Apparatus for sound velocity measurements in gases up to 10 kbar: Experimental data

for argon
P. J. Kortbeek, M. J. P. Muringer, N. J. Trappeniers, and S. N. Biswas

Citation: Review of Scientific Instruments 56, 1269 (1985); doi: 10.1063/1.1137990

View online: http://dx.doi.org/10.1063/1.1137990
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 Apparatus for sound velocity measurements in gases up to 10 kbar:
Experimental data for argon
P. J. Kortbeek, M. J. P. Muringer, N. J. Trappeniers, and S. N. Biswas
Van der Waals Laboratory, University of Amsterdam, The Netherlands
(Received 11 December 1984; accepted for publication 24 February 1985)

An apparatus for the measurement of sound velocity in gases up to pressures of 10 kbar and down
to temperatures of 77 K is described. Important features of the experimental setup include a
specially designed ultrasonic cell with double reflectors, based on the phase comparison pulse-
echo technique, and a vacuum type of cryostat using a cold finger system for temperature control.
Detailed measurements on argon down to the melting line show that the method is capable of
giving a precision of 0.02% for the sound velocity.

INTRODUCTION transmitter is applied to the electrodes of an X-cut quartz

Accurate measurement of the velocity of sound in real fluids
as a function of pressure and temperature is very useful in the
analysis of both experimental and theoretical equations of
state. Measurements at higher pressures are particularly im-
portant because of the possibility of achieving a very high
precision for the sound velocity data compared to those ob-
tained from classical pVT measurements. In addition, high-
pressure sound velocity data provide information on such
important thermodynamic properties as compressibilities
and specific heats of a fluid at high pressures where direct
measurements are extremely difficult.
Although a number of experimental methods have been
developed for sound velocity measurements at pressures up
to 10 kbar, \-4 the precision of the measurement has been
limited to a few tenths of a percent. Moreover, these mea-
surements were usually carried out at room temperature.
The purpose of the present work is, therefore, to develop an
experimental apparatus for sound velocity measurements in
gases up to 10 kbar which is capable of giving a much higher
precision than that of the existing methods of measurement
and which is also suitable for measurements at temperatures
down to the melting line.
The design of the present ultrasonic apparatus is based
on the wen-known phase comparison pulse-echo technique. 5
However, a special feature of the present experimental setup
is the use of two reflectors which are placed at unequal dis-
transducer. Because of the piezoelectric effect, the trans-
ducer is excited into a thickness mode of vibration and,
thereby, a longitudinal sound pulse is generated in the medi-
um. The pulse travels in both directions and is reflected by
both the reflectors. After an appropriate time T, a second
pulse is introduced in the medium such that the echo of the
first pulse traveling the longer path and the echo of the sec-
ond pulse traveling the shorter path coincide at their arrival
at the transducer. The phase difference (.J¢ ) between the two
echoes is then equal to
Ll¢={J)T, (1)
where (J) is the angular frequency and T is the difference in
transit time of the echoes. By slowly changing the frequency
of the transmitter, the phase difference between the pulses
can be changed. Therefore, at certain frequencies, the so-
called null frequencies, the two pulses can cancel each other.
The complete cancellation occurs when the phase difference
between the two echoes satisfy the relation
.J¢ = (2n + t)1T, (2)
where n is an integer. However, in order to reach the com-
plete cancellation, it is necessary to match the amplitudes
since the attenuation of the second pulse traveling the
shorter path is less than that of the first, traveling the longer
path. It foHows from Eqs. (1) and (2) that the nun frequencies
In = (J)n /21T satisfy the following relation:

tances from the quartz transducer. Although cells with two J"T=n+ 1/2. (3)
reflectors were previously reported in the literature,b.7 these
The quantity n, which is the order of interference, is easily
were not used for the measurement of sound velocity. The
found from the relation
present technique makes it possible to increase the precision
of the measurement to as high as 0.02% over a wide range of
experimental conditions. Because of the use of a two-reflec-

~)
First pulse
tor system, it is necessary to reduce, as much as possible, the
temperature gradient over the whole length of the ultrasonic Second puis ..

ceH. Therefore, a vacuum cryostat operating by the cold fin-

ger system has been designed in which the temperature gra-
Measuring point
dient can be virtually eliminated under all circumstances.

t PRINCiPLE OF THE METHOD OF MEASUREMENT

Quartz
The principle of the present phase comparison pulse- transduc .. r

echo method with two reflectors is as follows (see Fig. I). At FIG.!. Principle of the phase comparison pulse-echo method with two re-
the start of the operating cycle, a hf electrical pulse from a flectors.

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 (4)
as obtained from Eq. (3). Here, t1ln is the difference in Detail A

successive null frequencies, i.e., t1ln = In + I -In· However, s

since n must be an integer, the exact value of n is established
by rounding off the calculated value. It turns out that the
deviation of the calculated value of n from an integer is a
measure of the uncertainty in the measurement of nun fre-
quencies. The difference in transit time r of the two pulses
now follows easily from Eq. (3). Finally, the velocity of sound
v is calculated from the relation
v =117, (5)
where 1 is the difference in path lengths. T Q E

For measurements under various experimental condi-

tions, the variation of the path length due to changes in pres-
sure or temperature must be determined with sufficient ac-
curacy.1t can easily be shown thattheterm I (p, t) at pressure
@
p and temperature t is related to the corresponding term FIG. 2. Ultrasonic cell for sound velocity measurements in dense gases; (K)
suspension rod; (C) conical cavity; (R) reflector; (S) support; (T) conical ring;
1(0, 0) at zero pressure and 0 °C by the formula (Q) transducer; (E) silver pin.
I (p, t) = 1(0,0)[1 + a(t)Lit][1 + /3 (t )Lip], (6)
where a(t ) is the coefficient of linear thermal expansion and B. Cryostat
/3 (t ) is the linear compressibility of the construction materi- The details of the cryostat used in the ultrasonic experi-
als. mental setup are shown in Fig. 3. The design of the cryostat
is based on the vacuum-type principle. Essentially, it con-
sists of a high-pressure vessel surrounded by a chromium-
plated copper radiation shield which, in turn, is enclosed by
II. DESCRIPTION OF THE APPARATUS
a demountable stainless-steel vacuum jacket. The jacket is
A. Ultrasonic cell
A diagram of the ultrasonic cell is shown in Fig. 2. It is
made of a hollow copper cylinder (o.d. 18 mm, i.d. 16 mm, in
which an X-cut quartz transducer (Q) (diameter 8 mm, thick-
ness 0.28 mm) is clamped at its edges between a conical sup-
port (S) and a conical ring (T). The support and the ring are
fixed to each other by means of three screws (see detail A in
Fig. 2). Two solid copper reflectors (R), each of diameter 8
mm and having plane smooth surfaces, are fixed in the cell as
parallel as possible to the transducer at distances of, respec-
tively, 20 and 30 mm. This ratio 2:3 in the distances is neces-
sary in order to eliminate overlap of unwanted echoes. Cop-
per is chosen as reflector material because of its high acoustic
impedance, its good thermal conductivity, and because its
thermal expansion and compressibility are well known. The
lengths of the reflectors, 15 and 5 mm, respectively, are such HIgh pressure

that unwanted reflections from the lower parts of the reflec- capillary

tors reach the transducer only after the arrival of the two
echoes. Further, the end planes of the reflectors contain con-
ical. cavities (C), each with an angle of 103° and height 3.2
mm. Due to these cavities, the transmitted part of the signal Elpctncol
in the reflector material is scattered and moves to and fro in 'e~c1th,oU9h

the material before being completely attenuated. Each ofthe

transducer faces (Q) is provided with an evaporated alumi-
1010'00' pr.~su'~
num electrode ofcircular shape (diameter 6 mm) with a small 1I.5511(

extension, as shown in Fig. 2. The electrical contact between

Pr -res/sronce
the e1.ectronic system and the electrodes is made at the two tn@rmamet@F

extensions using a silver pin (E) pressed firmly by means of a

phosphor bronze spring at one side and the support ring (S)
at the other side. The cell is centered inside the pressure vesel
by means of a Kel-F suspension rod (K). FIG. 3. Cryostat and high-pressure vessel.

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1270 Rev. Scl. Instrum., Vol. 56, No.6, June 1985 Sound velocIty gases 1270
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 immersed in a bath of liquid nitrogen contained in a Dewar
vessel.
The details of the high-pressure vesseJ are also shown in
Fig. 3. The cylinder (o.d. 100 mm, i.d. 21 mm) is made from
40 Ni-Cr-Mo 18 steel. It is made suitable for pressures up to
10 kbar by subjecting it first to a process of hardening fol-
lowed by autofrettage. The mechanical properties of the ma-
terial are found to be as follows: hardness 41 Rc, yield
strength 1185 N/mm2, and tensile strength 1294 N/mm 2 •
The pressure vessel, together with the closure head, is sealed
from the outside by means of a special sealing ring developed
earlier in this laboratory. The closure head is provided with
two electrical feedthroughs. Details of the sealing ring and
the feedthrough are described elsewhere. 8 ,9 Further, a thick
copper plate is fixed on the top of the pressure vessel by
means of three screws. The plate contains three high-power
heating elements for temperature control and aPt-resistance
wire as temperature sensor. The cryostat is suspended from
the top by means of a stainless-steel tube whose lower end is
silver soldered to a copper flange, held tight against the cop-
per plate by means of a nut. All electrical leads are brought
out of the vacuum space by means of electrovac feed-
throughs. The stainless-steel capillary, fitted to the closure
head by a compression technique, is guided by the spacer and
brought out of the vacuum chamber through a brass cylin-
der.
The temperature of the pressure vessel is controlled by
balancing the heat loss through the copper cold finger with
heat input through the heating elements. The amount of heat
loss can be controlled by adjusting the distance and, hence,
the thermal contact, between the cold finger and the copper
plate on the pressure vessel using either coarse or fine adjust-
ment mechanisms. The temperature can be maintained con-
stant to within 2 mK of the desired temperature by means of
a proportional-integral temperature regulation system. The
sensing element of the system is a glass-enclosed Pt resis-
tance wire which forms one part of a Thomson bridge. The
temperature can be measured with an accuracy of 2 mK by
means of a calibrated glass-enclosed Pt resistance thermom-
eter situated at the bottom of the vessel. In order to improve
thermal contact between the vessel and the resistance wires,
the annular passage between the glass tubes and the cavities
is filled with apiezon grease. The temperature gradient in the
pressure vessel is continuously monitored during the course
of the measurement by means of two copper constantan ther-
mocouple junctions fixed, respectively, at the top and bot-
tom of the vessel. The gradient can be kept below 10 mK over
the full length of the pressure vessel by choosing optimum
operating conditions, in particular the level of liquid nitro-
gen in the Dewar which can be controlled automatically to
FIG. 4. Block diagram of the electronic system.
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any predetermined level, and the amount of electrical energy
to the heaters.
c. High-pressure system
Ine high-pressure system consists of a mercury gas
compressor coupled to an oil press and capable of producing
gas pressures up to 3 kbar, a 16:1 Harwood intensifier suit-
able for generating gas pressures up to 15 kbar and a calibrat-
ed Harwood manganin pressure gauge for precise measure-
ment of the pressure. Details of the mercury gas compressor
can be found elsewhere. 10 The manganin gauge is calibrated
against a controlled clearance piston gauge using a mixture
of kerosene and diethylhexylsebacate as a pressure transmit-
ting medium. The uncertainty in pressure measurement is
estimated to about 0.05% + 2 bar. The calibration of the
gauge at pressures up to 3 kbar can be checked occasionally
during the course of the measurement by connecting a Mi-
chels pressure balance to the oil side of the mercury gas
compressor.
D. Electronic system
A simplified block diagram of the electronic system is
shown in Fig. 4. The pulses are derived from a continuous
wave lO-MHz oscillator which is locked by a l-MHz Rock-
land model 5100 frequency synthesizer. By the use of a gate
circuit consisting of a pulse former and a timer, two pulses
are cut out of the continuous signal. The pulse width, the
separation time between the pulses and the repetition time
can be adjusted with the timer, while the amplitude of the
second pulse can be reduced with the pulse former. The
quartz transducer is connected to the electronic system by
means of two 3-mm-diam coaxial cables passing through the
suspension tube of the pressure vessel.
In order to adjust the amplitude of the second pulse, the
amplification in the transmitter is chosen to be linear. The
relatively high noise inherent to this method can be sup-
pressed by a suitable blocking mechanism. Details are shown
in Fig. 5. The amplitUde of the input pulse, initially 10 V
peak-to-peak, is increased to twice this value by transformer
Tl. If there is no input pulse, the FET switch (BSV81) re-
mains open. The noise from the transmitter which may pass
the switch due to its parasitic capacitance C I par can be mini-
mized by adding an opposite phase signal, adjusted by ca-
pacitor C I comp' The gate pulse from the timer is applied to
the amplification system, as well as to the FET switch. This
pulse closes the switch, thereby generating a signal of 20 V
peak-to-peak over both the primary coils of transformer T2,
resulting in a voltage of 40 V peak-ta-peak over the crystal.
Switching effects of the FET (denoted by C 3par)' which may
FIG. 5. Details ofthe blocking mechanism for noise reduction.
Sound velocity gases Download to IP: 152.92.173.34 On: Thu,
127113 Oct 2016
 1900
therms. The velocity pressure isotherms are terminated at
mls
pressures near the melting line, except for the isotherm at
t 298.15 K. The attenuation of sound pulses becomes so large
near the melting line as to prohibit any accurate measure-
1700
ment. The experimental velocity data for each isotherm are
smoothed by fitting into polynomials of the form
1500
(7)

by a least-squares analysis. It turns out that the average devi-

1300 ation of the experimental data from the smoothed curve is
less than 0.03%, showing high precision of the measure-
~, 298.1, K ment. In Table I, the smoothed values of the sound velocity
.. 2731,K
1100 .. 2.815K at intervals of 500 bar are given for several experimental
" 2211,K
" 1981,K temperatures.
.. 171.1,K
" '146.l!lK As experimental data of the pressure dependence of the
900 sound velocity for gaseous argon at lower temperatures are
not available in literature, comparison with previous data is
only possibl.e for the 298.15-K isotherm. This comparison
has been carried out after determining the velocities corre-
sponding to the pressures of the previous measurements us-
FIG. 6. Velocity of sound in argon as a function of pressure at several con- ing the interpolating polynomial (7) for 298.15 K. In Fig. 7,
stant temperatures. the deviations (.Ju) between the previous and present values
are plotted as a function of pressure. As shown, the present
data at 298.15 K agree with those of Vidal et al. 2 and Nishi-
result in distortion of the pulses, can be counterbalanced by take and Hanayama4 within their estimated accuracy. name-
C3comp'
ly 0.2% and 1%, respectively. For comparing with the data
The transmitting circuit can be tuned to about 10 MHz of Liebenberg et al. 3 where the experimental temperature
by means of the capacitor C 2 and extra damping is provided was slightly different from the present one, the sound veloc-
by the resistor (10 kfl ). The acoustical echo is converted to a ity data quoted in their paper are adjusted so as to conform
hf electrical signal by the transducer. The resulting signal is with the temperature ofthe present isotherm. As seen in Fig.
matched via transformer T2 to the receiver and monitored 7, the velocity data of Liebenberg are systematically higher
on an oscilloscope. than the present data, deviations being larger than the esti-
mated errors. It is shown further that the reported data of
HI. EXPERIMENTAL DATA FOR ARGON Pitaevskaya, I obtained from measurements at much lower
pressures (4 kbar) not only scatter appreciably but also lie
The apparatus for sound velocity measurements in gas-
es up to 10 kbar has been tested for its performance with TABLE I. Velocity of sound (in m/s) in argon at round values of the pressure
argon as a measuring gas. Apart from the theoretical impor- (in kbar).
tance, argon is particularly suitable as a first test of the appa-
ratus since this gas has previously been studied by several T
(K) 298.15 273.15 248.15 223.15 198.15 173.15 148.15
authors using other ultrasonic techniques, which makes it
possible to compare the present method of measurement
P
with other methods. (kbar)
Argon gas used in the present investigation has been I 737.7 757.7 784.7 816.4 857.2 906.4
1.5 887.5 909.3 935.0 964.9 1000.6 1042.4 1090.5
purchased from AGA gas B.V. and is specified to be 1005.2 1026.6 1050.9 1078.5 1110.7 1147.8 1190.6
2
99.9999% pure. The velocity measurements on argon have 2.5 1103.1 1123.7 1146.6 1172.3 1201.9 1235.7 1274.2
been carried out along seven isotherms ranging from 3 1187.6 1207.3 1229.1 1253.2 1280.7 1311.9
3.5 1262.3 1281.3 1302.0 1324.7 1350.5 1379.7
148.15-298.15 K in steps of 25 K. For each isotherm, data
4 1329.7 1347.8 1367.6 1389.2 1413.4 1441.2
are always taken in the decreasing order of pressure down to 4.5 1391.1 1408.6 1427.6 1448.2 1471.4
1 kbar, with intervals of about 500 bar. Below 1 kbar the 5 1447.8 1464.7 1482.9 1502.6 1524.8
acoustical impedance mismatch makes it impossible to pro- 5.5 1500.5 1516.8 1534.4 1553.4
6 1549.9 1565.7 1582.7 1601.0
duce echoes. The measurement consists of recording pres-
6.5 1596.4 1611.7 1628.2 1645.8
sure, temperature, and a set of nun frequencies. Appropriate 7 1640.4 1655.3 1671.3 1688.3
corrections for the change in acoustic path length due to 7.5 1682.2 1696.7 1712.2 1728.8
pressure and temperature are introduced using the reported 8 1722.0 1736.2 1751.3
8.5 1760.1 1774.0 1788.7
data of compressibility and thermal expansion of copper 11.12
9 1796.6 1810.3
in Eq. (6). 9.5 1831.8
In Fig. 6, the experimental data of the sound velocity in 10 1865.6
argon are plotted as a function of pressure for several iso-
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1272 Rev. Sci.lnstrum., Vol. 56. No.6. June 1985 Sound velocity gases 1272
20:11:24
 15
fly Argan 298.15 K
it is clear that the accuracy of measurements on other gases
m/s

i . .., . •
....
..,
will be close to the above figure.
The reproducibility of the sound velocity data at differ-
.. .. - ..
[;]
10
v ent pressures is, however, determined by the uncertainty in
• 9 • • • • • .. .. .. ..
pressure measurement. Using the measured velocity vs pres-
5 ••• 0°0 • ... ...
..,°. 0 [;]
[;] [;] -p
sure isotherms of argon and taking into account the error in
pressure measurements with the manganin gauge, one finds
° o02 o
4 o 6 8
0
10 kbar that the reproducibility of the velocity data at some pres-
- 5
0 0
[;] sures may be in the order of 0.08% while the absolute accu-
racy of the velocity measurements is 0.02%. This shows that
IF Liebenberg et al. it is worthwhile to increase the precision ofthe pressure mea-
-10 o Vidal et al.
[;] Nishitake and Hanayama surement by using a more sensitive technique. Development
-15
° Michels et al.
• Pitaevskaya et al.
of such a technique, based on the use of a differential pres-
sure null indicator coupled to a 10-kbar controlled clearance
FIG. 7. Comparison of the present sound velocity data at 298.15 K with
piston gauge, is now in progress in this laboratory.
those of the previous authors.
ACKNOWLEDGMENTS
This investigation is part of the research program of the
higher than the present ones. Finally, it is interesting to note "Stichting voor Fundamenteel Onderzoek der Materie
that sound velocities computed from the p VT data of Mi- (FOM)," supported by the "Organisatie voor Zuiver-We-
chels et al. 13 up to 3 kbar agree with the present results with- tenschappelijk Onderzoek (ZWO)." The authors wish to
in 0.5%. thank the technical staff of the Van der Waals Laboratory, in
particular W. J. Schuijlenburg and T. Jongeneelen for their
assistance with the design and the construction of the appa-
ratus. This is the 301st publication of the Van der Waals
IV. ACCURACY OF THE MEASUREMENTS Fund.

The accuracy of the measured velocities depends, of
course, on the accuracy with which the difference in acoustic
path lengths I and the difference in transit times T is deter-
mined. The quantity I at 1 bar and 20·C is determined by
means of a comparator with an accuracy of about 0.01 %.
The inaccuracies in pressure and temperature corrections of
I are negligibly small. The error in the measurement of T
depends mainly on the diffraction effects since the null fre-
quencies can be measured with a precision better than 3 in
106 while the value of the integer n is known exactly. The
effect of diffraction on the transit time has been analyzed
following the method described by Papadakis. 14 It turns out
from the analysis that the maximum error in T is less than
0.01 %. The overal1 accuracy of the sound velocity measure-
ments is, therefore, estimated to be about 0.02%. Although
the error analysis is carried out for the typical case of argon,
'L. L. Pitaevskaya. A. V. Bilevich. and N. B. lsakova. Russ. J. Phys. Chern.
43.1197(1969).
20. Vidal. L. Guengant. and M. Lallemand, Physica A 96,545 (1979).
JO. H. Liebenberg. R. L. Mills. and 1. C. Bronson. J. App!. Phys. 45. 741
(1974).
'T. Nishitake and Y. Hanayama. J. Phys. Soc. Jpn. 39.1065 (1975).
'J. William and J. Lamb. J. Acoust. Soc. Am. 30.308 (1958).
"J. Emery and C. Kammoun. C. R. Hebd. Seances Acad. Sci. B (France)
283. I3I (1976).
7V. F. Nozdrev, The Use of Ultrasonics in Molecular Physics lPergamon,
Oxford,1965).
"J. A. Schouten, N. J. Trappeniers. and w. Goedegebuure. Rev. Sci. In·
strum. 50, 1652 (1979).
·W. Goedegebuure, J. A. Schouten, and N. 1. Trappeniers, Rev. Sci. In·
strum. 48, 1213 (1977).
lOA. Michels, Ann. Phys. 72, 285 (1923); 73,579 (1924).
lip. Van 't Klooster, thesis, University of Amsterdam, 1978.
I2F. C. Nix and O. MacNair, Phys. Rev. 60, 597 (1941).
\3A. Michels, Hub. Wijker, and Hk. Wijker, Physica IS, 627 (1949).
I4E. P. Papadakis, J. Acoust. Soc. Am. 40, 863 (1966).

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