You are on page 1of 7

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
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/111/22?ver=pdfcov
Published by the AIP Publishing

Articles you may be interested in


Temperature, pressure, and isotope effects on the structure and properties of liquid water: A lattice approach
J. Chem. Phys. 127, 224106 (2007); 10.1063/1.2804418

Temperature and Hydrostatic Pressure Effects on the Band Gap of Semiconducting Carbon Nanotubes
AIP Conf. Proc. 772, 1047 (2005); 10.1063/1.1994471

Effect of Pressure and Temperature on the Wetting Behaviour of Volatile Drops


AIP Conf. Proc. 699, 174 (2004); 10.1063/1.1649572

Formation of Plutonium Hydride PuH2: Description of the Reaction Rate Surface as a Function of Pressure and
Temperature
AIP Conf. Proc. 673, 179 (2003); 10.1063/1.1594596

Pressure and temperature dependences of the relaxation dynamics of cresolphthalein-dimethylether: Evidence of


contributions from thermodynamics and molecular interactions
J. Chem. Phys. 114, 10872 (2001); 10.1063/1.1374556

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
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 intact with respect to the number of neighbors, four, and the
OO distances, 2.8 . However, on increasing the tem-
The importance of the viscosity for understanding the
perature or the pressure, a transformation takes place in the
structure and anomalies of water and its isotopic modifi-
outer-neighbor region from a stiff Ih-type OO structure at
cations cannot be overemphasized.1,2 From a practical point
4.5 to a less rigid, more dense II-type bent hydrogen-
of view, the importance of the viscosity of water to biology3
bonded OO structure near 3.5 . This model should be
and the environment,4 to engineering and reactor
carefully distinguished from all the many other mixture mod-
technology,5 to other technologies,6 and as a reference mate-
els for water, two-state or otherwise, where this explicit
rial in viscometry,79 has been discussed widely in past
outer-neighbor characteristic is not considered. The purpose
work. This importance is further evidenced by the continuing
of the present paper is to illustrate in a quantitative fashion
activity, since the time of Bingham,7 for whom a viscometer
how this extremely lucid idea can be used to gain a more
was named, in the measurement, refinement and analysis by
correct molecular-level understanding of the viscosity of liq-
national and international organizations of the viscosity data
uid water under temperature and pressure changes.
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- II. ANOMALOUS BEHAVIOR
lationship between the viscosities of the isotopic modifica- For a long time it has been known that the thermal varia-
tions of water have been of greatest interest. Yet, following tions of the viscosity, as well as other dynamic properties of
much past activity, these problems have remained unsolved. water, do not obey the Arrhenius equation. Attempts to take
We believe that the main difficulty with past attempts to this into account go all the way from T-dependent apparent
create an understanding of liquid water, or to develop valid activation energies with five adjustable parameters28 to two-
relationships for its viscosity, is the failure to recognize the parameter power law fits.29 In 1971, Eicher and Zwolinski,11
intrinsic differences between this liquid and others.19 Though on the basis of the analysis of their viscosity data from
suggested long ago by Tammann20 and later more explicitly 8.28 C to 40 C, concluded that the then common prac-
by Kamb,21 the consideration of temperature- and pressure- tice of fitting an Arrhenius equation to the higher tempera-
dependent outer-neighbor structural changes in water has ture data and a Vogel-type equation to the lower temperature
been absent in all but our own work.2225 These structural data may not be justified. They introduced a four-parameter
effects now seem well established experimentally.2527 Ex- equation for the T-dependent viscosity that was a generaliza-
cept for bending21,24 of the regular tetrahedral OOO tion of other equations in common use for Newtonian liq-
angle of 109.5, the inner structure in the liquid remains uids, where the viscosity itself is independent of the external
force acting on a molecule. They then claimed that, The
a
Electronic mail: gwrob@ttacs.ttu.edu necessity of defining two temperature regions for shear vis-

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


This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
10172 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 Cho, Urquidi, and Robinson

cosities remains an issue, and that their data for water in the distances can account for the density variations, the isother-
supercooled state, does not support the view of distinct mal compressibility and other structural properties of wa-
temperature regions in which glasslike transitions at lower ter. However, these OO transformations, while clearly the
temperatures influence the viscosity. However, in 1974, centerpiece for the description of the density, may have only
Kingham et al.4 returned to the VogelArrhenius-type fitting a secondary effect on the viscosity by helping to promote a
procedure, claiming that the EicherZwolinski equation did softening of some of the OHO structure. Distortions
not fit their data well. The two-temperature theme was also of the linear OHO assembly and the OOO bending
followed by Hindman30 in his analysis of relaxation times in may have to be considered as separate steps in the continu-
water. ous succession of structural transitions.2 On the other hand,
Coming up to more recent times, in the Introduction of a an increased fluidity could be produced by the overall
1991 Walrafen and Chu paper,31 it was stated that, the temperature-dependent transformation of Ih-type bonding to
strong temperature dependence of the activation energy of more fluid but more dense II-type bonding, accompanied by
the shear viscosity of liquid water at 1 atm, and especially an inherent softening of the OHO structure. This would
below 0 C, has been a longstanding problem, and that, an complement the ordinary temperature-dependent softening
explanation in terms of known mechanisms is particularly effects as the temperature rises, leading to the steeper than
troubling. They then state that, the corresponding Arrhen- expected increase of fluidity with increasing temperature.
ius activation energies and their temperature dependencies The pressure effect18,33 on the viscosity of water, which con-
may thus lack true, or complete meaning, and that, ln s tradicts the case met for ordinary liquids where pressure
vs T 1 plots fail to provide complete insights into the squeezes the molecules together and increases the viscosity,
mechanism of the shear viscosity. can also be understood in this way.

III. STRUCTURAL ASPECTS IV. EXPERIMENTAL VISCOSITY DATA


When explicit structural properties in liquid water are There exist many experimental papers concerned with
discussed, they continue to deal with nearest-neighbor bond- the viscosity of liquid H2O over normal to high temperature
ing considerationsthe formation of rings, the presence of ranges for atmospheric and elevated pres-
clathrate structures, random networks of hydrogen bonds sures.4,6,814,1618,3335 However, fewer data are available for
HB and the breaking of them. For example, in a more re- D2O1,10,12,15,17,3641 or for normal and elevated pressures in
cent Walrafen and Chu paper32 stressing structure, emphasis the supercooled region.9,11,41,42 Since any explicit mixture
is placed on the presence of small and large holes in the model would be expected to break down at high
liquid, giving two energetic steps with high and low activa- temperatures,23 the present paper will concentrate mainly on
tion energies. Water molecules can either squeeze through temperatures below 100 C.
hydrogen-bonded pentagonal rings or move through larger In 1978, Kestin et al.9 reanalyzed the then existing vis-
voids in bulky clathratelike polyhedra. This mixed high- cosity data for H2O, using four- or five-parameter empirical
viscosity/low-viscosity type description was said to explain relationships to represent the ratio of the viscosity at tem-
the high activation energies and large negative activation perature t C and the viscosity at some standard temperature,
volumes for the viscosity in supercooled water. In partial t * , taken to be 20 C, where the viscosity of H2O has been
qualitative agreement with the views to be expressed here, fixed as an international standard, 201.002 centipoise
two things take place as the temperature is lowered; a normal cP.43 A useful summary of the Kestin et al. smoothed vis-
stiffening of structure occurs, but on top of this, not easily cosities for 5 C increments is presented in Table VII of Ref.
penetrable structure grows in to further increase the viscos- 9, and some of those values are reproduced here in Table I.
ity. However, the fact that the higher viscosity component in These data are from two different equations, a low-
this Walrafen/Chu model corresponds to one of higher den- temperature equation 8 to 40 C and one used in an
sity makes it difficult to understand the pressure anomaly. earlier paper,35 best for higher temperatures 40 to
In the Krone paper,2 emphasis does seem to shift some- 150 C, having an additional parameter but with less over-
what towards bent hydrogen bonds and the possible impor- all precision for this extended temperature range.
tance of bonding in the various ice forms. It is said that The raw experimental data of Eicher and Zwolinski11
structures in water can be derived from its viscosity, and that match those of Kestin et al. very well from perhaps 5 C to
there is compelling evidence of structure in liquid water. nearly 40 C, though for t0 C and for t30 C the un-
It is then stated that a recently developed viscosity certainties are larger see Table I. For example, at 8.28 C,
temperature relation has led to a description of liquid water the Eicher/Zwolinski viscosity is about 0.009 cP higher than
in terms of a continuous succession of structural transitions the Kestin et al.9 value from their low-temperature equation.
as the bonding diminishes with rising temperature. However, Another useful set of viscosity data for H2O was published
the extended structures in the liquid described by Krone2 by Korosi and Fabuss6 in 1968. The temperatures of these
seem far too icelike, though missing any clearly formulated data ranged from 20 to 150 C. From about 110 to 140 C,
connection with outer-neighbor structural characteristics re- the Korosi/Fabuss viscosities are a modest 0.0005 cP
lated to the dense ice polymorphs.21 higher than those of Kestin et al.9 For the data from 80 to
In past work,24 we have summarized how the bending of 95 C, however, the situation is reversed. An even earlier
the OOO structure from normal ice-Ih-like 4.5 OO paper by Hardy and Cottington10 covered the broad tempera-
outer distances to more compact ice-II-like 3.5 OO ture range of 5 to 125 C. When compared with other com-
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
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.
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
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
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 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
FIG. 1. The pressure derivatives of the viscosity of H2O as a function of
known as a function of temperature from an earlier analysis
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 of the isothermal compressibility.48 Thus, it becomes easy to
curious-sounding unit of picoseconds, for / P arises from the fact that unify all the properties of this remarkable substance under a
1cP0.001 Pa s and 1bar105 Pa. Using the values give in Table III at t single, very simple structural property, the transformation
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. 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
changes of the viscosity components I and II with pressure well as the ever improving computational methods. First of
are expected not only to be small at low temperatures com- all, cluster studies and quantum theory are complementary,
pared with those from the f / P term, but their derivatives not only in their attributes, but also in their deficiencies. It
should not be so greatly affected by temperature either. In seems that it will be some time yet before the next generation
fact, a simplified first-approximation expression for the of water clusters 1001000 molecules that avoid edge
change of the viscosity of water with pressure at different effects can make an impact for describing the relevant
low temperatures can be obtained by neglecting the small outer structure in liquid water.
positive terms in Eq. 4 altogether, The application of statistical mechanics to the problem
of liquid water has more chance for immediate success. It
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,
intermolecular bonding and librational characteristics of the
As already remarked, the T-dependent f-values are known open Ih-like and dense II-like forms. If correctly constructed,
from the density analysis,23 I(T) and II(T) are known the transformation with increasing temperature or pressure
from the T-dependent viscosity analysis in the preceding sec- between these two forms should occur automatically. This
tion, and f / P as a function of temperature is known from modified statistical mechanical picture can then be used in
the compressibility analysis.48 No new parameters therefore conjunction with ordinary liquid state theories to calculate
need be considered to compute / P from Eq. 5. thermodynamic properties, not only of pure water, but also
What would be expected with the omitted small positive when water is subjected to solute and interface perturbations,
terms is a calculated / P function that more or less par- a most important extension.
allels at fairly close range the experimental function.18,33 Meantime, computational approaches using ever improv-
This is indeed what was found. In fact, by adding a small ing computer resources will continue to dominate this field.
positive constant term of 0.25 ps onto the calculated values Again, however, because of the impact the two-state trans-
to take into account the neglected terms in Eq. 4, pretty formation must make on the entropy and other thermody-
good agreement with the experimental values was obtained namic quantities, realistic results over wide temperature and
see Fig. 1. An expected variation of the 0.25 ps term with pressure ranges or in the presence of an interface, will be
temperature could bring the calculated and experimental val- obtained only if the outer structural characteristics of the
ues of / P into still better agreement. However, of most waterwater interactions are correctly incorporated. Compu-
importance here, the shape of the / P curve not only tational studies of liquid water, particularly with respect to
matches the shapes of the two experimental curves pictured, biological interface problems,49 are too important to wait un-
but the deviations across the entire temperature range, til the fundamental physics tells us what we already know
30 C to 100 C, are not much larger than the difference from ice polymorph studies21 about bonding characteristics
between those two curves. This latter difference reflects in the liquid, namely that there are two explicit outer-
This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34
10176 J. Chem. Phys., Vol. 111, No. 22, 8 December 1999 Cho, Urquidi, and Robinson

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

This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to IP:
137.112.220.81 On: Wed, 03 Dec 2014 21:21:34