The dehydration of copper(II) acetate monohydrate

The thermal dehydration of copper(II) acetate hydrate has been studied between 353 and 406 K, over a range of humidities. The dehydration is controlled by nucleation-and-growth kinetics at low temperatures, with an activation energy of 154 kJ·mol⁻¹, which changes to contracting-disc kinetics at higher temperatures with a lower activation energy of 76 kJ·mol⁻¹. Frequency factors have also been derived; the value for the high temperature process is low (10⁷s⁻¹) and that for the low temperature step is high (10¹⁷s⁻¹). Optical microscopy has been used to clarify the bulk kinetics; there is evidence for a reactive layer at the surface of the decomposing solid. In celebration of the 60^th birthday of Dr Andrew K. Galwey     

The six semifield planes associated with a semifield flock

In 1965 Knuth (J. Algebra 2 (1965) 182) noticed that a finite semifield was determined by a 3-cube array (a_ijk) and that any permutation of the indices would give another semifield. In this article we explain the geometrical significance of these permutations. It is known that a pair of functions (f,g) where f and g are functions from GF(q) to GF(q) with the property that f and g are linear over some subfield and g(x)²+4xf(x) is a non-square for all x∈GF(q)∗, q odd, give rise to certain semifields, one of which is commutative of rank 2 over its middle nucleus, one of which arises from a semifield flock of the quadratic cone, and another that comes from a translation ovoid of Q(4,q). We show that there are in fact six non-isotopic semifields that can be constructed from such a pair of functions, which will give rise to six non-isomorphic semifield planes, unless (f,g) are of linear type or of Dickson-Kantor-Knuth type. These six semifields fall into two sets of three semifields related by Knuth operations.     

The central limit problem for convex bodies

It is shown that every symmetric convex body which satisfies a kind of weak law of large numbers has the property that almost all its marginal distributions are approximately Gaussian. Several quite broad classes of bodies are shown to satisfy the condition.

     

Aggregated colloids under flow

Summary We have recently reported on a new scaling theory of the rupture of colloid aggregates. The scaling theory is compared with a simulation study of the transient response of sheared 2d aggregates. In this paper we discuss the origins of deviations from the predicted scaling behaviour. We also report some of the steady-state configurations formed post rupture. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Mechanically responsive films of variable hydrophobicity made of polyelectrolyte multilayers

Mechanically responsive surfaces that allow to switch reversibly from a hydrophobic to a hydrophilic substrate are reported. The surfaces are constituted of polyelectrolyte multilayers deposited on modified charged silicone sheets. n bilayers of poly(allylamine)-Nafion (PAH-Naf) and m bilayers of poly(allylamine)-poly(acrylic acid) (PAH-PAA) composed the multilayers. A (PAH-Naf)(n) film possesses a water contact angle of around 105 degrees, whereas the contact angle of a (PAH-Naf)(4)-(PAH-PAA)(m) multilayer is around 50 degrees. When such a film with m < 5 and terminated by PAA is stretched out, its water contact angle increases up to around 100 degrees. Successive elongation/retraction cycles allow the water contact angle to alternate reversibly between 100 and 57 degrees indicating the reversible mechanical responsive nature of the film.     

A chemoselective reduction of alkynes to (E)-alkenes

The trans reduction of all types of alkynes to give (E)-olefins is achieved through a two-stage trans hydrosilylation and protodesilylation. Reaction of an alkyne and a silane with the ruthenium catalyst [Cp*Ru(MeCN)3]PF6 results in clean hydrosilylation to give only the (Z)-trans addition product at ambient temperature with catalyst loadings of 1-5 mol %. The crude vinylsilane products are then protodesilylated by the action of cuprous iodide and TBAF at rt-35 degrees C. The reaction is compatible with many sensitive functional groups and provides a general trans-alkyne reduction not possible by other means.