The O-O bond length in the peroxide is about 1.45 |, and the R-O-O angle (R=H, C) is about 110 ° (water like). Typically, the dihedral angle of C-O-O-H is about 120 °. The O-O bond is relatively weak, and the bond dissociation energy is 45-50 kcal/mol (190-210 kJ/mol), less than half of the strength of C-C, C-H and C-O bonds. Hydroperoxide is usually more volatile than the corresponding alcohol:

Tert butyl alcohol (bp36 ° C) and tert butyl alcohol (bp82-83 ° C)

CH3OOH (bp46 ° C) and CH3OH (bp65 ° C)

Isopropylbenzene hydroperoxide (bp153 ° C) and isopropanol (bp202 ° C)

Hydroperoxide is weakly acidic. The range is represented by 11.5 of CH3OOH to 13.1 of Ph3COOH. Hydroperoxide can be reduced to alcohol by lithium aluminum hydride, as described in the following idealized equation: 4ROOH+LiAlH4 → LiAlO2+2H2O+4ROH This reaction is the basis of organic peroxide analysis method. Another method of evaluating the content of peracid and peroxide is volumetric titration with alkoxide such as sodium ethoxide. Phosphite ester and tertiary phosphine also play a reducing role: ROOH+PR3 → OPR3+ROH

Leave a Reply

Your email address will not be published. Required fields are marked *