I
Maryland D. Kemp
U.S. Army Engineer Research A Safe Method for Preparation
and Development Laboratories
Fort Belvoir, Virginia of Uncontaminated Hydrazoic Acid
H.s. Booth's "Inorganic Synthesis"' re-
ports that hydrogen azide can be prepared by the reac-
tion of strong sulfuric acid (40 per cent) upon a sodium
aside solution containing sodium hydroxide. Sodium
hydroxide is used as a moderator of the reaction since
hydrazoic acid vapor in high concentrations is spon-
taneously explosive. In the procedute, the solution of
sodium azide and sodium hydroxide colrtained in a
flask connected through a condenser is brought to boil-
ing and the acid is added to the hot boiling solution.
During efforts to make pure aqueous solutions of
hydrazoic acid in connection with the preparation of
some pure alkali metallic azides it was observed that
during the precipitation and crystallization of potas-
sium azide small amounts of potassium sulfate were
always present. Potassium sulfate is less soluble in
water than potassium azide, and during attempts to
grow potassium azide single tetragonal crystals, the
orthorhombic sulfate form was always present.
Sulfuric acid in the preseuce of its salts or more
volatile acids tends to fume a t temperatures much
below the boiling point, or a t about 160°C. During the
addition of the sulfuric acid to the boiling solution in
this procedure, it is obvious that the exothermic reac-
tion between the strong sulfuric acid and the solution
causes premature decomposition of the sulfuric acid,
and fumes carried into the receiving flask are subse-
quently transformed, in this case t o potassium sulfate.
I42 / Journal of Chemical Education
In an effort to eliminate the sulfate contamination
this laboratory has modified the procedures somewhat.
The same reagents are used as the source of the hydra-
zoic acid. The procedure is as follows: A saturated
solution of sodium azide is placed in the round bottom
flask and a stream of nitrogen is allowed to flow through
for a t least thirty minutes. One and ?,f0 times the
required stoichiometric amount of sulfuric acid is added
dropwise, cold, and the mixture heated slowly to boiling
and boiled 5 to 10 minutes. The evolved hydrazoic
acid is received in a flask surrounded with an ice bath.
The yield is almost quantitative, and any dilutions de-
sired in the prepared hydrazoic acid solution are made
by adding water to the receiving fiask. Nitrogen is
allowed to flow through the system during the entire
run although during the boiling it could be dispensed
with. In 40 to 50 preparations of hydrazoic acid not
once did any explosions occur although solutions 75 to
80 per cent in hydrazoic acid were often prepared.
This modification of the procedure eliminates the
hazard of high concentrations of hydrazoic acid in the
vapor phase and also yields a product free of the sulfate
impurity.
' AUDRIETH,L. F., AND GIBBS, C. F., I n o ~ g m i cSynthesis,
McGraw-Hill Book Company, New York, 1939, Val. 1, p.
7"
8 , .
Presented for publication with permission of the Department of
Defense.