224

SomeThermal Constants o f Solid and Liquid Carbon Dioxide.

By O. Maass and W. H. B arnes, McGill University, Montreal.
(Communicated by Prof. H. T. Barnes, F.R.S.—Received February 13, 1926.)

I.—Introduction.
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Carbon dioxide is a substance whose properties have been the subject of

innumerable investigations. Particularly the pressure-volume-temperature
relationships when in the gaseous and liquid phases have provided data for the
basis of equations of state. The thermal properties are not so well known
and an investigation of these is the purpose of the following paper.
The actual measurements to be described deal with the direct determination
of the latent heat of fusion, the latent heat of sublimation and the specific
heats of the solid and liquid over the temperature range of 0° C. to —184° C.
The experimental methods employed are of sufficient interest to warrant a
detailed description. Since it was found that the specific heat of the solid
carbon dioxide gave abnormally high results the expansion coefficient of the
solid was measured.
Carbon dioxide is one of a few substances that develop a large vapour pressure
in the solid state. The specific heat and thermal expansion coefficient values
are of interest in this connection. Furthermore with a possible use of carbon
dioxide as a refrigerant on a commercial scale the exact determination of the
thermal properties of carbon dioxide is of practical importance.

II.—Specific Heats and Latent Heat of Fusion.

{a) Method.—The method employed in the determination of the specific
heats and latent heat of fusion resembles that used by one of us for ice, benzene
and other substances and was briefly as follows.*
A closed metal container, filled with carbon dioxide, was weighed and then
allowed to come to an initial temperature in a brass tube, so arranged that
uniformity of temperature was established rapidly. The container and
contents were then removed to an adiabatic calorimeter where the heat taken
up by the carbon dioxide and its container was measured, this being corrected
to a final temperature of + 25° C. (see calculations). The container was
next emptied and weighed, after .which a blank test was made on the container
alone over the same temperature range.
* Maass and Waldbauer, ‘ J.A.C.S.,’ vol. 47, p. 1 (1925).
 Thermal'Constants of Solid and Liquid Carbon Dioxide. 225

From these values the total heat per gram of carbon dioxide from a known
initial temperature to + 25 ° C. was calculated. A number of determinations
were made with different initial temperatures and the total heats obtained were
plotted on a curve. From this curve the latent heat of fusion of carbon dioxide
was found and the specific heats calculated.
(b) Apparatus.—The adiabatic calorimeter that was used is shown in fig. 1.
The copper calorimeter vessel (D) had a capacity of 1300 c.c. while the outer
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Fia. 1.

bath (K) contained 10 litres of water. The copper calorimeter was set on
egs (G) that were cemented to the outer bath as shown. Considerable attention
was paid to the stirring because of the necessity for a rapid equalization of
temperature throughout the bath when hot or cold water was added. Four
VOL. cxi.— a . Q
 226 O. Maass and W. H. Barnes.

stirrers (not shown in figure), each with two pairs of propeller blades, were
rotated in different directions so that each stirrer forced the water in the
opposite direction to the one on each side of it. A multiple thermocouple (T)
of copper and constantan was placed in the bath and calorimeter as shown
and was used throughout the experiments as a null instrument.
By the addition of hot or cold water the outer bath was always kept at the
same temperature as the inner calorimeter water to within 0*0005° C. Even
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when large temperature changes were taking place in the calorimeter, as when
the cold container was suddenly introduced, it was possible to keep the
temperature difference to within 0*01° C. The temperature of the outer bath,
which was the same as that of the inner calorimeter, was measured by means
of a Beckmann thermometer. Readings were taken to 0*001° C. This
thermometer had been calibrated by the Bureau of Standards and all the
precautions necessary for its use as a precision instrument were taken.
The stirring in the calorimeter was accomplished by the up aiid down motion
of a copper disc (L), appropriately perforated to permit the free passage of the
thermocouple and the carbon dioxide container. The weight of the disc
was sufficient to permit rapid stirring, which was regulated by an electrically
driven, adjustable eccentric. The calorimeter vessel was insulated from its
jacket by three small ivory knobs affixed to pegs at the bottom. The cover of
the jacket was tightly clamped to a ledge at the top, which was well greased
with vaseline. This made a very effective water-tight joint. A tube, wider
than the carbon dioxide container, was soldered into the centre of the cover to
permit the entrance of the container to the calorimeter proper. Three other tubes
of appropriate diameters served for the thermocouple arm and for the two
stirrer wires.
The following constant temperature baths were used to enable the carbon
dioxide to be brought to a known initial temperature before placing in the
calorimeter.
An ice-water mixture gave the 0° C. bath. Solid carbon dioxide moistened
with ether was used for —78 •5° C. Liquid air, obtained from an air liquefaction
plant and therefore practically pure oxygen, gave the lowest constant tem­
perature bath employed. In the latter case analysis of the liquid air for
oxygen content was resorted to in order to obtain the exact temperature.*
For temperatures between 0° C. and —78*5° C. a large Dewar flask filled with
ether and vigorously stirred by a current of dried air was used. The ether was
brought down to the required temperature by the rapid addition of solid
* George Claude, * Liquid Air, Oxygen, Nitrogen,’ p. 231 (1913).
 Thewial Constants of Solid and Liquid Carbon Dioxide. 227

carbon dioxide, and could then be maintained at the desired temperature to

within 0 • 1° C. by the addition of small lumps of carbon dioxide. A somewhat
similar arrangement was employed to obtain a constant temperature bath for
any point between —78*5°C. and liquid air temperature. The ether was
replaced by the first distillate from petrolic ether which remains fluid to very
low temperatures. Liquid air was forced into a glass cooling bulb {see fig. 2)
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rapidly at first and then as required to

maintain a constant temperature. Stirring To B ridge &
/-GALVM™
was effected, as before, by bubbling dry air
from E through the petrolic, there a con­ *R
stancy of 0*1° being readily obtained.
The temperatures of the baths were read
by means of a platinum resistance thermo­
meter, with compensating leads, of the
Callendar-Barnes type which was operated
through a resistance box, a variable mer­
cury resistance, and the galvanometer used
in the thermocouple circuit.
(c) Procedure.—The container for the car­
bon dioxide was made of iron, had a
capacity of 10 c.c. and contained about 8
grams of carbon dioxide. It was metal
sealed and was strong enough to withstand
the pressure due to liquid carbon dioxide
up to room temperature. The container
was weighed before and after each run to
make certain that no loss of carbon dioxide F ig. 2.
occurred due to leakage.
This weighed container (see S in fig. 2), filled with carbon dioxide, was placed
in a brass tube of such a diameter that the container could just pass easily through
it. One end of the tube was closed water-tight while the other was stopped
with a cork to which the container was attached by means of linen thread.
Two copper discs enclosing wool (see W in fig. 2) served to insulate the container
from the upper part of the tube. Electric tape was wound over the side of the
cork and the top of the tube. This prevented any moisture condensing on
the cork or the tube and eliminated the danger of introducing water from
this source into the calorimeter.
The brass tube was then suspended in the constant temperature bath and
 228 O. Maass and W. H. Barnes.

allowed to remain at a known initial temperature for a sufficient length of time

to permit the carbon dioxide and container to come to this temperature. From
1 to l£ hours was found to be quite satisfactory. For the points below —60° C.
the brass tube and contents were kept in solid carbon dioxide moistened with
ether for 1 hour before placing in the constant temperature bath. This was
done to prevent supercooling of the carbon dioxide. It will be seen in the
curve obtained for the heat content of carbon dioxide (see fig. 3) that one
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determination at —61-4° C. did supercool. This happened before the necessity

for precooling the carbon dioxide well below its melting point was recognized.
While the carbon dioxide was in the constant temperature bath the adiabatic

F ig . 3.

calorimeter was prepared as follows. The inner calorimeter vessel was weighed
empty and dry. It was filled with water at a suitable temperature and re­
weighed. After placing in the calorimeter jacket the cover was immediately
clamped into place, the tubes in the coyer for the introduction of the thermocouple
and the container being stopped with corks. The calorimeter bath was
immediately filled with water to the overflow, which allowed water to completely
surround the calorimeter jacket, including the cover. The thermocouple
was set in place with one arm in the calorimeter and the other in the water of
the outer bath. By running in hot or cold water the temperature of the water
in the outer bath was brought slightly higher than that in the calorimeter
proper and maintained at this higher value until the calorimeter was required
 Thermal Constants of Solid and Liquid Carbon Dioxide. 229

for use. The reason for maintaining this slight difference in temperature was
to prevent any distillation of the water from the calorimeter to the top and
walls of the calorimeter jacket.
Shortly before the time for the introduction into the calorimeter of the
carbon dioxide and container the water in the outer bath was brought to
exactly the same temperature as the water in the calorimeter proper. From
this point to the end of the experiment the two baths were kept as nearly as
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possible at the same temperature.

The Beckmann thermometer was read every five minutes until three successive
readings did not vary more than 0*002° from one another. Conditions in
the calorimeter were then known to be constant.
The electric tape was removed from the brass tube in the constant temperature
bath and the carbon dioxide in its container was rapidly transferred to the
calorimeter (see A in fig. 1), the cork to which the container was affixed fitting
the tube through which the container was introduced into the calorimeter
(see J in fig. 1). Appreciable heat loss in the transference of the carbon dioxide
to the calorimeter was avoided since the time required to remove the container
from the constant temperature bath to the calorimeter was less than three
seconds. The insulating plug of wool and copper discs automatically fell off
as the container was removed from the brass tube.
Cold water was rapidly run into the water-bath surrounding the calorimeter
as the water in the calorimeter cooled down. When a constant temperature
had again been reached, readings of the Beckmann thermometer were taken
every five minutes until three successive readings agreed with one another
to 0*002°.

(d) Sample Set of Observations.—The following set of observations are

characteristic of those obtained throughout:—
Initial temperature .. .. .. .. .. = — 78*5° C.
Weight of calorimeter and water .. .. .. = 925*00 gms.
Weight of calorimeter .. .. .. .. = 269*45 gms.
Weight of water ................................................... = 655*55 gms.
Weight of calorimeter, stirrer and thermocouple
arm ............................................................... = 298*2 gms.
Specific heat of calorimeter, stirrer and thermocouple
arm .. ........................... .. .. = 0*0827 cals, per
gram.
 230 O. Maass and W. H. Barnes.

Beckmann thermometer readings :—

Time. Beckmann.
9.00 p.m. .. .. .. 3-543
0.05 „ .. .. ........................... 3-543
0.10 „ ............. 3-542
0 .1 5 ;,, .. .. ......................... 3-543
Introduced carbon dioxide and container :—
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Time. Beckmann.
9.20 p.m. 2-100
0.25 2-100
0.30 2-101
Weight of container and carbon dioxide => 29-5092 gms.
Weight of container = 21 •4800 gms.
Weight of carbon dioxide .. .. = 8-0292 gms.
(e) Calculations and Results.—The following set of sample calculations ar
based on the observations given above.
Calorimeter temperature :—
Initial .. .. .. —3-543 Final —2-100
Correction for standard .. 0-0001 0*0030
Temperature change of calorimeter .. .. .. = 1-4459° C.
Setting factor for Beckmann thermometer .. = 1 -000
Weight of water .. .. .. .. .. => 655-55 gms.
Heat given up by calorimeter, stirrer and thermocouple arm
= 298-2x0-0827x1-4459
= •35 •658 calories.
Heat given up by water
= 655-55x1-4459
= 3 947 •863 calories.

Total calorimeter heat change

== 983-52 calories.
Heat taken up by carbon dioxide and container near + 25° C.
=s 6-6 cals, per degree
(from preliminary curve of Total Heats).*
* Since the end temperature was always less than 1° either above or below 25° C, a
preliminary curve of Total Heat taken up by carbon dioxide and container was plotted
against Initial Temperature (neglecting end temperature) and the slope was determined
in the region of liquid carbon dioxide. From this slope the number of calories taken up
per degree was found and was used to correct the Total Heat taken up to an end
temperature of 25° C.
 Thermal Constants of Solid and Liquid Carbon Dioxide. 231

Final temperature of container and contents

= 2*10° (Beckmann)
= 23*65° C.
Total heat taken up by carbon dioxide and container from
—78*5° C. to + 2 5 ° C. = 992*43 calories.
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The calculation is self-explanatory and it will be seen from it how the heat
change is always calculated to the same end temperature.
The values for the total heat change, given in Table I, are the means of
several determinations that agreed with one another to within 0 •5 per cent.

Table I.

Initial Temperature of Carbon Dioxide Total Heat (Calories) taken up by

and Container. Carbon Dioxide and Container from
Initial Temperature to +25° C.

+25-0° C. 00
0 -0 ° c. 151-9
-3 7 -6 ° C. 396-5
—54 -3° C.. 509-5 ,
-6 1 -4 ° C. (Super-cooled) 547-8
—61-4°C. (Solid) 908-3
—70-6° C. 951 -4
—78-6° C. 990-3

The values given in Table I were plotted on a curve* from which the rise
in the heat taken up by the carbon dioxide at —56 •2° C. (the melting point)
was equal to 364 calories.
Hence the latent heat of fusion is equal to this rise in the heat taken up
divided by the weight of carbon dioxide in the container.
Latent heat of fusion of carbon dioxide

364
8*029
= 45*3 calories per gram
as compared with the value 43 •8 found by Kuenen and Hobson.f

* This curve is not given here but was similar to fig. 3, except that Total Heat of
container and contents was plotted against Initial Temperature on a large scale,
t ‘ Phil Mag.,’ vol. 3, p. 622 (1902).
 232 O. Maass and W. H. Barnes.

To obtain the specific heats of the solid and liquid carbon dioxide the specific
heat of the container* was determined over the temperature range —183*1° C.
to + 25° C. and a number of additional determinations of the total heats of the
carbon dioxide and container were made.
The heat content per gram of container and the heat content per gram of
carbon dioxide are given in Table II below.
#
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Table II.

Heat Content per Gram (Calories).

Temperature.
Container. Carbon Dioxide.

+25*0° C. 0-00 0-00

0 *0 ° c. 2-95 11-04
-37*5° C. 7-00 30-58
—54*3° C. 8-20 41-90
—61*4° C. (Super-cooled) 9-20 43-38
—61*4° C. (Solid) 9-20 88-47
—70*6° C. 10-02 91*70
—78*5° C. 10-78 94-34
—115-0° C. 13-30 104*7
-1 8 3 -1 ° C. 17*80 120-9

In Table II, column 1 gives the initial temperature of container and contents,
columns 2 and 3 the heat required to warm up one gram of container and
one gram of carbon dioxide respectively from the initial temperature to + 25° C.
Thus, for example, the third to last figure in column 3 (namely 94*34) means
that it requires 94*34 calories to warm up one gram of carbon dioxide from
—78*5° C. (its boiling point) to + 2 5 ° C., without evaporation.
The values for the heat content per gram of carbon dioxide given in
Table II are plotted against temperature in fig. 3, where H represents heat
content per gram of carbon dioxide and T represents temperature in degrees
centigrade.
In Table III below are given the average specific heats of carbon dioxide
over several temperature ranges.

* It is of interest to note that the average specific heat of iron over the range
— 183*1° C. to -J-25°C. was found to be 0*0855 in agreement with the value found by
Richards and Jackson over the same temperature range (‘ Z. phys. Chem.,’ vol. 70, p. 414
(1910)).
 Thermal Constants o f Solid and Liquid Carbon Dioxide. 233

Table III.

Temperature Range. Average Specific Heat.

+25° C. to —56-2° C. 0-490 cals, per gm. per deg.

—56-2° C. to —78-5° C. 0-348 cals, per gm. per deg.
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—78-5° C. to —115-0° C. 0 •284 cals, per gm. per deg.

—115-0° C. to -1 8 3 -1 ° C. 0 •231 cals, per gm. per deg.

By taking tangents to a curve of the total heats plotted to a large scale the
specific heats of the solid carbon dioxide (Cp) could be represented over the
temperature range ( —56° C. to — 110° C.) by the equation

C9 = 0*400 —0*00283 T + 0 *0000125 T2

where T represents temperature in degrees absolute.

The values for the specific heat at various temperatures are given in Table VII.
Eucken* obtained 0*294 and 0*295 at 195*2° A. and 196*4° A. respectively as
compared with 0 •324 and 0 •326 found by the authors.
The results obtained for the molecular heats (at constant pressure) of solid
carbon dioxide are of considerable interest. The average value for the molecular
heat over the temperature range from the boiling point ( —78 *5° C.) to the melting
point (—56*2° C.) was found from the foregoing results to be 15*312, this value
decreasing to 12*496 over the lower range of —115*0° C. to —78*5° C. Both
these values are much larger than the molecular heat obtained for carbon
dioxide in combination at much higher temperatures. The average molecular
heat of compounds such as R C 03 is 20*7 and that of the oxides HO is 11*1
so that the average molecular heat 6f carbon dioxide in combination is 9*6.
The molecular heats are of course all measured at constant pressure, and it is
to be inferred from the above comparison that the molecules in pure solid carbon
dioxide are not held together as firmly as the carbon dioxide when combined
with metallic oxides.
In corroboration of this fact it was noticed that solid carbon dioxide has a
much greater thermal expansion coefficient near its melting point than is
ordinarily attributed to a solid. Measurements of this expansion coefficient
have been made and will be described in detail later.

* 4 Ber. Deut. physikal. Ges.,’ vol. 18, pp. 4-17 (1916).

 234 O. Maass and W. H. Barnes.

I.— Latent Heats of Sublimation and Evaporation.

(a) Method.—In the determination of the latent heat of evaporation of
carbon dioxide a special apparatus was designed by means of which pure carbon,
dioxide could be generated and a known weight then condensed into a container.
The container and contents did not have to be weighed at room temperature
so that there was no necessity of having a container that would withstand any
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appreciable pressure.
The solid carbon dioxide was allowed to warm up in an adiabatic calorimeter,
and the heat taken up by it from a known initial to a known final temperature
was accurately determined.
During this rise in temperature the container was open to the air so that the
carbon dioxide evaporated, the final temperature of the gas formed being that
of the calorimeter.
(b) Apparatus.—The apparatus for the generation and condensation of the
carbon dioxide is shown in fig. 4.* Dilute sulphuric acid (1 : 6) was contained

in the dropping funnel (A) and allowed to drop on a saturated solution of

potassium carbonate in the flask (B). The carbon dioxide so produced was
dried by passage through the concentrated sulphuric acid bubblers (D) and
then over phosphorus pentoxide in the tube (E). By observation of the
mercury manometer (F) the pressure of the carbon dioxide generated could be
maintained at that of the atmosphere. The dried gas was collected in the
volume bulb (J), the pressure in this part of the apparatus being determinable
at all times by means of the mercury manometer (L).
Condensation was effected in the glass bulb (H). The first attempt was
made with a metal container fitted with a metal spiral as a receptacle for the
* The distillation flask and the (O) taps (P) and (Q) were sealed on for the determination
of the coefficient of expansion to be described later.
 Thermal Constants of Solid and Liquid Carbon Dioxide. 235

condensed carbon dioxide, but it was found to have too high a heat conductivity.
Even with the spiral surrounded by a steam coil it became so cold that carbon
dioxide was condensed in it, thus blocking the passage to the container proper.
Consequently the metal container was replaced by the glass bulb which was
found to be very satisfactory.
The bulb (H) was constructed to have a volume of about 20 c.c. A glass tube
at the top facilitated sealing to the main part of the carbon dioxide apparatus
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and could be sealed off completely after condensation of the carbon dioxide.
The bulb was also fitted with a thin-walled glass spiral of small bore through
which the carbon dioxide was allowed to escape during the heat change
measurements. The object of the spiral was to ensure the escaping carbon
dioxide being at the same temperature as the water in the calorimeter. This
spiral was a very important feature of the glass container. The thickness of
the walls was about 0 • 1 mm. and the diameter of the tube was less than 2 mm.
Before placing in the calorimeter the tip of this thin tube was broken, and since
the other tube from the bulb was sealed off, the carbon dioxide could only
escape through the spiral. In this way all the escaping carbon dioxide was
enabled to come to the temperature of the water before leaving its influence.
The whole apparatus could be evacuated by means of a vacuum pump.
It was found advantageous only to evacuate that part of the apparatus to the
right of tap (G), the left-hand section being maintained always at atmospheric
pressure. This eliminated the danger of air leakage through the rubber con­
nection between the flask (B) and the rest of the apparatus that might have
taken place due to the higher pressure on the air side of the tubing. A rubber
connection was used in order that the generator might be easily removed and
cleaned out when the solution of potassium carbonate was used up. Except
at (B) all connections were glass blown to prevent any leakage in the apparatus.
(c) Procedure.—The whole apparatus was swept out at least five times
with carbon dioxide by evacuation of the part to the right of tap (G) followed
by generation of carbon dioxide in the flask (B), which passed through the
partially opened tap (G). After filling all the apparatus with carbon dioxide
at atmospheric pressure, taps (G) and (M) were closed, care being taken to see
that taps (I) and (K) were open.
A piece of tissue paper was tied around the bulb (H) and a Dewar flask filled
with liquid air was carefully brought up under it. When using the bulb (H)
without the tissue paper it was found that during the condensation of the carbon
dioxide, even with dry air blowing around the condensation bulb, it was
impossible to prevent the deposition of a certain amount of water on the surface
 236 O. Maass and W. H. Barnes.

of the bulb. Consequently the values for the heat change when this took
place were found to be a few calories too high and therefore were rejected.
Results checking to better than 0 •5 per cent, were obtained by the use of the
tissue paper. This paper prevented the condensation of water on the bulb,
and the time to remove it before placing the bulb in the calorimeter was
negligible since it could be torn off at one stroke.
As condensation took place in the bulb (H) the left-hand column of the
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manometer (L) rose. Tap (I) was then closed and the positions of the mercury
in the two arms of the manometer (L) were obtained from the scale (N). The
apparatus was refilled with carbon dioxide at atmospheric pressure by partially
opening tap (G). Tap (G) was then reclosed and, on opening tap (I), further
condensation took place in the bulb (H) as shown by the rise in the left-hand
column of the manometer (L). Tap (I) was closed again and the mano­
meter read as before. The apparatus was filled a third time with carbon
dioxide at atmospheric pressure and condensation was effected as already
described.
Note was made at the time of barometric pressure, room temperature, and
the temperature of the water-bath surrounding the volume bulb (J). The
glass tube connecting bulb (H) to the apparatus was sealed off completely and
the bulb was immersed in liquid air for 30 minutes.
When the adiabatic calorimeter was ready the tip of the glass spiral of
bulb (H) was broken, the tissue paper was torn off and the bulb was transferred
rapidly to the calorimeter where the heat changes occurring were carefully
noted.
It was very important to have the end of the glass spiral project above the
cover of the calorimeter jacket when the bulb was in the calorimeter proper.
It was found that the total heat from —183 • 1° C. to + 25° C. was 191 *5 calories
as compared with the probably correct value of 183 calories when the carbon
dioxide was allowed to escape from the bulb (H) into the space between the
calorimeter proper and the calorimeter jacket. This is explained by the fact
that a certain amount of water probably evaporated into the dry carbon dioxide
gas circulating above it. Even the evaporation of a small amount of the
calorimeter water would have an appreciable effect on the heat measurements
because of the large latent heat of evaporation of water.
In order to calculate the amount of carbon dioxide in the bulb (H) it was
necessary to know accurately the different volumes present from which it was
condensed. The volume of the bulb (J) was determined in the usual manner
by filling with water and weighing. The volumes of the tubing and bulb (H/
 Thermal Constants of Solid and Liquid Carbon Dioxide. 237

were determined by filling bulb (J) with air at atmospheric pressure, evacuating
the tubing, opening taps (K) and (I) and reading the manometer pressure.
(d) Calculations and Results—The mean of several determinations, agreeing
with one another to better than 0*5 per cent., gave the total heat of carbon
dioxide (solid and gas) from —183*1° C. to +24*6° C.
= 183*0 calories per gram.
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From Table I the total heat of carbon dioxide (solid) from —183*1° C. to
-78*5° C.
= 26*56 calories per gram.
Taking the mean specific heat of carbon dioxide gas from tables* as 0*19,
then the total heat of carbon dioxide from 0° C. to + 2 4 •6° C.
= 4*67 calories per gram.
Hence the total heat of carbon dioxide from —78*5° C. to 0° C.
= 183*0—26*56—4*67
= 151*8 calories per gram.
Now the heat required to warm carbon dioxide gas from — 78*5° C. to 0° C.
= 78*5x0*19
= 14*9 calories per gram.
Hence the latent heat of sublimation of carbon dioxide
= 151*8—14*9
=3 136*9 calories per gram.
Andrews^ has recently measured the latent heat of sublimation of carbon
dioxide, obtaining the somewhat higher value of 151 calories per gram as the
mean of a large number of determinations that do not agree nearly as well with
one another as the various values obtained by the authors. The difficulty
pointed out by Andrews of obtaining good thermal contact due to the high
insulating property of the carbon dioxide snow itself falls away altogether
in the method adopted in this laboratory.
From Table III the average specific heat of solid carbon dioxide from —78 •5° C.
to —56*2° C. is 0*348, so that the heat required to warm solid carbon dioxide
from —78*5° C. to —56*2° C.
= 0*348x22*3
= 7*76 calories per gram.

* Landolt-Bornstein, ‘ Phys. Chem. Tab.,’ p. 1274 (1923).

t ‘ J.A.C.S.,’ vol. 47, p. 1597 (1925).
 238 O. Maass and W. H. Barnes.

And the heat required to warm carbon dioxide gas from —78-5° C. to
—56’2° C.
= 0 -1 9 x 2 2 -3
=s 4-24 calories per gram.
So that the latent heat of evaporation of carbon dioxide
= (1 3 6 -9 + 4 -2 4 )-(4 5 -3 + 7 -7 6 )
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= 88-1 calories per gram.

IY.—Coefficient of Expansion.
(а) Method.—The general method employed in the determination of the
coefficient of expansion of carbon dioxide was to condense a definite weight of
carbon dioxide in a small glass bulb fitted with a graduated capillary
tube. A known weight of gas was then condensed in the bulb as a liquid,
completely filling the bulb and part of the capillary tube, which was then
sealed off.
The position of the liquid in the capillary tube was read at different tempera­
tures from the graduations on the glass. Then, knowing the weights of carbon
dioxide and of liquid respectively, and the densities of the liquid at the various
temperatures, it was possible to calculate the densities of the carbon dioxide
at these temperatures. From the values so obtained the coefficient of expansion
of solid carbon dioxide at various temperatures was calculated.
(б) Apparatus.—The apparatus for the condensation of the carbon dioxide
and the liquid was the same as that used in the determination of the latent
heats of sublimation and evaporation. A distilling flask (0) for the liquefied
gas, together with taps (P) and (Q), was sealed to the apparatus between tap (M)
and the vacuum pump. (See fig. 4.) The gas was kept liquefied by surrounding
the distilling flask with liquid air.
The density bulb had a volume of about 3 •5 c.c. and was glass sealed to
the apparatus in the position occupied by the bulb (H) in fig. 4. The graduated
capillary sealed to it was carefully calibrated.
Constant temperature baths similar to those previously described were
used.
(c) Procedure.—Some preliminary tests were made on the solubility of carbon
dioxide in petrolic ether (B.P. <C 35° C.). The petrolic ether was cooled with
solid carbon dioxide and was then drawn through a filter of linen and glass
wool into lime water. There was no indication of the solubility of carbon
dioxide. Petrolic ether was, however, abandoned as a liquid suitable for the
 Thermal Constants of Solid and Liquid Carbon Dioxide. 239

m e a s u r e m e n t s because of its variable composition and the experimental difficulty

of adding definite quantities to the density bulb when filled with solid carbon
dioxide.
Since this ether consisted of a mixture of saturated hydrocarbons it was
replaced by propane which could be prepared with great purity, could be
handled in the gaseous state, and the density of which in the liquid condition
had already been determined to a certain extent.*
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The propane was made by allowing normal propyl iodide to act on zinc-copper
couple in the presence of alcohol. The liberated gas was passed through
concentrated sulphuric acid and then condensed by means of solid carbon
dioxide moistened with ether. The liquefied propane was then allowed to
distil into a gasometer in which it was stored over water. The propane so
obtained was purified by passing three times successively. through alcohol
and over more zinc-copper couple. It was then passed through concentrated
sulphuric acid to remove all moisture and was condensed by means of solid
•carbon dioxide moistened with ether. After several distillations, when no
residue remained in a flask on allowing it to warm up to 0° C., the propane
was finally distilled into the flask (0) attached to the condensation apparatus
{see fig. 4) which was then sealed off from the air.
Carbon dioxide was condensed into the density bulb by the same procedure
as before. The apparatus was then swept out with propane and the propane
was finally allowed to condense in the density bulb in the same manner as the
carbon dioxide, care being taken that the bulb was filled completely with the
liquid. The density bulb was then sealed off from the air.
Readings of the capillary were taken in solid carbon dioxide moistened with
ether, in liquid air, and at a number of temperatures between —78*5° C. and
—140° C. For these latter determinations the petrolic ether constant tem­
perature bath was employed.
Since the density of liquid propane was only known to about —78*5° C.
additional determinations were made using the method employed by Maass
and Wright. The density bulb for these experiments was fitted with a small
bulb at the top so that the liquid propane could be warmed up to room tem­
perature and then weighed. Readings of the capillary were taken in liquid
air and in the petrolic ether bath at different temperatures.
Table IY below gives the densities of propane as found. They agree with
those obtained by Maass and Wright at higher temperatures.

* Maass and Wright, ‘ J.A.C.S.,’ vol. 43, p. 5 (1921).

 240 O. Maass and W . H. Barnes.
Table IV.

Temperature (° C.). Density.

—183-3 0-7390
—1390 0-6895
—133-3 0-6841
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The density determinations of the carbon dioxide were repeated using a

larger amount of carbon dioxide in the density bulb and also a new sample of
propane, prepared and purified in the same manner as the first amount.
(d) Calculations and Results.—The following calculation is typical of those
made throughout this determination •—

Weight of propane .. .. .. .. .. = 0*4767 gms.

Weight of carbon dioxide .. .. .. .. = 4*8939 gms.
Temperature .. .. .. .. .. .. = —115*2° C.
Volume of density bulb to point of meniscus corrected for temperature
= 3-*7581 c.c.
Density of propane (from curve) . . = 0*6642

Volume occupied by propane _ Weight

Density
^ 0*4767
0*6642
= 0*7177 c.c.

Volume occupied by the carbon dioxide = 3*7581-0*7177

= 3*0404 c.c.

Density of carbon dioxide at —115*2° C. _ Weight

Volume
_ 4*8939
3*0404
= 1*6096

The following Tables V and VI show the results obtained with two different
samples of propane.
 Thermal Constants of Solid and Liquid Carbon Dioxide. 241

Table V.—Sample A.
Weight of Propane .. .......................... = 0-4767 gms.
Weight of Carbon Dioxide ........................... = 4-8939 gms.

Volume,
Carbon Volume, Density,
Density, Volume, Carbon Carbon
Temperature. Dioxide Propane. Propane.
and Dioxide. Dioxide.
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Propane.

(° c.). c.c. c.c. c.c.

- 81-5 3*879 0*627 0*760 3*119 1*569
- 83*6 3*869 0*629 0*758 3*111 1*573
- 85*5 3*863 0*631 0*755 3*108 1*575
- 95 -3 3*823 0*642 0*742 3*081 1*589
-105*2 3*788 0*653 0*730 3*058 1*600
-115*2 3*758 0*664 0*718 3*040 1*610
-128*8 3*722 0*679 0*702 3*020 1*621
-1 8 3 3*588 0*739 0*645 2*943 1*663

Table VI.—Sample B.
Weight of Propane .. .. .. .. = 0-2736 gms.
Weight of Carbon Dioxide .. .. .. = 5-3352 gms.

Volume,
Carbon Density, Volume, Volume, Density,
Temperature. Dioxide Propane. Propane. Carbon Carbon
and Dioxide. Dioxide.
Propane.

(°c.). c.c. c.c. c.c.

- 79*6 3*847 0*625 0*438 3*409 1*565
- 87*9 3*804 0*634 0*432 3*373 1*582
— 95*1 3*782 0*642 0*426 3*356 1*590
-105*1 3*749 0*653 0*419 3*330 1*602
—114*9 3*723 0*664 0*412 3*311 1*611
-125*2 3*694 0*675 0*405 3*288 1*623
—135*2 3*672 0*686 0*399 3*273 1*630
—183 3*557 0*739 0*370 3*187 1*674

It is interesting to note that Behn obtained a value of 1-56 for the density
of solid carbon dioxide at —79° C., this being the only temperature at which
it was determined.*
The densities given in the above tables are shown in fig. 5, where D represents
the density and T represents the temperature in degrees Centigrade. The
values obtained with Sample A (Table V) are designated by the circles
* * Ann. d. Phys.,’ vol. 3, p. 735 (1900).
vol. cxi.— a . R
 242 O. Maass and W . H. Barnes.

enclosing crosses, while the plain circles mark those found for Sample B (Table
VI).
By drawing tangents to this curve the coefficient of expansion of solid carbon
dioxide was obtained.
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-160

-n o

F ig . 5.

In Table YII the expansion coefficients are given in column 3, and it will be
seen that they are much greater than those of most solids.

Table YII.

Temperature (° A.). Cj> (Atomic). 3a (Cubioal). Cv (Atomic). Cv (Molecular).

183 0-301 0-00128 0-222 9-77

175 0-288 0-00118 0-223 9-81
171 0-282 0-00101 0-233 10-25
165 0-273 0-00096 0-232 10-21
155 0-262 0-00091 0-227 9-99
131 0-244 0-00083 0-220 9-68
109 0-240 0-00080 0-222 9-77
 Thermal Constants of Solid and Liquid Carbon Dioxide. 243

Griineisen has shown that the molecular heat at constant pressure can be
related to that at constant volume by means of the compressibility and expansion
coefficients in the following way :
9Ta2V\
KCy / ’
where
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C„ is the molecular heat at constant pressure

Cv is the molecular heat at constant volume
T is the absolute temperature
a is the linear coefficient of expansion
V is the molecular volume
K is the compressibility.

can be put equal to some constant Jc* then

Nowif^ ;
Cp = Cv (l+9&Ta2)

using the extreme values of CP, T and a in Table VII, and assuming Cv to be the
same in both instances, Jc is found to be equal to 1197 and Cv (atomic) is shown
to have the values given in column 4 of Table VII.
These values given an average for Cv (molecular) over the temperature range
183° A. to 109° A. of 9 •9 calories, which is considerably lower than the value for
Cp and more of the order of magnitude that one would expect. Taking the
values of Korenf for CaC03 and CaO over a similar temperature range, the
molecular heat for the bound C 02 comes out to be 6-4 calories. The high
values for the specific heat at constant pressure obtained for carbon dioxide
may therefore be ascribed to its enormous expansion coefficient and probably
its correspondingly high compressibility.

V.—Summary and Conclusion.

The specific heat of solid carbon dioxide was measured over the temperature
range 194-5° A. to 90° A., and that of the liquid from 298° A. to 194*5° A.
The latent heats of fusion and sublimation were determined directly and the
latent heat of evaporation was calculated.
As a test of the accuracy of the calorimetric measurements it is of interest
to compare the latent heat of sublimation of the solid with that calculated

* W. C. McC. Lewis, c System of Physical Chemistry,’ vol. 3, p. 65 (1919).

t * Ann. d. Phys.,’ vol. 36, p. 49 (1911).
 244 Thermal Constants of Solid and Liquid Carbon Dioxide.
from the Clausius-Clapeyron equation. From density measurements of
gaseous carbon-dioxide at low temperatures made in this laboratory* the
weight of one litre of the gas at —78*5° C. was found to be 2-840 grams. The
vapour pressure was taken from the measurements of Henning and Stockf
and the calculated value for the latent heat of sublimation was 137 •7 calories
per gram. This figure agrees to within 0-6 per cent, of the result obtained
directly, namely, 136-9 calories per gram.
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The expansion coefficient of the solid was shown to be abnormally large, and
values of so-called molecular heat at constant volume were calculated on the
basis of several assumptions which, in the opinion of the authors, invalidate
the accuracy of the absolute values. They do show, however, that the
abnormally high results for the molecular heat at constant pressure are connected
with this expansion coefficient.
The calculation of Trouton’s constant from the date contained in this paper
gives it a value of 20 - 7 which places carbon dioxide in the liquid state among the
unassociated normal liquids.
It would be of considerable interest to determine the crystal structure of the
solid because the expansion coefficient (especially near its melting point) is
greater than that recorded for any other solid. Probably the abnormally
high vapour pressure of the solid is connected with this fact.

* Maass and Mennie, * Roy. Soc. Proc.,’ A, vol. 110, p. 198 (1926).
f 4 Zeit. Phys.,’ vol. 4, p. 226 (1921).