Ammonia with ozonides

Ozone forms red-brown potassium ozonide, KO3, by reacting with dry potassium hydroxide. Ozonide is obtained by passing oxygen-ozone mixture containing 6 to 8% ozone over dry KOH at -10 to -15°C for several hours, followed by extraction with liquid ammonia at -60°C. Evaporation of the red solution forms red-brown needles of KO3. 

The Ozonide Ion.—The red crystalline substance potassium ozonide, KO3, is obtained by recrystallizing from liquid ammonia the product of reaction of ozone and potassium hydroxide.47 The corresponding ozonides NaO and CsO hasre been shown48 to have magnetic susceptibility corresponding to the presence of the OjT ion with one odd electron. The electronic structure of the ozonide ion is... 

It was not possible to isolate this from liquid ammonia solution after formation by an exchange reaction with caesium ozonide. It was possible to isolate a cryptand complex, which was violently explosive but permitted diffraction studies. Sodium ozonide behaved similarly, though the other three alkali ozonides do not oxidise ammonia during isolation attempts. 

Ozone reacts with a solution of sodium in liquid ammonia, yielding an orange to brown precipitate. The product is readily decomposed by water or dilute acids with evolution of oxygen. It is possibly an ozonide of sodium, but owing to interaction of the ozone and ammonia 7 it has not been found possible to isolate it in the pure state. Potassium, rubidium, and ejesium react similarly.8... 

The ozonides, MO3, have historically been prepared by the reaction of the metal hydroxide with ozone. They may also be prepared from the respective superoxide (for M = K, Rb, Cs) . They are isolated from the superoxide by filtration in liquid ammonia followed by slow removal of the ammonia through evaporation. The CsOs can then be used to form the Li and Na derivatives by ion exchange in situ. NaOs cannot be isolated in the solid but can, along with the heavier congeners, be isolated (and structurally characterized) as a cryptand complex ([M-cryptJ Os-) . ... 

When the concentration of ozone was less than 1 cc. per liter of mixed gases, 90 per cent yields of fonnaldehyde based on the ozone were obtained. Use of higher concentrations of ozone lowered the yields. In the absence of water, the ozonide decomposes to formic acid and fonnaldehyde but with water present formaldehyde and hydrogen peroxide are formed. With dilute ozone very little secondary oxidation of formaldehyde occurs. The addition of ammonia to the gases raises the yield, probably because it protects the formaldehyde from further oxidation by the fonnation of hexamethylenetetramine. 

Ozonides, MO3, containing the paramagnetic, bent [03] ion (see Section 15.4), are known for all the alkali metals. The salts KO3, Rb03 and CSO3 can be prepared from the peroxides or superoxides by reaction with ozone, but this method fails, or gives low yields, for LiOs and NaOs. These ozonides have recently been prepared in liquid ammonia by the interaction of CSO3 with an ion-exchange resin loaded with either Li or Na ions. The ozonides are violently explosive. 

PLATINUM (7440-06-4) Pt Powdered form is highly reactive catalyst, and may cause fire and explosions on contact with many substances including oxidizers, acetone, strong acids, finely divided aluminum, dioxygen difluoride, ethyl alcohol, hydrazine, hydrogen peroxide, lithium, methyl hydroperoxide, nitrosyl chloride, ozonides, peroxymonosulfliric acid, red phosp] oms. Incompatible with ammonia, arsenic, chlorine dioxide, hydrogen, methyl hydroperoxide, selenium, tellurium, vanadium dichloride. 

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