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Lithium peroxide, Li2O2

Addition of alcohol to the aqueous solution obtained by the interaction of hydrogen peroxide and lithium hydroxide precipitates the crystalline product Li2O2,H2O2,3H2O, a substance converted by drying over phosphoric anhydride into the anhydrous peroxide, Li2O2. The method resembles that employed in the preparation of the peroxides of the alkaline-earth-metals. The combustion of lithium in oxygen yields only a small proportion of peroxide, a distinction from sodium. The peroxide boils at 258° C.

The heat of formation of the peroxide from the monoxide and oxygen is given by the equation

[Li2O]+(O)=[Li2O2]+7.97 Cal.,

the corresponding equations for the peroxides of calcium, strontium, and barium being

[CaO]+(O)=[CaO2]+4.11 Cal.,
[SrO] + (O)=[SrO2] + 13.07 Cal.,
[BaO]+(O) =[BaO2] +18.36 Cal.

In this respect lithium displays close analogy to the alkaline-earth- metals, occupying a position between calcium and strontium. Further analogy is shown by the heat of formation of lithium peroxide from its elements

2[Li] + (O2)=[Li2O2] + 151.29 Cal.,

a value closely approximating to that of calcium peroxide,

[Ca]+(O2) =[CaO2] +150.43 Cal.

Divergence from the other alkali-metals is made evident by the fact that sodium peroxide has a considerably lower heat of formation -

2[Na]+(O2) =[Na2O2] +117.69 Cal.

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