The kinetics of the oxidation of gaseous acetaldehyde have been investigated from 60° to 120 °C. by observing the rate of pressure decrease in a system at constant volume. A considerable induction period exists, during which the main products of the reaction are carbon dioxide, water, and formic acid. The main reaction in the subsequent stages involves the formation of peroxides and their oxidation products. The heat of activation of the reaction is 8700 calories per gram molecule. The indications are that the reactions occurring during the induction period are heterogeneous. The subsequent reaction occurs by a chain mechanism. The chains are initiated at the walls of the reaction vessel, and are also largely broken at the walls.
Acetaldehyde, when freshly distilled, suffers immediate oxidation on coming into contact with oxygen or air. A compound is produced which in aqueous solution behaves as an organic peracid. This has a pronounced effect upon the subsequent gas-phase oxidation of the acetaldehyde.
RESEARCHES ON CYCLIC ACETALS. I 217 acids, the value for the second hydrogen of sulfuric acid being 3 X 10~3; for the first constant of oxalic acid, 3.8 X 10"2.6 The very sharp break occurring at the end-point of the curve of the free acid (Fig. 3) lends itself well to the quantitative estimation of the acid. Summary 1.2-Hydroxynaphthalene-6-sulfonic acid has been purified by recrystallization of the acid from aqueous solutions by means of the addition of hydrogen chloride. The identity of a monohydrate and a dihydrate has been established. Melting points for these three compounds have been determined.2. The 2-hydroxynaphthalene sulfonic acids have been studied electrometrically and values determined for their acid dissociation constants. The nature of the curve obtained for the 2-hydroxynaphthalene-6-sulfonic acid shows that the quantitative estimation of the acid or of its salts might be possible in the presence of the isomeric 2-hydroxynaphthalene-l-sulfonic acid, or of neutral salts.
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