MEASURING THE RATIO OF SPECIFIC

HEATS OF A GAS

Thermodynamic Experiments Involving

Harmonic Motion

JOSEPH A. SCHUFLE
New Mexico Institute of Mining and Technology,
Socorro, New Mexico

Om of the methods most frequently used in physical uniform bore can be purchased, but we have found
chemistry laboratory courses for the measurement of 7, that, with a little selection, pieces of sufficiently uniform
the ratio of specific heats of a gas, is that of Clement bore can be taken from stock tubing.
and Desormes.' Because of several inherent difficulties The cylinder is dropped from the top of the tube and
in this method its over-all accuracy is often of the order oscillates up and down on the air spring provided by a
of *5%, a factor somewhat discouraging to students. large volume of enclosed gas attached to the bottom
Equilibrium is reached slowly, so that leakage of the end of the glass tube.
apparatus and room temperature fluctuations are two
important causes of error. In the two methods de- The fundsmental equation can b~ derived as follons, n-here:
f = --..-
forre
scribed here the time for measurement is short, and the m = mass of metal cylinder
two causes for error mentioned above are minimized. a = sccelerstion
Considering the number of times the harmonic oscilla- P = pressure of the enclosed gas = P.k,. +-
mg
tor and wave motion are encountered in modern theories = croas sectional area of tube and cylinder
P
q
of chemistry and physics, it would be helpful to the z = distance through ahich t,he cylinder moves
student of chemistry to have laboratory experiments 1 "...."
= time
I' = volume of gas ~nclosedin system
in which these principles are used. The first experi- u = frequency of oscillation
ment described here uses an equation of motion for a r = llu = period of oscillation
harmonic oscillator. The secoud experiment uses r = C,/Cr, ratlo of specific heats of the gas
principles of wave motion. f =Py = force upward on cylinder
MODIFIED ASSMANN METHOD Differentiating: df = p dP

This method is an old one, originated over 100 years dt' = * dz

ago by C. A ~ s m a n n . ~His apparatus consisted of a For an adiabatic compression: PV7? = constant, (k)
U-tube containing mercury which oscillated in the Rearranging and differentiating:
tube between two large volumes of gas connected to the d P / d V = k(-r)i-(-?-l)
ends of the U-tube. This has been modified and im-
proved many times in the intervening years. One Substituting (1)in (5)and rearranging:
of the simplest improvements was suggested by E. dP = - yP di,
Riichardta in 1928. For the mercury he substituted a i-
steel ball, and for the U-tube, a vertical tube of uniform Substituting (3) in ( 6 , :
inside dia~neter.~
The apparatus used in our laboratory (Figure 1) was d P = - rP (q dz)
adapted from Riichardt, substituting a steel cylinder
Substituting (7) in (2!:
for the steel ball. Such a cylinder may be turned out
easily on a lathe to fit the tubing closely, whereas df = - %9 dr
fitting a steel ball to tubing size is a difficult operation. 1-
A 4-foot length of standard Pyrex tubing was used for Integration of (8) gives:
the vertical tube. Special glass tubing ground to

' For example: S ~ I N B A C0. H ,F., AND C. V. KING, "Experi- But since:
ments in Physical Ch~mistry,"American Book Co., New York, d%
1950, p. 41. f=ma=m--,
dl
ASSMANN, C., (fJber E r w i m u n g und Erkiiltung von Gasen
dureh plijteliche Vohuniinderung," Annala d m Ph& und (9) can be rewritten as:
Chemie, 85, 1-36 (1852).
R~~CELAEDT, E., P h y i k . Z.,30,58-9 (1929).
'Such an apparatus is available commercially from E. Ley-
bold's Nachfolger, in K d n , or their U. S. representative, J. Defining: u = qPrP
-, and z' =
Klinger, 82 160th Street, Jamaica, Nea York. Vm

JOURNAL OF CHEMICAL EDUCATION

(10) simplifies to:

Equation (11) can be seen to have the form of a second-order

differential equation which defines z as a harmonic function of 1.
A d n t i o n of such s. differential eqostion of motion is:
2 = .4 sin ~ $ 1 , (12)
m-here 4; is the period of oarillation. But for such a harmonic
oscillation, the period is also equal to 2 s times the frequency, v .
Therefore:

The time for one oscillation, r, is given by:

Therefore:

The quantities V , m, and y are easily determined

constants of the apparatus. P is evaluated for each
experiment.
The metal cylinder is dropped from the top of the tuhe
and allowed to oscillate as many times as the apparatus
\\ill permit. At least three or four oscillations should
he obtained, and the time .r for a single oscillation is
determined. Better results are usually obtained if the
first oscillation is disregarded. The measurement of r i 1. Modified Asamann Apparatus
is the biggest source of error. A variation of 0.01 sec.
in r causes a variation of 0.03 in the value of y. Parodis velocity with which sound travels through a gas can
describes methods for improving the measurement of r . be expressed by the equation:
Homver, results of sufficieut accuracy to show the
significance of y and its variation from one gas t,o an-
other can be obtained by students using a stopwat,ch.
n here: ,I = velocity of soirnd
Typical determinations of y for air at 25'C., with the P = pressure of the gas
use of two different tubes aud cylinders, are given in d = density oi the gas
Table 1. Gases other than air can he investigat,ed = C,,/L', for the gas
readily. The apparatus is evacuated and filled ~ ~ itheth Methods using the usual I(uudt tuhe for measuriug
the velocity of sound in gases halve been described in
laboratory manuals such as that of Mack and F r a n ~ e . ~
TABLE 1 We h a w tried a modification of the Kundt tube, using
Determination of y by Modified Assmann Apparatus
a 25-watt loudspeaker unit to generate t,he sound at
P known frequencies instead of the usual brass rod.
. ." ... . .
An auuaratus using: a similar loudsueaker source
.4ir 4200 18.91 1,733 64.5 0.926 10 1.42 MACK,E., AND \V. G. F ~ A N C "Laboratory
F, Manual of Ele-
4200 18.50 1.784 64.8 0902 20 1.38 mentary Phydral Chemistry," 2nd ed., D Van Nostt-and Co.,
Argon 4200 18.50 1.784 61.5 0.817 6 1.68 Inc., Nea. York, 1934.
CU- 4200 18.42 1 784 64 5 0.920 R 1 32

gas to be tested a t a pressure slightly above atmospheric

pressure. The top end of the glass tubing is closed
aith a rubber stopper during the filling operation. The
stopper is removed just before the run, an instant
allowed for the pressure to drop to atmospheric pressure,
and the metal cylinder inserted and dropped as usual.
Typical data a t 25°C. for carbon dioxide and argon are
given in Table 1.
MODIFIED KUNDT METHOD
The second method for measuring y also will help
the chemistry student to visualize wave motion. The

M., Compl. R e d . , 218, 311-13 (1944).

PARODI, Fagure 2. Us* of Loudspeaker w i t h K u n l t Tube

VOLUME 34, NO. 2, FEBRUARY, 1957 79

of excitation was described by Reynolds.' The TABLE 2
apparatus, shown in Figure 2, consists of a Lucite tube Determination of r by Kundt's Method
about 1 m. long and about 5 cm. in diameter, closed
Y =
a t both ends with a metal seal. The metal caps are uad
provided with inlet and outlet tubes for introducing A 11 average -
gases other than air. A movable piston is provided as Frequency (em.) (cm./sec.) u P
usual a t one end. This can be adjusted so that the Air ( y = 1.40):
distance from the sound generator to the piston is an 1424 23.70 33,820 34,563 1.39
1896 18.12 34,3i0
even number of half wave lengths. The loudspeaker 2844 12.48 36,500
unit is attached to the other end of the tube and is CO? ( y = 1.30):
connected through an amplifier to an audio oscillator 4i4 58.0 2i,500 27,143 1.31
1424 18.80 26,800
which can be set a t known frequencies. The frequency 1896 14.24 26,970
scale on the oscillator can be calibrated with tuning 2844 9.62 27,300
Argon (? = 1.6i):
forks. 966 33.3 32,230 32,208 1.69
A little lycopodium powder is sprinkled through the 1450 22.20 32,180
tube. The speaker is set a t a known frequency and the 1930 1680 32,420
2895 5.53 32,000
piston moved until the powder piles into little heaps
a t the vibration nodes. The average distance between
nodes gives the half wave length. Velocity is given The apparatns is very useful for demonstrations of
by frequency times wave length. standing waves. I t is more interesting in this respect
Data obtained a t 2S0C. are given in Table 2. than the usual Kundt tube, because the effect of varying
frequency on the u-ave length can be demonstrated
' REYNOLDS,
M. B., J. CHEWEDUC.,
20,121 (1943). more easily.

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