Aspects of tautomerism. 13. Alkaline hydrolysis of .gamma.-, .delta.-, and .epsilon.-keto esters and their desoxy analogs. Geometrical constraints on keto participation

The rates of alkaline hydrolysis of methyl &benzoylpropionate (I), methyl y-benzoylbutyrate (11) and methyll6-benzoylvalerate (In) decrease in the order I > I1 > III. Keto participation is the predominant pathway in the case of y-keto esters. Evidence has also been obtained for keto participation in the case of 6-keto esters, whereas no such evidence is available in the case of r-keto esters studied.

Aspects of tautomerism 12-Some causes and consequences of participation in the solvolysis of acid chlorides

Solvolysis of nine representative half ester acid chlorides in aqueous acetone have been studied. Isomers solvolyse at distinctly different rates and furnish the original acids. Contrary to the well accepted views, no evidence for tautomerism or isomerism between the isomeric pairs of acid chlorides could be detected. In a number of cases alkoxy group participates in the solvolysis of neighbouring acid chlorides. This results in (a) rate enhancement and (b) partial or total shift of the reaction pattern from SN2 to SN1. Isomeric half ester acid chlorides, in the presence of a sufficiently strong Lewis acid, could give the same oxonium salt. Rearrangements observed in the reactions of unsymmetrical 1,2- and 1,3-dicarboxylic acid derivatives could be ascribed to the prior formation of common oxonium salt intermediates in the presence of Lewis acids.

Numerical prediction of load-displacement behaviors of adhesively bonded joints at different extension rates and temperatures

The present work focuses on simulation of nonlinear mechanical behaviors of adhesively bonded DLS (double lap shear) joints for variable extension rates and temperatures using the implicit ABAQUS solver. Load-displacement curves of DLS joints at nine combinations of extension rates and environmental temperatures are initially obtained by conducting tensile tests in a UTM. The joint specimens are made from dual phase (DP) steel coupons bonded with a rubber-toughened adhesive. It is shown that the shell-solid model of a DLS joint, in which substrates are modeled with shell elements and adhesive with solid elements, can effectively predict the mechanical behavior of the joint. Exponent Drucker-Prager or Von Mises yield criterion together with nonlinear isotropic hardening is used for the simulation of DLS joint tests. It has been found that at a low temperature (-20 degrees C), both Von Mises and exponent Drucker-Prager criteria give close prediction of experimental load-extension curves. However. at a high temperature (82 degrees C), Von Mises condition tends to yield a perceptibly softer joint behavior, while the corresponding response obtained using exponent Drucker-Prager criterion is much closer to the experimental load-displacement curve.

High Oxygen Storage Capacity and High Rates of CO Oxidation and NO Reduction Catalytic Properties of Ce1-xSnxO2 and Ce0.78Sn0.2Pd0.02O2-delta

Ce1-xSnxO2 (x = 0.1-0.5) solid solution and its Pd substituted analogue have been prepared by a single step solution combustion method using tin oxalate precursor. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H-2/temperature programmed redution (TPR) studies. The cubic fluorite structure remained intact up to 50% of Sri substitution in CeO2, and the compounds were stable up to 700 C. Oxygen storage capacity of Ce1-xSnxO2 was found to be much higher than that of Ce1-xZrxO2 due to accessible Ce4+/Ce3+ and Sn4+/Sn2+ redox couples at temperatures between 200 and 400 C. Pd 21 ions in Ce0.78Sn0.2Pd0.02O2-delta are highly ionic, and the lattice oxygen of this catalyst is highly labile, leading to low temperature CO to CO2 conversion. The rate of CO oxidation was 2 mu mol g(-1) s(-1) at 50 degrees C. NO reduction by CO with 70% N-2 selectivity was observed at similar to 200 degrees C and 100% N-2 selectivity below 260 degrees C with 1000-5000 ppm NO. Thus, Pd2+ ion substituted Ce1-xSnxO2 is a superior catalyst compared to Pd2+ ions in CeO2, Ce1-xZrxO2, and Ce1-xTixO2 for low temperature exhaust applications due to the involvement of the Sn2+/Sn4+ redox couple along with Pd2+/Pd-0 and Ce4+/Ce3+ couples.

Fatigue crack growth rates and fracture toughness in electroslag refined En 52 steel

En 52 steel has been electroslag refined and the resultant effects of refining on its mechanical properties have been assessed. It was found that refining caused a decrease in fatigue crack growth rates and increases in fatigue strength, fracture toughness, Charpy fracture energy and tensile ductility. Fatigue crack growth rates in region I and in region III were found to be considerably lower in the electroslag refined steel: they were unaffected in region II. The fracture toughness values for the electroslag refined steel are nearly twice those estimated for the unrefined steel. Measurements on heat-treated samples have shown that the electroslag refined steel has a better response to heat-treatment. The improvement in the mechanical properties is explained in terms of the removal of nonmetallic inclusions and a reduction in the sulphur content of the steel.

Effect of electroslag refining on the fracture toughness and fatigue crack propagation rates in heat treated AISI 4340 steel

The AISI 4340 steel has been electroslag refined and the improvement in mechanical properties has been assessed. Electroslag refining (ESR) has improved tensile ductility, plane strain fracture toughness, Charpy fracture energy, and has decreased fatigue crack growth rates. The KIC values for the ESR steel are nearly twice those estimated in the unrefined steel and higher than those obtained in the vacuum arc remelted steel. Fatigue crack growth rates in region I and in region III are found to be decreased considerably in the ESR steel, while they are unaffected in region II. Measurements on heat treated samples have shown that the ESR steel has a better response to heat treatment. Both the suggested heat treatments namely austenitizing at 1140–1470 K as well as the conventional heat treatment of austenitizing at 1140 K have been followed. The improvement in the mechanical properties of ESR steel has been explained on the basis of removal of nonmetallic inclusions and reduction in sulfur content in the steel.

Role of alloys in the thermal decomposition and combustion of ammonium perchlorate

The participation of aluminum in the decomposition reaction of ammonium perchlorate (AP) is enhanced if magnesium is added—either as a mixture of Al and Mg powders or as an alloy of Mg in Al. The differential thermal analyses of the compositions show a sensitization in the temperatures of decomposition, as well as increase in the heat of reaction. The AP-Mg and Ap-(Mg---Li) alloy pellets also show increased reactivity. The burning rates of AP-(Al-10% Mg) alloy pellets increase with increase in the alloy content, while calorimetric values peak at 40% alloy content. The combustion product gases of AP-40% (Al-10% Mg) alloy contain large quantities of hydrogen.

Prediction of bubble growth rates and departure volumes in nucleate boiling at isolated sites

A model has been developed to predict heat transfer rates and sizes of bubbles generated during nucleate pool boiling. This model assumes conduction and a natural convective heat transfer mechanism through the liquid layer under the bubble and transient conduction from the bulk liquid. The temperature of the bulk liquid in the vicinity of the bubble is obtained by assuming a turbulent natural convection process from the hot plate to the liquid bulk. The shape of the bubble is obtained by equilibrium analysis. The bubble departure condition is predicted by a force balance equation. Good agreement has been found between the bubble radii predicted by the present theory and the ones obtained experimentally.

Rates of oxidation of thioketones by singlet oxygen

Rate constants for the quenching of singlet oxygen by a series of thioketones were measured by monitoring the inhibition of the self-sensitized photooxidation of rubrene. A correlation of the quenching rate with the nature of the substituents on the aromatic rings for the diarylthioketones and arylalkylthioketones was found, whereas correlation with the n orbital ionization potential was observed for the dialkylthioketones.

Anthranilate Hydroxylase from Aspergillus niger: Evidence for the Participation of Iron in the Double Hydroxylation Reaction

Evidence was obtained for the participation of iron in the double hydroxylation reaction catalyzed by anthranilate hydroxylase from Aspergillus niger (UBC 814). Omission of iron from the growth medium gave inactive preparations of anthranilate hydroxylase which could be reactivated by incubating the enzyme preparations with ferric citrate. The enzyme was susceptible to inhibition by metal chelating agents. The Ki for o-phenanthroline, which inhibited the enzyme activity non-competitively with respect to anthranilate, was calculated to be 0.9 mM. The inhibition by o-phenanthroline was counteracted by ferric complexes such as ferric-ethylenediaminetetraacetic acid and ferric citrate. Anthranilate afforded protection against inhibition by o-phenanthroline.

Combustion and Thermal Decomposition of Ammonium Perchlorate-Aluminium Composite Pellets: Mechanism for Aluminium Participation

Thermal behaviour of ammonium perchlorate-aluminium composites is studied using differential thermal analysis, thermogravimetry and differential scanning calorimetry. Electrical resistivity studies throw light on the mechanism of ammonium perchlorate decomposition at different aluminium contents. The differences observed in burning behaviour by earlier authors is explained in terms of porosity and thermal conductivity of the composite.

Absolute values of instantaneous corrosion rates by faradaic rectification

Doss and Agarwal 1 discovered the "redoxokinetic effect" which is now familiarly known as faradaic rectification. Subsequently, the theory and applications of faradaic rectification due to a single electrode reaction have been developed by several workers 2-5. The theory and application of faradaic rectification in the case of a corrosion cell sustaining mixed electrode reactions on a corroding metal was reported recently 6"7. This led to the development of a new electrochemical method of corrosion rate determination. It was shown that changes in the instantaneous corrosion rates of a metal are readily evaluated by faradaic rectification measurements at the corrosion potential of the metal in a given medium. The aim of the present work is to show that absolute values of instantaneous corrosion rates may also be obtained by the new method under certain conditions. The practical advantages that arise from this development are pointed out.

Why do birds participate in mixed-species foraging flocks? A large-scale synthesis

Mixed-species flocks of foraging birds have been documented from terrestrial habitats all over the world and are thought to form for either improved feeding efficiency or better protection from predators. Two kinds of flock participants are recognized: those that join other species ('followers') and are therefore likely to be the recipients of the benefits of flock participation and those that are joined ('leaders'). Through comparative analyses, using a large sample of flocks from around the world, we show that (1) 'followers' tend to be smaller, more insectivorous, and feed in higher strata than matched species that participate in flocks to a lesser extent and (2) 'leaders' tend to be cooperative breeders more often than matched species that are not known to lead flocks. Furthermore, meta-analyses of published results from across the world showed that bird species in terrestrial mixed-species flocks increase foraging rates and reduce vigilance compared to when they are solitary or in conspecific groups. Moreover, the increase in foraging rates is seen only with flock followers and not flock leaders. These findings suggest a role for predation in the evolution of mixed-species flocking. Species that are vulnerable to predation follow species whose vigilance they can exploit. By doing so, they are able to reduce their own vigilance and forage at higher rates. (C) 2009 The Association for the Study of Animal Behaviour. Published by Elsevier Ltd. All rights reserved.

The subsidence rates of suspensions of lithium stearate in n-heptane with n-alcohols as additives

Suspensions of lithium stearate in n-heptane are highly unstable, undergoing gelation even at concentrations as low as 1 g./1. The rate of subsidence of these weakly gelled suspensions is decreased at first by the addition of n-alcohols, but passes through a minimum in some cases. The minimum subsidence rate occurs while the adsorption of the alcohol is still below its saturation value. One possible explanation of the effect is that the solvent layer between particles at the junction points in the gel becomes simultaneously more polar, tending toward an increased gel strength, and also thicker, tending toward a decreased gel strength.