Percy E.

Pierce
Case Institute of Technology
Cleveland, Ohio A Simple Flow Calorimeter

I n elementary physical chemistry The heat dissipated by the heater is partly taken up
courses the heat capacities of gases are a topic which by the gas flowing over the heater and partly lost to
can be discussed from a kinetic theory viewpoint. the surroundings of the apparatus according to the
Unfortunately, there are few laboratory experiments following equation':
which allow a direct determination of the heat capacities Q = GATR+ L (1)
of gases and therefore an experimental verification of
some of the results of kinetic theory. This article where
describes a simple flow calorimeter that can be con- Q EI = rate of heat production in the resistor,
=
structed from materials that are available from chemi- cp the mean heat capacity of the gas over the temperature
=
cal supply houses. The calorimeter in this form interval AT,
gives heat capacities which deviate from the accepted AT = the temperature change of the gas flowing over the
values by *3%. The experimental results can be heater,
R = the rate of flow of the ges, and
compared with the predictions of kinetic theory and L = the rate of heat loss to the surroundings.
hence integrated into the results of elementary lecture
courses in physical chemistry. Furthermore with the Since AT is small, the heat losses t,o the surroundings
growing interest in high temperature phenomena, are proportional to AT
flow measurements are again of interest. The method = KAT (2)
of treatment of the data shows the student how heat
losses in calorimetric measurements can be taken The factor K is determined by the thermal characteris-
into account in calculations. tics of the materials that make up the calorimeter and
Figure 1 is a diagram of the calorimeter. The outer the geometry of the apparatus. The heat balance
jacket is the outer tube for a hydrogen electrode as- equation becomes
sembly. The two thermometers can be read to 0.2 Q = ?*ATR + KAT (3)
degree. The heater is made of Nichrome wire (BS 29) If we divide equation (3) by AT we obtain
&/AT = C n +~ K (4)
If we determine Q and AT at various flow rates and
plot Q/AT against R, the slope of the straight line
obtained will be the mean heat capacity of the gas.
I t is necessary to keep AT the same for all measure-
ments if * varies greatly with temperature.
The dot notation used here designate the variation of the
HEATER quantity with time. Thus Q = dQldt.

- # A 0 INLET

INLET TIERYOMETER

Figure 1. The Row calorirneler.

wound on a plastic cross; it has a resistance of 5 4

ohms. Auxiliary equipment to maintain a steady
gas flow and to control the heat input to the heater
are required. These will be discussed later. Gas
enters the inlet a t a steady rate and passes over the
heater, whose rate of power dissipation is held constant.
A steady state is established in the system when the
inlet and outlet thermometers attain constant readings. rigwe 2. k
t Oj-\~verrur far nitrogen g a r
~ i o of

338 / Journol of Chemical Education

 Figure 2 shows a plot of Q/AT versus R for nitrogen
gas. Typical student results for C,, (cal/mole) ranged
from 6.50 to 7.25, with an average of 6.92; u = 0.21;
u/<C,> X 100 = 3%. Theinitial temperaturesvaried
from 25 to 27C; the final temperatures varied from 35
to 41C.
The major source of error in the experiment is in not
waiting a sufficient length of time for the calorimeter to
attain a steady state; 10-15 minutes are required for
each point. A AT of 10C has been found to yield
satisfactory results with nitrogen.
An alternate scheme for calculating C, is to divide
equation (4) by R.
@ATR = C9 + K I R (5) BATTERY RHEOSTAT
The quantity Q/ATR is the apparent heat capacity of Figure 4. The heater sircult.
the gas if we neglect heat lossqs. If we plot this
apparent heat capacity versus 1/R and extrapolate to the orifice type and was calibrated using a wet test
1/R = 0 (i.e., infinite flow rate) the intercept of the meter. The students are supplied with a calibration
straight line obtained is the true heat capacity. This curve for the flowmeter. The flow rate is held con-
method has been employed by Pitzere to calculate the stant during the experiment by manually adjusting the
heat capacity of vapors. Figure 3 shows a plot of diaphragm valve on the pressure regulator. This step
Q/AT R versus 1/R for nitrogen. The first method is important and generdly requires some attention since
of calculation has been found the more suitable with the flow has a tendency to drift slightly during the
the apparatus described, since the heat losses to the course of a determination.
surroundings are rather large.
Procedure
The flow of gas through the calorimeter is adjusted
and maintained a t a constant value. The heater is
turned on and the rheostat is adjusted so that the volt-
age is in the range 2.3-2.9 volts. The apparatus is
allowed to warm up. This should take about 5 minutes.
The rheostat is adjusted so that for the given flow rate
the difference between inlet and outlet temperature is
approximately 10C. It is necessary to make minor
adjustments of the flow rate as the experiment proceeds.
After about 10-15 minutes the apparatus will have
achieved a steady state. The voltage, current, tem-
peratures of the inlet and outlet thermometers, and
flow rate are recorded. The above procedure is re-
peated at five different flow rates.
From the data, Q in calories per second and R in
moles per second are calculated. A plot of Q/AT
Figure 3. Plot of lhe a p p a r e n t heat caposity of nitrogen versus 1IR. against R yields a straight line whose slope is Cnin cal/
mole dcg.
The heater circuit is shown in Figure 4. An Edison
cell is used as a source of power. The voltage is con-
trolled by a slide wire rheostat. The voltage is ad-
justed to about 3 v and a current of 0.5 amps results.
I n practice the heater circuit is so stable that it re-
quires virtually no adjustment during the course of a
determination.
Figure 5 shows the gas train. The gas is fed from
a cylinder through a pressure regulator and needle
valve into the gas circuit. A two-stage pressure re-
duction from the cylinder results in more constant
flow rates. The pressure of the gas in the second stage
should he adjusted to about 10 psi. The gas flows into
a surge tank of 6-8 liter capacity to further reduce
fluctuations in eas flow. The flow meter used was of
' PITIER,K. S., J. Am. Chem. Soc., 63, 2413 (1941). Figure 5. The gar flow system.

+ + +

Volume 39, Number 7, July 1962 / 339