Diacyl peroxides determination

Work on the deflagration hazards of organic peroxides has been done using a revised Time-Pressure test, to determine the characteristics of ignition sensitivity and violence of deflagration. Some correlation is evident between these characteristics and the AO content within each structurally based peroxide type. Also, for the same AO content, the nature of the characteristics appears to decrease hi the order diacyl peroxides, peroxyesters, dialkyl peroxides, alkylhydroperoxides [18],... 

The RP-HPLC method based on the CL reaction of luminol (124) catalyzed by Co(II) (Section in.B.2.c) can be applied for determination of peroxycarboxylic acids, esters and diacyl peroxides (see examples of LOD in equation 67, Section V.B.2.c) . The biosensor prepared according to equation 70, that is effective in the determination of hydroperoxides (Section V.B.6.b), becomes deactivated after three days of operation when trying to determine t-butyl peracetate. ... 

The mimetic biosensor for ELD described in Section ni.B.4.b, incorporating polymerized Fe-protoporphyrin IX (75c) and Os(II) ions, can be used for determination of diacyl peroxides in organic solution. The electrode was tested for determination of BzOOBz extracted from a pharmaceutical geP. ... 

Diacyl Peroxides. Table 3 lists several commercial diacyl peroxides and their corresponding 10-h half-life temperatures, determined in benzene and other solvents (32). Although diacyl peroxides cleave at the oxygen—oxygen bond, decarboxylation can occur, either simultaneously or subsequently (eq. 22) ... 

In a series of papers in the early 1980s, Sokolov s group reported relative rate studies which were similar in nature to those of the early Szwarc studies. Sokolov generated various perfluoroalkyl radicals via thermal decomposition of the respective perfluoro diacyl peroxides in heptane containing various olefins [89] or arenes [90]. Determination of the ratio of olefin addition products to hydrogen abstraction products provided the relative rate data given in Table 4 [89]. 

For the past ten years we have been using free-radical systems to study the chemistry of organic solids. This work originated with studies of the photolysis of solid azoalkanes in P. D. Bartlett s laboratory at Harvard. U,2 ) Much of our effort has been devoted to epr spectroscopy of radical pairs generated in low concentration by photolyzing single crystals of such standard radical initiators as azoalkanes and diacyl peroxides. In several cases this tool has allowed us to determine where molecules in a solid move during chemical reaction and how easily they move. (3 )... 

---