Lithium reaction with oxygen

Lithium diphenylphosphide [4S41 -02-2] and related oiganophosphides are chemiluminescent in reaction with oxygen (127). Chemiluminescence is... 

A particularly fundamental chemical difference between lithium and its congeners, attributable to cation size, is the reaction with oxygen. When the metals are burnt in air or oxygen at 1 atm, lithium forms the oxide Li20, with only a trace of Li202, whereas the other alkali oxides (M20) react further, giving as principal products the peroxides M202 and (for K, Rb, and Cs) the superoxides M02. 

Lithium and magnesium exhibit a diagonal relationship in some chemical properties. How does lithium resemble magnesium in its reaction with oxygen and nitrogen Consult a handbook of chemistry and compare the solubilities of carbonates, fluorides, and phosphates of these metals. 

A particularly fundamental chemical difference between lithium and its congeners, attributable to cation size, is the reaction with oxygen. When the... 

The effect of lithium alkoxides on alkyllithium-initiated pol5nnerizations is important because these salts are ubiquitously present to some extent as impurities formed by the reactions with oxygen (13) (eq. 27) and hydroxylic impurities (eq. 28). In fact, it is common practice to utilize excess butyllithium, ie, more than the stoichiometric amount required to generate the required molecular weight, to scavenge impurities in the solvent and monomer feed. 

Reactions of the Hydroxyl Group. The hydroxyl proton of hydroxybenzaldehydes is acidic and reacts with alkahes to form salts. The lithium, sodium, potassium, and copper salts of sahcylaldehyde exist as chelates. The cobalt salt is the most simple oxygen-carrying synthetic chelate compound (33). The stabiUty constants of numerous sahcylaldehyde—metal ion coordination compounds have been measured (34). Both sahcylaldehyde and 4-hydroxybenzaldehyde are readily converted to the corresponding anisaldehyde by reaction with a methyl hahde, methyl sulfate (35—37), or methyl carbonate (38). The reaction shown produces -anisaldehyde [123-11-5] in 93.3% yield. Other ethers can also be made by the use of the appropriate reagent. 

The reaction of hydrogen and lithium readily gives lithium hydride [7580-67-8], LiH, which is stable at temperatures from the melting poiat up to 800°C. Lithium reacts with aitrogea, evea at ordiaary temperatures, to form the reddish browa nitride, Li3N. Lithium bums when heated in oxygen to... 

The concentration dependence of iron corrosion in potassium chloride [7447-40-7] sodium chloride [7647-14-5] and lithium chloride [7447-44-8] solutions is shown in Figure 5 (21). In all three cases there is a maximum in corrosion rate. For NaCl this maximum is at approximately 0.5 Ai (about 3 wt %). Oxygen solubiUty decreases with increasing salt concentration, thus the lower corrosion rate at higher salt concentrations. The initial iacrease in the iron corrosion rate is related to the action of the chloride ion in concert with oxygen. The corrosion rate of iron reaches a maximum at ca 70°C. As for salt concentration, the increased rate of chemical reaction achieved with increased temperature is balanced by a decrease in oxygen solubiUty. 

Most other studies have indicated considerably more complex behavior. The rate data for reaction of 3-methyl-l-phenylbutanone with 5-butyllithium or n-butyllithium in cyclohexane can be fit to a mechanism involving product formation both through a complex of the ketone with alkyllithium aggregate and by reaction with dissociated alkyllithium. Evidence for the initial formation of a complex can be observed in the form of a shift in the carbonyl absorption band in the IR spectrum. Complex formation presumably involves a Lewis acid-Lewis base interaction between the carbonyl oxygen and lithium ions in the alkyllithium cluster. 

The principal product of the reaction of the alkali metals with oxygen varies systematically down the group (Fig. 14.15). Ionic compounds formed from cations and anions of similar radius are commonly found to he more stable than those formed from ions with markedly different radii. Such is the case here. Lithium forms mainly the oxide, Li20. Sodium, which has a larger cation, forms predominantly the very pale yellow sodium peroxide, Na202. Potassium, with an even bigger cation, forms mainly the superoxide, K02, which contains the superoxide ion, O,. ... 

Lithium dialkylcopper reagents can be oxidized to symmetrical dimers by O2 at -78°C in THF. The reaction is successful for R = primary and secondary alkyl, vinylic, or aryl. Other oxidizing agents (e.g., nitrobenzene) can be used instead of O2. Vinylic copper reagents dimerize on treatment with oxygen, or simply on standing at 0°C for several days or at 25°C for several hours, to yield LS-dienes." ... 

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