复旦大学 无机化学IC11.pptVIP

2.3 Oxides, Peroxides, Superoxides, Ozonides and Suboxides of Alkali Metals The alkali metals form a fascinating variety of binary compounds with oxygen, the most versatile being Cs which forms 9 compounds with stoichiometries ranging from Cs7O to CsO3. When the metals are burned in a free supply of air the predominant product depends on the metal: Li forms the oxide Li2O (plus some Li2O2), Na forms the peroxide Na2O2 (plus some Na2O), whilst K, Rb, and Cs form the superoxide MO2. Under the appropriate conditions pure compounds M2O, M2O2 and MO2 can be prepared for all five metals. 2.3.1 Oxides Pure Li2O is best prepared by thermal decomposition of Li2O2: Li2O2 Li2O + ? O2 M2O (Na, K, Rb, Cs) is obtained by reaction of M2O2, MOH, or preferably MNO2 with the M metal: M2O2 + 2M 2M2O MOH + M M2O + ? H2 MNO2 + 3M 2M2O + ? N2 Li2O, Na2O pure white K2O yellowish white Rb2O bright yellow Cs2O orange The oxides M2O (Li, Na, K, Rb) have the antifluorite structures as do many of the corresponding sulfides, selenides, and tellurides. This structure is related to the CaF2 structure but with the sites occupied by the cations and anions interchanged so that M replaces F and O replaces Ca in the structure. Cs2O has the anti-CdCl2 layer structure. 2.3.2 Peroxides The peroxides M2O2 contain the perodide ion O22- which is isoelectronic with F2. Li2O2 is prepared industrially by the reaction of LiOH.H2O with hydrogen peroxide, followed by dehydration of the hydroperoxide by gentle heating under reduced pressure: LiOH.H2O + H2O2 LiOOH.H2O +H2O LiOOH.H2O Li2O2 + H2O2 + 2H2O (white) Na2O2 is prepared as pale-yellow powder by first oxidizing Na to Na2O in a limited supply of dry oxygen and then reacting this further to give Na2O2: 2Na + ? O2 Na2O Na2O2 Preparation of pure K2O2, Rb2O2, an