Methyl hydroperoxide hydrogen peroxide determination

Henry s law constants, 698 hydrogen peroxide determination, 629, 638 hydroperoxide determination, 678 Al-Ethyl-Al-(2-hydroxy-3-sulfopropyl)-3,5-dimethoxyanUine, 632, 634 Al-Ethyl-Al -methyl imidazohum (emim), transition metal peroxides, 1083 Ethyl plakortide Z, namral occurrence, 610... 

Lind, J.A. and Kok, G.L. Henry s law determination for aqueous solutions of hydrogen peroxide, methyl hydroperoxide, and peroxyacetic acid, J. Geophys. Res., 91(D7) 7889-7895, 1986. 

Disproportionation reaction 7 might be expected to be thermoneutral in the gas phase and perhaps less so in the liquid phase where there is the possibility of hydrogen-bonding. Only for gas phase dimethyl peroxide is the prediction true, where the reaction enthalpy is —0.2 kJmoD. The liquid phase enthalpy of reaction is the incredible —61.5 kJmoD. Of course, we have expressed some doubt about the accuracy of the enthalpy of formation of methyl hydroperoxide. For teri-butyl cumyl peroxide, the prediction for thermoneutrality is in error by about 6 kJmor in the gas phase and by ca 9 kJmoD for the liquid. The enthalpy of reaction deviation from prediction increases slightly for tert-butyl peroxide — 14kJmol for the gas phase, which is virtually the same result as in the liquid phase, — 19kJmol . The reaction enthalpy is calculated to be far from neutrality for 2-fert-butylperoxy-2-methylhex-5-en-3-yne. The enthalpies of reaction are —86.1 kJmoD (g) and —91.5 kJmol (Iq). This same species showed discrepant behavior for reaction 6. Nevertheless, still assuming thermoneutrality for conversion of diethyl peroxide to ethyl hydroperoxide in reaction 7, the derived enthalpies of formation for ethyl hydroperoxide are —206 kJmoD (Iq) and —164 kJmoD (g). The liquid phase estimated value for ethyl hydroperoxide is much more reasonable than the experimentally determined value and is consistent with the other n-alkyl hydroperoxide values, either derived or accurately determined experimentally. 

O Sullivan, D. W., M. Lee, B. C. Noone, and B. G. Heikes, Henry s Law Constant Determinations for Hydrogen Peroxide, Methyl Hydroperoxide, Hydroxymethyl Hydroperoxide, Ethyl Hydroperoxide, and Peroxyacetic Acid, . /. Phys. Chem., 100, 3241-3247 (1996). 

In addition to the S(IV) —H202 reaction, the reactions of other peroxides such as peroxymonosulfate, peroxyacetic acid, and methyl hydroperoxide with S(IV) are also sensitive to specific-acid catalysis (Hoffmann and Calvert, 1985). The rate of oxidation of S(IV) by HSO / is comparable to the rate of oxidation of S( IV) by hydrogen peroxide (Betterton and Hoffmann, 1988). We have proposed a general mechanism for the ROOH-S(IV) reaction in which the rate-determining step involves the acid-catalyzed decomposition of a peroxide-bisulfite intermediate. The rate expression applicable for this mechanism is... 

Therefore, it was of interest to determine which of these two parameters— permeability or mercaptan content—might contribute more to the rate of polymer add-on. Hair was bleached to varying extents with alkaline hydrogen peroxide and then treated with a bisulfite-cumene hydroperoxide system, using methyl methacrylate monomer. The data clearly show increasing polymer add-on with decreasing disulfide cross-links (Table... 

The reaction of various alkyl radicals with peroxides has attracted some interest. Thus the reactions of both the methyl radical and the hydroxymethyl radical with hydrogen peroxide and of the methyl radical with t-butyl hydroperoxide " have been reported and the rate constants for the processes determined. In related work it was reported that alkanes are iodinated by perfluoroalkyl iodides under free-radieal conditions (using r-BuOOH in AcOH) to give iodoalkanes. However, in the presence of excess r-BuOOH, the iodoalkanes were reduced back to the starting alkanes. The mechanism of 0—0 bond cleavage in 2-methyl-l-phenylpropan-2-yl hydroperoxide using iron(in) porphyrins has indicated that both homolytic and... 

---