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Volume Viscosity in Liquid Argon at High Pressures

D. G. Naugle, J. H. Lunsford, and J. R. Singer


Citation: J. Chem. Phys. 45, 4669 (1966); doi: 10.1063/1.1727553
View online: http://dx.doi.org/10.1063/1.1727553
View Table of Contents: http://jcp.aip.org/resource/1/JCPSA6/v45/i12
Published by the American Institute of Physics.

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4669

DIELECTRIC CONSTANT OF WATER

and the liquid is cooled below the normal melting


point.
(3) There is no statistically significant variation
from the parabolic relation of Eq. (1) representing the
complete set of data at any temperature between the
temperature limits of -1C and +21C.
(4) Two data points, at temperatures 17.61 C and
6.82C, were discarded from the complete set of 43
points because they deviated from values given by
Eq. (1) by more than 30', where 0' is the standard
deviation. When these points were included the value
of F was slightly above the 1% level of significance

THE JOURNAL OF CHEMICAL PHYSICS

for the case where 17C was the dividing point for the
two curve segments. However, since the end point of
the upper experimental subset for this particular case
showed a deviation greater than 30', the degree of
confidence that one could attach to the existence of a
discontinuity at this point is very small. A deviation
of 30' corresponds approximately to a value of the
dielectric constant differing by 0.02 from the value
represented by the least-squares fit of the data. This
small deviation altered significantly the statistical
results and confirmed our initial statement regarding
Drost-Hansen's interpretation of Devoto's data.

VOLUME 45, NUMBER 12

15 DECEMBER 1966

Volume Viscosity in Liquid Argon at High Pressures*


D. G.

NAUGLE,

t J. H. LUNSFORD,

AND

J. R.

SINGER

Texas ACl"M University, College Station, Texas


(Received 18 August 1966)

The volume viscosity in liquid argon has been calculated from ultrasonic attenuation measurements at
temperatures between 85 and 145K with pressures up to 157 kg/cm2 Measurements taken at densities
from 1.06 to 1.42 g/cm3 result in values of 2.3 to 0.8 for the ratio of volume to shear viscosity. These values
are compared with theoretical predictions of other investigators. It appears that the volume viscosity
increases with increasing density whereas the ratio of volume-to-shear viscosity decreases. The ultrasonic
attenuation rapidly increases as the temperature approaches the critical temperature. This increase in
attenuation is a consequence of the change in the density and compressibility of the medium. Thus no new
mechanism of dissipation is required within about 7K below the critical temperature.

INTRODUCTION

HE volume viscosity of a simple liquid like argon


is characterized by a transport coefficient which
appears in the stress-strain relationship and also in
the Navier-Stokes equation of motion. l The volume
or bulk viscosity plays a role in the dilational distortion
when ultrasonic waves are transmitted in liquid argon.
Along with thermal conductivity and shear viscosity
as dissipative factors, the volume viscosity also contributes to the attenuation of sound energy transported
through liquid argon. It is through attenuation measurements that volume viscosity is evaluated.
In recently published work from this laboratory,2.3
the attenuation of ultrasonic waves in liquid argon was
determined by a pulse technique with a single quartz
transducer and variable-path-Iength apparatus. Values
of the attenuation coefficient were made at frequencies

* Supported by the National Science Foundation.

t Present address: I Physical Institute, University of Gottingen,


Gottingen, Germany (as NATO Fellow 1966-1967).
1 S. A. Rice and P. Gray, The Statistical Mechanics of Simple
Liquids (John Wiley & Sons, Inc., New York 1965), p. 369.
2 D. G. Naugle and C. F. Squire, J. Chern. Phys. 42, 3725
(1965) .
3 D. G. Naugle, J. Chern. Phys. 44, 741 (1966).

from 30 to 70 Mc/sec in liquid argon at pressures up


to only 10 atm and over a temperature range of 84
to 112K. The excess attenuation, over and above that
caused by the thermal-conductivity and shear-viscosity
dissipative terms, was attributed to the volume viscosity and compared with the theoretical prediction
made by Gray and Rice. 4 These scientists used the
Rice-Allnatt5 ,6 theory of liquid transport. The present
paper extends the measurement of ultrasonic attenuation in liquid argon to temperatures as high as 145K
and pressures up to 157 kg/cm2 Data reported in this
new work give values at constant density while the
temperature and pressure were changed. This has
allowed a calculation to be made of the volume viscosity from the experimental data. These calculations
are compared with those of Gray and Rice,4 and with
the more recent calculations of Luks, Miller, and
Davis.7 A description of the new high-pressure equipment is given in detail.
P. Gray and S. A. Rice, J. Chern. Phys. 41, 3689 (1964).
5 S. A. Rice and A. R. Allnatt, J. Chern. Phys. 34, 2144 (1961).
6 A. R. Allnatt and S. A. Rice, J. Chern. Phys. 34, 2156 (1961).
7 K. D. Luks, M. A. Miller, and H. T. Davis, 59th National
Meeting of the American Institute of Chemical Engineers, Columbus, Ohio, May 1966, Preprint 13A.

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4670

NAUGLE, LUNSFORD, AND SINGER

EXPERIMENTAL

The precision variable-path-Iength apparatus previously used in this laboratory2.3 could not be used for
the high pressures required to explore the properties of
liquid argon up to 145K. The pressure bomb and
ultrasonic cell which is described in the following
paragraphs was designed to meet the new requirements.
Nevertheless, the ultrasonic attenuation and velocity
t~ken with the new equipment was carefully compared
wIth the absolute values obtained by the reliable
variable-path-Iength equipment. The diameter of the
tube through which the ultrasonic waves move in the
new pressure equipment is only 0.75 in. compared to
2.5 in. in the older cell. While the small diameter in the
new ultrasonic test cell described here gave no difficulty
at 50 Me/sec because the sound beam was so very
narrow, the beam spread at 30 Mc/sec was large
enough to require a 12% correction to all attenuation
measurements at that frequency. Those readers not
interested in the details of the new high-pressure test
cell may turn directly to the results and discussion.
The apparatus employed in these measurements was
a single-transducer double-path-Iength8 pulsed system
(Fig. 1) enclosed by a high-pressure cell capable of
withstanding 160 kg/cm2 of pressure. The sample
chamber consists of two reflectors and three spacers
(A, B, and C). The reflectors are right circular cylinders
1.000 in. in diameter and 0.25 in. in length. The
reflecting surface was ground flat within 0.00002 in.
and optically polished. Spacers A and B are hollow
right circular cylinders 1.000 in. o.d., 0.750 in. Ld.
Spacer A is 0.348 in. in length, while Spacer B is 1.923
in. in length. These distances allowed return echoes to
be clearly separated on the scope trace. The difference
in the signal strength of the two echoes determined the
attenuation caused by the extra path length of one
over the other. The inner surface of Spacers A and B
is uniform and round within less than 0.1 % throughout
the length. Spacer C is 0.089 in. in length. The crystal
which was 0.50 in. in diameter, was mounted to one
face of Spacer C, and was held in place by a Teflon
ring fitting over the crystal edge. Both Spacer C and
the Teflon ring were tapered along their inside circumference. Three spring-loaded screws were used to
connect the Teflon ring and spacer, and also to ensure
uniform tension around the crystal edge. The ends of
all three spacers were ground normal to the cylinder
axis and parallel within 5 sec of arc. Both ends of each
spacer were ground flat within 0.00002 in. All components of the sample chamber were made from the
same piece of lnvar stock. Thus, path lengths did
not change significantly over the temperature range
employed in these experiments.
The sample chamber was assembled in a Teflon
sleeve, closed at the lower end. This was then placed in
8

J. F. Mifsud and A. W. Nolle, J. Acoust. Soc. Am. 28, 469

(1956) .

a brass jacket. To the top of the jacket, on the inside


. was soldered to a BNC connector. The spring'
a sprmg
provided one electrical contact to the sample chamber
and also pressed the lnvar components together. The
second ele~trical contact was made by a brass strip in
contact WIth the crystal and passing through the
Teflon sleeve to the jacket. The brass jacket was
suspended from the top of the high-pressure cell by a
coaxial cable. The high-pressure cell shown as a separate .drawing in Fig. 1 was made of beryllium copper.
A hIgh-pressure seal was achieved by screwing the
compression cap down tightly against the body, thus
mating the top to the body and compressing the
aluminum ferrule which provided the seal. A brass lock
nut was then tightly screwed to the top and down
against the compression cap.
Argon gas which had been passed through an alcoholdry-ice cold trap to remove moisture was condensed
into the sample chamber through the filling tube. The
argon gas was purchased from Air Reduction Company
with the stated purity of 99.99%. The pressure in the
sample chamber was measured with a Heise-Bourdon
tube gauge which had been factory calibrated against
a dead-weight piston gauge.
The sample chamber was suspended by a stainlesssteel support tube in a Dewar filled with the appropriate cryogenic liquid. Temperatures between 85 and
92K were obtained by pumping on or over pressuring
a liquid-argon bath. Liquid methane was used as a
bath for temperatures between 103 and 115K and
liquid freon-14 for temperatures between 131'; and
H~-PRESSURE

SAMPLE CHAMBER

CELL
SUPPORT TLBE
FILLING TUBE
LOCK NUT
TOP
FERRULE
COMPRESSION CAP
COAXIAL CABLE
BNC CONNECTOR

Q-REFLECTOR

~SPACER
~TEFLON

A
RING

~ BRASS STRIP

TRANSDUCER

BODY
SPACER C
SAMPLE CHAMBER
BRASS JACKET
TEFLON SLEEVE
SPACER B

DEWAR

Q-REFLECTOR

FIG. 1. High-pressure cell and ultrasonic sample chamber.

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VISCOSITY OF LIQUID ARGON

4671

7
6

50 kg/cm 2
A

FIG. 2. Temperature and pressure dependence of alP in liquid argon: e,


50-Me/sec data; A, corrected 30-Mc/sec
data; 0, data of Naugle (Ref. 3).

<D '"

-o .,"

-;_VJ

~ Ie
'C;2.3

8=0~--~90~----ltOO~----lrI0------12~0----~13-0-----1+4-0-----15~0---
T(OK)

146K. The temperature was measured with a calibrated copper-constantan thermocouple imbedded in
the base of the high-pressure cell. Great care was
taken to allow the entire system to attain thermal
equilibrium at a constant pressure before ultrasonic
attenuation measurements were made.
The electronics were the same as described in Refs. 2
and 3. A quartz transducer with a fundamental frequency of 10 Mc/sec was driven at odd harmonics for
measurements of attenuation at 30 and SO Mc/sec.
Two Arenberg pulsed oscillators were used, one to
generate the ultrasonic signal and provide the triggering
signal and the other to generate a comparison pulse.
The signals were displayed on a Tektronix 585 oscilloscope. Attenuation measurements were made by adjusting the attenuation in the comparison network, so
that the comparison pulse amplitude was matched to
each echo amplitude after a change of pressure and/or
temperature.

RESULTS
The coefficient of attenuation in liquid argon was
measured at constant density with variable temperature and pressure, and also measurements were taken
at constant temperature with variable pressure. For
the constant-temperature measurements, the pressure
was varied from 1.5 to 107 kg/cm2 The pressures and
temperatures used for constant-density measurements
are shown in Table 1. The maximum pressure used
during constant-density measurements was 157 kg/cm2
The change in attenuation in the comparison attenuator
was recorded as a function of the change in pressure and
temperature. Fig. 2 shows the temperature dependence
of a/F. Attenuation became so great in the region of
the critical temperature, 151K, that return echoes
vanished. Indeed, only the 30-Mc/sec sound waves
could be measured above 130 0 K and with considerable
pressure.

The coefficient of attenuation is given by


01=

(2n-2P/pc3) {[(1'-1) /cp]K +h.+1].}'

(1)

where C is the velocity of sound, p is the density,


is the coefficient of shear viscosity, 1]. is the coefficient of volume viscosity, I' is the ratio of specific
heats, Cp is the specific heat at constant pressure, K is
the thermal conductivity, and f is the frequency. The
coefficient of volume viscosity can be related to the
coefficient of attenuation by

1].

1].=

(apc3/2rp) - {[(I'-l)/cp ]K +h.}.

(2)

Thus, the calculation of 1]. depends on the absolute


accuracy of a number of thermodynamic and transport
coefficients of liquid argon. Figure 3 shows the density
dependence of the volume viscosity. In Fig. 3 the
solid bars indicate the range of values calculated for
1]. at the density shown; the average values of 1]. are
omitted since it has not been determined that 1].
remains constant at constant density while the temperature is changed. Indeed, the theoretical calculations
of Gray and Rice4 indicate that 1]. does vary at constant
density with a change in temperature while 1]./1].
should remain constant. The data represented by the
symbols (circles and triangles) are single data-point
calculations or the average of several points at the
same temperature. The circles correspond to values
calculated from the 50-Mc/sec measurements, while
the triangles are the corrected values for the 30-Mc/sec
measurements. Figure 4 shows the density dependence
of the ratio of volume to shear viscosity. Again, the
circles and triangles represent the 50-Mc/sec and the
corrected 30-Mc/sec data, respectively. The solid
symbols are the average values calculated for 1]./1]. at
the indicated densities, and the open symbols are
single data-point calculations of 1]./1]. or the average
of several points at the same temperature. The bars

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4672

NAUGLE, LUNSFORD, AND SINGER


TABLE

1. Data and results for calculation of the volume viscosity in liquid argon.
Cpb

(OK)

(g/cm3)

(kg/cm2 )

(cal/g
OK)

1.062

146.2
142.4
140.4
135.2
133.4
131.2

158
126
108
62
47
26

0.299
0.319
0.341
0.368
0.370
0.405

p.

l'

2.92
3.14
3.22
3.20
3.19
3.78

KXI0 40

(m/sec)

(cal/oK
seccm)

'1.X 103 d
(g/cm.
sec)

a/f2X101s
(cm-1 sec2)

'1vXIOS
(g/cm
sec)

560
547
536
514
505
485

1. 70
1. 70
1. 70
1. 70
1.69
1.68

0.73
0.72
0.71
0.71
0.71
0.73

4.49
4.77
5.02
5.88
6.38
7.29

1.66
1.60
1.60
1.81
1.94
1.84

'1'/'1'

2.28
2.22
2.26
2.55
2.74
2.52
Av 2.43

1.068

145.4
142.4
137.9
134.2
131.2

153
127
91
57
27

0.296
0.318
0.330
0.365
0.395

2.81
3.14
2.98
3.16
3.76

559
547
535
515
492

1.72
1. 70
1. 74
1.72
1. 70

0.73
0.72
0.72
0.72
0.74

4.07
4.50
4.90
5.80
7.27

1.36
1.40
1.57
1.80
1.95

1.86
1.95
2.18
2.50
2.64
Av 2.23

1.280

114.8
112.6
110.9
109.0
106.0

156
126
103
77
32

0.259
0.266
0.271
0.275
0.284

2.43
2.39
2.42
2.50
2.48

752
746
742
737
726

0.253
0.252
0.251
0.250
0.250

1.44
1.45
1.46
1.47
1.50

2.02
2.07
2.18
2.25
2.40

1.60
1.67
1.83
1.83
1.95

1.11
1.15
1.25
1.24
1.30
Av 1.21

1.287

113.7
112.3
110.8
110.4
108.9
108.0
105.5

157
136
119
119
91
79
40

0.259
0.263
0.268
0.267
0.272
0.275
0.282

2.43
2.46
2.50
2.50
2.41
2.46
2.47

760
756
754
754
748
748
738

0.255
0.254
0.254
0.255
0.253
0.253
0.252

1.48
1.49
1.50
1.50
1.50
1.51
1.53

1.65
1. 71
1.72
1.72
1. 73
1. 76
1.93

1.35
1.67
1.39
1.39
1.41
1.45
1.71

0.91
1.12
0.93
0.92
0.94
0.96
1.12
AvO.99

1.294

112.6
110.2
108.5
106.0
105.0
103.1

156
122
96
63
43
13

0.259
0.266
0.271
0.278
0.281
0.287

2.39
2.41
2.43
2.44
2.38
2.38

764
758
752
745
735
727

2.56
2.56
2.54
2.55
2.53
2.53

1.52
1.54
1.52
1.57
1.55
1.60

1.69
1.77
1.81
1.89
1.96
2.05

1.54
1.65
1.68
1. 72
1.80
1.82

1.01
1.07
1.11
1.09
1.16
1.14
Av 1.10

1.294

112.6
112.3
110.7
109.2
108.1
106.6

155
148
125
106
87
69

0.259
0.261
0.265
0.270
0.272
0.276

2.35
2.45
2.43
2.40
2.48
2.47

767
764
760
756
751
749

2.56
2.56
2.55
2.56
2.54
2.54

1.52
1.51
1.53
1.53
1.52
1.53

1.67
1. 70
1.71
1. 76
1.81
1.84

1.58
1.55
1.50
1.57
1.62
1.68

1.04
1.02
0.98
1.03
1.07
1.09
Av 1.04

1.402

90.5
89.2
88.7
87.7
86.7

99
64
58
35
19

0.257
0.259
0.260
0.261
0.262

2.06
2.06
2.05
2.07
2.11

873
865
864

860
861

3.06
3.03
3.02
3.00
3.00

2.36
2.40
2.43
2.46
2.56

1.57
1.62
1.64
1.66
1.66

2.13
2.13
2.17
2.10
1.96

0.90
0.89
0.89
0.85
0.76
AvO.86

1.408

91. 7
90.4
90.1
88.9
88.2
87.7
86.8
85.0

149
124
113
91
79
65
47
28

0.255
0.256
0.257
0.258
0.260
0.260
0.261
0.262

2.00
2.02
2.01
2.00
2.02
2.03
2.00
2.01

885
881
879
876
874
870
869
870

3.11
3.10
3.03
3.09
3.07
3.07
3.05
3.08

2.42
2.44
2.42
2.45
2.50
2.54
2.56
2.80

1.31
1.35
1.35
1.37
1.40
1.42
1.46
1.54

2.01
2.08
2.10
2.11
2.12
2.05
2.26
2.30

0.83
0.85
0.87
0.86
0.85
0.81
0.88
0.82
AvO.85

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4673

VISCOSITY OF LIQUID ARGON


TABLE I (Continued)
p.

(g/eml )

1.410

T
(OK)

P
(kg/em2)

Cpb
(cal/gOK)

l'

C
(m/see)

KXIQ4

91.8
90.9
89.1
88.3
87.7

155
136
98
78
66

0.255
0.256
0.257
0.258
0.259

2.14
2.03
2.00
2.06
2.05

887
883
878
874
872

3.10
3.09
3.08
3.07
3.06

(calrKsec-em)

'1.X 1()3 d
(g/emsec)

(em-1 see2)

'1.Xl()3
(g/emsec)

2.41
2.41
2.45
2.48
2.54

1.34
1.38
1.41
1.46
1.48

2.13
2.34
2.33
2.40
2.39

a/rXlOl&

'1./"13

0.88
0.97
0.95
0.97
0.94
AvO.94

1.413

91.1
90.1
89.1
88.2
87.7
86.3

0.255
0.256
0.257
0.259
0.260
0.261

155
135
113
93
79
57

1.99
2.00
1.99
2.00
2.00
2.00

891
886
883
878
878
876

3.12
3.10
3.09
3.09
3.09
3.09

2.46
2.46
2.50
2.54
2.56
2.68

2.21
2.04
2.31
2.50
2.39
2.09

1.32
1.31
1.39
1.45
1.44
1.42

0.90
0.83
0.92
0.96
0.93
0.78
AvO.89

a Reference 10.
b Rl!ferences 9 and 10.
o L. D. Ikenberry and S. A. Rice, J. Chem. Phys. 39,1561 (1963); WADD
Tech. Rept. 60-56 "A Compendium of Properties of Materials at Low Tempera
tures (Phase I) ,n NBSCEL (1960).

dB. A. Lowry, S. A. Rice, and P. Gray, J. Chern. Phys.40,2673 (1964); H. T.


Davis and K. D. Luks, J. Phys. Chern.69,869 (1965); Y. Saiiand S. Kobayashi.
Cryogenics 4,136 (1964).

-..

I f)

o.

0
0

RAY It RICE---+I
(REF.41

O~

1.0

-+____________+-__________

__________~____________~__________
1.1

1.2

1.3

1.4

I,e

FIG. 3. Density dependence of '1.: Range of values calculated for "Iv at constant density under variable temperature and pressure
(bars). Single data-point calculations or averages of several points at the same temperature and pressure'I[O, 50-Mc/sec. dll-tll-i AI
corrected 30-Me/sec data); D, results of Naugle (Ref. 3) J.

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4674

NAUGLE, LUNSFORD, AND SINGER

~TJs

o~------------~------------~--------------~------------~---------1.4
1.1
L3
La
1.2

p< g/cm3 )

FIG. 4. Density dependence of 11./11.: Averages of values at constant density under variable temperature and pressure (e, 50-Me/sec
data; A, corrected 30-Mc/sec data). Single data-point calculations or averages of several points at the same temperature and pressure
[( 0, 50-Me/sec data; 1':.., corrected 30-Mc/sec data); 0, results of Naugle (Ref. 3); . , results of Luks, Miller, and Davis (Ref. 7);
<>, results of Gray and Rice (Ref. 4)].

attached to several of the symbols represent the error


in the calculated values. The estimated accuracy in
calculating the absolute value of 7]v and of 7]./7]. is
2S%. For the purpose of comparing the calculated
values with each other, the error is only 10% as
indicated by the error bars. The major source of error
is in the evaluation of 'Y.
Table I lists the experimental and calculated values
with references given to the thermodynamic and
transport coefficients taken by other scientists. The
resulting calculated values of 7]. and of 7]./7]. are also
presented. The values for 'Y in Table I were calculated
using the equation reported by Van Itterbeek and
Verbeke9 :
(3)
Measured values of c, and values for (iJp/iJPh determined from data presented by Van Itterbeek and
Verbeke9 and Van Itterbeek, Verbeke, and StaeslO
were used for the calculation of 'Y. The values listed
are in agreement with those in the above references
at the same conditions of density and temperature.
A. Van Itterbeek and O. Verbeke, Physica 26, 931 (1960).
A. Van Itterbeek, O. Verbeke, and K. Staes, Physica 27,
742 (1963).
9
10

The velocity of sound in liquid argon was measured


concurrently with the attenuation because the return
echoes from the fixed path lengths could be timed with
the Tektronix-S8S scope. The velocities were acquired
by measuring the difference in the time required for
the two pressure waves, one in Spacer A and the other
in Spacer B, to traverse their respective path lengths.
Figure S shows the pressure and temperature dependence of the velocity. The accuracy of the measured
velocities is better than O.S% which is as good or
better than the other quantities used to calculate the
volume viscosity. These velocities are within 1% of the
velocities reported by Carome, Cykowski, and Havlice. ll
The results reported here extend the experimentally
determined values of velocity in liquid argon up to
pressures of 1SS kg/cm2 and to temperatures of 14SK,
The estimated accuracy of the present values of alP
is 2.S%i however, the error in air is somewhat
greater at the higher temperatures than at the lower
temperatures as is indicated by the scatter in the data
points in Fig. 2. It is apparent from Fig. 2 that a/p is
rapidly increasing as the temperature approaches the
critical temperature (1S1"K.). Earlier work from this
11 E. F. Carome, C. B. Cykowski, and F. Havlice, Intern.
Congr. Acoustics 5th, D28 (1965).

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4675

VISCOSITY OF LIQUID ARGON


900

800

700

FIG. 5. Velocity of sound in


liquid argon.

C(m"'c)

600

500
50kg/cm 2

400~----~--~~--~~--~----~-----+-----+-------

80

90

laboratory had shown the attenuation to be a linear


function of the frequency squared over a range of
frequencies between 30 and 70 Me/sec and temperatures from 84 to 112K at 8 atm.2.3 With the new
pressure bomb, measurements of attenuation at SO
Me/sec were in agreement with our previous work at
the same temperature and pressure. However, with
the new pressure cell the measured values of attenuation at 30 Me/sec exceeded the SO-Me/sec values by
about 12% and did not agree with the variable-pathlength equipment. It is believed that this discrepancy
is an inherent property of the narrow diameter test
cell. All of the 30-Mc/sec measurements of attenuation have been corrected to make a value of a/F agree

100

110

130

140

150

with the SO-Me/sec measurements. This cell correction


has allowed us to report values of a/F at temperatures
as high as 14SK. No return echoes from the SO-Me/sec
ultrasonic waves could be observed at this high temperature even with the highest pressures allowed.
DISCUSSION AND CONCLUSIONS

The ratio of 'YJ./'YJ. did not change (within 10%)


at constant density while the temperature and pressure
were varied. According to the theoretical calculations
of Gray and Rice,4 'YJ./'YJa is constant at constant density.
The value of 'YJ./'YJa of 1.9 at a density of 1.12 g/cm3
from our work compares favorably with the value of
1.3 calculated by them, and is well within experimental

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4676

NAUGLE, LUNSFORD, AND SINGER

error of both values. The ratio of 71.111. is -i for a zerothorder rigid-sphere calculation,12l3 and very close to -i in
the small step diffusion theory of Rice and Kirkwood. l4
It appears that 71.171. decreases with increasing density.
Using a square-well potential and a pair correlation
function for hard spheres, Luks, Miller, and Davis7
have recently calculated the ratio of 71.1718 at the same
temperatures and pressures that were reported by
Naugle. s These calculated values, which are shown in
Fig. 4, are within the experimental error of our results;
however, they do not reflect that 71.1718 decreases with
increasing density.
Our values of 71. at constant density do not indicate
an increase of 71. with increasing temperature as the
theory of Gray and Rice4 predicts. Scatter in the
experimental data, however, is greater than the 10%
increase which they predict for a comparable temperature range. The data reported here suggest that
as density increases 71. also increases.
The increase in alP as the temperature approaches the
critical temperature is in agreement with the ultrasonic
attenuation work of Chynoweth and Schneider l5 on
liquid xenon. They have explained the increase in alP
in terms of structural relaxation processes; that is, a
high-density region formed by the acoustic wave does
not relax rapidly with respect to the time scale repre12 H. C. Longuet-Higgins and J. P. Valleau, Mol. Phys. I,
284 (1958).
13 H. C. Longuet-Higgins and J. A. Pople, J. Chern. Phys.
25,884 (1956).
14 S. A. Rice and J. G. Kirkwood, J. Chern. Phys. 31, 901
(1959).
16 A. G. Chynoweth and W. G. Schneider, J. Chern. Phys.
20, 1777 (1952).

sented by the acoustic wave. Consequently, the local


density of the medium will lag the sinusoidally varying
pressure imposed by the transducer, and in the critical
region the time lag is sufficient to appreciably attenuate
the acoustic wave. This mechanism for the dissipation
of energy is similar to the rate process theory of bulk
viscosity introduced by Hirai and Eyring. l6 For argon,
the attenuation increased, but the density and velocity
of sound, which is a function of the density and compressibility, decreased. As a result, in the calculation
of 71. the first term on the right-hand-side of Eq. (2)
actually decreased at the higher temperatures. While
alP increased by a factor of three, it may be observed
from Table I that the volume viscosity was essentially
constant over the temperature range from 112 to
14SK. Hence, it appears that the increase in alP does
not require an additional dissipative mechanism or an
increase in the volume viscosity, but can be explained
purely in terms of the change in the density and the
compressibility of the medium.
ACKNOWLEDGMENTS
The authors are indebted to Dr. C. F. Squire for
many helpful discussions and suggestions. They wish to
express thanks to the E. I. duPont de Nemours and
Company for providing the freon-14. The authors are
indebted to Mr. Sam Worden of Houston, Texas, for
his gift of the Invar spacers. The suggestions by Dr.
B. A. Younglove of National Bureau of Standards,
Boulder, Colorado, concerning the experimental techniques are gratefully acknowledged.
16

N. Hirai and H. Eyring,

J.

Appl. Phys. 39, 810 (1958).

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