Johns-Manville Co., Bulletin No.

IN-475A, New York, June for Measuring the Thermal Conductance of High Temperature
1963. Structural Materials,” ASD T D R 63-359, WPAFB, Ohio, May
Plunkett, J . D . , in “Lightweight Thermal Protection System 1963.
Development,” ASD T D R 63-596, Vol. 111, Materials-Existing (11) Wechsler, A. E., Kritz, M., “Investigation and Development
Data and Recommended Data acquisition. WPAFB, Ohio, of High Temperature Insulation Systems,” AFML T R 65-138.
June 1963. WPAFB, Ohio, June 1965.
Rolinski, E. J., M. Sc. thesis, Ohio State University, Columbus, (12) Woodside, W., Wilson, A. G., Rev. Sci Instr. 28, 1033-37
Ohio, 1966. (1957).
Rolinski, E . J., G. V. Purcell, Paper No. 128, Third Interna- (13) Woodside, W., Wilson, A. G., “Unbalance Errors in Guarded
tional Heat Transfer Conference, Chicago, Ill., August 1966. Hot Plate Measurements,” presented at ASTM Symposium
Ryan, J. M., Cross, R. I., Stockham, T., in “Lightweight in Thermal Conductivity Measurements, Philadelphia, Pa.,
Thermal Protection Svstem DeveloDment.“ AFML T R 65-26. ASTM Special Publication 217, 1957.
Vol. 11, WPAFB, Ohio, June 1965. RECEIVEDfor review November 7. 1966. Accepted December 19,
Sparell, J . K., Coumou, K. G., Plunkett, J. D., “An Instrument 1967.

Adiabatic Compressibility of Liquid Ammonia

D. E. BOWEN’ and J. C. T H O M P S O N
Physics Department, The University of Texas a t Austin, Austin, Tex. 78712

Values of the adiabatic compressibility of pure liquid ammonia, derived from sound
speed measurements between the freezing point and the normal boiling point are
reported. The sound speed was a linear, decreasing function of the temperature.
A comparison with other values is given.

V A L U E S for the adiabatic compressibility of pure liquid of the velocity requires two inputs: the length of the cell;
ammonia a t its vapor pressure between the normal freezing and the time between pulse and echo. As the cell was
and boiling points are reported. These data were obtained a modified optical absorption cell, its length could be deter-
as a part of a detailed study of the physical properties mined in terms of known absorbances of standard solutions.
of metal-ammonia solutions and are presented here because The authors also made measurements of the sound speed
of the scant information available on the pure solvent in in well known systems such as water, acetone, and methanol
this temperature and pressure range. and obtained agreement to 3+ significant figures a t room
The adiabatic compressibility, defined by ( 4 ) temperature. The length was 1.986 i 0.009 cm. with a
95% confidence level. Time measurements were made using
o?= - (au/ap),ia (1) the delayed sweep of a Tektronix 555 oscilloscope. The
was determined by measuring the velocity of sound, C,, manufacturer states the precision of the time base to be
using the published values of the density ( 5 ) , p , and the one part in lo4 (on the scale used) with an accuracy of
relation (6) 0.2%. Thus a precision of better than one part in lo3 is
attainable if the pulse initiation point can be determined
pq= l / C i p (2) with arbitrarily high precision. In the present apparatus,
The liquid ammonia was contained in a cylindrical quartz the measurement of the time between the original pulse
cell 2.0 cm. long and 1.6 cm. in diameter. The velocity and the first echo was limited by the width of the oscil-
of sound was determined by a standard time-of-flight tech- loscope trace to a precision of one part in lo3. Each datum
nique using pulsed 10 MHz. compressional waves generated reported is the average of four to 10 independent measure-
by crystal transducers cemented to the outside of the cell ments of the time interval. Thus, the quoted over-all preci-
(6). This system was calibrated by measuring the velocity sion in C, is reached.
in liquids with a well known velocity. The quartz sound The velocity was measured as the temperature of the
cell was placed in a system in which the temperature was system was changed between 194” and 240’K. All data
regulated to within +0.1” K . between 200” and 240” K . The were taken within 4 cm. of Hg of the vapor pressure.
temperature was measured by copper-constantan thermo- The experimental values of C, are given in Table I and

-
couples, calibrated in liquid N1(- 77”K.) and liquid
NH,( 240”) with interpolations from NBS tables ( 3 ) ,
placed next to the sample cell. Ammonia, 99.95% pure
are plotted in Figure 1. Values of C, obtained by Maybury
and Coulter (7, 8) are also shown in Figure 1. There is
considerable scatter in the data of Maybury and Coulter
N H 3 (Matheson Co.), was further purified by preparing when compared with the present data.
a sodium-ammonia solution and allowing the solution to The sound ve!ocity data were fitted by a straight line
stand for a t least 12 hours. The ammonia was then distilled in the form
from this solution into the previously evacuated (less than
IO-’ torr) cell. c, = co - c,T (3)
With the time-of-flight technique, it is possible to deter- where, by a least squares analysis ( I ) , the values of Co
mine the sound velocity to within one part in lo3 (9); and C1were determined to be
however with the present system this was not possible
owing to the temperature fluctuations; thus, for these experi- Co = 3209 + 3.6 meters per second
ments, the velocity as a function of the temperature was
determined to about one part in lo2. The determination C1 = 6.19 + 0.05 meters per second degree
The density data of Cragoe and Harper ( 5 ) are shown
IPresent address: Physics Department, The University of Texas in Figure 2. They have determined the density of one
at El Paso, El Paso, Tex. 79999 part in lo4. The present authors have chosen t o fit this

2 06 JOURNAL OF CHEMICAL AND ENGINEERING DATA

 Table I. Sound Velocity in Liquid Ammonia
T , K. C,, Meters/Second
240.0 1715
233.0 1775
228.0 1795
219.4 1850
218.7 1860
215.3 1876
213.8 1886
212.5 1897
210.9 1906
210.6 1904
210.5 1909
208.8 1920
208.5 1920
208.3 1923
206.8 1930
206.3 1934
206.1 1937
204.4 1946
204.2 1949
203.6 1948
202.3 1959
201.6 1962
201.2 1963
200.8 1968 TEMPERATURE, DEG.K .
199.6 1975
199.1 1979 Figure 2. Density of liquid ammonia
198.5 1982 according to Cragoe and Harper (5)
196.0 1998 Note the linear form of the curve

Table It. Compressibility of Liquid Ammonia

C,, Meters P, 35,
T , OK. /Second Grams/Cc. Sq. Cm./Dyne
240.2 1724 0.6814 49.38 x 10 I'
80- 238.2 1736 0.6830 48.52 x 10 I'
Ci 6 0 - 236.2 1749 0.6863 47.63 x 10 li
< 40- 234.2 1761 0.6888 46.82 x 10 I'
!i2 0 - 232.2 1773 0.6912 46.04 x 10 I'
g1900- 230.2 1786 0.6936 45.20 x 10 li
kj 80- i 228.2 1798 0.6960 44.44 x 10 I'
W
>
60- 226.2 1810 0.6984 43.71 x 10 I'
n 40- 224.2 1823 0.7008 42.94 x 10 "
5 20- 222.2 1835 0.7032 42.23 x 10 I'
1800- 220.2 1848 0.7056 41.50 x 10 "
80- 218.2 1860 0.7079 40.83 x 10
60 - 216.2 1872 0.7103 40.17 x 10 "
- 214.2
40 1885 0.7126 39.49 x 10 I'
20 - 212.2 1897 0.7149 38.87 x 10 I'
1700

192 4 6 8 200
l
2
l
4 6
l l
8
l
210 2
l
4 6
~ l
8 220 2
l
4
l
6 8
~ l
230 2
,l I
4
l
6 8 240
1 210.2
208.2
1900
1922
0.7172
0.7195
38.26 x 10 "
37.62 x 10 I -
TEMPERATURE, DEG K 206.2 1934 0.7218 37.04 x 10 I'
204.2 1947 0.7241 36.43 x 10 l'
figure 1 . Velocity of sound in liquid ammonia 202.2 1959 0.7264 35.87 x 10 "
along the vapor pressure curve 200.2 1971 0.7287 35.32 x 10 I'
Present d a t a 198.2 1984 0.7309 34.76 x 10 I'
196.2 1996 0.7332 34.23 x 10 "
t Data of M a y b u r y a n d Caulter (7,8)
194.2 2008 0.7354 33.72 x 10 I'

data with a straight line in the temperature range 200" sion for the compressibility, obtained by combining Equa-
to 240" K. and have obtained tions 2 , 3, and 4, is:

p = Do - DIT (4)
+
3, = ( A , , A I T + A'T' + AIT') I
(5)

where where
Do = 0.9646 + 0.0010 gram per cc A,, = DOC;= 0.9935 x 10" dyne/sq. cm.
D , = (1.1776 i 0.0048) x 10 ' gram per cc. degree A , = -(2D,,CICo+ D,C;) = -0.5045 x 10' dyneisq. cm. degree
The uncertainties in the numerical coefficients in Equations A , = (DOCl'+ 2DlClCo)= 0.8374 x lo6 dyneisq. cm. degreez
3 and 4 were fixed by standard least squares procedures A = -DICI' = -0.4512 x IO3 dyneisq. cm. degreeJ
( 1 ) and represent one standard deviation.
The compressibility, calculated from Equation 2 , is given This equation provides a representation of & for liquid
in Table I1 and is shown in Figure 3. An analytical expres- ammonia a t its vapor pressure over the temperature range

VOL. 13, No. 2, APRIL 1968 207

 A
I I I I I I I , I l l

N 48 Table Ill. Comparison of Present and Previous Work

0
dT, @% 67,
T,“K. NBS NBS This Paper Y
222.1 63.8 42.1 42.2 1.51
224.9 65.3 43.5 43.0 1.52
227.6 66.7 44.9 44.5 1.50
230.4 68.2 46.4 45.3 1.51
233.2 69.6 45.0 46.2 1.51
236.0 72.5 47.9 47.5 1.53
238.0 74.0 49.3 48.5 1.53

B,is in units of (sq. cm./dyne) x 10 ”. B T is in units of (sq.

cm./dyne) x 10 ”.

By combining os and B T , it is possible to obtain

Y = $713, = C” c,
1 1 1 1 1 1 1 1 i l I
194 202 210 218 226 234 This has been done for the temperature range for which
TEMPERATURE, DEG.K. values of P T have been reported. The results are shown
in Table I11 with
Figure 3. Adiabatic Compressibility
yav = 1.52
of liquid ammonia as calculated from
the density and sound speed
NOMENCLATURE
/33 adiabatic compressibility
=
from the freezing point to the normal boiling point. PT isothermal compressibility
=
Thermodynamic data on saturated KH7 for the tem- Y = heat capacity ratio
perature range 222” to 238°K. was reported some time P = density
ago by the National Bureau of Standards (2). I t is possible c, = specific heat a t constant pressure
to calculate & from this data by using the thermodynamic
c, = speed of sound
relations ( 4 )
c, = specific heat at constant volume
h = specific enthalpy
k = volume expansivity
P = pressure
T = absolute temperature
u = specific volume
where

LITERATURE CITED
(1) Baird, D.C., “Experimentation,” Prentice-Hall, Englewood
C, is the specific heat a t constant pressure, P T is the iso- Cliffs, N. J., 1962.
thermal compressibility, and h is the specific enthalpy. Since (2) Natl. Bur. Std. (U. S . ) Circ. Xo. 142 (1923).
C, PT, and (ahlap)T were reported by the National Bureau (3) Shenker, H., Lawitzen, J.I., Corruccini, R.J., Lonberger, S.T.,
of Standards (21, Ds can be calculated by combining Equa- Natl. Bur. Std. f U . S.) Circ. No. 561 (1955).
tions 6 and 7 (4) Callen, H.B., “Thermodynamics,” Wiley, S e w York, 1960.
(5) Cragoe, C.S., Harper, D.R., Natl. Bur. Std. ( U . S.) Sci. Papers
17, 287 (1922).
(6) Mason, W.P., “Physical Acoustics and the Properties of Solids,”
Van Sostrand, Princeton, N. J., 1958.
(7) Maybury, R.H., Ph.D. thesis, Boston University, Boston,
Mass., 1952.
B, as calculated in this manner is shown in Table I11 and (8) Maybury, R.H., Coulter, L.V., J . Chem Phys. 19, (1951).
compared with ps obtained from Equation 5 . With the (9) McSkimin, H.J., J . Acoust. Soc. Am. 29, 1185 (1957).
exception of the point a t 233.2”K., these data are higher
than the present data by an average of 0.9%. The authors RECEIVEDfor review December 15, 1966. Accepted November 8,
suggest that ( d h ’ d p ) ~as reported by NBS is in error a t 1967. Work supported by the Office of Naval Research and the
233.2”K. R.A. Welch Foundation.

208 JOURNAL OF CHEMICAL AND ENGINEERING DATA