Temperature Dependence of Bulk Viscosity in Liquid Argon

J. A. COWANAND R. N. BALL
Deparlmenl of Pl~ysics,Unioersily of Walerloo, Waterloo, Ontario
Received January 6, 1972

Attenuation measurements have been made on liquid argon for temperatures between 90 and 150 "K and
pressures between saturated vapor and 1000 p.s.i. Values of bulk viscosity were calculated and compared with
theoretical results. For densities above 1.15 g the P N M theory is in excellent agreement. However, below
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these values the theoretical results continue to decrease with density where the experimental results increase
sharply. The values of the ratio of bulk to shear viscosity for saturated vapor pressure are found to be a linear
function of ( T , - T ) - 3 / 2from 90 to 140 OK.

Des mesures d'attenuation ont ete faites dans I'argon liquide pour des temperatures entre 90 et 150 OK et des
pressions allant de la tension de vapeur saturante jusqu'a 1000 livres par pouce carre. Les valeurs de la viscosite
macroscopique ont ete calculees et comparees aux resultats theoriques. Pour des densites superieures a 1.15 g
la theorie PNM donne un excellent accord. Toutefois, au-dessous de ces valeurs les rtsultats theoriques
continuent de decroitre avec la densite, tandis que les resultats experimentaux augmentent brusquement. On
trouve que les valeurs du rapport de la viscosite macroscopique a la viscosite de cisaillement a la pression de
saturation est une fonction lineaire de ( T , - T)-"* entre 90 et 140 OK.
Canadian Journal of Physics. 50, 1881 (1972)

Introduction Measurements of the bulk viscosity of argon

The work of Gray and Rice (1964), based on have been made by Galt (1948 ), Naugle (1966 ),
For personal use only.

the Rice-Allnatt theory, and further work by
Palyvos et al. (1968), using the Prigogine,
Nicolis, and Misguich theory, predict values of
the bulk viscosity of simple liquids. Also,
theoretical work summarized by Egelstaff and
Ring (1968) and that of Kadanoff and Swift
(1968) have predicted exponents of (T, - T) as
the temperature, T, approaches the critical tem-
perature T,. To compare these theoretical pre-
dictions with measured values, the present
experiments were undertaken.
The best method known at present for deter-
mining the bulk viscosity, [, of a liquid is
through measurements of the ultrasonic ab-
sorption, a, using pulse techniques. The bulk
viscosity is found by calculating the excess
sound absorption over the classical value due
to the shear viscosity and the thermal con-
ductivity. The usyal definition of the bulk
viscosity is
where f is the frequency of the ultrasound, p is
the density of the liquid, C is the velocity of
sound in the liquid, q, is the shear viscosity, y is
the ratio of the specific heats, K is the thermal
conductivity, and C p is the specific heat at con-
stant pressure.
Naugle et a/. (1966), and Swyt et a/. (1967).
Since recent measurements of the physical
properties K, q,, etc. have increased in accuracy,
only the later work gives significant values of the
bulk viscosity. These authors concentrated on
a range of densities mainly greater than 1.05 g
cm-'. As stated by Naugle et a/. (1966), their
measurements were not conclusive in stating
that the bulk viscosity was a function of density
alone or of both density and temperature.
The present paper presents a broader picture
of the experimental values of bulk viscosity over
temperature and pressure ranges of 90 to 150 OK
and saturated vapor pressure to 1000 p.s.i.
respectively. Two properties have been found:
(1) The bulk viscosity becomes very large as the
critical point is approached and is a function
of temperature as well as density. The consis-
tency of the results indicates strongly that the
ratio of bulk to shear viscosity is also a function
of density and temperature although it is not
beyond the limits of error to have a function of
density alone except within a few degrees of the
critical point. (2) Along the saturated vapor
pressure curve the ratio of the bulk to shear
viscosity varies as (T, - T)-'" from 90 to
140°K. This agrees with the prediction of
Kawasaki and Tanaka (1967) but over a much
larger temperature range than normally con-
sidered as being the critical region.
 1882 CANADIAN JOURNAL OF PHYSICS. VOL. 50, 1972

Experimental
The pulse echo method with a variable path
length was used. The cryostat was designed to
withstand 1000 p.s.i. gas pressure and to have
external adjustments for varying the piston
position and fine adjustments to assure that the
crystal is kept parallel to the reflection surface.
The transducer acted as both transmitter and
receiver for the ultrasonic pulse which was
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reflected from a brass piston whose surface was

ground flat. The piston was connected by a thin
wall stainless steel tube to a micrometer head
at the top of the cryostat. In order to obtain
parallelism between the transducer and reflector,
the bore was honed as accurately as possible and
the piston was spring loaded against one side.
The crystal holder was held by three phosphor
bronze mounting straps which were kept taut
by a loading spring. By rotating cams, each strap
could be depressed horizontally to give a fine
adjustment of the vertical height to make the
crystal parallel to the reflector. Three hundred
For personal use only.

degrees of rotation of the cams gave a vertical
adiustment of 3 x cm. It is estimated that
the leveling mechanism kept the transducer
parallel to the reflection to within 1/15 of a
wavelength for the highest frequencies used.
Only slight adjustment of the cams was needed
before each reading of attenuation was taken.
To prevent back echos from interfering with the
signals from the reflector, an absorption cavity
was made below the crystal. This was designed
for a large number of reflections and filled with
glass wool.
Attenuation measurements were made using
a Matec 6000 Ultrasonic transmitter-receiver
and pulse height monitor. For maximum signal-
to-noise ratio, maximum transmitter power and
minimum receiver gain were used.
The transducer was 314 in. diameter 5 MHz
X-cut quartz crystal which was operated at its
6dd harmonics to increase the signal-to-noise
ratio for the first echo. Since the crystal is tuned
to resonance the first echo is almost totally
transmitted through the crystal and then ab-
sorbed in the bottom of the sample chamber
Consequently, second and succeeding echos
were minimized in the system.
By adding the RF transmitter pulse to a con-
tinuous wave signal on a high frequency scope,
the continuous wave could be adjusted to the
pulse frequency by noting a zero beat. The fre-
FIG.1. Plot of a l f 2 against pressure for the particular
values of temperature shown. All values taken at 55 MHz
are indicated by (+), 35 MHz (O), 25 MHz (a), and 15
M H z (A).
quency of the continuous wave was read on a
counter giving an estimated error of 0.2%.
The argon gas used was Ultra Pure Ionization
Grade Argon, 99.999% purity, from The
Matheson Company. To maintain sample
purity, the cryostat and gas handling system
were evacuated to Torr and rinsed several
times with argon before using. Direct connection
was made to the argon cylinder and the system
was refilled for each major run.
The temperature was controlled by a bridge
feedback system similar to that used by
Goodwin (1960). The cryostat had 112 in. walls
of brass and was cooled by a controlled heat
leak to liquid nitrogen. The temperature was
kept within 0.02 O K of the chosen values for all
readings. The temperatures were measured
using a Tinsley platinum resistance thermometer
calibrated by the National Physical Laboratory.
The value of cilf2 has been reported to be a
constant as frequency is varied. Some doubts
have been raised about values for lower fre-
quencies below 35 MHz especially when in the
vicinity of the critical point. Differences have
been found which are greater than that predicted
 COWAN A N D BALL: T E M P E R A T U R E DEPENDENCE O F BULK VISCOSITY IN LIQUID ARGON 1883
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For personal use only.

FIG.2. Bulk viscosity is plotted against density. The bars indicate the estimated error. The temperature at which the
points were taken are shown in brackets beside the curve. Theoretical points of Palyvos el a/. (1968) for ( P N M ) theory are
shown by 0, those of Gray and Rice (1964) are shown by 0. Experimental values of Naugle el a/. (1966) are shown by the
dashed curve.

by diffraction theory.' In the parallel case of
critical mixtures very large deviations of a / / ' ,
particularly in the vicinity of the critical point,
have been shown by Singh et al. (1966) and
Anantaraman el al. (1966). These cannot be
attributed to a single relaxation phenomenon
but are indicative of long range fluctuations in
the critical region. Because of this, all data
presented here were taken at 55 MHz except for
the very high attenuation values at 145 OK and
pressures less than 700 p.s.i. and at 150 OK. The
35, 25, and 15 MHz readings are identified in
Fig. 1.
- - Results-and Discussion
The results of a/f2 for liquid argon for in-
cremental temperatures between 90 and 150 OK
and for pressures varying from the saturated
vapor pressure up to 1000 p.s.i. are shown in
Fig. 1. From the consistency of the data and the
scatter of the points, the probable error is esti-
'See Williams (1970), Carome and Witting (1961), and
also extensions of these works to the dimension and fre-
quencies used in ultrasonic work in liquids by Ball and
Cowan, presented at the Conference of the Canadian Associ-
ation of Physicists, 1971.
mated to be +2% on the lowest readings,
gradually increasing to 3% around the 50 x
10-l7 cm-' s2 and again to 5% in the 300 x
10-l7 cm-' s2 range. Values at 1000 x 10-l7
+
cm-' s2 are estimated at 10% but the accuracy
diminishes greatly beyond this point, due mainly
to the decrease in the signal-to-noise ratio and
difficulties of reaching equilibrium in the sample
so near to the critical point.
Table 1 has been included in full due to the
differences in literature values of the constants
required to calculate the bulk viscosity. This is
particularly necessary near the critical point.
References are given to the data from which the
particular values were interpolated. For the
values of specific heat at constant pressure the
saturated vapor pressure values of Gladun were
used and the data of Theon et al. (1969) used to
estimate values for higher pressures.
The calculated values of bulk viscosity are
plotted in Fig. 2. These results agree very well
with those of Naugle el al. (1966) and also
Swyt et al. (1967). In fact, if more weight is
given to the results of Naugle (1966) where a
variable path length measurement is used, the
 1884 CANADIAN J O U R N A L OF PHYSICS. VOL. 50, 1972

TABLE1. Literature data and results for calculating the volume viscosity of liquid argon

T P
K X 10~"
(cal°K-'
C,
(cal g - '
'I.X
(g c m - ' P' Cc a r 2 x 10''
1 x 103
(g cm-'
' 1
CK (atm) s-' cm-') 1 OK-') s-') ( g ~ m - ~ )(m s - ' ) (cm-' s2) S-I)
Can. J. Phys. Downloaded from www.nrcresearchpress.com by San Diego (UCSD) on 01/05/15
For personal use only.

"Ziebland and Burton (1958).

'Gladun (1971 ),
'Theon er (11. (1969).
dHcllernans er 01. (1970).
-. . .-+.. .=:-Rudenko (194%):- . .

agreement is excellent. This is shown as a dashed
curve in Fig. 2. Since Naugle el al. (1966) did not
investigate the lower density region it is not
surprising that the data were interpreted as a
simple function of density. By the extension of
the data as shown in Fig. 2, it is clear there is also
a temperature dependence in the bulk viscosity
even a relatively long way from the critical
point. The ratio of the bulk to shear viscosity is
shown in Fig. 3. These results also suggest that
the ratio is a function of temperature as well as
density although not as conclusively as for the
bulk viscosity. Certainly the temperature effect
only becomes large much nearer to the critical
point.
Since the experimental results for C, p, y, C,,
q, are smoothed and interpolated, it is more
likely that the errors quoted would give a
 COWAN A N D BALL: TEMPERATURE DEPENDENCE OF BULK VISCOSITY I N LIQUID ARGON 1885
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70 .80 90 100 1.10 1.20 1.30 Density

(g ~ r n - ~ )
For personal use only.

FIG.3. The ratio of the bulk to shear viscosity is plotted against density. The saturated vapor pressure curve is drawn as
a solid line.

systematic error in the calculated values but that

the relative values indicate variations more
accurately. This is borne out in Figs. 2 and 3
where there appears to be much less scatter than
would be expected by the error analysis.
Figure 4 shows the ratio of the bulk to shear
viscosity plotted against ( T , - T ) on a log-log
scale for the saturated vapor pressure points.
A least-squares fit was made in the form
l / q s= A + B(T, - T)"
so that
'
A = [ ( l / ~ lobs
s - (l/qs) C ~ I C ] ~
was a minimum. This gave values of the con-
stants, A = 0.44, B = 178, and n = - 1.54. Al-
though*A is a large-fraction of l / q sfor the lower
temperature points, small variations in A give
approximately the same percentage variations
in n as well as A. A curve of slope - 312 is shown
with the data for comparison. This is a strong
indication that the effect of the long range
intermolecular forces normally found only FIG.4. Saturated vapor pressure values of the ratio of
near the critical point has a major effect down bulk to shear viscosity plotted against ( T , - T) on a log-log
scale in the temperature range 90 to 135OK, i.e. log
to at least 60 OK below the critical temperature. [([/q,)- A ] vs. log ( T , - T ) for A = 0.44. A line with slope
This is in excellent agreement with the critical -312 is drawn to show how well the data fits the prediction
exponent of (T, - T ) predicted by Kawasaki of Kawasaki and Tanaka.
 1886 CANADIAN JOURNAL OF PHYSICS. VOL. 50, 1972
et (11. (1967) to be - 312 depending on tempera-
ture and frequency ranges.
Gray and Rice (1964) predicted values of
bulk viscosity of 0.90 and 0.93 mP for a density
of 1.12 g cmP3 and at temperatures of 128 and
133.5 OK respectively. These values are 40% low
compared with our data but are just within the
maximum errors.
The predictions of Palyvos et al. (1968) based
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on the work of Prigogine, Nicolis, and Misguich
(PNM) are shown on Fig. 2. They are for
saturated vapor pressures. The agreement in the
1.2 to 1.4 g cm-3 density region is excellent.
However, as the density decreases their values
continue to decrease while the experimental
values increase rapidly. It would appear that
the long range fluctuations found near the
critical point have a major effect above 125 OK
and must be taken into account to derive the
values of bulk viscosity for the low density fluid
region.
Acknowledgments
For personal use only.
The authors wish to thank Professor P. A.
Egelstaff for many fruitful discussions on the
theories of liquids. The financial support of the
National Research Council of Canada is grate-
fully acknowledged.
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