Chemical Bonding Analysis on Amphoteric Hydrogen - Alkaline Earth Ammine Borohydrides

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications

Thermal oxidation kinetics of additive free polyamide 6-6

Thermal aging of an additive free PA 6-6 has been elucidated at 90, 100, 120, 140, 150 and 160 C in airventiled ovens by Fourier transform infrared spectrophotometry, viscosimetry in molten state and uniaxial tensile testing. Oxidation of methylene groups starts after a considerably shorter induction period but reaches a lower maximal rate than in additive free PE. Cleavage of CeN bonds constitutes the main source of chain scissions. It leads to the formation of aldehyde chain-ends and a catastrophic decrease in molar mass. Embrittlement occurs at a very low conversion ratio of the oxidation process, in particular when the concentration of aldehyde chain-ends reaches a critical value of [PH¼O]F z 5.6 10 3 mol l 1, corresponding to a critical value of the number average molar mass ofMnFz17 kg mol 1. At this stage, the entanglement network in the amorphous phase is deeply damaged. A non-empirical kinetic model has been derived from the oxidation mechanistic scheme previously established for PE, but improved by adding elementary reactions specific to polyamides such as the rapid decomposition of unstable hydroxylated amide groups. This model describes satisfyingly the main features of the thermal oxidation kinetics of PA 6-6, but also of other types of aliphatic polyamides studied previously in the literature such as: PA 6, PA 12 and PA 4-6, as long as it is not controlled by oxygen diffusion. At the same time, it confirms the existence of an universal character for the thermal oxidation kinetics of aliphatic polyamides whatever their origin, i.e. their initial molar mass, crystallinity ratio, concentration of impurities, structural irregularities, etc

Lipid oxidation kinetics of ozone-processed shrimp during iced storage using peroxide value measurements

In this research, in situ generated ozone exposure/wash cycles of 1, 3, and 5 min applied to shrimp samples either before (BIS) or during iced storage (DIS) has been used to study the lipid oxidation kinetics using the peroxide values (PV). The induction period (IP) as well as PV at end of the IP (PVIP) have been obtained. The rate constants (k) as well as half-lives (t1/2) of hydroperoxides formation for different oxidation stages were calculated. The results showed that both IP and PVIP were lower with BIS (IP between 4.35±0.09 and 5.08±0.23 days; PVIP between 2.92±0.06 and 3.40±0.18 mEq kg−1) compared with DIS (IP between 5.92±0.12 and 6.14±0.09 days; PVIP between 4.49±0.17 and 4.56±0.10 mEq kg−1). The k value for DIS seemed to be the greater compared to BIS. In addition, whilst decreases and increases in t1/2 were found at propagation, respectively, for BIS and DIS, decreases and increases were only found at the induction of oxidation stage(s) for BIS. Further, the PV of ozone-processed samples would fit first order lipid oxidation kinetics independent of duration of ozone exposures. For the first time, PV measurements and fundamental kinetic principles have been used to describe how increasing ozone exposures positively affects the different oxidation stages responsible for the formation of hydroperoxides in ozone-processed shrimp

The oxidation degradation of aromatic compounds

A series of experiments were conducted which focused on understanding the role that the O atom addition to aromatic rings plays in the oxidation of benzene and toluene. Flow reactor studies of the oxidation of toluene gave an indication of the amount of O atoms available during an oxidation and the degree to which the O atom adds to the ring. Flow reactor studies of the oxidation of toluene and benzene to which NO2 was added, have shown that NO2 appears to suppress the formation of O atoms and consequently reduce the amount of phenols and cresols formed by O atom addition. A high temperature pyrolysis study of phenol has confirmed that the major decomposition products are carbon monoxide and cyclopentadiene. A preliminary value for the overall decomposition rate constant was also obtained

Influence of alloying elements on the oxidation behavior of NbAl3

NbAL3 is one candidate material for advanced aeropropulsion systems because of its high melting point, low density, and good oxidation resistance. Although NbAl3 has the lowest oxidation rate among the binary Nb-Al alloys, it does not form exclusive layers of protective Al2O3 scales. Recently Perkin et al., have shown the feasibility of forming alumina scales on Nb-Al alloys at greatly reduced Al contents. However, the objective was to maintain the high Al content, and hence low density, while achieving the capability of growing protective alumina scales. Alloy development followed approaches similar to those used successfully for superalloys and oxidation resistant MCrAlY coatings. Among the three elements examined (Ti, Si, and Cr) as ternary additions to Nb-Al3, Cr was the most effective in favoring the selective oxidation of Al. Nb-41Al-8Cr formed exclusive layers of alumina and had a k sub p value of 0.22 mg squared/cm (sup 4)/hr at 1200 C. The addition of 1 wt percent Y to this alloy was also beneficial, resulting in nearly an order of magnitude decrease in K sub p at 1200 C. Further improvements were achieved by adding about 1 wt percent Si to the quaternary alloy. The k sub p value of 0.012 mg squared/cm (sup 4)/hr for Nb-40Al-8Cr-1Y-1Si at 1200 C was identical to the best NiAl + Zr alloys. These NbAl3 alloys also exhibited excellent cyclic oxidation resistance for 100 hr at 1200 C, being nearly equivalent to NiAl + Zr

Inhibitor specificity of amine oxidase

Although at the present time it appears clear that amine oxidase oxidation of adrenalin, or other o-diphenolic pressor amines such as were studied by Richter (6), does not play a significant physiological role, it is equally clear that the inactivation of aliphatic amines, phenethylamine and probably 4-hydroxyphenethylamine (tyramine), does predominantly take place by amine oxidase oxidation. In view of the evidence from the experiments of Ewins and Laidlaw (8) and a later study by Guggenheim and Löffler (9), such amine oxidations chiefly occur in the liver. In the present studies, an attempt was made to value quantitatively the inhibition of some of these particular type compounds by certain types of amines which are not themselves oxidized by the enzyme system (see Alles and Heegaard (10))

The role of the enzyme in the succinate-enzyme-fumarate equilibrium

The following is an account of an investigation into the role of the enzyme in the succinate-enzyme-fumarate equilibrium. The method consisted in the comparison of the value of the free energy change in this reaction obtained from oxidation-reduction potentials, with that calculated from the entropies and other physicochemical properties of succinic acid and fumaric acid

Influence of Environment on Creep Properties of MC2 Single Crystal Superalloy at 1150°C

In order to reveal the effect of oxidation on thin blade walls, a new machine allowing tests up to 1250°C under controlled atmosphere has been designed. Creep tests were performed on MC2 single crystal superalloy at 1150°C, under hydrogenated argon and dry air, but also with a switch from one atmosphere to the other after reaching the steady state creep stage. The results point out the decrease of the minimum creep rate in case of tests performed or at least started under hydrogenated argon, compared with the value obtained under synthetic dry air. This effect of oxidation was attributed to the protective oxide scale formed under hydrogenated argon. The low growth rate of alumina layer leads to a thinner zone affected by metal consumption, which is assumed to be non bearing, and prevents from vacancy flux toward the alloy. The second point results in slowing down creep mechanisms controlled by diffusion and therefore dislocation motion and microstructure evolution. Thermogravimetric tests confirm the difference of oxidation kinetics regards to environment (hydrogenated argon and dry air). However, oxide scales have different microstructures on thermogravimetric and creep samples when tested under air

Storage stability of whole and nibbed, conventional and high oleic peanuts (<i>Arachis hypogeae </i>L.)

Peanuts are increasingly being used as nibbed ingredients in cereal bars, confectionery and breakfast cereals. However, studies on their oxidative stability in this format are limited. Storage trials to determine the stability to oxidation were carried out on whole and nibbed kernels of conventional (CP) and high oleic (HOP) peanuts, with respect to temperature and modified atmosphere packaging. HOP exhibited the highest oxidative stability, with a lag phase in whole kernels of 12–15 weeks before significant oxidation occurred. HOP also showed higher levels of intrinsic antioxidants, a trolox equivalent antioxidant capacity (TEAC) of 70 mMol equivalence and radical scavenging percentage (RSP) of 99.8 % at the beginning of storage trials, whereas CP showed values of 40 mMol and 81.2 %, respectively. The intrinsic antioxidants at the beginning of these storage trials were shown to affect the peroxide value (PV), where RSP and TEAC decreased, and PV increased. Therefore, in peanuts the processing format (nibbed or whole) had the highest influence on susceptibility of lipid oxidation, highest to lowest importance: processing format &gt; temperature &gt; atmospheric conditions

Aqueous Phase C-H Bond Oxidation Reaction of Arylalkanes Catalyzed by a Water-Soluble Cationic Ru(III) Complex [(pymox-Me\u3csub\u3e2\u3c/sub\u3e)\u3csub\u3e2\u3c/sub\u3eRuCl\u3csub\u3e2\u3c/sub\u3e]\u3csup\u3e+\u3c/sup\u3eBF\u3csub\u3e4\u3c/sub\u3e\u3csup\u3e-\u3c/sup\u3e

The cationic complex [(pymox-Me2)RuCl2]+BF4− was found to be a highly effective catalyst for the C−H bond oxidation reaction of arylalkanes in water. For example, the treatment of ethylbenzene (1.0 mmol) with t-BuOOH (3.0 mmol) and 1.0 mol % of the Ru catalyst in water (3 mL) cleanly produced PhCOCH3 at room temperature. Both a large kinetic isotope effect (kH/kD = 14) and a relatively large Hammett value (ρ = −1.1) suggest a solvent-caged oxygen rebounding mechanism via a Ru(IV)-oxo intermediate species