The ^(26)Al(p,γ)^(27)Si reaction : stellar origins of galactic ^(26)Al

To explain the ^(26)Mg isotopic anomaly seen in meteorites (^(26)Al daughter) as well as the observation of 1809-keV γ rays in the interstellar medium (live decay of 26Al) one must know, among other things, the destruction rate of ^(26)Al. Properties of states in ^(27)Si just above the ^(26)Al + p mass were investigated to determine the destruction rate of ^(26)Al via the ^(26)Al(p,γ)^(27)Si reaction at astrophysical temperatures.

Twenty micrograms of ^(26)Al were used to produce two types of Al_2O_3 targets by evaporation of the oxide. One was onto a thick platinum backing suitable for (p,γ) work, and the other onto a thin carbon foil for the (^3He,d) reaction.

The ^(26)Al(p,γ)^(27)Si excitation function, obtained using a germanium detector and voltage-ramped target, confirmed known resonances and revealed new ones at 770, 847, 876, 917, and 928 keV. Possible resonances below the lowest observed one at E_p = 286 keV were investigated using the ^(26)Al(^3He,d)^(27)Si proton-transfer reaction. States in 27Si corresponding to 196- and 286-keV proton resonances were observed. A possible resonance at 130 keV (postulated in prior work) was shown to have a strength of wγ less than 0.02 µeV.

By arranging four large Nal detector as a 47π calorimeter, the 196-keV proton resonance, and one at 247 keV, were observed directly, having wγ = 55± 9 and 10 ± 5 µeV, respectively.

Large uncertainties in the reaction rate have been reduced. At novae temperatures, the rate is about 100 times faster than that used in recent model calculations, casting some doubt on novae production of galactic ^(26)Al.

Spatial correlation of heat release rate and sound emission from turbulent premixed flames

The two-point spatial correlation of the rate of change of fluctuating heat release rate is central to the sound emission from open turbulent flames, and a few attempts have been made to address this correlation in recent studies. In this paper, the two-point correlation and its role in combustion noise are studied by analysing direct numerical simulation (DNS) data of statistically multi-dimensional turbulent premixed flames. The results suggest that this correlation function depends on the separation distance and direction but, not on the positions inside the flame brush. This correlation can be modelled using a combination of Hermite-Gaussian functions of zero and second order, i.e. functions of the form (1-Ax2)e-Bx2 for constants A and B, to include its possible negative values. The integral correlation volume obtained using this model is about 0.2δL3 with the length scale obtained from its cube root being about 0.6δ L, where δ L is the laminar flame thermal thickness. Both of the values are slightly larger than the values reported in an earlier study because of the anisotropy observed for the correlation. This model together with the turbulence-dependent parameter K, the ratio of the root-mean-square (RMS) value of the rate of change of reaction rate to the mean reaction rate, derived from the DNS data is applied to predict the far-field sound emitted from open flames. The calculated noise levels agree well with recently reported measurements and show a sensitivity to K values. © 2012 The Combustion Institute.

Local strain rate and curvature dependences of scalar dissipation rate transport in turbulent premixed flames: A direct numerical simulation analysis

The statistical behaviours of the instantaneous scalar dissipation rate Nc of reaction progress variable c in turbulent premixed flames have been analysed based on three-dimensional direct numerical simulation data of freely propagating statistically planar flame and V-flame configurations with different turbulent Reynolds number Ret. The statistical behaviours of N c and different terms of its transport equation for planar and V-flames are found to be qualitatively similar. The mean contribution of the density-variation term T1 is positive, whereas the molecular dissipation term (-D2) acts as a leading order sink. The mean contribution of the strain rate term T2 is predominantly negative for the cases considered here. The mean reaction rate contribution T3 is positive (negative) towards the unburned (burned) gas side of the flame, whereas the mean contribution of the diffusivity gradient term (D) assumes negative (positive) values towards the unburned (burned) gas side. The local statistical behaviours of Nc, T1, T2, T 3, (-D2), and f(D) have been analysed in terms of their marginal probability density functions (pdfs) and their joint pdfs with local tangential strain rate aT and curvature km. Detailed physical explanations have been provided for the observed behaviour. © 2014 Y. Gao et al.

Measurement of the inelastic branch of the O-14(alpha, p)F-17 reaction: Implications for explosive burning in novae and x-ray bursters

A measurement of the inelastic component of the key astrophysical resonance in the 14O(α,p)17F reaction for burning and breakout from hot carbon-nitrogen-oxygen (CNO) cycles is reported. The inelastic component is found to be comparable to the ground-state branch and will enhance the 14O(α,p)17F reaction rate. The current results for the reaction rate confirm that the 14O(α,p)17F reaction is unlikely to contribute substantially to burning and breakout from the CNO cycles under novae conditions. The reaction can, however, contribute strongly to the breakout from the hot CNO cycles under the more extreme conditions found in x-ray bursters.

Negative apparent kinetic order in steady-state kinetics of the water-gas shift reaction over a Pt-CeO2 catalyst

The kinetics of the water-gas shift reaction Were Studied on a 0.2% Pt/CeO2 catalyst between 177 and 300 degrees C over a range of CO and steam pressures. A rate decrease with increasing partial pressure of CO was experimentally observed over this sample, confirming that a negative order in CO can occur under certain conditions at low temperatures. The apparent reaction order of CO measured at 197 degrees C was about -0.27. This value is significantly larger than that (i.e, -0.03) reported by Ribeiro and co-workers [A.A. Phatak, N. Koryabkina, S. Rai, J.L. Ratts, W. Ruettinger, R.J. Farrauto, G.E. Blau, W.N. Delgass, F.H. Ribeiro, Catal. Today 123 (2007) 224] at a similar temperature. A kinetic peculiarity was also evidenced, i.e. a maximum of the reaction rate as a function of the CO concentration or possibly a kinetic break, which is sometimes observed in the oxidation of simple molecules. These observations support the idea that competitive adsorption of CO and H2O play an essential role in the reaction mechanism. (C) 2008 Elsevier B.V. All rights reserved.

Ionic Liquid Effect on the Reversal of Configuration for the Magnesium(II) and Copper(II) Bis(oxazoline)-Catalysed Enantioselective Diels-Alder Reaction

Ionic liquids have been used to support a range of magnesium-and copper-based bis(oxazoline) complexes for the enantioselective Diels-Alder reaction between N-acryloyloxazolidinone and cyclopentadiene. Compared with reaction performed in dichloromethane or diethyl ether, an enhancement in ee is observed with a large increase in reaction rate. In addition, for non-sterically hindered bis(oxazoline) ligands, that is, phenyl functionalised ligands, a reversal in configuration is found in the ionic liquid, 1-ethyl-3-methylimidazolium bis[(trifluoromethanesulfonyl)imide], compared with molecular solvents. Supported ionic liquid phase catalysts have also been developed using surface-modified silica which show good reactivity and enantioselectivity for the case of the magnesium-based bis(oxazoline) complexes. Poor ees and conversion were observed for the analogous copper-based systems. Some drop in ee was found on supporting the catalyst due a drop in the rate of reaction and, therefore, an increase in the contribution from the uncatalysed a chiral reaction.

Powder semiconductor photocatalysis in aqueous solution: An overview of kinetics-based reaction mechanisms

A brief, historical overview of 10 apparently different, although in some cases, upon inspection, closely related, popular proposed reaction mechanisms and their associated rate equations, is given and in which the rate expression for each mechanism is derived from basic principles, Appendix A. In Appendix B, each of the 5 main mechanisms are tested using datasets, comprising initial reaction rate vs. organic pollutant concentration, [P] and incident irradiance, ρ, data, reported previously for TiO2, where P is phenol, 4-chlorophenol and formic acid. The best of those tested, in terms of overall fit, simplicity, usefulness and versatility is the disrupted adsorption kinetic model proposed by Ollis. The usual basic assumptions made in constructing these mechanisms are reported and the main underlying concerns explored.

In situ catalyst activity control in a novel membrane reactor-Reaction driven wireless electrochemical promotion of catalysis

A dual chamber membrane reactor was used in order to study the effect of macroscopically applied oxygen chemical potential differences to a platinum catalyst supported on a mixed oxygen ion and electronic conducting membrane. It is believed that the oxygen chemical potential difference imposed by the use of an oxygen sweep in one of the reactor chambers causes the back-spillover of oxygen species from the support onto the catalyst surface, resulting in the modification of the catalytic activity. The use of different sweep gases, such as ethylene and hydrogen was investigated as the means to reverse the rate modification by removing the spilt over species from the catalyst surface and returning the system to its initial state. Oxygen sweep in general had a positive effect on the reaction rate with rate increases up to 20% measured. Experimental results showed that hydrogen is a more potent sweep gas than ethylene in terms of the ability to reverse rate modification. A 10% rate loss was observed when using an ethylene sweep as compared with an almost 60% rate decrease when hydrogen was used as the sweep gas. © 2009 Elsevier Ltd. All rights reserved.

Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

(A) Photoregulation of DNA Functions by Cyclic Azobenzene-tethered Oligonucleotides (B) Site-specific Fluorescent Labeling of DNA using Inverse Electron Demand Diels-Alder Reaction between trans-Cyclooctene Derivatives and BODIPY-Tetrazine Adducts

(A) Most azobenzene-based photoswitches require UV light for photoisomerization, which limit their applications in biological systems due to possible photodamage. Cyclic azobenzene derivatives, on the other hand, can undergo cis-trans isomerization when exposed to visible light. A shortened synthetic scheme was developed for the preparation of a building block containing cyclic azobenzene and D-threoninol (cAB-Thr). trans-Cyclic azobenzene was found to thermally isomerize back to the cis-form in a temperature-dependent manner. cAB-Thr was transformed into the corresponding phosphoramidite and subsequently incorporated into oligonucleotides by solid phase synthesis. Melting temperature measurement suggested that incorporation of cis-cAB into oligonucleotides destabilizes DNA duplexes, these findings corroborate with circular dichroism measurement. Finally, Fluorescent Energy Resonance Transfer experiments indicated that trans-cAB can be accommodated in DNA duplexes. (B) Inverse Electron Demand Diels-Alder reactions (IEDDA) between trans-olefins and tetrazines provide a powerful alternative to existing ligation chemistries due to its fast reaction rate, bioorthogonality and mutual orthogonality with other click reactions. In this project, an attempt was pursued to synthesize trans-cyclooctene building blocks for oligonucleotide labeling by reacting with BODIPY-tetrazine. Rel-(1R-4E-pR)-cyclooct-4-enol and rel-(1R,8S,9S,4E)-Bicyclo[6.1.0]non-4-ene-9-ylmethanol were synthesized and then transformed into the corresponding propargyl ether. Subsequent Sonogashira reactions between these propargylated compounds with DMT-protected 5-iododeoxyuridine failed to give the desired products. Finally a methodology was pursued for the synthesis of BODIPY-tetrazine conjugates that will be used in future IEDDA reactions with trans-cyclooctene modified oligonucleotides.

Studies on nonlinear dynamics of certain reaction systems

The nonlinear dynamics of certain important reaction systems are discussed and analysed in this thesis. The interest in the theoretical and the experimental studies of chemical reactions showing oscillatory dynamics and associated properties is increasing very rapidly. An attempt is made to study some nonlinear phenomena exhibited by the well known chemical oscillator, the BelousovZhabotinskii reaction whose mathematical properties are much in common with the properties of biological oscillators. While extremely complex, this reaction is still much simpler than biological systems at least from the modelling point of view. A suitable model [19] for the system is analysed and the researcher has studied the limit cycle behaviour of the system, for different values of the stoichiometric parameter f, by keeping the value of the reaction rate (k6) fixed at k6 = l. The more complicated three-variable model is stiff in nature.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

Correlation-type structure activity relationships for the kinetics of gas-phase RO2 self-reactions and reaction with HO2

Structure activity relationships (SARs) are presented for the gas-phase reactions of RO2 with HO2, and the self- and cross-reactions of RO2. For RO2+HO2 the SAR is based upon a correlation between the logarithm of the measured rate coefficient and a calculated ionisation potential for the molecule R-CH=CH2, R being the same group in both the radical and molecular analogue. The correlation observed is strong and only for one RO2 species does the measured rate coefficient deviate by more than a factor of two from the linear least-squares regression line. For the self- and cross-reactions of RO2 radicals, the SAR is based upon a correlation between the logarithm of the measured rate coefficient and the calculated electrostatic potential (ESP) at the equivalent carbon atom in the RH molecule to which oxygen is attached in RO2, again R being the same group in the molecule and the radical. For cases where R is a simple alkyl-group, a strong linear correlation observed. For RO2 radicals which contain lone pair-bearing substituents and for which the calculated ESP<-0.05 self-reaction rate coefficients appear to be insensitive to the value of the ESP. For RO2 of this type with ESP>-0.05 a linear relationship between log k and the ESP is again observed. Using the relationships, 84 out of the 85 rate coefficients used to develop the SARs are predicted to within a factor of three of their measured values. A relationship is also presented that allows the prediction of the Arrhenius parameters for the self-reactions of simple alkyl RO2 radicals. On the basis of the correlations, predictions of room-temperature rate coefficients are made for a number of atmospherically important peroxyl-peroxyl radical reactions. (C) 2003 Elsevier Ltd. All rights reserved.

Study of the pozzolanic reaction kinetics in sugar cane bagasse-clay ash/calcium hydroxide system: kinetic parameters and pozzolanic activity

This paper presents a study of the pozzolanic reaction kinetics between calcium hydroxide and a mixture of sugar cane bagasse with 20 and 30% of clay, burned at 800 and 1000 degrees C (SCBCA) by electrical conductivity measurements. A kinetic-diffusive model produced in previous studies by some of the authors was used. The model was fitted to the experimental data, which allowed the computation of the kinetic parameters of the pozzolanic reaction (reaction rate constant and free energy of activation) that rigorously characterised the pozzolanic activity of the materials. The results show that SCBCA demonstrated reactivity and good pozzolanic qualities in the range 800-1000 degrees C.