Persulfate decomposition mechanisms

A number of mechanisms for thermal decomposition of persulfate in neutral aqueous solution have been proposed.232 They include unimolccular decomposition (Scheme 3.40) and various bimolecular pathways for the disappearance of persulfate involving a water molecule and concomitant formation of hydroxy radicals (Scheme 3.41). The formation of polymers with negligible hydroxy end groups is evidence that the unimolecular process dominates in neutral solution. Heterolytic pathways for persulfate decomposition can he important in acidic media. 

The ethylenediamine derivative [31] possesses higher promoting activities than other diamines. This phenomenon may be ascribed to the copromoting effect of the two amino groups on the decomposition of persulfate through a CCT (contact charge transfer complex) formation. So we proposed the initiation mechanism via CCT as the intimate ion pair and deprotonation via CTS (cyclic transition state) as follows ... 

MMA onto cellulose was carried out by Hecker de Carvalho and Alfred using ammonium and potassium persulfates as radical initiators [30]. Radical initiators such as H2O2, BPO dicumylperoxide, TBHP, etc. have also been used successfully for grafting vinyl monomers onto hydrocarbon backbones, such as polypropylene and polyethylene. The general mechanism seems to be that when the polymer is exposed to vinyl monomers in the presence of peroxide under conditions that permit decomposition of the peroxide to free radicals, the monomer becomes attached to the backbone of the polymer and pendant chains of vinyl monomers are grown on the active sites. The basic mechanism involves abstraction of a hydrogen from the polymer to form a free radical to which monomer adds ... 

The activation of persulfates by various reductant viz. metals, oxidizable metals, metal complexes, salts of various oxyacid of sulfur, hydroxylamine, hydrazine, thiol, polyhydric phenols, etc. has been reported [36-38]. Bertlett and Colman [39] investigated the effect of methanol on the decomposition of persulfates and proposed the following mechanism. 

In the derivation of the kinetic relations it was assumed that free radicals enter the particles one by one the initiation process just described satisfies this condition. This is not the case when radicals are formed by thermal decomposition of an oil-soluble initiator. Such decomposition produces pairs of radicals in the hydrocarbon phase. One would expect a pair of radicals, confined to the extremely small volume of a latex particle, to recombine rapidly. The kinetics of this type of polymerization have been described above. It is recalled here that the subdivision factor, z, and hence rate and degree of polymerization are smaller than 1 and decrease with a. These predictions from kinetic theory are in contradiction to experimental observations. Although some oil-soluble initiators, which are good catalysts in solution systems, are poor initiators in emulsion polymerizations—e.g., benzoyl peroxide—other thermally decomposing peroxides and azo compounds produce polymer in emulsion at rates comparable to those observed in polymerization initiated by water-soluble catalysts, where the radicals enter the particles one by one. Such is the case for cumene hydroperoxide, which at low concentrations yields a rate of polymerization per particle equal to that of a persulfate-initiated reaction. It must therefore be concluded that, although oil-soluble initiators may decompose into radical pairs within the particles, polymer radicals are formed one by one. The following mechanisms are consistent with formation of polymer radicals singly. 

Chemiluminescence of the uranium is observed not only in solution but also in the solid phase. For instance, solid-phase decomposition of the uranyl or europium (III) persulfate leads to the formation of U02 in excited state by energy transfer mechanism, whereas electron transfer is responsible for the uranyl ion excitation (through the intermediary uranium (V)) in the oxidation of U(S04)2 by XeFj. 

Vinyl acetate polymerizes by a free-radical mechanism. Free radicals generated by the decomposition of organic peroxides such as benzoyl or hydrogen peroxide or of inorganic per salts such as potassium or ammonium persulfate are commonly used to initiate polymerization. Reactions ordinarily are accomplished at temperatures above room temperature. Other techniques of polymerization have been used to make novel products low temperature redox polymerization, irradiation, and ionic catalysis. 

Sahoo and Mohapatra [66] studied the catalytic effect of the in situ developed Cu(II)-EDTA complex with ammonium persulfate on the surfactant-free emulsionpolymerization of methyl methacrylate. The rate ofpolymerization at 50 °C is proportional to the concentrations of Cu(II), EDTA, ammonium persulfate, and methyl methacrylate to the 0.35, 0.69, 0.57, and 0.75 powers, respectively. In addition, the apparent activation energy and activation energies of the initiator decomposition, propagation, and termination reactions, respectively, are 34.5,26.9,29, and 16 kJ mol. It was proposed that the complex just acts as an effective surfactant in stabilizing the polymethyl methacrylate nanoparticles nucleated during polymerization. Independent experiments are required to verify this speculation and clarify the related stabilization mechanism. 

The thermal decomposition of persulfate produces both sulfate and hydroxyl radicals, according to the mechanism ... 

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