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THE PREPARATION O F CYANAMIDE, ETC. 1325

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XC V 11.-The Prepamtion of Cyunamide j * o m Calcium

@an urnid e.
By EMILALPHONSE
WERNER.
ALLthe methods which have hitherto been recommended for the
preparation of cyanamide from the calcium derivative suffer from
a similar serious dis'advantage. The preliminary stage in every
case leads to the production of a more or less concentrated aqueous
solution of cyanamide, the evaporation of which a t a moderate heat
even in a vacuum is a decidedly tedious operation. This, more-
over, is accompanied by much loss of cyanamide, as a result of
polymerisation, particularly if the solution is allowed t o become
even faintly alkaline (compare Morrell and Burgen, T., 1914, 105,
588, and the author, T., 1915, 107, 720). P o o r yields of
cyanamide, in consequence, have been obtained; thus, from 100
grams of commercial calcium cyanamide a yield of 10 grams of
3 €7"
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1326 THE PREPARATION O F CYANAMIDE, ETC.

cyanamide has been coiisidered a good result. This, as a matter

of fact, is less than half of the theoretical, even from a specimen
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of calcium cyanamide below the average quality.

I n a recent communication (Zoc. c i t . ) i t was shown that,
cyanamide is very stable in the presence of acetic acid, and
advantage has been taken of this in devising a process for its
preparation from the calcium derivative, whereby the tedious
process of evaporation has been completely eliminated and a nearly
theoretical yield of cyanamide easily obtained.
The details of the method may be best described by giving the
results of an actual experiment as carried out with a sample of
crude calcium cyanamide, 1 gram of which was neutralised by
1.2 grams of pure acetic acid. A n assay of the sample showed
t h e presence of the calcium compound in proportion equivalent to
28.8 per cent. of pure cyanamide.
To 125 grams of pure acetic acid, diluted with 120 grams of
water in a large mortar, 100 grams of calcium cyanamide, in por-
tions of about 15 grams, were gradually added with constant
stirring. When about four-fifths of the calcium cyanamide had
been added, the product was a rather thick, pasty mass; it was
necessary a t this stage t o use a pestle in order t o secure thorough
mixing when the last portions of the calcium cyanamide were
added.
Throughout this operation, which occupied about thirty-five
minutes, the temperature did not rise above 55O, and external cool-
ing, by standing the mortar in cold water, was found quite
sufficient.
After the pasty ma'terial had been well kneaded, and the calcium
cyanamide thoroughly neutralised, the product was allowed to
remain exposed to the air for twenty-four hours, a t the end of
which time it had become a friable and easily pulverisable solid.
The coarsely powdered product was transferred to a Soxhlet
apparatus, and extracted six o r seven times with ether in the usual
manner. The ether extract, which was almost colourless, was con-
centrated by distillation a t a gentle heat, and finally evaporated
to dryness in a desiccator over sodium hydroxide.
The weight of cyanamide obtained was 27.2 grams, a yield equal
t o 94.4 per cent. of the theoretical.
I n another experiment, fro'm 100 grams of a sample of calcium
cyanamide which contained 25.2 per cent. of available cyanamide,
24.1 grams were obtained, equal to 95.6 per cent .of the theoretical.
Whilst the assay of the calcium cyanamide is not a necessary
part of the process, the following points must be carefully observed
in order to secure a successful result.
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THEORY OF VEGETABLE TANNING. 1327

Having accurately determined the iieutralisiiig power of the

calcium cyanamide towards acetic acid, a small excess of the latter
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should be taken in order to ensure t h a t the product, before extrac-

tion with ether, shall be faintly acid throughout. If the pasty
mass, as the result of imperfect mixing, be allowed t o remain
alkaline in parts, the ether will be found to extract a dark brown
colouring matter (derived from the carbonaceous material present
in crude calcium cyanamide), the removal of which is very trouble-
some and entails much loss of cyanamide. Should the pasty pro-
duct, after exposure to air for the stated period, fail to' have
assumed a sufficiently dry condition suitable for extraction with
ether, this can be remedied by the addition of powdered pumice,
or, better still, of coarsely powdered anhydrous sodium acetate.
A very good yield of cyanamide has also been obtained from the
sodium derivative in a similar manner.
UNIVERSITY
CHEMICALLABORATORY,
TRINITYCOLLEGE,
DUBLIN. [Received, November 'ith, 1916.1