610

THE DENSITY OF PROPYLENE IN THE LIQUID AND VAPOR

PHASES NEAR THE CRITICAL TEMPERATURE1
Bv C. A. WrNxr,Bnz aNo O. Maasss
Abstract
The density of propylene in the liquid and vapor phases was measured over
the range 66" to'926 C. by a refined dilatometer method and at the higher
temperalures at the same time by a float method. Good agreement was found
between the two methods, the latter being preferable in the neighborhood of the
critical temperature. It u'as found that at temperatures below the critical, no
variation in vapor density accompanied a change in the relative volume of the
liquid. The data rvere obtained principally for an investigation to be published
simultaneously on discontinuities above the critical tenperature.
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In the past few -years, the use of propylene in the study of critical and other
phenomena has become very widespread, probably owing to the suitable
critical constants of this substance, and to its polar molecular nature. Coin-
cidentally, there has been an increased demand for accurate data on the
physical constants of this substance. Many of these constants have been
determined with sufficient accuracy for most purposes. Data on the density
of propylene over a temperature range approaching the critical, in the liquid
and gaseous phases, are not available however. Since these data were essential
for the calculation of the surface tension reported previously (3), and for
other investigations in progress in this laboratory, they were ascertained over
a range of approximately 60o-92o C.
The densities of the vapor at several temperatures were determined with
For personal use only.

the apparatus described elsewhere (4). In so doing, the float was elevated
to some position in the bomb above the liquid phase, and the extension of
the spiral ascertained in the usual manner. The temperature of the bath
was rnaintained equalized throughout, and constant at arry desired temper-
ature to within 0.03" C. The effect of varying the relative volume of the
liquid to the total bomb space was investigated, since it was known that at
temperatures above the critical a decrease in the space available for propylene
was paralleled by an increase of density. It was found, however, that at
temperatures belo*- the critical, no significant variation in vapor density
accompanied a change in the relative volume of the liquid. Great care was
taken in determining vapor densities below the critical temperature to ensure
equiiibrium between the phases. The values of the density rvhich are recorded
represent those obtained for constant readings of the extension during the lapse
of at least an hour. It was found possible to obtain values for the density of
the liquid phase by the same method, at temperatures not more than approxi-
mately 3o C. removed from the critical point. The error in the determination
of the vapor density of the liquid very near to the critical temperature should
not exceed that involved in the calibration of the float, namely,0.37c.
I Manuscript rece,iaed, Noaernber 16, 1933.
Contribution from the Phys'icol, Chemistry Laborator'i,es, McGill' Uniaersi.ty, Montreal',
Quebec, LAnAdA,
2
Ilolder of a fel,lowship under tke Nati,onal Research Council' oJ Canad'a.
3
Macdonald' ProJessor oJ Physical Chemi,stry, McGi'l'I, Unhersity.
 DENSITY OF PROPYLENE NEAR THE CRITICAL TEMPERATURE 6II

The density of the liquid phase through the temperature range from
60o-90o c. was determined by the dilatometer method. A dilatometer was
constructed from Pyrex capillary tubing of approximately 1 mm. bore and
2 mm. wall thickness. A bulb of approximately 0.7-cc. volume was blown
at one end. Immediately above this bulb was sealed a finely drawn glass
pointer to serve as a zero point on the stem. A bulb of some 1 .5-cc. capacity
was blown at a distance of 18 cm. from the pointer. The volumes ol the
bulbs were such that when the dilatometer was filled to a convenient distance
above the pointer, the liquid occupied very nearly fi$ of the total volume.
This precaution was taken to avoid excessive motion of the meniscus, since
it has been found from experience that in a tube containing this ratio of liquid
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to total available space, the meniscus remained practically motionless as the

critical temperature was approached.
The stem of the dilatometer r'vas calibrated by introducing weighed quantities
of mercury, and measuring the height of the mercury column, relative to the
pointer, with a cathetometer after the addition of each successive portion. The
volume lvas calculated for various positions in the stem, and a calibration curve
plotted. The total volume was also ascertained by calibration with me(cLrry.
The dilatometer was thoroughly cleaned and dried, and propylene, prepared
by the dehydration of isopropyl alcohol over alumina at 362" c. and purified
by low temperature fraction-
ation (as described by Coffin
and Maass (1) and Maass
and Wright (2) ), u'as intro-
For personal use only.

duced by low temperature

condensation, until approxi-
3* of the entire
mately
volume was occupied by
liquid. The dilatometer was
then sealed off just above
the upper bulbj and im- t
mersed in a bath of glycoline E
oil, the temperature of rn'hich
could be maintained at any
desired value, constant
within 0.03o C., by manual
control of resistances in series
with the electrical heating
elements. The position of
the meniscus was ascertained
at various temperatures with
a cathetometer,'with an error TEMpERATURE. "c.
not exceeding 0.04 mm., the Frc. 1. Dens,ities oJ aapor and liquid, below the
position in each case being cr'iticaltemperature as delermined 6y dil,atometer
and "f.oat" methods.
determined with reference to
the pointer affixed to the stem of the dilatometer.
 6t2 CANADIAN JOURNAL O].' RESEARCH

The dilatometer r,vas then carefully cleaned, dried and weighed with its
contents. The tip 'w'as broken off, care being taken to prevent loss of frag-
ments of glass, and the propylene allowed to evaporate. The dilatometer
was then flushed with air and reweighed. From the data obtained dilato-
metrically, in conjunction with the data for the vapor densities, the density
of the liquid propylene at each temperature was calculated' The vapor
densities were not determined at the same temperatures as the liquid densities;
consequently, those values of the vapor density necessary in the calculation
of the densities of the liquid li'ere obtained from the vapor density-temperature
curve.
The data obtained for the vapor densities by the float method are set forth
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in Table I, those for the liquid densities, in Table II. Fig. 1 is a graphical
representation of all the data obtained.
TABLE I
Tne nBNsItrBS oF pRoprrLENE vApoR rnolt 67.70'C. ro rnn cRITTcAL.TEMPERATURE

Temp., o
C. 67 .70 71.40 80.10 82so
I

Vapor density 0.0747 0. 0 0.11sol

TABLtr II
Tne nBNstues oF pRoprrLENE LreurD rnolt 67.60" C. ro rnB cRITTcAL TEMPERATURE
For personal use only.

Temp., o
C. 67 .60 72 so 60 sz.zo 89.70* oo.zo- or.oo-
Density l7? l |
of liquid 0.4080 o.3e37l o.s77rl 0.3s4 ,l':::,,1 0.2983 0.27761 0.23e0

* These ztalues were obtained, by the float method; the remainder by the dilatometer method'.

Discussion
These results need little or no discussion, except, perhaps to mention that
the density of the liquid determined dilatonretrically at 87.5" C. is probably
somervhat too low, rather than the values at 89. 7o C. being too high' The
reason for this conclusion is not far to seek. At temperatures approaching
the critical, the meniscus in the dilatometer became very restless, and also
quite diffuse, both of r,vhich factors contributed to a relatively large experi-
mental error in the case of the value at 87 .5" C. The float method, on the
other hand, is not subject to these disadvantages.

References
1
Corrrn, C. C. and Maess, O. Can. J. Research, 3 : 526-539. 1930.
2. Mea.ss, O. and Wnrcnr, C. H. J. Am. Chem. Soc. 43 : 1098-1111. 1921.
WrNr<r,en, C. A. and Meess, O. Can. J. Research, 9 :65-79, 1933.
n
WrNr<r.nn, C. A. and Mee,ss, O. Can. J. Research, 9 : 613-629. 1933.