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RAKER AND BAKER : CHANGE IN THE ROlLTNG POINTS, ETC. 2339

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CCXLV1.-The Change in the Boiling Points o f the

Trioxide and Tetroxide of Nitrogen on Drging
By HERBERT BAKERand MURIELBAKER.
BRERETON
INconsequence of a private communication from Prof. A. Smith
with regard to the volatility of dried calomel, a search was made
through our old laboratory notebooks to see if any abnormalities
in the vaporisation of dried substances had been recorded. None
was found in regard to ammonium chloride or calomel, but among
the determinations of the vapour density of nitrogen trioxide two
instances had been noticed in which this substance, carefully dried,
had failed to boil at + 15O, the ordinary boiling point being - 2 O .
I n Prof. Smith’s interesting work on calomel, the drying had been
more complete than in the investigation carried out by one of us on
that substance, and i t was thought worth while to determine the
boiling point of very dry nitrogen trioxide. It fortunately happened
that we had kept, as a lecture exhibit, a tube with the attached
series of bulbs, in which the liquid trioxide had been sealed up with
phosphoric oxide for three years. The trioxide was distilled into the
bulbs by coding the latter with liquid air,and in this way it was
divided by seding the capillary tubes between the bulbs into three
portions. These sealed bulbs were dried on the outside by allowing
them to remain in a desiccator over phosphoric oxide. For the deter-
mination of the boiling point a Jena-glass tube wits used about
40 cm. in length and 15 cm. in internal diameter. Into one end was
ground a hollow glass stopper, which opened into a wide tube
contaicing phosphoric oxide, this tube being drawn out into a
long capillary about 2 mm. in diameter. The other end of the
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2340 BAKER AND RAKER : THE CHANGE IN THE BOILING POINTS

Jena tube was drawn out so that its internal diameter was about
8 mm., its wall being as thin as was consistent with safety. After
drying by heating in a current of air dried by phosphoric oxide, a
bulb of nitrogen trioxide was introduced. A piece of Jena-glass
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rod was placed above the bulb containing the dried liquid so as to
facilitate the fracture of the bulb. The tube was filled with
nitrogen dried by phosphoric oxide, and kept for three months, the
ground joint being protected by a mercury Beal. A t the end of
this time a thermometer was bound t o the thin end of the tube,

and the capillary end of the phosphoric oxide tube was broken
under previously dried mercury. The bulb was broken while the
tube waa surrounded by melting ic0, and no boiling was percepb
ible. The temperature of the bath was allowed t o rise, and the
liquid was found not to boil until a temperature of 43O was
reached. A second experiment indicated a boiling point of 42'5O.
The vapour of the very dry trioxide was red, and on cooling to
+loo it condensed t o the green liquid, which on further cooling
turned bright blue, showing t h a t it was still nitrogen trioxide.
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OF THE TKIOXIDE AND TE'I'ROXIDE OF NITROGEN ON DRYING. 2341

On allowing some nitrogen, dried by passage through a long column

of phosphoric oxide, to enter the tube, the small amount of moisture
it contained caused rapid dissociation, and the resulting sudden
increase of pressure blew out the stopper of the tube.
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A similar experiment was tried with a specimen of nitrogen

tetroxide which had been drying f o r over a year, The amount of
liquid available unfortunately was small, less than 1 C.C. On
raising the temperature the liquid was apparently unchanged a t
2 2 O , the ordinary boiling point. Further heating of the bath
produced evaporation, but a t 6 9 O the liquid was still visible, and
not in a state of ebullition. Above this temperature the liquid,
which wa5 orange-red in colour, disappeared. The pressure in each
of the three experiments was 757 mm.
The explanation of these abnormal boiling points is probably to
be found in thQ difference of complexity in the liquids. It is likely
that the liquid nitrogen trioxide has a more complex molecule
than t h a t represented by the formula N203;in fact, in one of our
former experiments a vapour density was obtained, which indicated
a mixture of three molecules of N40, to one molecule of N,O,
(Trans., 1907, 91, 1862). It may be supposed that a liquid consist-
ing of more complex molecules would have a higher boiling point
than one of simpler constitution, and that the almost complete
absence of water would enable the complex liquid to boil as such.
It is possible that a more complex molecule exists in the liquid
below - 2 O , since a t this temperature a marked change in colour
takes place from olive-green to bright blue, It may be worthy of
remark t h a t a flat bulb containing this liquid, which had been used
to show this change of colour a t the reading of our former paper,
has, during the five years' contact with phosphoric oxide, acquired
a bright Glue colour, which is permanent a t the ordinary tempera-
ture.
Further experiments are in progress to determine the boiling
points of dried liquids, in order t o see if the dissociability of the
vapours is an essential condition for the raising of the boiling
points.

The work was carried out in the laboratory of Christ Church,

Oxford.
IMPERIAL
COLLEGEOF SCIENCEAND TECHNOLOGY,
LONDON, S.W.