Alkali metal ozonides

The stability of the alkali metal ozonides increases from Li to Cs alkaline-earth ozonides exhibit a similar stability pattern. Reaction of metal ozonides with water proceeds through the intermediate formation of hydroxyl radicals. 

Petrocelli, A. W. et al., J. Chem. Educ., 1962, 39, 557 This is the least stable of the alkali-metal ozonides. 

Complexes of alkali metal ozonides with cryptand[2.2.2] and various crown ethers have been prepared in order to increase the solubility range of these compounds in solvents other than NH3. The first structural analysis reported for such complexes was that of ([18-crown-6]Rb)03 NH3 (334), carried out by single-crystal XRD. The Rb+ cation is part of... 

IR spectrophotometry, 661, 662 TEARS assay, 667 hydroperoxide oxidation, 692 Upid hydroperoxides, 977-8 decomposition, 669 DNA adducts, 978-84 protein adducts, 984-5 ozone adducts, 734 ozonide reduction, 726 ozonization characterization, 737, 739 peroxydisulfate reactions, 1013, 1018 Alkali metal ozonides, 735-7 Alkaline peroxide process, pulp and paper bleaching, 623... 

The deep red ozonide ion has a bent structure, and sodium ozonide is isostructural with sodium nitrite (NaNC>2). The X-ray structural data of the alkali metal ozonides show that an increase in cationic size corresponds to a decrease in 0-0 bond length and an increase in 0-0-0 angle, as summarized in the following table ... 

The ozonide subsequently reacts with water to give KOH(aq) and 02(g). By using other methods of preparation, it has been possible to prepare other alkali metal ozonides. However, the stability of these ozonides decreases as the size of the metal cation decreases because, as discussed in Chapter 21, a large polarizable anion, such as Os , is not particularly stable in the presence of small, highly polarizing cations. 

In addition to the oxides MO, peroxides MO2 are known for the heavier alkaline earth metals and there is some evidence for yellow superoxides M(02)2 of Ca, Sr and Ba impure ozonides Ca(03)2 and Ba(03)2 have also been reported. As with the alkali metals, stability... 

Alkali metals can form ozonides, and an ozonide is formed when 03 is bubbled into liquid NH3. Although such ozonides have theoretical interest, their instability makes their practical use in rocketry also appear remote. 

Why do some of the alkali metals form oxides, while others form peroxides when they burn in the air How does the stability of the alkali metal oxides and peroxides change (from lithium to cesium) when heated Why is the formation of peroxides and also of ozonides the most characteristic of the alkali metals ... 

O3" Ozonide 134 Formed from reaction of O3 with dry alkali metal hydroxides, decomposes to Oa ... 

The isolation and study of triatomic radical anions is also a matter of considerable interest. The ozonide ion has been successfully studied as alkali metal salts in an argon matrix (74) and the S3 ion as a substitutional species in a sodium chloride crystal as host 69,75). The latter species has also been identified by resonance Raman studies as the one responsible for the blue colour of ultramarine blue and lapis lazuli (70). Sulphur also forms deep blue solutions under certain circumstances in many other media (e.g. hexamethylphosphoramide and dimethylformamide), and it is unquestionably the S3 ion which is the species responsible for the colour in these cases also. 

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. 

W. Hesse, M. Jansen and W. Schnick (1989) Progress in Solid State Chemistry, vol. 19, p. 47 - A review of alkali metal oxides, peroxides, superoxides and ozonides. 

Potassium ozonide, KO3 (formed in reaction 15.14), is an unstable red salt which contains the paramagnetic [03] ion (Figure 15.4). Ozonide salts are known for all the alkali metals. The compounds [Me4N][03] and [Et4N][03] have been prepared using reactions of the type shown in equation 15.15. Ozonides are explosive, but [Me4N][03] is relatively stable, decomposing above 348 K (see also Sections 10.6 and 10.8). 

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