined from a previous for the viscosity of D2O is found. For example, the viscosity
density analysis23 see also Ref. 44.
For the experimental data sets considered in the present
paper, these smoothed values are given in Table I to four TABLE II. Empirical fitting parameters and error estimates for experimental
significant figures for 10 or 20 C intervals, over not only the H2O viscosities using Eq. 1. In all cases, T 0 225.334 K.
temperature range considered by the original authors in bold A, cP T a, T 1 b, T 2 c, T 3
type but over the entire 20 to 100 C extended temperature
range. Some indication of the reliability of the sets of data, in Refs. 10, 11 802.25 3.47E-3 1.74E-5 2.77E-8 1.530 1.06E-4
Ref. 10 883.08 2.28E-3 1.14E-5 1.55E-8 1.570 6.28E-5
particular the reasonableness of the curvature, can be had by
Ref. 11 813.97 3.15E-3 1.48E-5 1.79E-8 1.537 6.91E-5
examining how well these smoothed data hold up outside Ref. 6 1189.18 3.73E-4 3.70E-6 3.99E-9 1.675 1.10E-4
their experimental range.
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 10174 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 Cho, Urquidi, and Robinson

of D2O at 26.498 C is equal to the viscosity of H2O at 20 C TABLE III. T-dependent quantities of interest.a
multiplied by the square-root-mass ratio of 1.05437. This f / P I II
offset effect can also, of course, be applied directly to em- t, C f 106 bar1 cP cP
pirical H2O viscosity formulations to obtain excellent D2O
20.0 0.5757 95.10 36.93 1.982
formulations without any further work. The agreement in the 10.0 0.5199 66.21 13.13 1.420
thermal offset D2O viscosities, which is sometimes better 0 0.4746 46.10 7.194 1.068
than the experimental uncertainty, ranges from 0.2% or less 10.0 0.4357 32.10 4.854 0.8347
for t20 C well into the supercooled region, up to 2% at 20.0 0.4014 22.35 3.678 0.6731
100 C, where the simple mixture model idea has broken 30.0 0.3704 15.56 2.993 0.5569
40.0 0.3422 10.83 2.552 0.4707
down.23 Complaints about the two-state outer-neighbor mix- 50.0 0.3163 7.54 2.249 0.4051
ture model for liquid water being oversimplified and too 60.0 0.2925 5.25 2.028 0.3539
structural need to be judged against quantitative successes 80.0 0.2501 2.55 1.732 0.2803
such as these. 100.0 0.2137 1.23 1.544 0.2310
a
The f-values are from the purely algebraic density analysis fit i in Ref. 23,
while f / P are somewhat revised from the original isothermal compress-
ibility analysis of Ref. 48. The other necessary parameters
VI. TWO-STATE ANALYSIS OF H2O VISCOSITY are (I)0.7395 cP, (II)0.0280 cP, E I 0.9045 kJ mol1, E II
4.1711 kJ mol1 , T I0 225.334 K, and T II0135.361 K.
In this section and the next, a two-state mixture model
formulation of the temperature and pressure dependence of
the viscosity will be provided. These dependencies will be more viscous component-Ih has a viscosity with temperature
seen to be directly related to f (T, P), the T,P-dependent frac- dependence similar to that of a mildly polar organic mol-
tion of the low density ice-Ih-type structure in the liquid. If ecule such as 2-chlorophenol.
we suppose that the fluidity, I and II , of each component
is distinct, then the fluidity of liquid water can be approxi- VII. PRESSURE EFFECTS
mately expressed as,
Usually, when pressure is applied to a liquid, the mol-
H2O f I 1 f II . 2 ecules are forced together, holes and defects vanish, and the
where the fluidity of each component is described by a modi- viscosity of the liquid rises. In liquid water below about
fied Arrhenius equation, 33 C, the situation is reversed.18,33 This decreasing viscosity
with increasing pressure can therefore be classed as one of
1 exp E /RT . 3 this substances most interesting anomalies. How can this
1 1 strangest anomaly of all be understood?
Here, R is the ordinary gas constant, 8.31451 J K mol ,
and for I , TTT 0 , where T 0 again is the limiting We have seen in the last section that the shear viscosity
temperature, 225.334 K,44 at which all bonding in liquid (T) of water can be expressed in terms of mixed fluidities
H2O is of the open low density variety ( f 1). The compo- using a two-state formalism. Converting Eqs. 2 and 3
sitional fraction f sharply decreases from unity with both to viscosity and differentiating with respect to pressure
increasing T and P, this feature being the dominant cause of yields,
all the anomalies of water.24 In fact, this feature is central to
the model used here for the viscosity, explaining its steep f II 1 f I 2
P
non-Arrhenius rise with decreasing T as the stiffer Ih-type
structure grows in. The T-dependence of f (T, P) has been
derived directly from the T-dependent density of water.23 In
that particular analysis fit i, it is important to note that the

f II2
I
P
1 f I2
II
P
I II I II
f
P
.

parameters were obtained from an exact algebraic fit, not a 4

least-squares fit. Remarkably, the resulting parameters from Remembering from Table III that I for the stiff Ih-type
that fit were found to reproduce ice Ih and ice II volume structure is quite a bit larger than II , and noting that f / P
properties very accurately. is negative, means that the last term in this expression is
The last row of Table I reproduces these two-state mix- negative. On the other hand, the preceding two terms are
ture model viscosities of water from Eqs. 2 and 3. The positive because the viscosities of each of the contributing
good agreement throughout the whole range of temperatures components in the two-state mixture are considered normal,
should be noted. The necessary data for these calculations that is, both I and II increase with increasing pressure.
are presented in Table III. There, it is seen, as expected, that, The overall negative / P for water as observed ex-
from this two-state analysis, there is a large difference be- perimentally at sufficiently low temperatures can be seen to
tween the Ih-type and II-type viscosities, I and II . The arise from the dominance of the last negative term in Eq. 4
analysis also indicates that distinct T 0 values for the two over the other two positive terms. This dominance is caused
components in liquid water should be used, since these com- by the strong decrease with pressure of f at low temperatures
ponents are distinct substances. For instance, the viscosity seen in Table III. The particularly steep decrease is caused
and its temperature dependence of the more fluid by the greater preponderance of Ih-type structure at low tem-
component-II is similar to that of methyl alcohol, while the peratures and ordinary pressures. On the other hand, the
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 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999
FIG. 1. The pressure derivatives of the viscosity of H2O as a function of
temperature. The experimental data from Kestin et al., Ref. 35, and from
Sengers and Watson, Ref. 18, are compared with the two-state results. The
curious-sounding unit of picoseconds, for / P arises from the fact that
1cP0.001 Pa s and 1bar105 Pa. Using the values give in Table III at t
20 C, Eq. 5, for example, gives 860.9106 cP bar1 or 8.609 between outer-neighbor Ih-type structure and II-type struc-
ps, to which the 0.25 ps value should be added to obtain the point on the
graph. See text.
changes of the viscosity components I and II with pressure
are expected not only to be small at low temperatures com-
pared with those from the f / P term, but their derivatives
should not be so greatly affected by temperature either. In
fact, a simplified first-approximation expression for the
change of the viscosity of water with pressure at different
low temperatures can be obtained by neglecting the small
positive terms in Eq. 4 altogether,
I II f would appear that all one has to do is to create a partition
2 I II . 5
P f II 1 f I P function for the liquid that correctly contains the structures,
As already remarked, the T-dependent f-values are known
from the density analysis,23 I(T) and II(T) are known
from the T-dependent viscosity analysis in the preceding sec-
tion, and f / P as a function of temperature is known from
the compressibility analysis.48 No new parameters therefore
need be considered to compute / P from Eq. 5.
What would be expected with the omitted small positive
terms is a calculated / P function that more or less par-
allels at fairly close range the experimental function.18,33
This is indeed what was found. In fact, by adding a small
positive constant term of 0.25 ps onto the calculated values
to take into account the neglected terms in Eq. 4, pretty
good agreement with the experimental values was obtained
see Fig. 1. An expected variation of the 0.25 ps term with
temperature could bring the calculated and experimental val-
ues of / P into still better agreement. However, of most
importance here, the shape of the / P curve not only
matches the shapes of the two experimental curves pictured,
but the deviations across the entire temperature range,
30 C to 100 C, are not much larger than the difference
between those two curves. This latter difference reflects
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Viscosity of water 10175
some measure of the difficulty of obtaining experimentally
or by extrapolation accurate values of / P at supercooled
temperatures.
VIII. CONCLUSIONS
This paper has further illustrated the validity of the two-
state mixture model approach for an important and previ-
ously poorly understood property of water, the viscosity.
Earlier, we demonstrated45 that isotope effects on the viscos-
ity quantitatively fall out of this type of analysis, quite natu-
rally and quite straightforwardly. No new equations or pa-
rameters are required. The same was found to be the case for
the pressure dependence of the viscosity described here. In
fact, it was found that when the modified Arrhenius fluidities
are used in the mixed fluidity equation, and the resulting
expression is differentiated with respect to pressure, the most
prominent new parameter is f / P, a quantity already
known as a function of temperature from an earlier analysis
of the isothermal compressibility.48 Thus, it becomes easy to
unify all the properties of this remarkable substance under a
single, very simple structural property, the transformation
ture.
Finally, one might be wondering how to proceed with
this water problem using the more traditional approaches of
cluster studies, quantum theory and statistical mechanics, as
well as the ever improving computational methods. First of
all, cluster studies and quantum theory are complementary,
not only in their attributes, but also in their deficiencies. It
seems that it will be some time yet before the next generation
of water clusters 1001000 molecules that avoid edge
effects can make an impact for describing the relevant
outer structure in liquid water.
The application of statistical mechanics to the problem
of liquid water has more chance for immediate success. It
intermolecular bonding and librational characteristics of the
open Ih-like and dense II-like forms. If correctly constructed,
the transformation with increasing temperature or pressure
between these two forms should occur automatically. This
modified statistical mechanical picture can then be used in
conjunction with ordinary liquid state theories to calculate
thermodynamic properties, not only of pure water, but also
when water is subjected to solute and interface perturbations,
a most important extension.
Meantime, computational approaches using ever improv-
ing computer resources will continue to dominate this field.
Again, however, because of the impact the two-state trans-
formation must make on the entropy and other thermody-
namic quantities, realistic results over wide temperature and
pressure ranges or in the presence of an interface, will be
obtained only if the outer structural characteristics of the
waterwater interactions are correctly incorporated. Compu-
tational studies of liquid water, particularly with respect to
biological interface problems,49 are too important to wait un-
til the fundamental physics tells us what we already know
from ice polymorph studies21 about bonding characteristics
in the liquid, namely that there are two explicit outer-
 10176 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 Cho, Urquidi, and Robinson

neighbor OO distances in this substance, and that
temperature- and pressure-induced transformations24 be-
tween these two structures are what primarily determine the
properties of this important liquid.
ACKNOWLEDGMENTS
Acknowledged for financial support of this work are the
R. A. Welch Foundation D-0005 and D-1094 and the Pe- 27
troleum Research Fund ACS-PRF# 32253-AC6. Private fi- 28
nancial support from Dr. Joel Kwok, Dr. and Mrs. Jamine
Lee and the Chemistry Support Fund at Texas Tech is also
acknowledged. Dr. Surjit Singh is also acknowledged for
some of his earlier contributions to this problem.
1
F. J. Millero, R. Dexter, and E. Hoff, J. Chem. Eng. Data 16, 85 1971.
2
R. B. Krone, Chem. Eng. Commun. 128, 1 1994. 34
3
Hydration Processes in Biological and Macromolecular Systems, The 35
Royal Society of Chemistry, Faraday Division General Discussion No.
103, April 13, 1996, Sheffield, England.
4
D. J. Kingham, W. A. Adams, and M. J. McGuire, J. Chem. Eng. Data 19,
1 1974.
5
N. Matsunaga, M. Hori, and A. Nagashima, Physica A 156, 547 1989. 38
6
A. Korosi and B. M. Fabuss, Anal. Chem. 40, 157 1968. 39
7
E. C. Bingham and G. F. White, Z. Phys. Chem. Leipzig 80, 670 1912;
E. C. Bingham, Fluidity and Plasticity McGrawHill, New York, 1922, 40
p. 76.
8
G. F. White and R. H. Twining, Am. Chem. J. 50, 380 1913.
9
J. Kestin, M. Sokolov, and W. A. Wakeham, J. Phys. Chem. Ref. Data 7,
941 1978. 43
10
R. C. Hardy and R. L. Cottington, J. Res. Natl. Bur. Stand. 42, 573 1949.
11
L. D. Eicher and B. J. Zwolinski, J. Phys. Chem. 75, 2016 1971.
12
N. A. Agayev and A. D. Yusibova, Dokl. Akad. Nauk SSSR 180, 334
1968. See also, N. A. Agayev, in Proceedings of the 9th International 44
Conference on the Properties of Steam, 1014 September, 1979, Tech-
nische Universitat Munchen, Federal Republic of Germany, p. 362.
13
J. T. R. Watson, R. S. Basu, and J. V. Sengers, J. Phys. Chem. Ref. Data
9, 1255 1980.
14
Compilations of H2O viscosities with many early references can be found
in A. Nagashima, J. Phys. Chem. Ref. Data 6, 1133 1977.
15
N. Matsunaga and A. Nagashima, J. Phys. Chem. Ref. Data 12, 933
1983.
16
J. V. Sengers and B. Kamgar-Parsi, J. Phys. Chem. Ref. Data 13, 185
1984.
17
J. Kestin, N. Imaishi, S. H. Nott, J. C. Nieuwoudt, and J. V. Sengers,
Physica A 134, 38 1985.
18
J. V. Sengers and J. T. R. Watson, J. Phys. Chem. Ref. Data 15, 1291
1986.
19
See the introductory paragraphs in two articles by F. Franks, in Water: A
Comprehensive Treatise, edited by F. Franks Plenum, New York, 1972,
1973, Vol. 1, pp. 120 and Vol. 2, pp. 154.
20
G. Z. Tammann, Anorg. Allgem. Chem. 158, 1 1926. 48
21
B. Kamb, in Structural Chemistry and Molecular Biology, edited by A.
Rich and N. Davidson Freeman, San Francisco, 1968, p. 507. 49
22
M.-P. Bassez, J. Lee, and G. W. Robinson, J. Phys. Chem. 91, 5818
1987.
23
M. Vedamuthu, S. Singh, and G. W. Robinson, J. Phys. Chem. 98, 2222
1994.
24
C. H. Cho, S. Singh, and G. W. Robinson, J. Chem. Phys. 107, 7979
1997.
25
G. W. Robinson, C. H. Cho, and J. Urquidi, J. Chem. Phys. 111, 698
1999.
26
L. Bosio, S.-H. Chen, and J. Teixeira, Phys. Rev. A 27, 1468 1983.
A. V. Okhulkov, Yu. N. Demianets, and Yu. E. Gorbaty, J. Chem. Phys.
100, 1578 1994.
L. Korson, W. Drost-Hansen, and F. J. Millero, J. Phys. Chem. 73, 34
1969.
29
A. Matczuk, L. Kuak, and C. Bojarski, Phys. Rev. B 50, 777 1994.
30
J. C. Hindman, J. Chem. Phys. 60, 4488 1974.
31
G. E. Walrafen and Y. C. Chu, J. Phys. Chem. 95, 8909 1991.
32
G. E. Walrafen and Y. C. Chu, J. Phys. Chem. 99, 10635 1995.
33
J. Kestin, H. E. Khalifa, H. Sookiazian, and W. A. Wakeham, Ber. Bun-
senges. Phys. Chem. 82, 180 1978.
J. Kestin and J. V. Sengers, J. Phys. Chem. Ref. Data 15, 305 1986.
J. Kestin, H. E. Khalifa, S.-T. Ro, and W. A. Wakeham, J. Chem. Eng.
Data 22, 207 1977.
36
G. N. Lewis and R. T. McDonald, J. Am. Chem. Soc. 55, 4730 1933.
37
J. R. Heiks, M. K. Barnett, L. V. Jones, and E. Orban, J. Phys. Chem. 58,
488 1954.
D. L. Timrot and K. F. Shuiskaya, Sov. J. At. Energy 7, 925 1959.
A. Selecki, B. Tyminski, and A. G. Chmielewski, J. Chem. Eng. Data 15,
127 1970.
A. Kellomaki, Finn. Chem. Lett. 2, 51 1975.
41
Yu. A. Osipov, B. V. Zheleznyi, and N. F. Bondarenko, Russ. J. Phys.
Chem. 51, 748 1977.
42
J. Hallett, Proc. Phys. Soc. 82, 1046 1963.
See Ref. 15 for some of the background of this. Since the use of the unit
poise spans at least a century, and the unit centipoise is still in common
scientific use, it will be used in the present paper. To convert cP to the
recommended unit Pa s, one merely multiplies the cP value by 1000.
M. Vedamuthu, S. Singh, and G. W. Robinson, J. Phys. Chem. 98, 8591
1994. The T 0 values for H2O and D2O from Table I of this reference
differ by 6.498 C compared with the 7.201 C difference in the tempera-
tures of maximum density. For this reason, the T 0 values for H2O and D2O
from the above reference will be used for the viscosity analysis, 225.334
K for H2O and 231.832 K for D2O. The T 0 value of 234.1 K for T2O is an
estimate based on the trend of the two T 0 values for the lighter isotopic
forms.
45
C. H. Cho, J. Urquidi, S. Singh, and G. W. Robinson, J. Phys. Chem. 103,
1991 1999.
46
M. Vedamuthu, S. Singh, and G. W. Robinson, J. Phys. Chem. 100, 3825
1996.
47
This vibrational force constant description forms the basis for standard gas
phase calculations of the viscosity from intermolecular potential functions.
See, for example, the problem on p. 561 of J. O. Hirschfelder, C. F.
Curtiss, and R. B. Bird, Molecular Theory of Gases and Liquids Wiley,
New York, 1954.
M. Vedamuthu, S. Singh, and G. W. Robinson, J. Phys. Chem. 99, 9263
1995.
G. W. Robinson and C. H. Cho, Biophys. J. in press.

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