The following crystalline nitronium salts have been prepared in a pure state : (1) nitronium perchlorate, (NOa+) (ClO,-) ; (2) nitronium hydrogen disulphate, (SO2+) (HS,O,-) ; (3) nitronium disulphate, (NO,+),(S,O ,--) : (4) nitronium trisulphate, (X02+)?(S3010--) : and (5) nitronium fluorosulphonate, (NO,+) (FSO,-). The assigned ionic constitutions are spectroscopically established (MiIlen) in examples ( l ) , (2), (3). and ( 5 ) , while the constitution of salt (4)is assumed by analogy. (6) Crystalline dinitrogen pentoxide, which is nitronium nitrate, (SO2+) (KO3-) (Ingold, Millen, and Poole), belongs t o the series, its structure having likewise been spectroscopically established (Ch6din ; Millen). Nitronium polyselenates have been obtained, but only as mixtures. Nitronium hydrogen sulphate probably has temporary existence as a solid, but i t could not be prepared in a pure form, because it passed into nitronium hydrogen disulphate. Nitronium chlorosulphonate could not be obtained, because i t decomposed t o give nitryl chloride, providing a new route t o the preparation of that substance.Hantzsch's work on the preparation of the alleged salts (H,NO$)(ClO,-) and (H3N03++) (C1O4-)*, from nitric acid and perchloric acid, could not be repeated. The following reactions were elucidated in which nitronium perchlorate is formed :Nitronium hydrogen disulphate was prepared by treating nitric acid with more than two molecular proportions of sulphur trioxide in nitromethane solution, from which the salt crystallised :The same salt resulted from all attempts to prepare nitronium hydrogen sulphate, apparently because the ions of this salt interact reversibly, 2 (NO2+) (HSO,-) =+ (NO,+) (HS,O,-) + HNO, HNO3 + 2S0, = (NO,+)(HSaO,-)Normal nitronium disulphate was also produced in the reaction between nitric acid and sulphur trioxide, but i t could not thus be obtained free from the hydrogen disulphate. It was prepared in a pure form by treating dinitrogen pentoxide with less than two molecules of sulphur trioxide : N,05 + 2SO, = (NO$),(S,O,--) Normal nitronium trisulphate was obtained in a pure state when dinitrogen pentoxide was treated with more than three molecular proportions of sulphur trioxide : N,O, + 3% = lo--^ KO more than three molecules of sulphur trioxide could be induced to enter into reaction with dinitrogen pentoxide. The existence of Pictet and Karl's allegedly stable compound, pLT,O5,4S0,, could not be confirmed.Nitronium fluorosulphonate was prepared from dinitrogen pentoxide and fluorosulphonic acid. Since dinitrogen pentoxide is nitronium nitrate, this reaction may be regarded as a simple anion exchange : N,O, + F*SO,H = (NO,+)(F*SO,-) + HNO, The corresponding reaction with chlorosulphonic acid did not yield nitronium chlorosulphonate, apparently because the ions of this salt interact, t o give nitryl chloride and nitronium hydrogen disulphate : (NOf) (Cl*SO,-) + HNO, = N0,Cl + (NO$) (HS0,-j 2(NO,+) (HSO,-) = (NO,+) (HS,O,-) + HNO, NZO, + CI*SO,H = (NOa+)(Cl*SO,-) + HNO, Chlorine and dinitrogen tetroxide ...

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Nitryl chloride, NO,Cl, was prepared by Dachlaucher's method as a pale yellow liquid, b. p. -14~3"~ m. p. -141" f 2". Gaseous nitryl chloride decomposes a t room temperature very slowly. The alkaline hydrolysis of nitryl chloride to hypochlorite and nitrite was confirmed. The nature of nitryl chloride in various organic solvents was studied as a preliminary to examining its reactions with organic compounds. Its solutions in less polar solvents are colourless, and those in polar solvents are yellow, the latter owing their colour to nitrosyl chloride and chlorine, formed by the hydrolysis of nitryl chloride by traces of moisture in these solvents. It also reacts with hydrogen chloride.