492

The Specific Heats of ,A

ir Oxygen, Nitrogen from
By P. S. H . H e n r y , Coutts Trotter Student, The Laboratory of Physical
Chemistry, Cambridge.

(Communicated by E. K. Rideal, F.R.S.—Received June 19, 1931.)

Some time ago a new flow method for comparing the specific heats of gases
was described by P. M. S. Blackett, E. K. Rideal, and the author.* It is the
purpose of this paper to give an account of further developments of the method,
and of the results which have been obtained by it from room temperature up
to 370° C. for air, oxygen, nitrogen.

1. The Apparatus.
The chief improvements in the apparatus over that described previously
have been a different construction of the calorimeter, ensuring more uniform
temperature surroundings for the tube ; potentiometric measurement of the
temperature differences ; double glands to the pump, eliminating leakage
or contamination of the gas ; and automatic control of the pumping speed
and heating current.
A section through the calorimeter is shown in fig. 1. The fine iron tube AA

F ig . 1.

through which the gas flows has an external diameter of 2 mm. and a wall-
thickness of about 0-3 mm. It is surrounded by the massive iron tube BB
which has conical holes at the ends to fit the conical steel plugs CC. These
are held in place by the screwed collars DD and are electrically insulated from
B by thin mica, which, however, allows of easy heat transfer between B and C.
The conical plugs in their turn carry the cylindrical plugs EE which are adjusted
to a good sliding fit in them, and which fit tightly on to the gas tube AA. The
fine constantan wires which, with the tube, form the thermocouples are arranged
* Blackett, Henry and Rideal, ‘ Proc. Roy. Soc.,’ A, vol. 126, p. 319 (1930).
 Specific Heats of Air, Oxygen, Nitrogen. 493

as before and pass through holes in one of the plugs E, being insulated by small
porcelain tubes. The tube AA and the wires and plugs can be slid out without
disturbing anything else. The screws SS serve to adjust the position of the
tube and thermocouples to symmetry so that there is no galvanometer deflection
when the gas is not flowing. The gas-tube is heated, as before, by passing an
alternating electric current from a transformer through it. The whole is
placed inside an iron tube-furnace wound with a nichrome strip and well
packed with asbestos wool. The temperature of the jacket B is measured by
means of an iron-constantan thermocouple which was calibrated by means of
the melting points of ice, tin, lead, zinc and aluminium. The cool junctions
of all thermocouples are kept in oil in a Dewar flask, whose temperature is
measured by means of a mercury thermometer. It was found possible to
regulate the temperature of the furnace by hand to within a degree or two.
The improvement over the calorimeter described previously lies in the more
complete uniformity in temperature of the surroundings of the gas tube, better
thermal contact between the ends of the gas tube and the jacket, and increased
protection from air currents. Also the new calorimeter is of a shape and size
to fit into the tube of an electric furnace; and being made of iron instead of
copper, can be used up to 400° C.
Instead of measuring the thermal e.m.fs. by means of the galvanometer
deflections, the greater parts of them are balanced out by means of a potentio­
meter, and the small residual galvanometer deflections are read. This proce­
dure obviates the necessity for accurate determinations of the galvanometer
sensitivity, and renders negligible any errors due to variations in this sensitivity
or to non-linearity of the scale. It also enables the galvanometer to be used
in a more sensitive state, so that slower rates of gas-flow can be employed.
The thermo junctions which measure the difference in temperature between
the centre of the tube and the ends are connected straight to the potentiometer;
whilst the symmetrical thermojunctions, whose e.m.f. may be only one-
fortieth of th at of the other pair, are connected to the potentiometer through
a potential divider. At the start of an experiment the potentiometer is adjusted
so that the central temperature difference e.m.f. (0w;) is as nearly as possible
balanced out. The potentiometer is not again touched during the whole
experiment, the small variations in central temperature being deduced from
the residual galvanometer deflections. The potential divider is then adjusted
so that for a given rate of flow the e.m.f. of the symmetrical thermoj unctions
(0) is nearly cancelled out. The potential divider reading, corrected for the
residual galvanometer deflections, thus gives directly the ratio 0/Om which
494 P. S. H. Henry.

is the quantity required, for, as is shown in the previous papers (pp. 327-328)
the sensitivity, .,ie0 divided by the rate of gas flow, is proportiona
ceteris paribus. A reading of dm is taken between every three readings of 0,
which are taken with the gas flow in alternate directions. It will be seen that
any slow changes in 0m or in the potentiometer current produce no effect on
0 /0 m, for they affect both 0 and dmequally. The sliding contact of the potentio­
meter is never moved during the whole experiment, so that no variations in
its resistance need be feared ; nor does the accuracy of the potentiometer
affect the results. The potential divider, however, must be accurate.
Since the A.C. mains showed considerable variations in voltage, it was
necessary to devise some means of regulating automatically the current which
is passed through the gas tube. A fixed solenoid was connected in series with
the tube and with the secondary of the transformer, and a piece of soft iron
rod was suspended so that it could swing in and out of the solenoid. The whole
can be tilted and the iron rod takes up a position in which the pull due to the
solenoid balances that due to gravity. If the mains voltage rises the rod is
pulled further into the solenoid, and the inductance of the latter is increased,
thus partially compensating for the increase in voltage. In practice it was
found possible to adjust the instrument so that a variation in voltage of
5 per cent, either way produced a variation in current of only \ per cent. The
period of the regulator is about half-a-second and it is damped by means of a
vane in an oil pot. The current can be varied by varying the tilt.
In order to keep the flow rate constant a differential gear system was con­
structed as shown in fig. 2, the two bevel wheels A and B being driven in
opposite directions by the pump motor and by a Tinsley phonic motor

F ig . 2.
 Specific Heats of ,A
ir , Nitrogen.
495

respectively. The speed of the latter is maintained constant by means of a

tuning fork. A and B rotate loosely on the main axle, and as long as A is
driven round at the same speed as B, the cross axle which carries the small
bevel wheels C and D remains stationary, but as soon as A gains or loses on B,
the cross axle moves round, carrying with it the main axle and the pinion
wheel F. This moves the slider of a rheostat in the armature circuit of the
driving motor by means of the rack G, and this goes on until the difference in
speed is corrected. Any difference in speed is reduced to half value in a second
or two, which is fast enough, since the calorimeter has a much longer period.
Different speeds of pumping are obtained by different gear ratios.
With the gas pump described in the previous paper (p. 326) it was impossible
to prevent a slight leakage in of air when the apparatus was being filled with
a new gas by evacuation. This was prevented in the present series of experi­
ments by constructing a new pump similar to the first, but provided with double
glands. The space between the glands is connected separately to the Hyvac
pump during filling and is kept exhausted so that any leakage past the inner
gland is outwards and produces no contamination. The space is finally filled
with the same gas as the rest of the apparatus, and serves as a guard ring to
prevent diffusion in of air during an experiment. The glands are packed
with asbestos and graphite steam packing and are nearly sufficiently gas tight
to serve without the double glands.
The pump cylinders are surrounded by a thick layer of cotton wool to
obviate quick changes of temperature, and thermocouples are fastened in
contact with the outer surfaces of the cylinders and with the inner surfaces of
the plungers. Small corrections are applied to the results if the temperature
varies during an experiment.
Great care has been taken to avoid stray thermal e.m.fs. at connections by
using stout brass wire to connect brass terminals and by wrapping all external
connections in cotton-wool.

2. TheExperimental Procedure.
A complete experiment consists of a comparison of the specific heats of air
and another gas, and to this end a run is first done with air, then a run with the
other gas, and then again one with air, so as to eliminate as far as possible
effects due to any small and slow changes in, e.g., temperature distribution
in the furnace. The deflections obtained in the first and second air runs some­
times differ by as much as 1 per cent., but a few trial experiments in which air
was used the whole time showed that these changes were probably slow and
VOL. c x x x iii .— A. 2 K
496 P. S. H. Henry.

progressive, and not dependent upon disturbances due to changing the gas.
Hence it is unlikely that errors greater than \ per cent, at most would be intro­
duced thus, and at present no greater accuracy than this is claimed for the
experiment.
Bach run with air usually consists of three determinations of the e.m.f.
produced by the symmetrical thermocouples, two with a flow rate of about
11 c.c. per minute and one at 22 c.c. per minute. The run with the other gas
usually comprises three determinations at the slow rate and one at the fast.
Each determination of the e.m.f. involves three strokes of the pump in
alternate directions, a reading of the galvanometer being taken towards the
end of each stroke. The double galvanometer deflection is obtained by
subtracting the second reading from the mean of the first and third, so that
slow changes in the galvanometer zero are allowed for. Between each deter­
mination of the e.m.f. from the symmetrical thermocouples (0) readings are
taken of the e.m.fs. from the couples which give the central temperature
difference (0W) and from those which indicate the temperature of the pump
cylinders and plungers. The e.m.fs. corresponding to 0 and 0Ware calculated
from the settings of the potentiometer and of the potential divider and from
the residual galvanometer deflections obtained as above.
The potentiometer current is reversed between each stroke of the pump to
correspond with the sign of the e.m.f. The sensitivities of the galvanometer
in two circuits which measure 0 and 0m are determined at the start of an
experiment by noting the galvanometer readings for various settings of the
potentiometer.
Though the e'.m.fs. are given to the nearest hundredth of a microvolt in
the sample set of readings below, it is not claimed that this degree of accuracy
was attained in their measurement. The probable error in the measurement
of a given e.m.f., as judged from the agreement between successive readings
of the galvanometer, was of the order of l/20th of a microvolt. It will be
seen that the method of taking alternate readings with the gas flow in opposite
directions eliminates the effect of any but rapidly varying parasitic e.m.fs.,
since the electrical circuit was not disturbed between readings except to reverse
the potentiometer current, and any e.m.f. at the reversing switch is reduced to
about 1/100,000th before it reaches the galvanometer.
The value of 0m corresponding to each value of 0 is taken as the mean of
0m values found immediately before and after, and R0/Om is worked out for
each value of 0 , where K is the gear ratio employed in the pump drive and is
inversely proportional to the flow rate. This is then corrected for variations
 Specific Heats of Air, Oxygen, Nitrogen. 497

in tlie mean pump temperature on the assumption th at the mass of gas passing
per second is inversely proportional to the absolute temperature, since the
pressure in the apparatus is kept constant and equal to the atmospheric pressure.
This correction is usually only just appreciable.
Corrections are then applied to the values of R 0 /0 mfor the slight curvature
of the relation connecting 0 /0 m and the flow rate (see pp. 323 and 349 of the
previous communication, where it is shown that it is the initial slope of the
graph which is proportional to the specific heat). This correction is deduced
from the difference between R 0 /0 mfor the fast flow rate and for the slow flow
rate, obtained from the mean of several experiments, on the assumption that
the curvature is due to a cubic term (see the previous papers, loe. cit.). Thus
if the fast flow rate is twice the slow, the corrections required to the fast and
slow values of R 0 /0 m are 4/3 and 1/3 of their mean difference respectively,
and amounted to 0-7 per cent, and 0-2 per cent, respectively in the case of
air. The ratio of the corrected values of R 0 /0 Wnow gives the ratio of the
specific heats at constant pressure of the two gases concerned.
The temperature of the calorimeter as a whole, and of the cool junction in
the Dewar flask, are noted at the beginning and end of the run with each gas.
The former seldom varies more than a degree or two during the course of an
experiment.
The gas is changed by evacuating the whole apparatus with a Hyvac pump,
shutting off the apparatus from the Hyvac except for the spaces between the
glands, waiting for a minute to see that there is no leakage, and finally letting
the new gas in slowly, first to the main part of the apparatus and then to the
space between the glands.
After a run has been done with any gas other than air, a sample is withdrawn
for analysis into a modified Haldane apparatus. Contamination with air
during the process of withdrawal is avoided by evacuating the connection to
the analysis apparatus and washing out with the gas to be analysed once or
twice. Further details of the analysis are given later.
The probable fortuitous error of a given experiment, as estimated from the
differences between the several values of R 0 /0 m obtained in a single day’s
run, is about per cent, at the lower temperatures, and 1 per cent, at the
higher temperatures, when conditions were less steady. A somewhat condensed
set of readings is given on next page.

2 k 2
 Experiment of March 17, 1931. Comparison of Air and Helium at about 350° C.
498

Galvanometer sensitivity in 0OTcircuit = 0-40 cm ./|A .

Galvanometer sensitivity in 0 circuit = 0-59 cm./pV. (for double deflections).

Ph
CO
CO

CO
CO

CD
CO

>o
05

JlO
lO

4^
lO

m
CO

03

03

p
p
Ph

O
r— i
CO

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CO

CO
oq

<C3

P ^
P

Ph
■
O
P
03 0 3

03
oo
o

Ph
. Ph

P h rH

Ph

O O
op *3
Ph

rH o
go

’4o3 .2

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“P

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d

s *
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6

nd

p ‘43
olO Oi 03

ft
m
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-4H
S
Ph

Mean
Gas and pump Residual Potential Potential Corrected
0m ©

O
©

CD
divider divider

S
gear ratio. deflections. tempera­ deflections. e.m.f. K 0 /e m.
ture. setting. e.m.f.

!
P. S. H. Henry.

t>

cm. °C. °C. cm. °C.

'i-co
•©
—0-4 5-50 14-4 - 0 15 1 : 41 0-130 0 0951
-0 -4 1C
4©
. lO 00

5-50 14-6 + 0-03 0-264 0 0962

•jiy
1 : 21

H Cl H
1+ +
o o

rH rH rH
■o r-H pH rH
*CO
©4i
lO C\l r-H

-0 -3
1C l>

5-50 14-7 + 0-17 1 : 43 0-128 0-0974

1C tH

CDCDC5 2
5-50 14- 8 -0 -3 3 -0 -5 6 1 : 56 5-71 5-15 0-0889 0-0650

© o
5-52 15- 0 + 0-07 + 0-12 1 : 31 10-32 10-44 0-180 0-0656

1+ +
5-52 15-2 + 0-03 + 0-05 1 : 62 5-16 5-21 0-0899 0-0656

• u m ip H
i

O O
CO (N ^ O

H ©4 H H
v____ v _____J
©0 CO CO CO CO CO
5-52 15-3 -0 -0 5 -0 -0 8 1 : 61 5-24 5-16 0-0891 0-0650
i

320 5-52 15-3 + 0-02 + 0-03 1 : 42 7-62 7-65 0-132

321 5-54 0-264

M iy
15-3 + 0-47 + 0-80 1 : 22 14-53 15-33

+ + +
? ? ?

o o o

rH rH rH
o o o

rH 1C 00
322 5-55 15-5 -0 -1 5 -0 -2 5 1:41 7-80 7-55 0-130
j

£
o
8p

p
-H

r-C
P
-H

-H

Hie figures in the last column have been corrected for the variations in pump temperature,
oe

Ph
 Specific Heats of Air, Oxygen, Nitrogen. 499

Corrected
Gas. Flow rate. R 0 /0 m. Means. for Weighted
curvature. means.

c.c./min.
0-0951 i
0-0974
11-3 | 0-0965 j. 0-0959 0-0961
0-0947 > 0-0964
0-0962
22-6 ^ 0-0963 0-0962 0-0969

r 0-0650 1
11-3 J 0-0656 y 0-0652 0-0652
Helium \ 0-0650 J 0 0653
L 22-6 0-0656 0-0656 0-0656

The analysis showed that the helium contained 0 **48 per cent, of oxygen.
If this came from the water, there will be 0-96 per cent, of nitrogen. The
specific heat of the impure helium will thus be 5-00 cals./mol. °C. Thus at
350° C. we have :—

CL for air = 5*00 X ^ cals./gm. mol. °C.

* 0-0653 /&
= 7-38 cals./gm. mol. °C.
and
Cvfor air = 5-39 cals./gm. mol. °C. at 350° C.

3. The Results.
(a) Comparison of Air with Argon and Helium.—The two latter gases serve
as the standards, but as they were not available in large quantities, the com­
parison with air was made so that the latter could be used as a substandard in
finding the specific heats of other gases. The air used in all experiments was
freed from carbon dioxide by passage through a long soda-lime tube and then
dried by means of calcium chloride. It received further drying during the
run by the phosphorus pentoxide tubes included in the apparatus. The argon
and helium were obtained from the British Oxygen Company, and their com­
positions as given by the Company were: argon 99-0 per cent., oxygen 0-4
per cent., nitrogen 0-6 per cent. ; and helium 98 per cent., neon 2 per cent.
The argon was discarded after each run, and a sample was analysed for oxygen
by absorption with alkaline pyrogallol, care being taken to obviate errors due
to solution of the argon in the reagent. In most cases the oxygen found agreed
nearly with the composition given by the Company, but on a few occasions
500 P. S. H. Henry.

more was found, and this was assumed to be due to admixture of air during
the filling process. A correction was applied for the impurities on this
assumption. This amounted to 2-4 per cent, in one case (the experiment at
345°), but in all other cases it was less than 1 per cent. The helium was used
several times over for economy’s sake, and had to be stored over water. The
water was boiled under reduced pressure for 5 or 6 hours before it was used,
to get rid of dissolved gases. It was impossible to prevent slight contamination
of the helium in the later runs, however. This was allowed for by analysing
the gas for oxygen before each run, and assuming that the oxygen had come
from the water and was accompanied by twice its volume of nitrogen. In
five cases no correction was required and in the remaining three the corrections
were 0-6 per cent., 1*2 per cent, and 0-8 per cent., for the runs at 348°, 190°
and 18° respectively. There was no possibility of air getting in during filling
in this case. The values obtained for the molecular heat at constant volume
of air, on the assumption that those of argon and helium are equal to 4-97
cals, per degree per gram molecule are shown in fig. 3. It will be seen that
the values obtained with argon and helium do not differ by more than the
fortuitous error of the measurements in spite of the widely different thermal
5 -6 i
P Aiir s'
I 5 -4
____
^ - --------
V ^ s ^-
s
\ 5-2
jn
8 1 ?
5 5 0 7^ = ^ 3<*
^ :
4 8
100 ° 200 300 4 0 0 °1
Temperature
F ig . 3.
by comparison with h e l i u m \ The au th o r-s results.
(_) by comparison with argon J
X Shilling and P artin g ton’s results.
£ Eucken and Lude’s results.
------ Theoretical curve.
---- Curve used in calculating C„ for other gases.

conductivities of the gases concerned. The conductivities of helium, argon

and air at 0° C. are about 34 X 10~5, 4 X 10~5, and 5 X 10” '*units respectively.
Moreover, such difference as there is between the specific heat values is in the
opposite direction to that which one would expect if the conductivity were to
affect the measurements ; for argon, having a lower conductivity than helium,
 Specific Heats of Air, Oxygen, Nitrogen. 501

would in this case appear to have a lower specific heat, and would thus give a
high value for air. A reference to the figure will show that, on the whole,
the opposite is the case. This should dispose of any suspicion that the results
of the method used depend upon the conductivity of the gas, a criticism which
is often levelled at constant flow methods. The dotted line gives the values
which have been assumed in calculating the specific heats of nitrogen, oxygen
and methane from comparisons of these gases with air. The significance of
the full line will be discussed later.
(b) Comparison of Oxygen with A ir.—Four of the oxygen values were obtained
with commercial oxygen from a cylinder, and the remaining six with oxygen
prepared by the electrolysis of a solution of caustic soda. The commercial
oxygen contained 4 | per cent, of nitrogen which was estimated by absorbing
the oxygen in alkaline pyrogallol. The correction to the specific heat required
on this account varied from zero at room temperature (when the specific heats
of oxygen and nitrogen are nearly equal) to 0*3 per cent, a t 400° C. The
electrolytic oxygen did not contain enough impurity to require a correction.
The results are shown in fig. 4.

Oxygen

o 5-6

Temperature
F ig . 4.

O The au th o r’s results.

X Shilling and P artin g to n ’s results.
£ Eucken and L iide’s results.
------ Planck curve using spectroscopic frequency.
------- Curve deduced from spectra.

(c) Comparison of Nitrogen with Air.—The nitrogen employed was com­

mercial nitrogen containing 2 per cent, of oxygen, as shown by absorption
with alkaline pyrogallol in the Haldane apparatus. This, however, involved
502 P. S. H. Henry.

a correction of only 0 •1 per cent, at the higher temperatures, and none at all
below 200° C. The results are shown in fig. 5.

Nitrog-en

Temperature
F ig . 5.
Q The a u th o r’s results.
X Shilling and P artin g to n ’s results.
0 Eucken and Liide’s results.
----- Theoretical curve.

4. Discussion of Results.
Few experimental values are available for comparison above room tempera­
ture, but at room temperatures the specific heats of the simple gases are fairly
well established. Values taken from the International Critical Tables are
compared below with the author’s values at 15° C. in calories per 0 C. per
gram molecule.
I.C.T. Author.
Air ............................. 4-95 4-97
Nitrogen ..................... 4-95 4*97
Oxygen ..................... 4*98 5-02

It will be seen that the differences are less than 1 per cent., which is about
the degree of accuracy which is claimed for these experiments.
It is also worth noting that the author’s oxygen-air and nitrogen-air ratios
are compatible with each other within the experimental error. This is shown
by the table below, where the smoothed experimental values of C„ for air
are compared with those calculated from the smoothed experimental values
for oxygen and nitrogen and the assumed value for argon by means of the
relation :
100 Cv (air) = 78-1 C„(Ni) + 21-0 Cp(0l) + 0-9

There is no reason to suspect the accuracy of the additive law where, as

 Specific Heats of Air,Oxygen, Nitrogen.
503

here, it is known that the corrections to zero pressure for C„ are negligible
both for the constituents, and for the mixture.

15° C. 200° C. 350° C.

C, for air—found.................... 4-97 5-14 5-38
Cv for air—calculated............ 4-97 5-14 5-40

The only results between room temperatures and 350° C. with any claim to
accuracy, so far as the author is aware, are a number of sound velocity experi­
ments, in particular those of Shilling and Partington* and of Dixon,*)* and the
adiabatic expansion experiments of Eucken and Liide.j These are shown on
the diagrams for comparison with the author’s results. In the case of nitrogen
there are also available the results of Holborn and Austin,§ though these have
been subjected to considerable criticism on account of the uncertainty of the
amount of heat conducted from their heater to their calorimeter. The two
sets of sound velocity experiments gave identical results for air and nitrogen
and are not shown separately. I t will be seen that the author’s results, whilst
agreeing with the others at room temperatures, indicate a much more rapid
increase of specific heat with temperature. The difference rises to as much as
14 per cent, for oxygen at 370° C. It is worth noting that, whilst the sound
velocity experiments agree well together, they are alone in the small values
which they indicate for air, nitrogen and oxygen at high temperatures. This
may be seen from the following table, which compares the values of Gv for
air and nitrogen at 1000° C., obtained by sound velocity methods, by explosion
methods, and by the method of mixtures :—
Nitrogen. Air.*§
Sound velocity—
Shilling and Partington .......................... 5-32 5 •32
Dixon, Campbell and Parker .................. 5*32 —

* Shilling, ‘ Phil. Mag.,’ vol. 3, p. 273 (1927) ; Shilling and Partington, ‘ Phil. M ag.,’
vol. 6, p. 920 (1928). See also King and P artington, ‘ Phil. Mag.,’ vol. 9, p. 1020 (1930).
t Dixon, Campbell and Parker, ‘ Proc. Roy. Soc.,’ A, vol. 100, p. 1 (1921).
+ Eucken and Liide, ‘ Z. Phys. Chem.,’ B, vol. 5, p. 413 (1929).
§ Holborn and Austin, ‘ Abh. Phys. Tech. Reich.,’ vol. 2, p. 133 (1905). Their results
show a value of 4-59 cals./gm. mol. ° C. for nitrogen a t 0° C., which is recognised as being
about 7 per cent, too lo w ; so th a t it does not seem worth while comparing their absolute
values with the others. I t may be noted, however, th a t they obtained a value for the
tem perature coefficient much in excess of th a t indicated by the sound-velocity experiments.
504 P. S. H. Henry.

Nitrogen. Air.
Explosion—
Pier,* recalculated by Siegelf .................... 5*81 —
WomersleyJ .................................................. — 6-00
Mixtures—
Holborn and Austin§ ................................. 5*65 —

The values of Cv for the explosion and mixture methods given above were
obtained by applying the relation

C„ = | ( f . C J

to the values of the mean specific heats between temperatures 0 and t given
by the authors quoted. It may be pointed out th at the sound velocity method
suffers from two considerable difficulties, these being the uncertainty of the tube
correction, 11 which may amount to a considerable percentage on the specific
heat, and the accuracy with which the temperature of the gas must be measured.
This latter necessity is due to the fact that the velocity of sound varies as the
square root of the absolute temperature if the ratio of the specific heats remains
constant. Now an error of 1 per cent, in the velocity produces an error of
about 7 per cent, in Ct, in the case of air so that the mean temperature of the
gas in that part of the sounding tube used in the measurements must be found
with a percentage accuracy at least three or four times that desired for Cu.
With tubes over a metre in length whose ends have to be kept cool this must
be a matter of considerable difficulty, and it does not seem to the author that
the method of assuming the temperature of the piston head to be that of the
gas, which was adopted by Shilling and Partington, is sufficiently accurate.
The full lines shown in the diagrams are the values for the specific heats
deduced from spectroscopic data on the assumption that the rotational specific
heats have their “ classical” values and that the vibrational specific heats
are independent of the rotation, and are given by Planck terms using the*§

* Pier, ‘ Z. Phys. Chem.,’ vol. 66, p. 759 (1909) ; ‘ Elektrochem.,’ vol. 15, p. 536 (1909)
and vol. 16, p. 897 (1910).
t Siegel, ‘ Z. Phys. Chem.,’ vol. 87, p. 641 (1914).
%Womersley, * Proc. Roy. Soc.,’ A, vol. 100, p. 483 (1921).
§ Holborn and Austin, ‘ Abh. Phys. Tech. Reich.,’ vol. 2, p. 133 (1905).
|| See Henry, ‘ Proc. Phys. Soc.,’ vol. 43. p. 340 (1931).
 Specific Heats of A i r ,Oxygen, Nitrogen.

spectroscopic frequencies, Thus, for oxygen and nitrogen the curves are
given by
^ rp&pX
c*= l R + R ( 7 ^ I f
where
he con
x = ——-

and oj0, the vibration frequency of the molecule in wave numbers for small
amplitudes of vibration, • is taken as 1565 for oxygen and 2345 for nitrogen.*
The curve for air was calculated from those for oxygen and nitrogen, and the
constant value for argon by means of the formula given on p. 502. The dotted
line on the diagram for oxygen is the curve calculated direct from the spectro­
scopic data in the manner used for hydrogen by McCrea,f thus allowing for the
stretching effect of the rotation and the anharmonic nature of the vibration.
The normal state of the oxygen molecule is the 3S, which fact introduces a
multiplicity in the rotational states. McCrea showed, however, that it was
sufficient to assume that the rotations of the hydrogen molecule were classical,
and this approximation will be even more close to the truth with the oxygen
molecule with its greater moment of inertia, so th at the multiplicity of the
rotational states need not trouble us. The calculations wTere based on the
assumption that the vibrational and rotational energy of the molecule is given
by
= 1565^ — 11-37ft2 + (1 — 0-013ft) E ro
he

where E ro is the energy of rotation wdiich the molecule wxrald have if there
were no vibration. The anharmonic term was obtained from tables given by
Birge, t and the stretching term from a paper by Dieke and Babcock.§
Below is given a table of smoothed values of in calories per gram-molecule
°C. for air, oxygen and nitrogen. They should not be trusted further than
about 1 per cent., except at 20° C., where they are probably correct to | per
cent, at least.*§

* See, e .g B,. irge, ‘ Bui. N at. Res. Coun. W ash..’ vol. 11, p. 233 (1926).
t McCrea, ‘ Proc. Camb. Phil. Soc.,’ vol. 24, p. 80 (1928).
t See, e.g., Birge, ‘ Bui. N at. Res. Coun.,’ vol. 11, p. 233 (1926).
§ Dieke and Babcock, ‘ Proc. N at. Acad. Sci.,’ vol. 13, p. 670 (1927).
506 A. F. H. Ward.

Temperature. Air. Oxygen. Nitrogen.

i
o

0 4-95 500 4-96

20 4-97 5-02 4-97
50 4-99 507 4-98
100 503 5-17 5-00
150 5-08 5-29 5 04
200 5 14 5-43 5-09
250 5-21 5-57 515
300 5-30 5-71 5-23
350 5-41 5-85 5-33

It is hoped to extend the range and accuracy of these experiments during

the next few years by the use of a new and improved calorimeter which is now
being constructed of platinum, and by certain modifications in the procedure
which will be described later.
Finally, I wish to place on record my thanks to Professor E. K. Rideal and
Mr. P. M. S. Blackett for their unfailing encouragement and advice during the
course of this work, and to Imperial Chemical Industries, Ltd., for defraying
the cost of the apparatus.

The Sorption of Hydrogen on Copper. Part I .— Adsorption and the

Heat of Adsorption.
By A. F. H. W a r d , M.A., Ph.D.
(Communicated by E. K. Rideal, F.R.S.—Received June 19, 1931.)

Introduction.
A knowledge of the adsorption of gases on solid surfaces and the energy
changes resulting is of great value in investigating the structures of surfaces
and understanding their catalytic action. Evidence about the energy changes
is usually acquired from experimental determinations of the heat of adsorption,
but it must be clearly understood that this will only equal the total energy of
adsorption if the adsorbed molecule is in the same condition on the surface as
it was in the gas phase, which, in general, will not be true. If the molecule is
distorted when adsorbed, the energy of adsorption will be the sum of the energy
of distortion and the heat liberated. It is probable that an increasing total
energy of adsorption will correspond to an increasing heat of adsorption, and