The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere

The gas-phase reactions of ozone with unsaturated hydrocarbons are significant sources of free radical species (including *OH) and particulate material in the Earth's atmosphere. In this tutorial review, the kinetics, products and mechanisms of these reactions are examined, starting with a discussion of the original mechanism proposed by Criegee and following with a summary presentation of the complex, free radical-mediated reactions of carbonyl oxide (Criegee) intermediates. The contribution of ozone-terpene reactions to the atmospheric burden of secondary organic aerosol material is also discussed from the viewpoint of the formation of non-volatile organic acid products from the complex chemistry of ozone with alpha-pinene. Throughout the article, currently accepted understanding is supported through the presentation of key experimental results, and areas of persistent or new uncertainty are highlighted.     

Organic acid formation in the gas-phase ozonolysis of alpha-pinene

The mechanism of formation of pinonic and norpinonic acids from alpha-pinene ozonolysis has been investigated by studying the products of the ozonolysis of an enone derived from alpha-pinene using gas chromatography coupled to mass spectrometry.     

Reactions of alkenes with ozone in the gas phase: a matrix-isolation study of secondary ozonides and carbonyl-containing reaction products

Gas phase ozonolysis reactions of the alkenes ethene, cis- and trans-but-2-ene, isoprene and the monoterpenes alpha-pinene, beta-pinene, beta-carene, limonene and beta-myrcene have been carried out and the reaction products have been trapped in O2-doped-argon matrices onto a Csl window held at 12 K. Products have been identified by IR spectroscopy. Comparison with previous matrix spectra, where secondary ozonides have been generated either in situ by annealing or in solution reactions allows a positive identification of the secondary ozonides of ethene and of cis- and trans-but-2-ene to be made. These observations are backed up by experiments utilising the isotopes 13C and 2H (D). It appears that secondary ozonides have also been formed from isoprene and the range of monoterpenes studied; this hypothesis is based upon the similarity of spectral features seen in the products of these reactions within those of the simpler alkenes. A number of other primary and secondary products are also identified from these reactions. Ethene gives formaldehyde as a primary product and acetaldehyde as a secondary product; it is found that the yield of acetaldehyde compared to formaldehyde increases as the reaction times are increased. Formaldehyde, one of the expected primary products, is formed by ozonolysis of beta-pinene, although the other expected primary product, nopinone, is not seen. A range of secondary reaction products have been identified from the ozonolysis of the monoterpenes studied.     

Multi-layer film flow down an inclined plane: experimental investigation

We report the results from an experimental study of the flow of a film down an inclined plane where the film itself is comprised of up to three layers of different liquids. By measuring the total film thickness for a broad range of parameters including flow rates and liquid physical properties, we provide a thorough and systematic test of the single-layer approximation for multi-layer films for Reynolds numbers \(Re = \rho Q/\mu \approx 0.03 - 60\) . In addition, we also measure the change in film thickness of individual layers as a function of flow rates for a variety of experimental configurations. With the aid of high-speed particle tracking, we derive the velocity fields and free-surface velocities to compare to the single-layer approximation. Furthermore, we provide experimental evidence of small capillary ridge formations close to the point where two layers merge and compare our experimental parameter range for the occurrence of this phenomenon to those previously reported.     

Symmetric cubic graphs via rigid cells

Journal of Algebraic Combinatorics - Properties of symmetric cubic graphs are described via their rigid cells, which are maximal connected subgraphs fixed pointwise by some involutory automorphism...     

A note on Cayley graphs

An example is given of a finite group A of order 144, with a generating set X = {x, y} such that x³ = y² = 1 and such that the Cayley graph C(A, X) has genus 4 and characteristic −6 (both of which are small relative to the order of A), although there is no short relator of the form (xy)^r with r < 12 or of the form [x, y]^r with r < 6. Accordingly this and other possible examples do not fit into a pattern suggested by [5.], 244–268).     

The Symmetric Genus of the Mathieu Groups

The (symmetric) genus of a finite group may be defined as thesmallest genus of those closed orientable surfaces on whichG acts faithfully as a group of automorphisms. In this paperthe genus of each of the five Mathieu groups M₁₁, M₁₂, M₂₂,M₂₃ and M₂₄ is determined, with the help of some computer calculationsand a little-known of Ree on permutations.     

An infinite Family of 4-Arc-Transitive Cubic Graphs Each with Girth 12

If p is any prime, and is that automorphism of the group SL(3,p) which takes each matrix to the transpose of its inverse,then there exists a connected trivalent graph (p) on vertices with the split extensionSL(3, p) as a group of automorphisms acting regularly on its4-arcs. In fact if p 3 then this group is the full automorphismgroup of (p), while the graph (3) is 5-arc-transitive with fullautomorphism group SL(3,3)0 x C₂. The girth of (p) is 12, exceptin th case p = 2 (where the girth is 6). Furthermore, in allcases (p) is bipartite, with SL(3, p) fixing each part. Alsowhen p 1 mod 3 the graph (p) is a triple cover of another trivalentgraph, which has automorphism group PSL(3, p)0 acting regularlyon its 4-arcs. These claims are proved using elementary theoryof symmetric graphs, together with a suitable choice of threematrices which generate SL(3, Z). They also provide a proofthat the group 4⁺(a¹²) described by Biggs in Computational grouptheor(ed. M. Atkinson) is infinite.