What do we mean by “catalytic activity”?

The relative reactivities of the lower alkanes in hydrogenolysis on a Pt/Al₂O₃ catalyst depend on the H₂ pressure used, as do those of a Ru/Al₂O₃ catalyst, pretreated in various ways, for propane hydrogenolysis. Apparent activation energies also vary with H₂ pressure. No single rate measurement adequately represents catalytic activity, which is properly defined as the rateconstant for the slow step.     

A Semi‐Batch Process for Nitroxide Mediated Radical Polymerization

Summary: A semi‐batch process using nitroxide mediated polymerization, was explored for the design of low molecular weight solvent‐borne coatings, typical of those used in the automotive industry. While living radical polymerization (LRP) offers many advantages in the control of polymer chain microstructure that may confer important physical and chemical property benefits to coatings, adapting LRP to a semi‐batch process poses significant challenges in the design and operation of the process. Using styrene monomer, various two‐component initiating systems (free radical initiator, 4‐hydroxy‐TEMPO) were studied to understand the effects of different initiators on the course of polymerization. In addition, an alkoxyamine was synthesized and used as the initiating source. The initiators Luperox 7M75 and Luperox 231 give higher polymerization rates and reasonable control over polymerization, while benzoyl peroxide (BPO), Vazo 67, and the alkoxyamine are less effective. The number of polymer chains in the final product is always less than the theoretical value, reflecting poor initiation efficiency, probably resulting from undesirable termination reactions that become important due to the nature of the semi‐batch process. Adding camphorsulfonic acid (CSA) or charging initiator concurrently with monomer during semi‐batch feed, can increase the polymerization rate while maintaining the living character of the polymerization. The copolymerization of styrene and butyl acrylate is also shown to exhibit living character.

Schematic representation of the exchange reaction to produce N‐TEMPO capped polymer chains.     

Structural analysis of Au/Mg(OH)2 during deactivation by Debye function analysis

Using a Debye function analysis, the presence of icosahedral and face centered cuboctahedral gold in a 1 1 ratio has been found in freshly prepared Au/Mg(OH)₂ catalyst. The results support earlier studies which suggest the icosahedral form to be more stable at small nanometer sizes. Interactions between the gold and the Mg(OH)₂ support appear to be weak, with the gold rapidly coagulating over a period of three months. Re-analysis of the aged sample shows the gold to be mainly in the form of truncated decahedra.     

Small-angle neutron scattering studies of polyethylene crystallized at high pressure

The technique of small-angle neutron scattering (SANS) has been used to study the chain configuration in pressure crystallized polyethylene. Two narrow molecular weight fractions of deuterated molecules (PED) of M_w 23 000 and 54 000 were solution blended with a protonated matrix polymer of M_w 81 500. Although pressure crystallization was shown to have produced a clustering of the PED molecules, the radii of gyration $\text{〈}\text{S}{}^2\text{〉}{}_{\mathrm{z}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ were, nevertheless, shown to be consistent with a model in which the PED molecules possessed rod-like configurations. The predicted rod lengths were in close agreement with the molecular stem lengths of the PEH matrix polymer, which were independently determined by nitric acid etching. Furthermore, a doubling of the PED molecular weight produced no change in the value of $\text{〈S}{}^2\text{〉}{}_{\mathrm{z}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$. This was interpreted in terms of a chain folding mechanism in which a molecule is bounded by the surfaces of a lamellar block and is therefore unable to increase its' rod length.     

Preparation and properties of ABA block polymers of styrene and butadiene or isoprene made with sec-C4H9Li·2(C2H5)2O

ABA-type “tapered” block polymers were prepared from styrene (monomer A) and butadiene or isoprene, using an initiator of sec-butyllithium complexed with two molecules of ethyl ether. The stress–strain curves of polymers containing about 20–50% styrene show the usual resemblance to curves of crosslinked elastomers. The SBS polymers had higher tensile strengths than the SIS polymers. They also had slightly higher tensile strengths than comparable SBS polymers made with sec-butyllithium. The SIS polymers, however, had generally lower tensile strengths than those made with sec-butyllithium. This is probably caused by higher styrene content of the isoprene block, brought about by increased randomization of the styrene–isoprene copolymerization due to the presence of the ether. The A and B blocks become more compatible, producing loss of strength in the polymer. Infrared analyses of polydienes made with the sec-C₄H₉Li·2(C₂H₅)₂O initiator showed a 6% to 8% increase in 1,2-content (for polybutadiene) or 3,4-content (for polyisoprene), compared to polymers made with sec-butyllithium. The polymer microstructures still have high (>80%) total 1,4-content, however. Thus, this amount of ether can be tolerated in the polymerization system without great loss of rubbery properties or block structure in the resultant polymers.     

Influence of dry operating conditions: observation of oscillations and low temperature CO oxidation over Co3O4 and Au/Co3O4 catalysts

A Sm(III) exchanged NaY zeolite prepared from aqueous SmCl₃ was modified with various amounts of fluorine using NH₄F. These fluorinated zeolites exhibit enhanced catalytic activity for the dealkylation of cumene. The evaluation of acid sites by infrared spectroscopy and pyridine adsorption was correlated with fluorine content.     

Comparison of various modeling methods for analysis of powder compaction in roller press

Recently used models relating basic properties of the feed material, roller press design and its operating parameters are reviewed. In particular, we discuss the rolling theory for granular solids proposed by J.R. Johanson in the 1960s, later trials utilizing slab method and newly developed final element models. These methods are compared in terms of efficiency and accuracy of predicting the course of basic process variables like nip angle, pressure distribution in roll nip region, neutral angle, roll torque and roll force.

The finite element method offers the most versatile approach because it incorporates adequate information about powder behavior, geometry and frictional conditions. This enables to perform realistic computer experiments minimizing costs, time and resources needed for process and equipment optimization.     

Twelve years of postgraduate education in desalination

The Master of Engineering course in Desalination Technology has now 130011 running at the University of Glasgow for Twelve years. It has had a total throughput of 82 students from all over the world. This paper describes -the development of the course over this period, and discusses some of the lessons learnt and the experience gained. Various components of the desalination. education 'market' are identified and their differing, and often conflicting, requirements are discussed. In conclusion some thoughts on future trends and training requirements are presented.     

Mosaic organization of DNA nucleotides

Long-range power-law correlations have been reported recently for DNA sequences containing noncoding regions. We address the question of whether such correlations may be a trivial consequence of the known mosaic structure ("patchiness") of DNA. We analyze two classes of controls consisting of patchy nucleotide sequences generated by different algorithms--one without and one with long-range power-law correlations. Although both types of sequences are highly heterogenous, they are quantitatively distinguishable by an alternative fluctuation analysis method that differentiates local patchiness from long-range correlations. Application of this analysis to selected DNA sequences demonstrates that patchiness is not sufficient to account for long-range correlation properties.