Constructing a rational kinetic model of the selective propane oxidation over a mixed metal oxide catalyst

This research presents a kinetic investigation of the selective oxidation of propane to acrylic acid over a MoVTeNb oxide (M1 phase) catalyst. The paper contains both an overview of the related literature, and original results with a focus on kinetic aspects. Two types of kinetic experiments were performed in a plug flow reactor, observing (i) steady-state conditions (partial pressure variations) and (ii) the catalyst evolution as a function of time-on-stream. For this, the catalyst was treated in reducing atmosphere, before re-oxidising it. These observations in long term behaviour were used to distinguish different catalytic routes, namely for the formation of propene, acetic acid, acrylic acid, carbon monoxide and carbon dioxide. A partial carbon balance was introduced, which is a ‘kinetic fingerprint’, that distinguishes one type of active site from another. Furthermore, an ‘active site’ was found to consist of one or more ‘active centres’. A rational mechanism was developed based on the theory of graphs and includes two time scales belonging to (i) the catalytic cycle and (ii) the catalyst evolution. Several different types of active sites exist, at least as many, as kinetically independent product molecules are formed over a catalyst surface

Tunnelling in quantum superlattices with variable lacunarity

Quantum fractal superlattices are microelectronic devices consisting of a series of thin layers of two semiconductor materials deposited alternately on each other over a substrate following the rules of construction of a fractal set, here, a symmetrical polyadic Cantor fractal. The scattering properties of electrons in these superlattices may be modeled by using that of quantum particles in piecewise constant potential wells. The twist plots representing the reflection coefficient as function of the lacunarity parameter show the appearance of black curves with perfectly transparent tunnelling which may be classified as vertical, arc, and striation nulls. Approximate analytical formulae for these reflection-less curves are derived using the transfer matrix method. Comparison with the numerical results show their good accuracy.Comment: 12 pages, 3 figure

Spatial properties of π−π\pi-\pi conjugated network in semicrystalline polymer thin films studied by intensity x-ray cross-correlation functions

We present results of x-ray study of spatial properties of $\pi-\pi$ conjugated networks in polymer thin films. We applied the x-ray cross-correlation analysis to x-ray scattering data from blends of poly(3-hexylthiophene) (P3HT) and gold nanoparticles. The Fourier spectra of the intensity cross-correlation functions for different films contain non-zero components of orders $n=2,4$ and $6$ measuring the degree of structural order in the system.Comment: 6 pages, 2 figures, Proceedings ICXOM22 Conference, 2-6 September 2013, Hamburg, German

Enhanced observability of quantum post-exponential decay using distant detectors

We study the elusive transition from exponential to post-exponential (algebraic) decay of the probability density of a quantum particle emitted by an exponentially decaying source, in one dimension. The main finding is that the probability density at the transition time, and thus its observability, increases with the distance of the detector from the source, up to a critical distance beyond which exponential decay is no longer observed. Solvable models provide explicit expressions for the dependence of the transition on resonance and observational parameters, facilitating the choice of optimal conditions

Long time deviation from exponential decay: non-integral power laws

Quantal systems are predicted to show a change-over from exponential decay to power law decay at very long times. Although most theoretical studies predict integer power-law exponents, recent measurements by Rothe et al. of decay luminescence of organic molecules in solution {Phys. Rev. Lett. 96 (2006) 163601} found non-integer exponents in most cases. We propose a physical mechanism, within the realm of scattering from potentials with long tails, which produces a continuous range of power law exponents. In the tractable case of the repulsive inverse square potential, we demonstrate a simple relation between the strength of the long range tail and the power law exponent. This system is amenable to experimental scrutiny

Hadronic Vacuum Polarization and the Lamb Shift

Recent improvements in the determination of the running of the fine-structure constant also allow an update of the hadronic vacuum-polarization contribution to the Lamb shift. We find a shift of -3.40(7) kHz to the 1S level of hydrogen. We also comment on the contribution of this effect to the determination by elastic electron scattering of the r.m.s. radii of nuclei.Comment: 7 pages, latex, 1 figure -- Submitted to Phys. Rev. A -- epsfig.sty require

Neutron star properties and the equation of state of neutron-rich matter

We calculate total masses and radii of neutron stars (NS) for pure neutron matter and nuclear matter in beta-equilibrium. We apply a relativistic nuclear matter equation of state (EOS) derived from Dirac-Brueckner-Hartree-Fock (DBHF) calculations. We use realistic nucleon-nucleon (NN) interactions defined in the framework of the meson exchange potential models. Our results are compared with other theoretical predictions and recent observational data. Suggestions for further study are discussed.Comment: 13 pages, 9 figures, 1 table; Revised version, accepted for publication in Physical Review

X-ray Near Field Speckle: Implementation and Critical Analysis

We have implemented the newly-introduced, coherence-based technique of x-ray near-field speckle (XNFS) at 8-ID-I at the Advanced Photon Source. In the near field regime of high-brilliance synchrotron x-rays scattered from a sample of interest, it turns out, that, when the scattered radiation and the main beam both impinge upon an x-ray area detector, the measured intensity shows low-contrast speckles, resulting from interference between the incident and scattered beams. We built a micrometer-resolution XNFS detector with a high numerical aperture microscope objective and demonstrate its capability for studying static structures and dynamics at longer length scales than traditional far field x-ray scattering techniques. Specifically, we characterized the structure and dynamics of dilute silica and polystyrene colloidal samples. Our study reveals certain limitations of the XNFS technique, which we discuss.Comment: 53 pages, 16 figure