Infrared spectroscopy hydroperoxides

Deprotonation of H2O2 yields OOH , and hydroperoxides of the alkali metals are known in solution. Liquid ammonia can also effect deprotonation and NH4OOH is a white solid, mp 25° infrared spectroscopy shows the presence of NH4+ and OOH ions in the solid phase but the melt appears to contain only the H-bonded species NH3 and H202. " Double deprotonation yields the peroxide ion 02 , and this is a standard route to transition metal peroxides. 

A series of reactions with gases have been selected for the rapid quantification of many of the major products from the oxidation of polyolefins. Infrared spectroscopy is used to measure absorptions after gas treatments. The gases used and the groups quantified include phosgene to convert alcohols and hydroperoxides to chloroformates, diazomethane to convert acids and peracids to their respective methyl esters, sulfur tetrafluoride to convert acids to acid fluorides and nitric oxide to convert alcohols and hydroperoxides to nitrites and nitrates respectively. 

Figure 7 Hydroperoxide index (HI) determined from mid-infrared spectroscopy (ratio of the integrated intensity of the 3,552 cm 1 band to the integrated intensity of the band at 2,010 cm-1) as a function of total hydroperoxide content measured by iodiometric titration.

The nature of the titanium-containing active site has been investigated with different techniques, including theoretical calculations. The formation of a hydroperoxidic species or of a bidentate side-on titanium peroxo structure was suggested by many authors . Alternatively, some DFT calculations indicated an undissociated molecule of H2O2 weakly interacting with Ti centers or an active Ti-O-O-Si peroxo moiety as a reactive site . Recently, Lin and Frei reported the first direct detection, obtained using in situ FT-infrared spectroscopy, of a Ti-OOH moiety as active species in the oxidation of small olefins like ethylene or propylene . 

Analytical methods for measuring hydroperoxides in fats and oils can be classified as those determining the total amount of hydroperoxides and those based on chromatographic techniques giving detailed information on the structure and the amount of specific hydroperoxides present in a certain oil sample (8). The PV represents the total hydroperoxide content and is one of the most common quality indicators of fats and oils during production and storage (9, 18). A number of methods have been developed for determination of PV, among which the iodometric titration, ferric ion complex measurement spectrophotometry, and infrared spectroscopy are most frequently used (19). 

A rapid Fourier transform infrared spectroscopy (FTIR) method based on the stoichiometric reaction of triphenylphosphine (TPP) with hydroperoxides has been developed and successfully applied to determination of PV of edible oils (32). The hydroperoxides present in oil samples react stoichiometrically with TPP to produce triphenylphosphine oxide (TPPO), which has an intense absorption... 

When polymers have been degraded photochemically in the presence of air, oxygen-containing groups, such as hydroperoxide, carbonyl groups and alcohols, are observed in the polymer by infrared spectroscopy. These groups are formed by the chain reactions of oxidation (Eq. (23)). Other kinds of chemical bonds may also be influenced by... 

Hair after treatment with TGA cumene hydroperoxide using methyl methacrylate monomer was hydrolyzed with 5N hydrochloric acid to dissolve away the keratin from the polymer, and part of the resultant fiberlike residue was dissolved in organic solvents. The solute (in the organic solvents) was shown to be polymethyl methacrylate by refractive index and infrared spectroscopy [87]. 

Ethylene-styrene copolymer Ethylene-vinyl acetate copolymer Ethylene-vinylchloride copolymer Fourier transform infrared spectroscopy Gas chromatography High-density polyethylene Hydroperoxide decomposition Isobutylene... 

Whereas the distribution profile of the radicals in the bulk cannot be determined, the distribution of the products of their reaction with oxygen can. In other words, the degree and distribution of oxidative degradation in the bulk can be determined by measuring the distribution of the hydroperoxides and of their decomposition products using infrared spectroscopy (FTIR) [43, 44]. In Figure 21.1 the oxidation products after NO (nitrogen monoxide) treatment for a new prosthesis are reported [41-42]. 

In 1993, Blatter and Frei [34] extended the Aronovitch and Mazur [28] photo-oxidation into zeolitic media, which resulted in several distinctive advantages as described below. Irradiation in the visible region (633 nm) of zeolite NaY loaded with 2,3-dimethyl-2-butene, 16, and oxygen resulted in formation of allylic hydroperoxide, 17, and a small amount of acetone. The reaction was followed by in situ Fourier-transform infrared (FTlR) spectroscopy and the products were identified by comparison to authentic samples. The allylic hydroperoxide was stable at - 50°C but decomposed when the zeolite sample was warmed to 20°C [35]. In order to rationalize these observations, it was suggested that absorption of light by an alkene/Oi charge-transfer complex resulted in electron transfer to give an alkene radical cation-superoxide ion pair which collapses... 

Chemical vapor deposition (CVD) using TiC was used to prepare Ti/Si02, Ti/MCM-41, and Ti/MCM-48 catalysts. These catalysts were characterized by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, nitrogen adsorption, and were used to catalyze the epoxidation of propylene to propylene oxide (PO) with in situ prepared ethylbenzene hydroperoxide (EBHP). CVD time and CVD temperature affected the catalyst performance significantly. The optimum temperature range was 800-900 °C, and the optimum deposition time was 2.5-3 h. The maximum PO yields obtained in a batch reactor were 87.2, 94.3, and 88.8% for Ti/Si02, Ti/ MCM-41, and Ti/MCM-48, respectively. Ti/MCM-41 had higher titanium... 

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