Use of isothermal microcalorimetry data for the determination of integral molar entropies of adsorption at the gas—solid interface by a quasi-equilibrium procedure

The aim of this paper is to describe the present position in the experimental determination of entropies of adsorption. After pointing out the limitations of the “isosteric” approach and after stressing the fact that the most interesting entropy to know is the integral molar entropy of adsorption, the authors show how the use of isothermal adsorption microcalorimetry, with a special quasi-reversible procedure, allows this entropy to be determined satisfactorily from the thermodynamic point of view.     

Study of double pomeron exchange in pp collisions at √s=31GeV

The reaction pp→ppπ⁺π^? at √s=31GeV was studied at the Split Field Magnet Facility of the CERN-ISR. Selecting events with two leading protons of x>0.9 and a rapidity gap Δy>2 between the protons and both pions a sample of 720 events is obtained representing a cross section of 25±10μb. The mass distribution of the dipion system, x and p_T distributions for the protons are presented and analyzed for the presence of double pomeron exchange.     

Oxidation of tertiary polycycl1c amines by RuO4

The reactions of certain tertiary polycyclic amines such as N-benzyl-9-azabicy-clo- [3,3,1]-nonane, N-benzyl-5, 6-dihydro-11H-dibenz [b,e] azepine, and N-benzyl-1,2,3,4-tetrahydroisoquinoline with ruthenium tetroxide, taking place in both heterogeneous and homogeneous systems, have made it possible to establish the order of reactivity of the various methylene groups adjacent to the nitrogen with respect to this oxidizing agent.     

The photoelectron spectrum and molecular geometry of bicyclo[2.1.1]hexane

The He(I) photoelectron spectrum of bicyclo[2.1.1]hexane shows excellent correlation with a theoretical spectrum based on the eigenvalues obtained in an ab initio calculation at the theoretical molecular geometry. By contrast, a calculation performed at the experimental geometry exhibits an effect of enhanced ring strain in showing a first ionization energy which is considerably lower than the experimental value. This observation offers experimental support for the recent claim that the published structure for bicyclo [2.1.1]hexane based on electron-diffraction measurements is incorrect. It also accounts for inconsistencies observed in the calculated values of some spin—spin coupling constants for substituted bicyclo[2.1.1]hexanes.     

Comparison between experimental decay of the compound nuclei150Gd and evaporation calculations

The deexcitation of the compound nucleus¹⁵⁰Gd formed by¹⁵⁶O+¹³⁴Ba and⁴⁰Ar+¹¹⁰Pd have been studied. Excitation functions were determined for various exit channels: (HI, × n) withx=3, 4, 5 (HI, pxn) withx=2, 3, 4 (HI, axn) withx=3 and 5. A systematic comparison has been made between these experimental data and the results of evaporation calculation using the ALI CE code. The very good agreement obtained for the total residue cross section disappears completely when a more detailed analysis of the different contributions is performed. Absolute and relative cross sections are not reproduced; excitation functions of each individual channel (HI, 3n), (HI, 4n) etc. ... are not found at the right place in energy. A very preliminary explanation for such a shift towards higher energies is suggested.     

Heteronuclear decoupling interference during symmetry-based homonuclear recoupling in solid-state NMR

We examine the influence of continuous-wave heteronuclear decoupling on symmetry-based double-quantum homonuclear dipolar recoupling, using experimental measurements, numerical simulations, and average Hamiltonian theory. There are two distinct regimes in which the heteronuclear interference effects are minimized. The first regime utilizes a moderate homonuclear recoupling field and a strong heteronuclear decoupling field; the second regime utilizes a strong homonuclear recoupling field and a weak or absent heteronuclear decoupling field. The second regime is experimentally accessible at moderate or high magic-angle-spinning frequencies and is particularly relevant for many realistic applications of solid-state NMR recoupling experiments to organic or biological materials.     

The Suzuki homocoupling reaction under high-intensity ultrasound

The Pd-catalysed Suzuki homocoupling of boronic acids was successfully carried out in water under high-intensity ultrasound (HIU). Heterogeneous catalysis with Pd/C, facilitating work up and purification, could be used without adding phosphine ligands. Reaction rates and yields were strongly influenced by the oxidant employed; excellent results were obtained using either molecular oxygen or 3-bromo-4-hydroxycoumarin. 3-Arylation of the latter with the Suzuki procedure had failed, exclusively affording the homocoupling products, symmetric biaryls. Besides offering a number of operational advantages, the use of HIU broadens the field of application for the Suzuki reaction.     

Chemical modification of chitosan under high-intensity ultrasound

Chitosan (CTS), a biocompatible, biodegradable, non-toxic polymer, dissolves in water only if pH is lowered under 6.5, when a substantial fraction of the amino groups is protonated. Its range of application has been much extended by partially depolymerising it or converting it to water-soluble derivatives. Working under high-intensity ultrasound at 17.8-18.5 kHz, using either a simple horn or a cup horn, we achieved a controlled depolymerization of CTS, also prepared in high yields several derivatives that can be useful intermediates for further chemical modification, as well as several water-soluble derivatives that lend themselves to a host of industrial applications. Compared to conventional methods, all these reactions went to completion in considerably shorter times at lower temperatures.     

Atomic control of water interaction with biocompatible surfaces: the case of SiC(001)

The interaction of water with Si- and C- terminated beta-SiC(001) surfaces was investigated by means of ab initio molecular dynamics simulations. Irrespective of coverage, varied from 1/4 to 1 monolayer, we found that water dissociates on the Si-terminated surface, substantially modifying the clean surface reconstruction, while the C-terminated surface is nonreactive and hydrophobic. Based on our results, we propose that STM images and photoemission experiments may detect specific changes induced by water on both the structural and electronic properties of SiC(001) surfaces.     

Long Term Stability of Proper Rotations of the Perturbed Euler Rigid Body

We study the long term stability of the proper rotations of the perturbed Euler rigid body, in the framework of Nekhoroshev theory. For simplicity we treat here in detail only the kinetically symmetric case (the potential needs not to be symmetric), but we indicate how to extend the results to the triaxial case. We show that the proper rotations around the symmetry axis are Nekhoroshev stable: more precisely, if the initial datum is sufficiently close to a proper rotation, then for a very long time it remains such, and the tip of the unit vector parallel to the angular momentum precesses, up to a small noise, along the level curves of a regular function on the unit sphere. If the proper rotations are resonant, chaotic motions with positive Lyapunov exponents are possible, but chaos (unlike the case of ordinary motions, that is motions not close to proper rotations) is always localized, and does not affect in an essential way the motion of the angular momentum in space. Preliminary numerical results indicate that the theory is, in many aspects, optimal, although in some points it can still be improved.