M-2684

j. Chem. Thermodynamics 1992, 24, 531-547

An apparatus based on a spherical

resonator for measuring the speed of
sound in gases at high pressures.
Results for argon at t e m p e r a t u r e s
b e t w e e n 255 K and 300 K and at
pressures up to 7 M P a
M. B. E W I N G and A. R. H. G O O D W I N "
Department of Chemistry, University College London,
20 Gordon Street, London WCIH OAJ, U.K.

(Received 22 July 1991; in final form 28 August 1991)

An apparatus, based on a spherical resonator, suitable for measurements with gaseous mixtures
at temperatures in the range 250 K to 350 K and pressures up to 21 MPa is described. Speeds of
sound in argon at pressures below 7 MPa have been determined. These measurements have
provided evidence for coupling between radial gas motion and non-radical shell motion.
Second acoustic virial coefficients for argon obtained from several resonators are compared.

1. Introduction
M o l d o v e r a n d M e h l (1) p i o n e e r e d the use of spherical a c o u s t i c r e s o n a t o r s for precise
m e a s u r e m e n t of the p r o p e r t i e s of gases and, with others, (2'3) they recently
d e m o n s t r a t e d the s t r e n g t h of the technique b y d e t e r m i n i n g the gas c o n s t a n t R with a
fractional e r r o r o f 1.7- 10 6. F r o m m e a s u r e m e n t s with a v a r i e t y of gases n e a r r o o m
temperature,(4 9) it is clear t h a t reliable speeds of s o u n d u c a n be o b t a i n e d with
relative ease using spherical resonators; a precision of 5- 10 6 in a u2(p) i s o t h e r m is
typical, a n d virial coefficients a n d perfect-gas heat ,ocapacities are d e t e r m i n e d
fractionally to 0.001 o r better. M o r e recently, we e x t e n d e d the t e m p e r a t u r e range of a
spherical r e s o n a t o r d o w n to 90 K and, as expected, o b t a i n e d results of similar
quality.(1 o, 11 )
H o w e v e r , all these m e a s u r e m e n t s have been restricted to pressures below 1 M P a
and, in m a n y cases, b e l o w 100 k P a ; u n d e r these conditions, the t h e r m a l b o u n d a r y
lajyer usually d o m i n a t e s the corrections t h a t m u s t be a p p l i e d to the e x p e r i m e n t a l
r e s o n a n c e frequencies. By contrast, at higher pressures, c o u p l i n g between the m o t i o n

a To whom correspondence should be addressed.

Present address: Thermophysics Division, National Institute of Standards and Technology,
Gaithersburg, MD 20899, U.S.A.

0021 9614/92/050531 + 17 $02.00/0 © 1992 Academic Press Limited

532 M . B . E W l N G A N D A. R. H. G O O D W I N

p/(kg.m 3)
25 50 75 100 125
I I I

//
300
// -1300
/
/
/
200
/ - 200 ,~
/
/
/
/

l°iL , '
- 100

I I 0
0 1 2 3 4 5 6
p/MPa

F I G U R E 1. Fractional contributions to the measured resonance frequency for mode (0, 4) in argon at a
temperature of 273 K in an aluminium resonator as a function of pressure p and density p arising from:
, the shell motion Af~ (right-hand axis); , the thermal boundary layer Afh (left-hand axis).

in the gas and the wall of the resonator becomes important. The dependence on
pressure of the shell correction Afs and of the thermal boundary-layer correction Afh
is shown in figure 1 for the (0, 4) radial mode in argon at 273 K in an aluminium
resonator. Measurements with a fractional imprecision of 1.10 5 are usually not
difficult with argon at 25 kPa and, we note from figure 1, that Afth at 25 kPa is
approximately equal in magnitude to Afs at 7 MPa. However, the theory of the
thermal boundary layer is highly developed for a spherical resonator (for example,
small second-order terms that account for the curvature of the surface are included)
and the work of Moldover et al. (2) demonstrates that uncertainties in Afth contribute
less than 1" 10 - 6 to the fractional error of speeds of sound measured in a practical
spherical resonator, albeit one constructed with great care. Although the approach
we have used to describe the shell motion is based on elastic theory t12' 13) that is
exact for a thick spherical shell, our resonator is neither a spherical shell nor
isotropic when fitted with the transducers and thermometers necessary for
measurements. Consequently, we have used measurements with argon at high
pressures to characterize the resonator and, in particular, to assess the effects of shell
motion.
 SPEEDS O F S O U N D IN GASES AT HIGH PRESSURES 533

2. Apparatus and experimental

The apparatus is shown in figure 2. The spherical resonator was constructed as two
hemispheres from a single cylindrical bar of aluminium alloy. ~14~ Before turning
commenced, the two transducer ports were drilled at a polar angle of n/4 and
separated by an azimuthal angle of rt in the upper hemisphere and then reamed to a
diameter of 10 mm. The outer 5 m m of each port was tapped with a 1 m m pitch
thread to accept a housing of 19.05 m m diameter. These ports were then plugged
with aluminium inserts and the interior surface of each hemisphere was turned with a
worm-driven tool to give an internal radius of 40 ram. The external surface was
machined using a spherical turning tool to produce a wall of thickness 10 ram; a
cylindrical boss of diameter 25.4 m m was left at each pole. The hemispheres were
machined at the equator to form an interlocking step, which ensured accurate
concentric alignment about the polar axis, with the polar depth 3 m m greater than

E , I I U ~1.1 V C 1-

OFHC copper
0 4,0 m m Stainless
steel ~ Aluminium alloy
AI l_x_y zSixMgyMn z

F I G U R E 2. Cross-section through the high-pressure speed of sound apparatus. The pressure vessel was
suspended in a stirred-fluid thermostat. A long-stem resistance thermometer, with its platinium sensing
element located at about the resonators equator, was inserted into the thermometer well. To improve
thermal contact, this well, was filled with ethanol or n-octane depending on the operating temperature.
534 M. B. EWING AND A. R. H. GOODWIN

the equatorial radius. Tooling marks on the interior surface were reduced by
mechanical polishing and any resulting rounding of the equatorial edge was
subsequently removed in the final dimensional adjustment. To form the 1 mm
diameter inlet tube, a hole was drilled through the upper boss and the length
extended to a total of 40.9 mm by embedding a stainless-steel tube in the boss. Since
the perturbation resulting from an open tube, length L, in the wall of the sphere,
radius a, is proportional to cot(vL/a) and the eigenvalues Vo~ of the (0, n) radial
modes are approximately ( n - 1/2)re, n = 2, 3,. •., this design for an inlet tube with
L ~ a results in small perturbations to the radial resonance frequencies. After final
assembly, the sphere was welded by an electron beam which penetrated about 6 mm
into the wall. Although the resonator could have been used as its own pressure
vessel, the radius would have increased fractionally by about 170.10 -6 with a
pressure difference of 7 M P a across the wall. By contrast, when pressure
compensated, the radius decreased fractionally by only 30.10 -6 at a total pressure of
7 MPa. Furthermore, for measurements with methane or natural gas, a separate
vessel offered additional protection against leakage39)
The inner surfaces of the brass transducer housings were machined with a 40 mm
radius of curvature to match that of the sphere. A nominal clearance of 10 ~tm
between the transducer housing and the resonator reduced the area of the annular
slot but allowed pressure equalization. Machineable ceramic or P T F E were used for
insulation while springs were used to complete electrical connections which passed
through leads sealed in ceramic to the pressure vessel.
The electrostatic transducers are shown in figure 3. The source was formed by
clamping a 6 mm disk of 12 ~tm thick polyester between the housing and a ceramic
sleeve. The active area, 2 mm diameter, was coupled to the sphere by a tube 0.25 mm
long. A spring tensioned the disk by way of the 1.9 mm diameter back electrode
which had six 0.3 mm diameter holes drilled to a depth of 0.5 mm so that the
compliance of the disk was increased. The housing, which made contact with the
50 nm layer of aluminium on the disk, was held at ground potential while a 60 V
r.m.s, signal superimposed on a d.c. bias of 180 V was applied to the back electrode.
Theory~Z, xs~ suggests that this transducer, including its annular slot, perturbed the
resonance frequencies fractionally by less than 2.10 6.
The detector was formed from a commercially available microphone which had a
permanently polarized polyvinylidene fluoride disk as its active element. The disk
had a capacitance of only about 5 pF and its high impedance was matched to the
external electronics using a simple J-FET circuit which was mounted inside an
electrical shield close to the disk to avoid signal loss from stray capacitances. The
transducer was clamped in place within its brass housing by a P T F E slgeve and
acoustically coupled to the sphere through a 15 mm a volume and a 0.7 mm diameter
wave-guide of length 4 mm. Such an arrangement in principle forms a Helmholtz
resonator but, as noted previously, {5~ leakage conductance dominates and the wave
guide behaves as an open tube which has a resonance above the (0, 10) radial mode.
Consequently, the perturbations for the modes used in this work are small and the
corrections can be made with negligible uncertainty.
Figure 2 also shows the pressure vessel which was designed using the relevant
 SPEEDS OF SOUND IN GASES AT HIGH PRESSURES 535
-

. . .
•_•_•_••Shield
V/"////~zZd(ZZ6Zdg~MZ~////../] V/JJ////////////////////J///J Electrical
B,asc, r c m t ~ ~ ~ U//AI ~ - - lead-through

Eltec ,c , NI --Contact
lead-through ~ ~ HI I ~ / A l ~ l ~ l it _ screw
-P g

Sprlng---------~//~ ~ ~ 1 Vent ~ ~

Seal g r o o v e - ~ ~ ~ ~Membrane
Electret / 0 5 10 mm
microphone- - / ' . . . . ' .... '
capsule

~ Brass ~ PTFE ~ceramic

FIGURE 3. Electroacoustic capacitance transducers used in the high-pressure apparatus. Left, The
detector which contained a commerciallyavailable electret capsule. Right, Sound source,constructedfrom
a 12.5gm thick polyestermembrane coated with a 50 nm aluminium layer, that facedinto the resonator.

standards(16, 17) to operate at temperatures up to 600 K and pressures up to 20 MPa.

The cylinder with its sealing surfaces and end-cap mountings was machined from a
length of seamless drop-forged tube (316 stainless steel) to give an internal diameter
of 134 mm and a 16.5 mm wall. A recess was cut in each end of the tube to hold
20 mm of the 22 mm thick 316 stainless-steel end plates which were secured by 321
stainless-steel screw caps. When the pressure vessel was assembled, about 20 mm of
the threads (ISO coarse metric, 3 mm pitch, internal angle of ~/3) were engaged; the
use of slightly different materials for the components of the join and the very high
rating of the thread (18) ensured that there were never any problems with seizure or
permanent deformation. The threads were appropriaLely undercut, and sharp corners
on the end plates and screw caps were removed to reduce concentration of stress in
these components3 TM Five pipes were sealed through the top plate of the pressure
vessel using unsupported O-ring seals between the underside of the plate and flanges
that were welded to the pipes. Two 6 mm pipes were used for electrical leads and
were terminated outside the thermostat by three-pin leads-through (Amphenol Ltd)
rated for 17 M P a at 365 K. Pipes of 12.7 mm diameter admitted gas to the resonator
and the pressure vessel and a third 12.7 mm pipe was used for the thermometer. The
apparatus was assembled using O-ring seals for the transducers, the end plates, and
the pipes through the top plate. The grooves for the gaskets were machined to accept
PTFE-coated pressurized stainless-steel O-rings. Viton O-rings were used for the
536 M.B. EWING AND A. R. H. GOODWIN

measurements reported here and additional mounting rings were required for the
seals between the end plates and cylinder.
The apparatus, including the valve used to seal the gas sample, was suspended
inside a stirred fluid thermostat the temperature of which was controlled to 1 mK.
The lower end of the thermometer tube sat in a copper well that was clamped to the
two poles of the resonator using copper blocks, and the temperature of the resonator
and the gas sample was measured on IPTS-68 using a long-stem platinum resistance
thermometer. Heaters were mounted on the thermometer block so that the
temperature of the resonator could be increased rapidly during a bake-out and
following a decrease in pressure along an isotherm.
The pressure difference across the resonator wall was monitored using a
differential strain-gauge transducer connected between the pipes to the resonator
and pressure vessel. The nitrogen in the outer vessel could be connected to an oil-
lubricated pressure balance and, consequently, the sample pressure could be
determined. The transducer (Schaevitz Inc, model P642-0001) could operate at a line
pressure of 21 M P a a n d withstand a pressure difference of 21 MPa. The active
elements were confined to the reference (nitrogen) side and the transducer had an
asymmetric response. Using an air-lubricated pressure balance, the transducer was
found to be reproducible to 0.0002. p for pressure differences between - 30 k P a and
0 and to 0.0001 •p between 0 and + 100 kPa; measurements were made at a total of
23 pressure differences. Recalibration was required if pressure differences outside the
range - 5 0 k P a to 500 k P a were applied. The zero, when checked at 15 line pressures
up to 7 MPa, was found to vary by 1.1 k P a but the shift was linear to 4 Pa with the
line pressure. All these results were comfortably within the manufacturer's
specifications and we estimate that the imprecision in a pressure difference was less
than 15 Pa. This uncertainty is negligible at pressures above 1 M P a compared with
the imprecision (5" 10 5.p) of the oil-lubricated pressure balance. Since U-2(~U2/~p)T
is about 5.10 -3 M P a -1 for argon at 273 K, the uncertainty arising from the
imprecision in pressure was always less than 2 . 1 0 6 of u 2.
The argon was supplied by the British Oxygen C o m p a n y plc with a stated mole-
fraction purity of at least 0.99998. Before a series of measurements, the resonator was
baked at 350 K until the pressure indicated by an ionization gauge in the pumping
line had been below 1 m P a for 24 h. The zero of the differential pressure gauge was
adjusted and the resonator filled with argon to 7 M P a in steps of 100 kPa; after each
pressure increment nitrogen was added to the pressure vessel to null the pressure
difference. When thermal equilibrium had been reached, the resonance frequencies
fon and half widths gon of a set of radial modes were determined by analysis a9~ of
comparative measurements of the amplitude and phase of the transmitted~ and
received signals at a series of frequencies near each fon. For most resonances, our
usual procedure t6~ based on 1 l frequencies in the range (f0n + g0~) was adequate but
in some cases sample averaging was used to increase the signal-to-noise ratio and,
where overlap with non-radial modes occurred (see section 5), measurements were
usually made at 22 frequencies over a wider range of frequencies. The pressure of the
sample was measured before and after the acoustic measurements, and the pressure
vessel was isolated from the gauges while the pressure balance was adjusted so that
 SPEEDS O F S O U N D IN GASES AT H I G H P R E S S U R E S 537
the thermal equilibrium of the resonator was not disturbed by the changes in the
nitrogen pressure. The temperature and pressure of the sample were constant to
0.1 m K and 30 Pa during a set of acoustic measurements. The pressure was then
reduced by about 700 kPa, in steps of about 100 kPa for the next point on the
isotherm. These pressure changes reduced the temperature of the resonator by about
1 K and the output from the resistance bridge was used to drive the heaters on the
thermometer block via a simple servo-loop until the temperature had returned to
within a few m K of its previous value. About 2 h was allowed between points on an
isotherm. Finally, the resonator and pressure vessel were evacuated and the zero of
the differential pressure gauge was checked.

3. Theory
Although the acoustic model for spherical resonators has been described in detail
elsewhere, t1,2, 5, 6, 12, 13) the effects of shell motion are particularly important at high
pressures (see figure 1) and, consequently, the relevant parts of the theory will be
discussed here. Mehl t12! generalized the theory for the motion of a thick spherical
shell to include both radial and non-radial modes. Although direct coupling between
the gas and the shell motions should occur only when the modes have the same
symmetry, we have some evidence (see section 5) that non-radial shell motion can be
important for radial modes in the gas. Moldover, Mehl, and Greenspan ~13) have
considered the additional effect of radiative losses from the external surface of the
shell; for a pressure-compensated resonator !
this is potentially an important loss
mechanism.
First-order perturbation theory ~12'13) gives the frequency shift Afs and the
contribution gs to the half width arising from shell motion as
(Afs + igs)/f = - (pg u2/ps u2)So, (1)
where p and u denote the density and the speed of sound and the subscripts s and g
refer to the shell and gas. We note immediately that the perturbation is linear in the
gas density. In equation (1) the dimensionless function So is given by
S O = - q{(G 1 + qR~Gz)/(G 3 + qRrG4) }, (2)
where the factor q introduces Poisson's ratio a:
q = (1 - a)/2(1 - 2a), (3)
and where
Rr -- (pg, eUg,
e/psUs){kg.e/(12
2 2 -ikg, eb)}, (4)
accounts for the radiation from the external surface at r = b into the surrounding
unbounded fluid (denoted by the subscript e); kg, e = 27zf/Ug,~ is the propagation
constant in the gas external to the resonator. The parameters Gi in equation (2),
which depend on the propagation constant k s in the shell and its radii, have been
defined by Moldover et al. ~13) If radiation is neglected then So = -q(G1/G3).
538 M.B. EWING AND A. R. H. GOODWIN

The theory implies that coupling will be greatest when the motions in the gas and
the shell have the same symmetry; Moldover, Mehl, and Greenspan t13)
demonstrated experimentally the importance of symmetry in determining coupling
between the gas and the shell. On this basis, radial modes in the gas will couple most
strongly with radial modes in the shell such as the breathing mode which has a
frequency fb (the first radial mode of the shell). For argon at a density of 100 kg. m-3
contained in an aluminium shell, the appropriate acoustic resistances are pgu~
1" 10 7 Pa and psu 2 "~ 1.1.1011 Pa and, provided the radial acoustic frequencies fg
are less than about 0.7 of the shell breathing frequency fs, the function So is close to
unity. Therefore, the perturbation (equation 1) is approximately psUs/pgUg 2 2 ,~ 10 -4
and the above expressions are, in principle, adequate.
Other shell modes which have both transverse and radial components may also
couple to the gas motion but, again, the coupling should be weak except when the
frequencies or acoustic resistances are comparable3 TM The remaining shell modes (in
contrast to those noted above which describe deformations at constant volume) are
purely torsional, have no radial component, and should couple only through weak
viscous effects;~12) we have not included these modes in our calculations.

4. Results
Values of the quantity (u/a) were calculated from the resonance frequencies fo.,
determined as described in section 2, using
(u/a) = 2r~{fo, -- (Afth+ Aft + aL)}/Vo., (5)
where Afth, Aft, and Afs are the corrections for the thermal boundary layer, the
coupling tubes, and the shell motion; %, is the eigenvalue for the (0, n) mode and
a(T, p) is the radius of the resonator.
The acoustic model used to calculate Aft~ and Aft has been described in detail
before/2'3'5'7) The thermal boundary layer correction varies as (f/p)l/2 and its
fractional contribution to (u/a) ranged between 20.10 -6 {for the (0, 6) mode at
21 kHz, 255 K, and 7 MPa} to 464" 10 - 6 {for the (0, 2) mode at 5.8 kHz, 300 K, and
60 kPa}. The thermal conductivities x required for this correction were calculated at
each point using literature results3 z° 22) Had we neglected the density dependence of
then the corrections would have differed by up to 0.08" Afth or 5" 10 -6. (u/a). The
accommodation coefficient was taken as 0.84, as determined previously ~5) for argon
in an aluminium resonator, although a choice of 1.0 would not have altered our
results significantly. The corrections Aft for the openings in the resonator's wall were
calculated using mechanically measured dimensions. The wave guide to the detector
was treated as a simple open tube and the correction was always less than 11" 10-6fo .
while, as noted in section 2, the length of the gas inlet tube was selected to minimize
the corrections which were always less than 2.10-6fo,. Each tube also made a small
contribution 9t to the resonance half width. In addition to x, the shear viscosity q is
required for Aft, and to calculate the bulk-loss. The values of r/were also taken from
the literature; ¢2°) the density dependence of q made a negligible contribution to these
 SPEEDS OF SOUND IN GASES AT HIGH PRESSURES 539

calculations. The second and third virial coefficients of Michels et al. ~23' 24) were used
to calculate the densities p and heat capacities Cp, re(P) and Cv, re(P)'
The correction Afs for the shell motion was calculated from equation (1). The
Young's modulus E of the shell at each temperature was obtained from a literature
correlation for aluminium alloys t25) while Poisson's ratio tr was assumed to be 0.335
and independent of temperature326) The density of the shell was calculated from the
mass of an alloy billet of known dimensions and the thermal expansivity of pure
aluminium327) The speeds of sound, ug in the gas and u s in the shell, required for
these corrections were obtained, respectively, from a preliminary analysis of the
results or calculated from the elastic properties. In our experimental pressure range,
AfJfo . varied from 6- 10 -4 {at a frequency of 24.4 kHz for mode (0, 7) at 5.8 M P a
and 255 K} to 2.6" 10 -6 {for mode (0, 2) at 5.8 kHz, 300 K, and 60 kPa}. At the
highest density, a fractional error of 0.01 in E leads to uncertainties in AfJfo, of
between 4.10 - 6 and 14- 10 -6 for modes (0, 2) to (0, 7) and the uncertainties decreases
linearly with density. We estimate from the temperature dependence of a for other
aluminium alloys ¢26) that our assumption might introduce a fractional uncertainty in
u of 5" 10 -6 but 2.10 6 would be more likely. Radiation losses from the external
surface of the resonator had little effect except at high frequencies due to the
comparatively low density of the nitrogen used to pressure-compensate the vessel.
For example, inclusion of radiation for the (0, 8) mode at 255 K (at about 28 kHz)
increases the speed of sound by 0.001 m" s 1 and the excess half width is reduced by
20" 10 -6 of f0s; typically the radiation corrections for the (0, 3) and (0,4) are
fractionally less than 1.10 -6.
Table 1 lists mean values <u/a> in argon along four isotherms between 255 K and
300 K at pressures up to 7 MPa; the (u/a> at each point was determined from the
results of equation (5) for up to seven radial modes. The results of one of the
isotherms at 273.16 K were obtained using prototype transducers for which the
source had a tensioned active element of diameter 6 mm while the detector was
coupled to the resonator through a 1 mm diameter by 6 mm tube. These transducers
were very efficient between 25 kPa and 250 kPa but at high pressures, and especially
at high frequencies, their sensitivity was seriously impaired. Several modifications to
the overall dimensions, to the back plate, and to the mounting arrangement,
produced transducers, described in section 2, that performed well at high pressures
but measurements were rather difficult below 50 kPa; the other isotherms given in
the table were studied using these transducers. "Table 1 also gives the standard
deviations s of ( u / a ) , the number N of radial modes from which the mean was
calculated, and the fractional deviations 6 of ( u / a ) z from the smoothing equation:

(u/a) 2 = (Ao/ a 2) + (A1/aZ)p + (Az/aZ)p z + (A3/aZ)p 3 + .... (6)

The agreement between results obtained from different modes at a given temperature
and pressure, and those included in the final regression analysis described below, will
be discussed in section 5.
In equation (6), A o = RT])Pg/M, where R is the gas constant, M the molar mass,
]JPg = c P , m --R~J~ C ppg
p , gn /v '(, c ppg ,m the molar heat capacity at constant pressure, and the
540 M. B. EWlNG AND A. R. H. GOODWlN

TABLE 1. Mean values of the quantity (u/a) with the standard deviations s of (u/a) determined from N
radial modes, and deviations 6 = lO%(u/a)2-(u(calc.)/a}Z]/{u(calc.)/a} 2 from equation (6) with four
terms at temperatures T and pressures p in argon

T/K p/kPa (u/a)/s- 1 s N 6 p/kPa (u/a)/s- ~ s N

255.000 7022.029 7579.975 0.003 3 --0.3 2608.368 7457.388 0.016 3 --7.7

5808.954 7532.787 0.010 2 3.9 1668,715 7447.216 0.021 5 4.6
5137.365 7511.295 0.006 2 2.1 840.341 7442.040 0.037 6 -- 5.7
4593.837 7496.151 0.001 2 --15.1 189.479 7440.375 0.018 4 2.8
4101.097 7484,256 0.011 3 0.6 115.850 7440.298 0.019 4 1.0
3266.735 7467.620 0.011 3 11.9 63.342 7440.285 0.004 2 6.8
273.160 6342.753 7852.869 0.017 2 2.6 1667.122 7719.179 0.039 5 2.3
5790.772 7830.732 0.023 2 --6.9 975.569 7708.826 0.020 5 2.8
5124.476 7806.472 0.018 2 1.5 248.466 7700.204 0.021 6 --3,3
4392.389 7782.721 0.001 2 7.5 206,440 7699.780 0.027 5 --2.1
3720.628 7763.487 0.001 2 3.8 153.455 7699,255 0.021 5 -1,2
3002.582 7745.546 0.031 4 -7.0 101.646 7698.771 0.018 5 4.7
2295.899 7730.516 0.024 5 --0.9
273.160 a 6271.313 7850.394 0.015 2 3.6 1451.355 7715.605 0.019 5 --0.1
4869.252 7798.129 0.002 2 38.6 717,482 7705.379 0.017 6 --10.8
4222.437 7777.553 0.008 2 -22.2 214,000 7699,759 0.028 5 --11.7
3473.029 7756.978 0.002 3 5.2 172.560 7699.380 0.025 5 --2.5
2826.949 7741.557 0.012 3 9.7 124,141 7698.918 0.025 5 0.9
2119.151 7727.074 0.012 3 9.7 70.764 7698.483 0.012 5 21.0
300.000 6798.196 8283.906 0.009 2 7.6 1608.874 8097.651 0.003 2 --3.0
6050.542 8249.950 0.091 3 --0.1 854.115 8079.675 0.053 5 --12.7
5273.117 8217.228 0.084 3 --13.7 224.301 8066.378 0.030 6 --9.6
4505.108 8187.556 0.063 3 --6.1 149.409 8064.939 0.019 4 1.5
3794.813 8162.415 0.008 2 18.5 93.190 8063.876 0.024 3 10,9
3087.985 8139.342 0.036 3 8.4 60.953 8063.288 0.025 4 20.3
2368.781 8117.995 0.023 3 7.0

aIsotherm performed with prototype transducers.

superscript pg denotes the perfect gas. T h e second acoustic virial coefficient was
o b t a i n e d from the coefficient A 1 using fla = R T A I / A o .
O n l y the leading four terms of e q u a t i o n (6) were required to fit the results. All the
selected modes, typically m o r e t h a n 40 for a n isotherm, were used in the regression
analysis rather t h a n j u s t ( u / a ) at each pressure. I n this analysis, literature values for
R a n d M were assumed a n d the leading term was used to d e t e r m i n e the radius a. ~z)
The results of the analysis are given i n table 2 together with the n u m b e r N of
r e s o n a n c e frequencies in the final regression a n d the fractional s t a n d a r d deviations of
(u/a) z, for each isotherm. The q u o t e d uncertainties are one s t a n d a r d deviation. T h e
similarity of the fractional s t a n d a r d deviations of ( u / a ) 2 for the selected mod~s at
each pressure, a n d of the (u/a) 2 for a whole isotherm, shows that e q u a t i o n (6) gives a
good representation of the results. T a b l e 3 gives the values of the a a n d fla
d e t e r m i n e d from the coefficients of table 2. The high level of repeatability of the
e x p e r i m e n t is d e m o n s t r a t e d by the results at 273.16 K; the two estimates of the
radius differ by 0.00026 m m a n d the values of ft, lie within 0.02s cm 3- t o o l - 1. I n view
of the close agreement of o u r two isotherms at 273.16 K, a n d despite the d i m e n s i o n a l
differences in transducers, we have c o m b i n e d the selected (u/a) at each pressure for
 SPEEDS OF S O U N D IN GASES AT H I G H PRESSURES 541
TABLE 2. Coefficients for the leading four terms of equation (6), and standard deviations sN = s(u2)/u2
obtained by analysis of N modes for argon at temperatures T

T lO-6(Ao/a 2) lO(A1/a2) 108(A2/a2) lO16(A3/a2

) 106.sN
N s 2 s-2.pa 1 s-2.pa-2 s-2.pa-3

255.000 39 55.35708 + 0.00020 0.0405 +_0.0029 3.258 -+ 0.010 13.406 ± 0.098 9

273.160 50 59.25602+0.00010 1.4224_+0.0022 3.174+0.010 9.10±0.11 6
273.160 a 46 59.25523+0.00020 L4151___0.0047 3.183___0.021 9.48+0.23 12
300.000 43 64.99639_+0.00030 3.0838_+0.0060 3.003-1-0.023 4.51_+0.23 15

a Isotherm performed with prototype transducers.

TABLE 3. The resonator radii a(T, p = 0) and second acoustic virial coefficients fla of argon at
temperatures T determined from regression analysis with a pressure-explicit expansion

T/K a/mm flJ(cm 3. m o l - 1)

255.000 39.97401 _+0.00028 0.155 _±0.011

273.160 39.98863 ± 0.00014 5.452 +_0.009
273.160 a 39.98889 _+0.00027 5.424 + 0.018
300.000 40.01383 _ 0.00037 11.835 + 0.023

a Isotherm performed with prototype transducers.

our discussion in section 5. Regression analysis with the combined results at

273.16 K returned a = (39.98880 + 0.00037) mm and fla = (5.440 - 0.023) em3" mol- 1.
We have considered the effects of imposing a closed-form representation of the
results on the values of fla obtained, l~or each isotherm, inclusion of higher-order
terms did not improve the fit and lead to estimates of fa that agree with those listed
in table 3 to within the combined standard deviation. We have also investigated the
use of an expansion in powers of amount-of-substance density in place of (6) and, in
each case, found that four terms were required to accommodate the results; densities
were calculated correct to the third virial coefficient using the results reported in
references 23 and 24. As expected, using the amount-of-substance-explicit acoustic
virial expansion, did not significantly alter the estimates of a. In all but one case, the
resulting estimates of fa agreed with the values given in table 3 to within a small (less
than 0.5) multiple of the combined standard deviation. The isotherm at 255 K, the
temperature close to where fa = 0, gives~ a value of fa that is
(0.052+0.01jcm3.mo1-1 below that obtained from the four-term fit with the
pressure-explicit expansion. These observations are, with perhaps one exception,
consistent with the hypothesis that the systematic errors in fa that arise from
truncating the infinite series (6) are comparable to the random uncertainties.
Amongst other sources of systematic error, that we have considered, the uncertainty
in the elastic properties of aluminium, that enter into the calculation of both the
dilation of the shell and of the correction for coupling between the gas and shell
vibrations, have a negligible effect on the determination of fla" Finally, the
uncertainty in the thermal conductivity at a temperature of 300 K propagates into an
error of about 0.008 cm 3. mol-1 in fla.
542 M. B. E W I N G A N D A. R. H. G O O D W I N

We shall not consider further the higher terms used to represent the results in this
paper, but note that our values of A 3 were used to assist in the analyses of both the
recent acoustic determination of the gas constant t2) and the thermodynamic
temperature of the triple point of gallium3 TM

5. Discussion
For all isotherms, the values of Uo. obtained from the (0, 3), (0, 4), and (0, 5) modes
cover a range of not more than 8- 10-6. Uon over the full pressure range; such internal
consistency is comparable with that obtained by us with other resonators at
pressures below 250 kPa. t5-8) However, UOn for n = 2, 6, and 7 are in serious
disagreement at higher pressures. This behaviour is illustrated in figure 4 where the
fractional deviation Auo, = (Uon- (u))/(u) from the mean ( u ) of modes (0, 3) to
(0, 5) is shown for all the modes that were studied. A satisfactory explanation for the
deviations of modes (0, 6) and (0, 7) is provided by perturbations arising from
coupling between resonances in the gas and the aluminium shell.
Figure 5 compares the shell resonances predicted, using the theory discussed in
section 3, t12'13) for a perfect isotropic aluminium spherical shell with radii 40 mm
and 50 mm with the in-phase response of the transducers recorded under vacuum
over the frequency range 0 to 42 kHz. Such a crude experiment may detect
resonances other than those due solely to the shell, but there is surprisingly good
agreement between the predicted and observed resonances although the observed
response is much more complicated. In particular, the bending modes predicted by
theory at frequencies of 18kHz (with 7 components) and 24kHz (with 9
components) appear to have merged into a multiplet at about 21 kHz; the response

I I I I I I I i l l l l ~

(b) (c)
5C • 5O

A x x x x

v 0
# 0
• 0
[] O# 0 0 i ~A .A . . ~ .
<1 -50
,,~. #

× a

- 100 O ~ -50 X
#

-50F , , , ,~ , , I I x I I I I
0 2 4 6 0 2 4 6
p/MPa p/MPa p/MPa
FIGURE 4. Fractional deviations A(ula)/(u/a) = { ( u / a ) - ( u / a ) } / ( u / a ) for individual modes in argon
from (u/a) of the modes finally selected for analysis with equation (6) as a function of pressure p: (a),
255 K. (b), 273.16 K. (c), 300 K. O, (0, 2); I , (0, 3); A, (0, 4); V, (0, 5); ~, (0, 6); x, (0, 7). For the isotherm
performed at 273.16 K with prototype transducers: ©, (0, 2); 12],(0, 3); A, (0, 4); V, (0, 5); O, (0, 6); +,
(o, 7).
 SPEEDS OF SOUND IN GASES AT HIGH PRESSURES 543

I I
T/K (0,2) (0,3) (0,4) (0,5) (0,6) (0,7)
255.00 • • Frequency
1 273.16 • • • • • range of
300.00 • • • • • acoustic
modes

Predicted shell
resonance
frequencies -'lb
0 I
0 10 20 30 40
f/kHz
FIGURE 5. Bottom: Amplitude w of the signal detected at frequencies between 0 and 42 kHz using the
electrostatic transducers while the resonator was under vacuum. The ordinate axis has been scaled to the
maximum w at 41 kHz. Middle: Predicted shell-resonance frequencies for a perfectly spherical isotropic
shell with the same dimensions with A, breathing; b, bending; and e, extensional motion. Top: Frequency
range of the (0, 2) to (0, 7) acoustic modes over the experimental pressure range at the three temperatures
studied.

observed above 35 k H z might be associated with high-frequency motion in the

transducers mounts. Virtually identical results were obtained at other temperatures
and when the resonator was suspended by wires in an evacuated desiccator which
suggests that this spectrum is due solely to the metallic parts of the resonator and is
independent of the method of mounting. Figure 5 also shows the frequency ranges in
which the radial modes occur in argon at the three temperatures studied. F o r 255 K,
the broad shell resonance at 21 k H z falls between the (0, 6) and (0, 7) radial modes
and, as figure 4(a) shows, the (0, 6) mode is perturbed to values lower than ( u ) while
Uo7 is perturbed to higher values. As the temperature increases, fo6 moves into the
centre of the shell resonance and, as shown in figure 4(b), u06 is seriously perturbed
but to values higher than ( u ) while the (0, 7) mode moves to the upper limits of the
shell resonance and, at 300 K, shown in figure 4(c), Uo7 deviates from ( u ) in a more
r a n d o m fashion.
The resonance half widths also contain information that is useful when assessing
the performance of the resonator. The excess half width Ag for a mode is defined as
the excess of the experimental value over that calculated from the acoustic model
which includes contributions from the thermal boundary layer, the coupling tubes,
the shell motion, and bulk-loss mechanisms.
The excess half widths, shown in figure 6 as a fraction of the observed resonance
frequencies, provide further evidence for the perturbation of the (0, 6) and (0, 7)
modes by the shell resonance. At 255 K, figure 6(a), Agon/fon increases more or less
~linearly with pressure except for mode (0, 6) where it increases rapidly above about
3 M P a and exceeds 250" 10 -6 at 7 MPa; the resonance frequencies in argon increase
with pressure and fo6 coincides with the strong spike in the shell response at
20.8 kHz. For the isotherms at 273.16 K, figure 6(b),. mgo6/f06 is significantly larger
than for any other m o d e and even at 1 M P a the excess half width exceeds 1.10 -5 of
544 M. B. EWING AND A. R. H. G O O D W I N
I I I I I I [ i i i , i ,

260; (a) , (c) *

150[ 50 (b)
@ I •
i
0 ~
1001-
401 . o I •
0

<I 3(?
J * •
5C
201 °** • 501 • ,
¢ v v v
. x x • • • •
,b

10
.,;it;". AI= &=~

00
*J
2
,
4
I ,
6
, 0
0
+x

2
+

4
o t '
I ,- " ! ~ ; ~ •" ,
p/MPa p/MPa p/MPa
FIGURE 6. Fractional excess half widths Ag/f as a function of pressure in argon: (a), 255 K, (b),
273.16 K, and (c), 300 K. O, (0, 2); II, (0, 3); A , (0, 4); V, (0, 5); 0 , (0, 6); x, (0, 7). For the isotherm
performed at 273.16 K with prototype transducers: O, (0, 2); D, (0, 3); ~ , (0, 4); ~ , (0, 5); ~ , (0, 6); +(0, 7).

f06; while at 300 K, figure 6(c), Ago6/fo6 increases linearly with pressure and is never
greater than 22-10 -6. In earlier measurements (6) with argon at 273.16 K in an
aluminium resonator, it was necessary to reject the (0, 6) mode and the results
reported here confirm our earlier conjecture that the additional perturbation was
caused by a minor shell resonance. It should be noted that the frequency and
amplitude of the shell resonances will depend strongly on the material of the shell
(for example, the amplitude would be about a factor of three smaller for a stainless-
steel resonator) and the resulting perturbation to the radial modes will depend on the
gas and its temperature and pressure but not on the radius of the sphere.
Consequently, we anticipate that for measurements in methane, where the resonance
frequencies and speeds of sound are approximately 1.3 times higher than in argon,
the (0, 5) mode at about 22 kHz in this resonator at 255 K will be perturbed by the
bending resonance of the shell but the (0, 6) mode at about 27 kHz will be unaffected
by the bending mode but may be perturbed by the breathing resonance of the shell at
32 kHz. Figure 5 shows that the (0, 2) mode is far removed from any shell resonance
and an alternative explanation must be sought for its discrepant behaviour. The
frequency of the (3, 1) non-radial mode is fractionally only 0.0046 greater than fo2
but the non-radial has a node at an angle of re/2 and the orientation of the
transducers usually avoids interference between the two modes. However, figure 7
shows the amplitude and the real and imaginary parts of the resonator's re~onse
over a frequency range covering the (0, 2) and (3, 1) modes in argon at 255 K. At a
pressure of 6.7 MPa, the seven components of (3, 1) are split superficially into a
doublet and the lower component is only partially resolved from the (0, 2) mode, but
at 3.8 MPa the splitting of the non-radial mode is no longer apparent and there is no
evidence of coupling with the radial mode. The pressure dependence of splitting of
(3, 1) and its coupling to (0, 2) is probably due to elastic anisotropy in the shell.
Below 3.5 MPa, Uo2 always agreed fractionally with <u> to better than 10.10 -6,
 SPEEDS O F S O U N D IN GASES AT HIGH PRESSURES 545

(a)
.~lll~(0,2) I ~(3,1)

-1 I I I I
5.40 5.41 5.44 5.45

(b) (0,2)

0
\i ',. /

- 1 ~
5.33 5.34 5.37 5.38
flkHz
F I G U R E 7. Complex potential-difference ratio w = w. cos ~b+ iw. sin ¢, calculated from measurements
of the relative amplitude w and phase ¢ between the received and reference signals at frequencies in the
vicinity of the (0, 2) and (3, 1) modes in argon at 255 K: (a), at a pressure of 6.7 MPa, where the ordinate
axis has been scaled to a maximum w of 0.68; (b), at a pressure of 3.8 MPa, where the ordinate axis has
been scaled to a maximum w of 3.11. - - - - , Re(w); . . . . , I m ( w ) ; - - , w.

with the discrepancy decreasing linearly with pressure, and these results were
included in the final regression analysis. The pressure range over which mode (0, 2)
gave useful results would have been increased if the relative amplitude and phase at
each of the discrete frequencies had been analysed t25) with terms for both (0, 2) and
(0, 3) but no such analysis was attempted.
We have used the observations, described above, of the difference between the
value of (u/a) obtained from each resonance frequency at a point to form the basis for
omitting modes from the regression analysis with equation (6) (discussed in section
4), and so determine values of a and fla reported in table 3. The success of our mode
selection procedure may be judged by comparison of our present experiment results
with those from the literature.
The radius of this resonator has also been obtained at temperatures from 99.97 K
to 303.88 K, from acoustic experiments with argon, at pressures between 66 kPa and
500 kPa, (11) and from microwave resonance measurements under vacuum; (29) the
l~tter measurements are subject to quite different systematic errors. Values of a
obtained from both of these independent experiments are in excellent agreement with
those reported here in the overlapping temperature range, even though quite
different transducer housings were located in the resonator ports. When the results
reported in reference 11, from three-term fits to equation (6), are combined with our
546 M.B. EWING AND A. R. H. GOODWIN

I I I I [ I I

0.4 _o

O []
--<> O
o

0.2
_ <>

O
_e ¥ ~ ~ ~ a
<>

%
-0.i
r I I I I I J <?
250 300
T/K

FIGURE 8. Deviations A/~a = { f l a - - / ~ , ( H F D B - 2 ) } of the experimental second virial coefficients from the
values calculated using the HFDB-2 pair-potential energy functions including the first two quantum
corrections. O, This w o r k ; . , reference 2; D, reference 28; O, reference 6; V, reference 5; 0 , reference 11;
• , reference 30.

three values the radius so determined is given by

a(T)/mm = 39.990071-1 +22.69 • 10-6{(T/K)--273.15} +
2.35. 10 8{(T/K)-273.15}2], (7)
with a standard deviation of 0.8 ~m; the linear thermal expansivity at obtained from
these results agrees to 0.01.at with the precise measurements of Kroger and
S w e n s o n (26) o n pure aluminium.
In figure 8 the present experimental values of/~a, and those reported in the recent
literature,(2, 5, 6, 11,28,3o) are shown as deviations from those calculated using the
H F D B - 2 potential-energy function, ~31) which was derived solely from independent
information. Our results differ from the HFDB-2 by 0.12 c m 3 .mol 1 at 300 K and
diverge further at lower temperatures to lie 0.41 cm 3. mo1-1 above at 255 K. Other
values we have reported recently show similar trends. ~6, 11,30) At 273.16 K there are
six determinations of/~a which span only 0.22 c m 3 .mol 1. The measurement of
Moldover et al. (2) lies only 0.039 c m 3. t o o l - : below the value obtained by combining
our two isotherms, while the value of Ewing, McGlashan, and Truslgr ~5) is
0 . 2 c m 3. mol- 1 below our result. Although this range exceeds the reported precision
of each determination, it is small considering that the pressure ranges used for these
measurements varied considerably. Moldover et al. ~2) used pressure between 25 kPa
and 500 kPa for their recent measurement of the gas constant, while Ewing,
McGlashan, and Trusler operated below 250 kPa, with pressures as low as 15 kPa
where the temperature-jump effect becomes important35) One other set of
measurements from this laboratory use pressures between 13 kPa and 500 kPa31 ~)
 SPEEDS OF SOUND IN GASES AT HIGH PRESSURES 547

Since there will be significant differences b e t w e e n the e s t i m a t e s of A 2 g i v e n b y

three- a n d f o u r - t e r m fits to the infinite series (6) o v e r w i d e l y different p r e s s u r e ranges,
we h a v e n o t m a d e c o m p a r i s o n s b e t w e e n t h o s e v a l u e s o b t a i n e d here f r o m t h e four-
t e r m fits a n d t h o s e f r o m t h r e e - t e r m fits r e p o r t e d elsewhere. (a' 11, 28, 30)
I n a later p a p e r we shall use these results to p r e s e n t speeds o f s o u n d in m e t h a n e , a
n a t u r a l gas, a n d air.

A . R . H . G . a c k n o w l e d g e s the a w a r d of a R e s e a r c h S c h o l a r s h i p b y British G a s plc. T h e

a u t h o r s also a c k n o w l e d g e m a n y useful a n d s t i m u l a t i n g d i s c u s s i o n s with D r M i c h a e l
M o l d o v e r a n d D r J i m Mehl.

REFERENCES
1. Mehl, J. B.; Moldover, M. R. J. Chem. Phys. 1981, 1981, 74, 4062.
2. Moldover, M. R.; Trusler, J. P. M.; Edwards, T. R.; Mehl, J. B.; Davis, R. S. J. Res. Nat. Bur. Std.
1988, 93, 85.
3. Moldover, M. R.; Trusler, J. P. M.; Edwards, T. R.; Mehl, J. B.; Davis, R. S. Phys. Rev. Lett. 1988,
60, 249.
4. Mehl, J. B.; Moldover, M. R. J. Phys. Chem. 1982, 77, 455.
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9. Goodwin, A. R. H. Ph.D. Thesis, University of London. 1988.
10. Ewing, M. B.; Trusler, J. P. M. J. Chem. Phys. 1989, 90, 1106.
11. Ewing, M. B.; Owusu, A. A.; Trusler, J. P. M. Physica A 1989, 156, 899.
12. Mehl, J. B. J. Acoust. Soc. Am. 1985, 78, 782.
13. Moldover, M. R.; Mehl, J. B.; Greenspan, M. J. Acoust. Soc. Am. 1986, 79, 253.
14. Aluminium alloy 6082 in the TF condition is defined with British Standards Specification 1474.
British Standards Institution: London. 1987.
15. Trusler, J. P. M. unpublished notes.
16. British Standards Specification 5500. British Standards Institution: London. 1976.
17. American Society of Mechanical Engineers. Unified Pressure Vessel Code. Section VIII. Division 1 and
2. 1962.
18. High Pressure Safety Code. Cox, B. G.; Saville, G.: Editors. High Pressure Technology Association.
1975.
19. Ewing, M. B.; Trusler, J. P. M. J. Acoust. Soc. Am. 1989, 85, 1780.
20. Maitland, G. C.; Rigby, M.; Smith, E. B.; Wakeham, W. A. Intermolecular Forces: Their Origin and
Determination. Clarendon: Oxford. 1981, p. 571.
21. Kestin, J.; Clifford, R. R.; Wakeham, W. A. Physica 1980, 100A~,349.
22. Kestin, J.; Ro, S. T.; Wakeham, W. A. J. Chem. Phys. 1972, 56, 4119.
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25. Ledbetter, H. M. Cryogenics 1982, 22, 653.
26. Kroeger, F. R.; Swenson, C. A. J. Appl. Phys. 1977, 48, 853.
27. Read, D. T.; Ledbetter, H. M. J. Eng. Mat. Tech. 1977, 99, 181.
28. Moldover, M. R.; Trusler, J. P. M. Metrologia 1988, 25, 165.
2,9. Boyes, S.; Ewing, M. B.; Trusler, J. P. M. unpublished work.
30. Goodwin, A. R. H.; Moldover, M. R. J. Chem. Phys. 1990, 93, 2471.
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