Part 6 (1/2)

[2] Ann. chim. phys. (3) 60, 18 (1860).

[3] D. R. P. 180,668; Frdl. 8, 27 (1907); J. Am. Chem. Soc. 42, 2096 (1920).

[4] D. R. P. 197,309; Frdl. 9, 34 (1908).

[1b] D. R. P. 197,308; Frdl. 9, 33 (1908).

[2b] D. R. P. Anm. 23,510; 16,579; Frdl. 9, 36 (1908).

[3b] D. R. P. 201,230; Frdl. 9, 35 (1908).

X

HYDRAZINE SULFATE

2 NH3 + NaOCl--> NH2NH2 + H2O + NaCl

Prepared by ROGER ADAMS and B. K. BROWN. Checked by J. B. CONANT and W. L. HANAWAY.

1. Procedure

A NORMAL solution of sodium hypochlorite is prepared as follows: in a 5-l. round-bottom flask are placed 1800 g. of sodium hydroxide solution (300 g. of sodium hydroxide to 1500 g.

of water) and 1500 g. of ice. Chlorine gas is then pa.s.sed into the solution until it has gained in weight approximately 213 g.

During this addition, the solution must be kept thoroughly cooled with ice, in order that chlorates will not be formed.

After all the chlorine has been pa.s.sed in, it is necessary to be certain that the mixture is slightly alkaline, since any excess of free chlorine in the solution prevents the formation of hydrazine.

In a 14-inch evaporating dish are placed 1500 cc.

of c. p. ammonia water (sp. gr. 0.90), 900 cc. of distilled water, 375 cc. of 10 per cent gelatine solution, and 1200 cc.

of the normal sodium hypochlorite solution prepared as above.

This mixture is heated as rapidly as possible and boiled down until one-third of the original volume is left. This solution is then cooled thoroughly with ice and filtered with suction, first through two layers of toweling and then through one thickness of ordinary filter paper over cloth, in order to remove finely divided solid impurities. The solution is then placed in a precipitating jar, and cooled down thoroughly (0'0) with ice and salt; 10 cc. of concentrated sulfuric acid for each 100 cc.

of solution are gradually added with constant stirring.

A precipitate of hydrazine sulfate (NH2NH2<.>H2SO4) forms.

The mixture is allowed to stand in the cold for a few hours in order to complete the precipitation, and is then filtered by suction in the usual way and washed with cold alcohol. The yield varies from 53 g.

to 58 g. per 1500 cc. of ammonia water (34-37 per cent of the theoretical amount). The product is perfectly white and crystalline, and satisfactory for almost any purpose. If an absolutely pure product is desired, it must be recrystallized from water.

For every 21 g. of crude product, 100 g. of boiling water are used.

If the crude hydrazine is brown, it is advisable to use a little bone-black. After the mixture has been filtered and cooled to 0'0, 19 g.

of pure white crystals are obtained.

2. Notes

In the preparation of the sodium hypochlorite solution it is quite necessary that the mixture be kept cold and be alkaline to red litmus paper at the end of the reaction, if good yields of hydrazine are to be obtained.

Since iron is an anti-catalyzer, it is necesssary{sic} to use distilled water throughout the process.

As a viscolizer, a substance such as starch, glycerol, glue or gelatine may be used; the last, however, gives by far the most satisfactory results.

In order to obtain a pure white hydrazine sulfate as the first precipitate, it is necessary to cool the hydrazine solution thoroughly and filter it twice before the sulfuric acid is added.