Perchlorate, oxidation with

Percussion mortar 155 Perchloric acid oxidation with, 112 titration with (nonaqueous), 408 Periodates, D. of as silver iodide, (g) 483 Peroxides analysis of, (ti) 373 Persistent lines 759... 

Compd (I) was obtained by treating ethylene oxide with 60% perchloric acid, and compd (11) by the action of 60% perchloric acid on epichlorohydrin. Both compds are oils immiscible with w, and according to these investigators, both produce an expl effect greater than NG. They are both readily hydrolyzed by w at RT, or in the presence of atm moisture... 

Hydroxylammonium perchlorate is another high energy oxidizer with stability, high impulse and high density claimed to be an improvement over AP (Ref 59). Several preferred proplnt compns incorporating this oxidizer are listed in Table 17... 

Oxidation of chalcones with TTN has been studied in detail (95, 96), and it has been shown that the products obtained depend on the amount of reagent and the solvent employed. Oxidation with 1 equivalent of TTN in methanol, methanol-chloroform, or methanol-boron trifluoride leads to acetals of the type (XXXIV) (see also Scheme 21) in yields of 20-80%. When 3 equivalents of TTN are employed, however, and aqueous glyme containing a little perchloric acid used as solvent, the products are benzils. This remarkable transformation, which proceeds in yields varying from moderate to good (40-80%), involves three distinct oxidations by TTN, and these are outlined in Scheme 22. Each individual step in this reaction sequence has been investigated in detail, with the result that useful procedures have been developed for the oxidation of both deoxybenzoins and benzoins to benzils with TTN (96). 

The rate of oxidation with Ce(IV) perchlorate depends on the method of preparation . The material from certain preparations gives a deep red complex, containing two equivalents of Ce(IV) to one molecule of H2O2, which decomposes in second order fashion-presumably by means of two concerted one-equivalent oxidations of the substrate. Other preparations give no complex and decompose peroxide much faster. The difference is thought to lie in the degree of association of the oxidant cf. the Ce(IV) oxidation of iodide ion, p. 359). 

Typical non-enolising aldehydes are formaldehyde and benzaldehyde, which are oxidised by Co(III) Ce(IV) perchlorate and sulphate , and Mn(III) . The main kinetic features and the primary kinetic isotope effects are the same as for the analogous cyclohexanol oxidations (section 4.3.5) and it is highly probable that the same general mechanism operates. kif olko20 for Co(III) oxidation of formaldehyde is 1.81 (ref. 141), a value in agreement with the observed acid-retardation, i.e. not in accordance with abstraction of a hydroxylic hydrogen atom from H2C(OH)2-The V(V) perchlorate oxidations of formaldehyde and chloral hydrate display an unusual rate expression, viz. 

The Co(ni) perchlorate oxidation of substituted and unsubstituted benzal-dehydes has kinetics and a low isotope effect (2.3 at 10 °C) in complete analogy with cyclohexanol and formaldehyde . Ring-substitution by electronegative groups accelerates reaction. 

Oxidation of hydroquinone" by Mn(III) in acid perchlorate media is simple second-order. The acidity dependence indicates both Mn and MnOH to be effective oxidants with second-order rate coefficients at 25 °C of (0.48 + 0.12) x 10 ... 

Dining dehydration of manganese(II) perchlorate [1] or nickel(II) perchlorate [2] with dimethoxypropane, heating above 65°C caused violent explosions, probably involving oxidation by the anion [1] (possibly of the methanol liberated by hydrolysis). Triethyl orthoformate is recommended as a safer dehydrating agent [2] (but methanol would still be liberated). 

A filtered solution, prepared by heating mercuric oxide with a slight excess of perchloric acid, after standing for several months precipitated a little unidentified white solid. This (but not the supernatant liquid) was very shock sensitive, and detonated as it was being rinsed out with water. (Traces of a volatile amine may have been absorbed into the acid liquor to give an amminemercury perchlorate, expected to be explosive). 

The determination of an inorganic element in an organic matrix usually requires a preliminary treatment to remove the organic matter completely, either by dry-ashing or by oxidation with acids such as nitric, sulfuric or perchloric. Then, the problem reverts to the determination of an inorganic analyte in an inorganic matrix, as above. You should be aware that losses of trace elements can occur during such oxidation processes, either by volatilization or by adsorption onto the surface of the equipment used. 

Using a fluidized bed electrode, this process was studied by Jircny 1985 [118]. Jircny [119] worked with a laboratory scale cell and subsequently a pilot plant. The pilot plant was designed to produce one ton of D-arabinose per year. The electrochemical reactor was 0.3 x 0.6 x 0.6 m and contained five 225 A cells in series. A major advantage of the electrooxidation over the usual chemical route (oxidation with sodium perchlorate) was the ease of separation of D-arabinose from the reactor outflow. In chemical routes, the separation is made difficult by the presence of large amounts of sodium chloride. 

Dichlorine heptoxide Cl O is a colorless liquid that is an excellent oxidizer. It is perchloric acid with the water removed. 

Therefore, the initial choice for an oxidizer is one with an exothermic heat of decomposition such as potassium chlorate (KCIO 3). However, mixtures of both chlorate and perchlorate salts with active metal fuels are too ignition-sensitive for commercial use, and the less-reactive - but safer - nitrate compormds are usually selected. Potassium perchlorate is used with aluminum and magnesium in some "photoflash" mixtures these are extremely reactive compositions, with velocities in the explosive range. 

---