SUBLIMATION

G . Ross ROBERT~ON, OF CALIFORNIA

UNIVERSITY AT LOSANOELES

The process of sublimation affords one of the neatest methods of purijying a

crystalline chemical preparation. A few substances have vapor pressures as
high as 760 mm. in the solid state, and are easily sublimed. A number of
others must be specially treated, as by dilution of heated vapor with air, to
permit sublimation m'thout distillation. To illustrate these cases hexachloro-
ethane and naphthalene may be sublimed in beakers and Aasks for lecture
demonstration. Anthracene i s sublimed in a student experiment involving
suction of diluted vapors through a funnel. Benzoic acid i s sublimed from a
retort into a cloth bag with the aid of refrigerated air.
. . . . . .
One of the most elegant methods of purification is that of sublimation.
Unfortunately, its elegance is not always attended with practical laboratory
efficiency. In the laboratory one usually does little more than play with
sublimation-perhaps with a watch glass as apparatus. Nobody expects a
yield of any consequence.
Orthodox Sublimation
Strictly interpreted, purification by sublimation first calls for the direct
vaporization of a solid without intervention of the liquid state. Next
follows a direct return from vapof- to solid, again without liquid. In many
cases, however, it is convenient to melt a solid, boil the resulting liquid,
and then return the vapor to the solid form wjthout passage through the
liquid state. This modification often expedites matters, and for practical
purposes gives the sort of purification desired.
A sublimed crystalline preparation is normally purer than a distilled
product because there is no liquid to extract impurities from the vapors
in the cooling chamber. The newly deposited crystals do not dissolve the
gaseous impurities to a significant extent. The partial vapor pressures of
these gaseous impurities, while sufficient to cause them to dissolve in a
liquid condensate, are insufficient to permit the formation of a new in-
dependent phase, either liquid or solid. Accordingly the undesired impuri-
ties escape from the field of the subliming crystals and are eliminated.
Only a second solid of high volatility and large amount would come over
and stay with the sublimate being collected. The chances of such an
occurrence are slight, since but few substances may be sublimed anyway.
Simple lecture demonstrations serve to illustrate the theory of sub-
limation. Hexachloroethaneand naphthalene. two inexpensive substances,
may be used.
Hexachloroethane, C&ls
This unusual compound' attains a vapor pressure of about 760 mm. at
1 STABDBL, .
Ber 11, 1736 (1878).
1713
1714 JOURNAL OF CHEMICAL EDUCATION OCTOBER,
1932

185", two degrees below its melting point. For an organic compound this is
remarkable behavior. Naturally i t affords an ideal set-up for sublimation,
as represented in the phase diagram of Figure 1. In this diagram, as well as
Figure 2, scales are some-
what distorted to bring
out the principles involved.
LIQUID A few grams of pure
hexachloroethane a r e
placed in a large conical
flask and strongly heated
SOLID over a flame. As the tem-
7 perature reaches 185", the
VAPOR cryst5.1~appear to be rest-
less and stir about. Thev
shrink in size but do not
185 187" TEMP melt. The escapingvapor,
FIGURE SUBLIMATION OF HEXACHLOROBTHANE
reaching the cool walls of
the flask, deposits a white crystalline sublimate which sticks to the vessel.
The original pile of crystals on the bottom vanishes.
In this case the vapor, slightly superheated but a t the fixed pressure of
one atmosphere, is cooled along the line AX. At X the substance passes
largely to the solid state, missing the liquid field entirely. Finally, after
complete sublimation the temperature will have fallen to B, the final tem-
perature of the receiver, virtually room temperature.
Naphthalene
The sublimation of this hydrocarbon presents more difficulties, but is
more typical of common
practice. N a p h t h a l e n e
has a vapor pressure of
but 7 mm. a t 80°, its
B
melting point. Naturally,
its boiling point is high 'P.
M M.
(218O) and distillation is
easier than sublimation.
Dired cooling of the pure
vapor, prepared a t 760
7.
mm. pressure and 2N0,
causes most of the material 80' 2W
condense to liquid, as Frcuns ~ . S U B L ~ T IOPONAPHTHALENE
N
suggested by the traversal
of the continuous line BM, Figure 2. At 80° sublimation begins, and
a small, unsatisfactory yield of sublimate is obtained over the path MY.
Vor. 8. No. I n SUBLIMATION 1715

Most of the product is in the form of a compact cake of frozen distiiate in

which volatile impurities may easily be occluded.
Suppose, however, that we insist on subliming the whole available
supply of naphthalene with complete avoidance of distillation. I n graphic
terms, we must steer the lower dotted course BX, which lies wholly within
the vapor field. As the point X is reached, sublimation occurs. It only
remains t o be shown how practically to follow BX rather than BM.
Plainly the reduction in pressure must be specially promoted. I t must
outrun reduction in temperature in order that the line BM may be escaped.
This is simply illustrated on the lecture table by boiling a few grams of
naphthalene in a large beaker. A round-bottomed flask, containing cold
water, is allowed to rest over the mouth of the beaker. The temperature
at the bottom of the beaker is of course 21g0, and the vapor pressure 760
mm. As would be expected, more or less reflux distillation will occur in the
lower half of the beaker; with this we are not concerned. A part of the
vapor, escaping the distillation, rises, and is both diluted and cooled with
air. Most important is the fact that it is diluted rapidly until its partial
pressure falls below 7 mm. The vapor now strikes the cold surface of the
flask, where it deposits beautiful snowlike crystals.
Limited Field for Sublimation
Comparatively few substances exert sufficientvapor pressure below the
melting point to permit effective sublimation. Striking contrasts are
noted in the accompanying table.
TABLE I E
V o m Pressure
Suhiloncr ot Mclling Poi", Dlrlling Poiel
Carbon Dioxide 5 . 1 atm. - 57O
Acetylene 1 . 2 atm. - 81.5"
Hexachloroethane 800 mm. 187"
Phosphoorus pentachloride ca. 1 atm. 166"
Camphor 370 mm. 179"
Nitrogen 96 mm. -210"
Iodine 90 mm. 114'
Ammonia 45 mm. - 78"
Benzene 36 mm. 5.5"
Naphthalene 7 mm. 80"
Benzoie Acid 6 mm. 121"
Water 4.58 mm. 0"
Bromine 0.44 mm. - 7"
Zinc 0.15 mm. 419"
Sulfur 0.03 mm. 119"
p-Nitrobenzaldehyde 0.01 mm. 106'
Toluene 0.001 mm. - 95"
Mercury 0.000001 mm. - 39"
The high position of carbon dioxide in the above list is illustrated in the
convenient dryness of "dry-ice." The vapor pressure of solid carbon di-
1716 JOURNAL OF CHEMICAL EDUCATION . O c r o ~ s n 1932
,

oxide is so great that the substance never gets warm enough to melt, ex-
cept in storage under pressure. In the open evaporation keeps it solid
until the supply vanishes.
Subliming Point
For the unusual substance like carbon dioxide or hexachloroethane one
may record a "subliming point" in likeness to the familiar boiling point of a
liquid. Naturally such would be the temperature a t which the vapor
pressure reaches 760 mm. As in simple boiling, the vapor threatens to
push the atmosphere away.
For other cases one finds questionable statements in the literature.
For example, a certain substance "sublimes a t 200 degrees," according to
printed authority, when it is well known that the .vapor pressure of the
solid phase never approaches 760 mm. The citation probably means that
one must raise the temperature of the substance to 200' before enough
sublimation occurs to be noticeable. There is of course no fixed point of
sublimation in such a case.

Rapid Crystallization
The ability to form crystals rapidly is intimately connected with effec-
tive sublimation. Apparently simple symmetrical molecules such as
benzene, naphthalene, anthracene, and even water are thus enabled to
form beautiful crystalline sublimates even at their rather low vapor pres-
sures in the solid state. E
Although common ice has a maximum vapor pressure under normal
conditions of but 4.58 mm., Nature practices its sublimation readily in the
familiar form of a snowstorm. When the temperature falls too fast,
and the partial pressure is too great (humid air) the line BM as of Figure 2
is encountered, and hail eventually reaches the earth. The product is of
course largely frozen distillate.
Other phases of sublimation are discussed a t lengtb by Kempfa and
Lassar-Cohn.3 These authorities describe ingenious apparatus employed
in sublimation, including research equipment for vacuum sublimation.

Student Laboratory Experiment

Anthracene is one of the best substances for student practice, prefer-
ably conducted in the elementary organic laboratory. The student is
provided with a cheap, impure grade of the hydrocarbon readily obtainable
in the market. Purified anthracene is prepared first, and i t is then con-
* KEMW,"Die Methoden der Organischen Chemie," by HOWEN,Thieme, Leipzig,
3rd edition, Vol. 1, p. 663.
a L~ssnn- con^, "Organic Laboratory Methods," qiilliams and Wilkins Co.,
Baltimore, 1928, p. 373.
VOL.9, NO. 10 SUBLIMATION 1717

verted into anthraquinone by a standard method much like that of F i ~ h e r . ~

The anthraqui'none in turn is sublimed.
The sublimation of anthracene, ordinarily a tedious process, is simply
accomplished by the method of T. W. Deakers, student in this laboratory:
Three to 4 grams of anthracene are placed in a 400-cc. beaker which stands
over a wire gauze. The beaker is covered with a piece of stiff card, or
asbestos paper, about 15 cm. square, which has a central circular opening
about 2 to 3 cm. in diameter. A piece of filter paper, slightly oversize, is
wedged tightly against the perforated plate of a common Biichner funnel.
The funnel is inverted over the beaker and card, and is connected by rubber
hose to the suction service or aspirator. It should be held securely in
position with the aid of a clamp.
Gentle suction now draws air from the beaker through the filter paper.
When the anthracene is strongly heated, its vapors, highly diluted within-
rushing air, pass freely into the funnel used as subliming chamber. A
beautiful cream-white mass of sublimate is collected ready for the oxidation
experiment normally following.
Preparation of Sublimates in Quantity
Genuine sublimation of an ordinary organic compound, whose vapor pres-
sure in the solid state seldom reaches 10 mm., is bound to be slow. We
may then resort to "pseudo-sublimation," using the apparatus of Figure 3.
A small current of ordi-
nary compressed air passes
into the retort, blowing
upon the surface of the
melted substance under-
going purification. A sec-
ond current, of larger vol-
ume, is iirst chilled by
passage through a copper
FIGURE 3
tube coil immersed in ice
water. Both supplies of air pass into a wide-mouthed bottle, the bottom
of which has been cut off. A common flour or sugar bag is tied over the
opening. Cotton batting or cheesecloth is stuffed into the spaces beside
the two entering tubes to prevent leakage backward.
The substance in the retort never boils, but is kept a t a temperature
so high that it may have a vapor pressure of perhaps 100 mm., varied as
practice warrants. The aerated vapor, blown out into the bag, tends to
condense into a mist. The mist of course is finely divided liquid, and the
process so far is really distillation. Before the liquid has time to aggre-
"FISHER, ''Laboratory Manual of Organic Chemistry," John Wiley and Sons. Inc.,
New York City, 1931, p. 220.
1718 JOURNAL OF CHEMICAL EDIJCATION OCTOBER,1932

gate, i t mixes with the turbulent stream of chilled air. Each droplet of
mist freezes promptly. As a result a fluffy crystalline product collects
in the bag. It is retrieved much like dust from a vacuum cleaner. Per-
sons working during severe winter weather should be able to modify the
above procedure to advantage by pumping air from outdoors.
Despite the formation of liquid mist, i t is probable that pseudo-sublima-
tion gives nearly as pure a product as genuine sublimation. To be sure,
the individual liquid droplet, in rough conformity with Henry's law, would
absorb for the moment any volatile impurity which accompanied the
preparation from the retort. As the droplet freezes, however, i t forms so
small a crystal, or so simple a cluster of crystals, that the volatile impurity
is quickly squeezed out and blows away.
The loose structure of the cotton bag permits a few crystals to get away
a t first, but the pores in the fabric are soon choked. Such losses are
sufficient,however, to necessitate the use of a hood in the process.
Naphthalene is readily "sublimed" in quantity by this process, the
material in the retort being heated to about 140'. Benzoic acid is handled
with like facility a t about 170". With iodine--probably because of its
high vapor pressure a t room temperatures-serious losses occur.
It is suspected that some of the so-called sublimates of commerce are
really products of the frozen mist process. Substances as zinc, v. p. 0.15
mm., and sulfur, v. p. 0.03 mm., could hardly be produced in quantity if a
vapor must be reduced to such rarity before deposition of product were
allowed. Although zinc dust and flowers,of sulfur are often called subli-
mates, they may actually deserve another designation. Substances such as
iodine and arsenic, however, may readily come into commercial form as
genuine sublimates in conformity with their catalog designations.
Steam Sublimation
When the melting point of a substance exceeds 100°, but where the
vapor pressure is appreciable at 100" (e. g., iodine and quinone), sublima-
tion in steam may be employed. When steam is passed through liquid
iodine, a mixture of the two substances passes to a condenser, where prac-
tically the entire quantity of iodine must sublime, since the entire quantity
of steam condenses. Thus losses caused by the escape of a non-condens-
able gas like air are avoided. Unfortunately, the resulting product not
only does not have a beautiful appearance, but moreover has to be dried.
The drying process of course raises problems with a volatile solid.
In semitropical states an interesting project for high-school students
is available in the recovery of camphor from camphor leaves by steam
sublimation. In California the camphor is a common street tree. Steam
is passed through a five-gallon can full of leaves, the fresh young spring
growth being taken. A beautiful, glistening, highly aromatic sublimate is
collected in an ordinary Liebig condenser.