Relationship between Relaxation Time and Viscosity for Water

E. H. Grant

Citation: The Journal of Chemical Physics 26, 1575 (1957); doi: 10.1063/1.1743585
View online: http://dx.doi.org/10.1063/1.1743585
View Table of Contents: http://aip.scitation.org/toc/jcp/26/6
Published by the American Institute of Physics

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 PERPENDICULAR BANDS OF ALLENE 1575

Comments on (i): Recently, Rao and Palik14 carried TABLE Ir. Molecular constants of allene.
out additional investigations on the "11 band of allene
Band centers: Ps=3089' 6 cm-I, P9= 1014.s cm-I ,
and also resolved and analyzed the corresponding band Plo=840. s cm-I , Pll =351. 3 cm-I ,
in allene-d 4 observed at 33 J.L. The spectra obtained by 2ps=6136 cm-I , 2PlO= 1688 cm-I
keeping allene at room temperature and at -80C (Q branches).
confirm the earlier conclusions of these authors.6 r values: rs=O.04, r9+rlO=O.16
Furthermore, by making use of the well-known prin- rll=O.82
ciple that the wave number of a "difference" band is A=5.04 cm-I IA=5.5 6 X1O- 40 g cm2
identically equal to the difference in wave numbers of aBo=O.29653 cm-I IB=94.3~X1o-40g cm 2
rO_H=1.0~ A "0_0 = 1.3~ A
the two bands involved even if anharmonicity is taken 'Y= 116'9
into account,15 it can be shown14 that it is difficult to
reconcile the identification of the 2680 cm-1 band with B. P. Stoicheff."
either ("6-"11) or ("1-"11) as suggested by Overend
and Thompson. expression 4[A (1- (r9+rlO)/2)-B] would be 17.35
Comments on (ii): It has been found also by Rao and cm-l This value of "9, however, appears not to be in
Palikl4 that the data on the C= C= C bending modes agreement with any previous workers. It may be hoped
of allene and allene-d 4 are consistent with a value of that the rigorous theory concerning the anharmonic
17.50 cm-l for the expression 4[A(1-(r9+r10)/2)-B] factors in the potential functions of the allene mole-
assuming, of course, the validity of the r -sum rule. cule that is being worked out by W. H. Shaffer, R.
This value is closer to that which is given in Eq. (3) Herman, and J. Louck may throw more light on these
than that obtained by adopting the set of band centers considerations and systematize the analysis of the per-
chosen by Overend and Thompson for the "9 and "10 pendicular bands of allene. The main point in favor of
bands. On the other hand, if Overend and Thompson's the molecular constants evaluated in the present paper
analysis of "10 is assumed it would be necessary to shift is that by combining the A, r, B relations deduced by
the band center of "9 to 1033 cm-l in order that the us with the results on the low-frequency type E funda-
mentals of allene and allene-d 4 we obtain an internally
14 K. Narahari Rao and E. D. Palik, J. Molecular Spectroscopy consistent set of values for the rotational constant A of
(to be published).
16 Reference 9, p. 269. allene and allene-d 4 14

THE JOURNAL OF CHEMICAL PHVSICS VOLUME 26. NUMBER 6 JUNE. 1957

Relationship between Relaxation Time and Viscosity for Water

E. H. GRANT
Department of Physics Applied to Medicine, The Middlesex Hospital Medical School, London W.l., England
(Received October 24, 1956)

The Debye relationship connecting relaxation time, viscosity, molecular size, and absolute temperature
appears to hold almost exactly in the case of water. The Debye equation was formulated on the basic as-
sumption that each molecule can be considered as turning in a viscous continuum as it rotates in dielectric
relaxation, and it is well known that this molecular picture is inapplicable to water.
It is shown that a similar relationship can be deduced directly from equations based on the hydrogen
bonded structure of the liquid.

INTRODUCTION where a is the radius of the molecule, T the absolute

temperature, 1] the viscosity of the liquid, k is Boltz-
F OR many polar liquids a close relationship exists
between relaxation time and viscosity, thus indi-
cating that similar molecular changes are involved in
mann's constant, and c is the velocity of light in vacuo.
More recent work of Hill2 has modified Eq. (1) for
pure polar liquids with the result that the numerical
both phenomena.
If a relaxing molecule is considered as akin to a
factor of 471' is replaced by !(3-\"1) and a3 is replaced
sphere rotating in oil, then it was shown by Debyel that by a more complicated expression which has, however,
the relaxation time T and the relaxation wavelength As approximately the same magnitude.
Both Hill's equation and Debye's equation can be
are given by
used to interpret experimental results in terms of
A. 47ra3 '1 molecular quantities. Hill shows that most of the polar
T=-=--'-, (1) substances studied by Conner and Smyth,3 and Hen-
2'71'c k T
2N. Hill, Proc. Phys. Soc. (London) B67, 149 (1954).
P. Debye Polar Molecules (Chemical Catalog Company, Inc.,
1 3W. P. Conner and C. P. Smyth, J. Am. Chern. Soc. 65, 382
New York, 1929). (1943).
1576 E. H. GRANT

that the five states which are present may be listed as

ID
POIS/,
10 so 40 '0 '0
FIG. 1. The experimental relationship between relaxation
wavelength and viscosity. (Note: :>..=2".C1', where 1'= the relaxa-
tion time and c=the velocity of light.)
nelly, Heston, and Smyth4 give good agreement be-
tween experimental relaxation times and those calcu-
lated on her theory, while the agreement is much less
satisfactory if Debye's equation is employed. In the
case of the two hydrogen-bonded polar liquids investi-
gated by Conner and Smyth (2-methyl heptanol-3 and
octanol-1), neither of the above two theories gives good
agreement with experiment. This is not surprising,
however, since both theories are formulated on the
basic idea of a central molecule being involved in colli-
sions with neighboring molecules as it rotates in dielec-
tric relaxation. For hydrogen-bonded liquids (such as
water and alcohols) this must be superseded by a
different molecular picture.
In view of the above facts, it would seem remarkable
that Eq. (1) should hold for water almost exactly,
yet this appears to be the case. The experimental plot
of A. vs 'YIlT is shown in Fig. 1. The value of a as de-
duced from the slope, which is 1.4 A, is in close agree-
ment with half the distance between the oxygen atoms
in four-bonded molecules, r; this distance being taken
as a measure of the "molecular diameter" insofar as this
term has any physical significance.
The purpose of this short paper is to show that the
proportionality between T and 'YIlT is compatible with
modern ideas of molecular relaxation, and, in particular,
with the theory proposed by Haggis, Hasted, and
Buchanan. 6 1
four bonded, three bonded, two bonded, one bonded,
and zero bonded. It is further assumed that a certain
number of bonds are broken as ice melts to form liquid
water and that bonds are broken as the temperature
increases, until at 370C all the molecules are zero
bonded. Assuming that ni represents the percentage of
molecules which are "i bonded" then sixteen equations
can be developed 6,7 from which the n's can be calcu-
lated at any temperature providing that the percentage
of bonds broken (p) is determined independently at that
temperature. The basic assumption of the theory is
that the a priori probability of breaking is the same for
all bonds.
The values of n; and p, which were calculated by
Haggis 7 on Pauling's assumptionS that 16% of the
bonds are broken in water at OC, are shown in Table I.
In a later publication Haggis et 0,1.6 chose alternative
values of p and ni, but the original method is simpler
and requires fewer assumptions.
The relaxation time as deduced from Haggis's7
theory can be expressed by the following relationship
1
-ocnzh(T)e-AHIRT, (2)
T
where llH is the activation energy for the formation of
a one-bonded molecule from a molecule which is two
bonded and h(T) is a function of temperature only.
A plot of logn2T vs liT gives a satisfactory straight line
with a slope corresponding to an activation energy of
about 3.3 kcal/mole.
Before passing to the viscosity relationship it is
necessary to consider whether equations of the type (2)
refer to the "molecular relaxation time" or to the macro-
scopic relaxation time as deduced from dielectric
measurements. The relationship between these quanti-
ties in terms of an "internal field correction" has been
discussed fully by Powles. 8 While for certain substances
it may be meaningful to draw a distinction between
these two parameters,9 in the case of water most
workers 6 7,HH2 prefer to equate them, and this pro-
TABLE I. Relative distribution of water molecules
in the bonded states.

STRUCTURE OF WATER TOC p% n, n. n. HI no

ice
According to Haggis et 0,1. 6 7 water is considered as at OC 0 100
consisting of five different types of molecule, each type 0 16 58 26 11 3.6 0.64
differing in the number of hydrogen bonds made with 25 19 51.7 28 13.9 5.3 1.1
60 23 45 29 16.7 7.3 1.8
neighboring molecules. For water, the maximum num- 100 28 37 30 20 10.5 3.0
ber of bonds which a molecule can make is four, so
8 J. G. Powles, J. Chem. Phys. 21, 633 (1952).
'Hennelly, Heston, and Smyth, J. Am. Chem. Soc. 70, 4102 9 C. P. Smyth, Dielectric Behavior and Structure (McGraw-Hill
(1948). Book Company, Inc., London, 1955).
L. Pauling, The Nature oj the Chemical Bond (Cornell Uni- 10 Collie, Hasted, and Ritson, Proc. Phys. Soc. (London) B60,
versity Press, Ithaca, 1939). 145 (1948).
8 Haggis, Hasted, and Buchanan, J. Chem. Phys. 20, 1452 11 R. P. Auty and R. H. Cole, J. Chem. Phys. 20, 1309 (1952).
(1952). 12 K. Higasi and Y. Asami, Borderland Problems between Physical
1 G. H. Haggis, thesis for the Degree of Doctor of Philosophy, Chemistry and Physiology (Kasai Publishing and Printing Com-
London (1951). pany, Minato-ku, Tokyo, Japan).
 RELAXATION TIME AND VISCOSITY FOR WATER
cedure will be adopted in the present work. As pointed
out by Auty and Cole,ll the use of an internal field
correction for substances such as water is of dubious
significance.
VISCOSITY AND DIELECTRIC RELAXATION
AS RATE PROCESSES
In 1941, Eyring13 proposed the following relationships:
A correspond to only small changes in their logarithms.
T=- exp(HT/kT) (3)
T In addition Saxton's results seem to indicate that
'I]=B exp(H~/kT), (4)
where HT and H~ are considered as the free energies
associated with these processes. Eyring further sug-
gested that A=h/k and B=hN/V, where N is Avo-
gadro's number, V is the molar volume, and hand k
are Planck's constant and Boltzmann's constant,
respectively. If these two identities are correct then A
should be independent of temperature and B should
slightly decrease as temperature increases.
If Eqs. (2) and (3) are compared it is seen that in the
t~mperature range OC to 100C n2 is roughly propor-
tIOnal to T so that Eq. (2) can be said to be a particular
case of Eq. (3) as applied to water. Considering now the
viscosity in terms of the bond breaking theory, it is
proposed to write by analogy with Eqs. (2) and (3)
1 ft(T)
-o:--exp(-H /kT) (5)
'I] f(p) ~,
where f(p) must be chosen so as to decrease as p
increases. Logarithm '1]/ f(p) has been plotted against
l/T for the three alternatives f(p) = 1- p, 1- p2 or 1/p.
It is found that the choice of f(p) = 1- P gives quite
the best approximation to a straight line. It seems
reasonable that over the temperature range OC to
100C the viscosity at any temperature should be
directly related to the number of hydrogen bonds which
are not broken. Thus Eq. (5) can be rewritten
1 ft(T)
-0:-- exp( -H~/kT), (6)
'I] 1-p
where Eq. (6) is a particular case of Eq. (4) as applied
to water.
Saxton14 concluded from his results that A and B
[Eqs. (3) and (4)J both vary with temperature, but
the precise variation is difficult to estimate since the
experimentally determined quantities are 10gA and
13 Eyring, Glasstone, and Laidler, The Theory of Rate Processes
(McGraw-HilI Book Company, Inc., New York, 1941).
14 J. A. Saxton, Proc. Roy. Soc. (London) A213, 473 (1952).
1577
TABLE II. The ratio T/n2(1-p) at various temperatures.
273 0.295
298 0.265
333 0.260
373 0.260
10gB and consequently large changes in A and B
HT=H~ and this is a fact of fundamental importance
since it suggests that little translational motion is
involved in the case of viscosity.
Dividing Eq. (6) by Eq. (2) and using Saxton's
result that HT=H~ it follows that
'I]
or (7)
T 'I]
TO:---
n2(1-p) T
Using the data in Table I, Table II has been com-
piled, and shows that T/[n2(1-p)J is constant over
the range OC to 100C, apart from a divergence at OC.
Equation (7) therefore provides a theoretical basis
for the linear relationship between T and 'I]/T from a
molecular picture of water more modern and more
likely than Debye's model. The final equation may be
written
T=C'I]/T, (8)
where C replaces the 47ra /k in Debye's theory. It
3
would be unwise to try to draw any specific conclu-
sions from the magnitude of Ck, but the fact that it is
of the order of the volume occupied by one molecule
may give support to the idea that the "relaxing unit"
is the molecule itself and not a "domain of molecules."
If the probability of the breaking of a hydrogen bond is
independent of the nature of the bond (as is assumed
in the theory of Haggis et al. 67) then water molecules
would not be expected to group together in preferred
"domains" ; the volume of the liquid must be considered
to be one constantly changing branched polymer.
ACKNOWLEDGMENTS
Thanks are due Professor J. E. Roberts and Dr. H. F.
Cook for their interest in this work and to Mr. G. W.
Roderick for several discussions.
The author is particularly grateful to Dr. G. H.
Haggis for reading the manuscript and for making
helpful suggestions.