Hydrogen peroxide experimental data

Keairns and Manning AIChE J., 15 (660), 1969] have used the reaction between sodium thiosulfate and hydrogen peroxide in a well-stirred flow reactor to check a computer simulation of adiabatic CSTR operation. Data on their experimental conditions and the reaction parameters are listed below. The reaction may be considered second-order in sodium thiosulfate. 

As mentioned in Section II. C., the concerted bond cleavage of 1.2-dioxetane derivatives has been proposed to be of general importance in respect of the excitation step of a large number of chemiluminescence reactions. The first experimental results concerning simple dioxetanes were obtained by M. M. Rauhut and coworkers in their work on activated oxalic ester chemiluminescence 24>. From experimental data on the reaction of e.g. bis (2.4-dinitrophenyl)oxalate with hydrogen peroxide in the presence of rubrene, they concluded that 1.2-dioxetanedione... 

The experimental data on the reactions of ketyl radicals with hydrogen and benzoyl peroxides were analyzed within the framework of IPM [68]. The elementary step was treated as a reaction with the dissociation of the O—H bond of the ketyl radical and formation of the same bond in acid (from acyl peroxide), alcohol (from alkyl peroxide), and water (from hydrogen peroxide). The hydroperoxyl radical also possesses the reducing activity and reacts with hydrogen peroxide by the reaction... 

The detailed mechanism of P aeruginosa CCP has been studied by a combination of stopped-flow spectroscopy (64, 65, 84, 85) and paramagnetic spectroscopies (51, 74). These data have been combined by Foote and colleagues (62) to yield a quantitative scheme that describes the activation process and reaction cycle. A version of this scheme, which involves four spectroscopically distinct intermediates, is shown in Fig. 10. In this scheme the resting oxidized enzyme (structure in Section III,B) reacts with 1 equiv of an electron donor (Cu(I) azurin) to yield the active mixed-valence (half-reduced) state. The active MV form reacts productively with substrate, hydrogen peroxide, to yield compound I. Compound I reacts sequentially with two further equivalents of Cu(I) azurin to complete the reduction of peroxide (compound II) before returning the enzyme to the MV state. A further state, compound 0, that has not been shown experimentally but would precede compound I formation is proposed in order to facilitate comparison with other peroxidases. 

In this paper, we apply the three algorithms to the determination of the V effect of the torsional levels of hydrogen peroxide. The size of this molecule is optimum for the comparison of the three methods. In addition, a previous study shows that torsion of the central bond can be separated from the rest of the vibrational modes, thereby simplifying the problem. Finally, the torsional pseudopotential ofD202 is also calculated for determining the isotopic substitution effects. The experimental data are from Camy-Peiret et al [15]. 

Tables 1 and 2 show the lowest torsional energy levels of hydrogen peroxide and deuterium peroxide which have been determined variationally using as basis functions the rigid rotor solutions. Experimental data are from Camy-Peiret et al [15]. The first set of leval data are from Camy-Peiret et al [15]. The first set of levels (SET I) has been calculated without including the pseudopotential V = 0). The levels corresponding to the other sets (SET II, SET III and SET IV) were obtained including pseudopotentials calculated with different numerical and analytical algorithms. Finally, the zero point vibration energy correction was introduced in the SET V [14],...

Much of what is understood today about the influence of solvent on rates of oxidation reactions with hydrogen peroxide, alkyl hydroperoxides and peroxyacids can be attributed to the seminal studies by Edwards and his collaborators over thirty years ago " . They provided convincing experimental data that showed that a hydroxylic solvent (e.g. ROH) can participate in a cyclic transition state where a proton relay can in principle afford a neutral leaving group attending heterolytic 0-0 bond cleavage (equation 13). 

Since its discovery by Chandross and to this day, peroxy-oxalate chemiluminescence has been controversial because of its enormous complexity in view of the many alternative steps involved in this process. The principal mechanistic feature of the peroxy-oxalate chemiluminescence pertains to the base-catalyzed (commonly imidazole) reaction of an activated aryl oxalate with hydrogen peroxide in the presence of a chemiluminescent activator, usually a highly fluorescent aromatic hydrocarbon with a low oxidation potential . A variety of putative high-energy peroxide intermediates have been proposed for the generation of the excited states . In the context of the present chapter, it is of import to mention that recent work provides experimental evidence for the intervention of the 1,2-dioxetanedione 18 (Scheme 11) as the high-energy species responsible for the chemiexcitation. Furthermore, clear-cut experimental data favor the CIEEL mechanism as a rationalization of the peroxy-oxalate chemiluminescence . 

Equation (57) applies to material transport in tubes and yields an average deviation of 9.5% from the experimental data. An expression of similar form yielded an average deviation of 14.8% for the thermal transport. The ratio of thermal to material transport was found to be 1.09 with an average deviation of 13.7% (S3). Somewhat better agreement with predicted behavior was encountered for the studies on packed beds (S2). These data serve to illustrate the uncertainties which presently exist in the prediction of simultaneous material and thermal transfer under a variety of conditions. Satterfield s work has made a distinct contribution to understanding the macroscopic influences of combined thermal and material transport. Some of the discrepancy he noted may relate to assumptions concerning the nature of the chemical reaction associated with the decomposition of hydrogen peroxide. 

The formation of formaldehyde by reaction (17) is not consistent with the experimental data. H02 yielding peroxide is obtained besides formaldehyde. The reaction of the CH2OH radical with 02 was investigated63 under conditions comparable to those for the reaction O + CH3OH. The CH2OH radical was obtained by the reaction of hydrogen atoms with methyl alcohol. It was found that hydrogen atoms reacted with alcohol only, by abstraction of the H atom. The radical obtained yielded... 

We investigated the oxidation of only propane at the high temperature (430°C.) pic darret—first with factors affecting the type of reaction, then with analyses for some reaction products (aldehydes, hydrogen peroxide, alcohols, and hydrocarbons). All experimental data can be explained by a radical reaction mechanism which is discussed. 

The experimental results obtained with these reactors are summarized in Table I. Both reaction temperature and the molar ratio of propane to oxygen in the feed were kept constant at 430°C. and 3, respectively, while residence time was varied from 5 to 15 sec. Each experimental run was continued for about 4 hours. The hydrogen peroxide concentration in the liquid product sample was frequently checked by titration during the run. After the constant analytical value was attained, the products were subjected to the analytical procedure described before for obtaining the data given in the table. 

Table III gives the results for each reaction temperature. The experimental data are of the runs at the optimum residence time which give the maximum hydrogen peroxide yield at the respective temperature.

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