Relative rate measurements of some reactions of hydroxyl radicals with alkanes studied under atmospheric conditions

A flow system has been developed to study relative rate coefficients of hydroxyl radicals reacting with alkanes under conditions relating to tropospheric chemistry. Relative Arrhenius parameters have been measured over the temperature range 243–328 K for pairs of alkanes from a list consisting of n-butane, 2-methylpropane, n-pentane, n-hexane, 2,2- and 2,3-dimethylbutane, 2,3,3-trimethylbutane, and 2,3,4-trimethylpentane. The results have been incorporated into a Structure-Activity Relation for hydroxylalkane reactions which leads to the following group rate coefficients for a temperature range of 240–500 K.      

The kinetics of the addition of alkyl radicals to carbonyl groups. II. The addition of methyl radicals to trifluoroacetone in the gas phase. The formation reaction of the trifluoro-t-butoxy radical

By photolyzing azomethane over the temperature range 331–491 K in the presence of trifluoroacetone the kinetics of the addition reaction (1), ?H₃ + CF₃COCH₃ → CF₃C(?)(CH₃)₂ have been studied. Detailed analyses have shown that the principal product of the adduct radical, CF₃C(?)(CH₃)₂, is CH₃COCH₃ from reaction (?2), CF₃C(?)(CH₃)₂ → CH₃COCH₃ + ?F₃. The rate constant of the addition reaction has been determined to be k₁(dm³/mol s) = (4.5 ± 1.4) × 10⁷ exp(-(3370 ± 120)/T) over the temperature range 331–491 K, based on the value k₃ = 2.2 × 10¹⁰ dm³/mol s for the reaction (3), 2?H₃ → C₂H₆. The results are discussed in relation to existing data for radical additions to groups.     

Improvement of the hydrothermal stability of SAPO-34

Hydrothermal stability of SAPO-34 is greatly improved by the treatment of the acidic form of the SAPO-34 with NH3.     

Multidentate ligands for the synthesis of multi-metallic complexes

The reaction of the Schiff base species tris-((2-hydroxybenzylidene)aminoethyl)-amine (TrenSal) and tris-((2-hydroxy-5-bromobenzylidene)aminoethyl)amine (Tren5BrSal) with the acetates of nickel and zinc are reported. Two trimetallic complexes (M₃L₂) of Tren5BrSal with nickel and zinc have been crystallographically characterised. The attempted crystallisation of bis-(tris-((2-hydroxybenzylidene)aminoethyl)amine nickel) nickel from solutions containing TMEDA lead to the production of two novel complexes: namely a nickel adduct of the partially hydrolysed TrenSal ligand and an interesting nickel bromide–carbonate salt. [(TrenSal)₂Ni₃] is reacted with PbCl₂ to form a novel tetrametallic complex, [{(TrenSal)Ni}Pb(NC₅H₅)Cl]₂, where a Pb₂Cl₂ moiety replaces the nickel at the core of the complex. Extending the study to include the related hexadentate ligand, 1,1,1-tris-((2-hydroxybenzylidene)-aminomethyl)propane (TEtSal), we were able to isolate and characterise both [(TEtSal)₂Ni₃] and [{(TEtSal)Ni}₂Pb].     

Development of tip-enhanced optical spectroscopy for biological applications: a review

Tip-enhanced optical spectroscopy is an approach that holds a good deal of promise for the nanoscale characterisation of matter. Tip-enhanced Raman spectroscopy (TERS) has been demonstrated on a variety of samples: inorganic, organic and biological. Imaging using TERS has been shown for carbon nanotubes due to their high scattering efficiency. There are a number of compelling motivations to consider alternative approaches for biological samples; most importantly, the potential for heat damage of biomolecules and long acquisition times. These issues may be addressed through the development of tip-enhanced coherent anti-Stokes Raman scattering microscopy.     

Assessing Number Sense of Students in Australia,Sweden, Taiwan,and the United States

This paper reports selected findings from a study of number sense proficiency of students aged 8 to 14 years in Australia, Sweden, United States, and Taiwan. It comments on the meaning and importance of number sense, the development of the assessment instruments, and student responses to the items. Some implications for classrooms of the findings are then discussed.     

An Algorithm for Non-Linear Network Programming: Implementation,Results and Comparisons

This paper evaluates an algorithm for solving network flow optimization problems with quadratic cost functions. Strategies for fast implementation are discussed and the results of extensive numerical tests are given. The performance of the algorithm measured by CPU time is compared with that of the convex simplex method specialized for quadratic network programming. Performance of the two methods is analysed with respect to network size and density, and other parameters of interest. The algorithm is shown to perform significantly better on the majority of problems. We also show how the algorithm may be used to solve non-linear convex network optimization problems by the use of sequential quadratic programming.     

Rainbow refractrometry: On the validity domain of Airy’s and Nussenzveig’s theories

To measure the temperature of individual droplets or the average temperature in a section of a spray, the analysis of the light scattered around the rainbow angle provides an attractive approach. Up to now, the analysis of recorded rainbow signals has been carried out in the framework of the full Lorenz-Mie theory or of the Airy theory. In this paper, we consider four approaches (Lorenz-Mie, Debye, Airy and Nussenzveig approaches) to compute the light scattered around the rainbow angle, and we compare them in terms of accuracy and time-consumption. It is shown that the Complex Angular Momentum (CAM) theory proposed by Nussenzveig, modified by using empirical coefficients, allows one to accurately compute the light scattered around the rainbow angle in a large angular domain for particles with diameters as small as 10 μm.     

Rainbow refractrometry on particles with radial refractive index gradients

The rainbow refractrometry, under its different configurations (classical and global), is an attractive technique to extract information from droplets in evaporation such as diameter and temperature. Recently a new processing strategy has been developed which increases dramatically the size and refractive index measurements accuracy for homogeneous droplets. Nevertheless, for mono component as well as for multicomponent droplets, the presence of temperature and/or of concentration gradients induce the presence of a gradient of refractive index which affects the interpretation of the recorded signals. In this publication, the effect of radial gradient on rainbow measurements with a high accuracy never reached previously is quantified.