129Xe NMR study of the homogeneity and the size distribution of small sodium metal particles in NaY zeolite

NaY zeolite samples loaded with sodium metal by vapor phase deposition have been investigated using¹²⁹Xe NMR spectroscopy. At low sodium concentration, the¹²⁹Xe NMR spectrum showed three resonance lines which clearly indicate the existence of distinct domains in the zeolite sample. Such an observation suggests that the diffusion of the xenon atoms into each domain only occurs with respect to the NMR time scale (2.9 ms). As the sodium concentration increases, observation of a single broad line indicate a macroscopic homogenization of the system. The shift of this line is explained in part due to a paramagnetic interaction between the xenon atoms and the unpaired electrons of particles containing an odd number of sodium atoms. The linewidth is due to the distribution of the local magnetic fields partially averaged by the rapid motion of the xenon atoms and to the statistical distribution of the sodium particles in the supercage cavities. The paramagnetic interaction vanishes with the oxidation of the sample leading to a narrowing and a shift of the line to higher magnetic fields.     

Evolved gas analysis (EGA) of brick clays

Using a system based on non-dispersive infrared (NDIR) detectors, evolved gas analysis (EGA) was able to identify and quantify the principal volatiles produced by heating powdered samples of UK brick clays. From these results, atmospheric emissions likely to result from brick production can be predicted. In addition, EGA results for extruded brick clay test pieces are significantly different from those of powdered samples. Within an extruded brick clay body, evolved gases are contained within a pore system and evolved gas-solid phase reactions also occur. This EGA study provides further evidence on the nature of firing reactions within brick clay bodies. The qualitative and quantitative influence of heating rate — a key process condition in brick manufacture — on gas release is also outlined.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthday     

Effect of iodine sorption on the free volume of polycarbonate

 The effect of iodine sorption on the free volume of polycarbonate is investigated by Positron Annihilation Lifetime method. The observed results are interpreted in terms of the Charge Transfer Complex formation and precipitation of iodine at the initial and final stages of sorption, respectively. At higher levels of sorption, changes in the second lifetime and its intensity seem to suggest a conformational transformation, probably due to the net change in the amorphous-crystalline boundary regions of the polymer matrix. The free volume cavities have been predominantly occupied by I^- ₃ species and the diffusion process obeys Fick’s law. An exponential type correlation has been observed between fractional free volume and the diffusion coefficient. Received: 13 June 1996/Accepted: 20 September 1996     

The lead tetraacetate oxidation of bisacylhydrazones of α-diketones: A scope re-assesment

Oxidation of the title compounds yields, besides the reported isoimides 3 and/or the amides 4 , also the imides 5 . The observed product dichotomy is considered as the result of an intramolecular nucleophilic attack on the aroyl group, of the pressumed zwitterionic intermediate 2 , by O or N present in the ambident N-aroylimine site of 2 . The results of AM1 calculations agree with the product studies and both permit the formulation of a set of rules correlating structure and selectivity.