gTOKES.] 
HIGHER CIILORONITRIDES. 
125 
ties large enough to admit of the isolation of its supposed constituents, 
but a fractional distillation of the few grams at my disposal showed 
that it contained crystalline substances of higher boiling points than 
those of the two bodies thus far known. 
The method of preparation then employed consisted in distilling 
phosphorus peutachloride with a large excess of ammonium chloride 
in a retort, at atmospheric pressure; it offered but little prospect 
of obtaining the higher members. The total yield of phosphoni- 
trilic chloride was but 15 per cent of the theoretical, most of the 
peutachloride being converted into "phospham" by the excess of ammo- 
nium chloride, while only those members could be obtained which dis- 
till unchanged at atmospheric pressure. Decreasing the amount of 
ammonium chloride resulted only in a loss of peutachloride by volatiliza- 
tion, without increasing the yield of the bodies sought after. 
The following method has been found to give entirely satisfactory 
results; several new bodies have been obtained, and the simpler phos- 
phonitrilic chlorides, at least, are now easily accessible substances. If 
equal molecular weights of phosphorus peutachloride and ammonium 
chloride be heated in a sealed tube, there results a mixture of chloro- 
uitrides, which is partly crystalline and soluble in gasoline, but for 
the greater part liquid and insoluble in this solvent, and of a high 
degree of complexity. This may be distilled almost without residue, 
the distillate being a crystalline mass, impregnated witli an oil, and 
composed almost wholly of a mixture of members of the series (PNCl2) n 
in nearly theoretical amount, containing about 50 per cent P 3 N :i 01,;, and 
25 per cent P 4 N 4 C1 8 , the remainder consisting of the higher homologues. 
From this distillate the new bodies, witli one exception, have been 
solated. 
The series, as at present known, consists of the following: 
Triphospkonitrilic chloride, (PNCI>) :! . 
Tetraphosphouitrilic chloride, (PNCl 2 )i. 
Pentaphosplionitrilic chloride, (PNCL).-,. 
Hexaphosphonitrilic chloride, (PNCL),,- 
Heptaphosphonitrilic chloride, (PNCI-Jt- 
Polyphosphouitrilic chloride, (PNC1 2 ) X - 
Melting 
point. 
(Corrected.) 
Boiling point. 
(Corrected.) 
Degrees. 
114 
123. 5 
40.5-41 
91 
Below— 18 
Degrees. 
127 
188 
223-224. 3 
261-263 
289-294 
760 nun. 
Degrees. 
a 256. 5 
&328.5 
Polymerizes 
Polymerizes 
Polymerizes 
Below red Depolj merizes <>n distilla- 
heat. tion. 
a 1*:;.K J at 100 mm. 
h'ln ;il 100 mm. 
There were obtained, further, a liquid residue of the same empirical 
omposition, of a mean molecular weight corresponding nearly to 
