Non-idealities in lab-scale kinetic testing: a theoretical study of a modular Temkin reactor

The Temkin reactor can be applied for industrial relevant catalyst testing with unmodified catalyst particles. It was assumed in the literature that this reactor behaves as a cascade of continuously stirred tank reactors (CSTR). However, this assumption was based only on outlet gas composition or inert residence time distribution measurements. The present work theoretically investigates the catalytic CO2 methanation as a test case on different catalyst geometries, a sphere, and a ring, inside a single Temkin reaction chamber under isothermal conditions. Axial gas-phase species profiles from detailed computational fluid dynamics (CFD) are compared with a CSTR and 1D plug-flow reactor (PFR) model using a sophisticated microkinetic model. In addition, a 1D chemical reactor network (CRN) model was developed, and model parameters were adjusted based on the CFD simulations. Whereas the ideal reactor models overpredict the axial product concentrations, the CRN model results agree well with the CFD simulations, especially under low to medium flow rates. This study shows that complex flow patterns greatly influence species fields inside the Temkin reactor. Although residence time measurements suggest CSTR-like behavior, the reactive flow cannot be described by either a CSTR or PFR model but with the developed CRN model

Spectra of comet P/Halley at R = 4 - 8 AU

Spectra of Comet Halley (lambda lambda = 3400-6500 A) were acquired at pre- and post-perihelion distances of 4.8 AU on 1985 Feb. 17 (Coma V equals 18.9 mag) and 1987 Feb. 1 (coma V = 15.9 mag) using the 4.5-m Multiple-Mirror Telescope (MMT) and the CTIO 4.0-m telescope, respectively. The CN(0,0) violet system band flux at 4.8 AU was approx. 15 times greater at the post-perhelion phase compared to pre-perihelion. Additional post-perihelion spectra, obtained on 1986 Nov. 28 to 30 with the MTT, showed CN(0,0) and very weak C3 4040 A emission. The MMT data are one-dimensional spectra (aperture: 5 arc sec diameter) obtained with an intensified Reticon while the CTIO data are two-dimensional spectra (slit length = 280 arc sec) obtained with a 2D-Frutti photon counting system. Extended CN(0,0) emission was detected in the 1987 Feb. 1 (at 4.8 AU) spectra to a distance of at least 70 arc sec in the solar and anti-solar directions. Additional CCD spectra obtained with the KPNO 2.2-meter telescope on 1988 Feb. 20 (at 7.9 AU) show scattered solar continuum approx. 32 arc sec diameter. However, no emission features were detected at 7.9 AU

Crystal Growth with Oxygen Partial Pressure of the BaCuSi2O6 and Ba1-xSrxCuSi2O6 Spin Dimer Compounds

BaCuSi2O6 is a quasi-two-dimensional spin dimer system and a model material for studying Bose-Einstein condensation (BEC) of magnons in high magnetic fields. The new Bai(1-x)Sr(x)CuSi(2)O(6) mixed system, which can be grown with x <= 0.3, and BaCuSi2O6, both grown by using a crystal growth method with enhanced oxygen partial pressure, have the same tetragonal structure (I4(1)/acd) at room temperature. The mixed system shows no structural phase transition so that the tetragonal structure is stable down to low temperatures. The oxygen partial pressure acts as a control parameter for the growth process. A detailed understanding of the crystal structure depending on the oxygen content will enable the study of the spin dynamics of field-induced order states in this model magnetic compound of high current interest with only one type of dimer layers, which shows the same distance between the Cu atoms, in the structure

X-ray Observations and Infrared Identification of the Transient 7.8 s X-ray Binary Pulsar XTE J1829-098

XMM-Newton and Chandra observations of the transient 7.8 s pulsar XTE J1829-098 are used to characterize its pulse shape and spectrum, and to facilitate a search for an optical or infrared counterpart. In outburst, the absorbed, hard X-ray spectrum with Gamma = 0.76+/-0.13 and N_H = (6.0+/-0.6) x 10^{22} cm^{-2} is typical of X-ray binary pulsars. The precise Chandra localization in a faint state leads to the identification of a probable infrared counterpart at R.A. = 18h29m43.98s, decl. = -09o51'23.0" (J2000.0) with magnitudes K=12.7, H=13.9, I>21.9, and R>23.2. If this is a highly reddened O or B star, we estimate a distance of 10 kpc, at which the maximum observed X-ray luminosity is 2x10^{36} ergs s^{-1}, typical of Be X-ray transients or wind-fed systems. The minimum observed luminosity is 3x10^{32}(d/10 kpc)^2 ergs s^{-1}. We cannot rule out the possibility that the companion is a red giant. The two known X-ray outbursts of XTE J1829-098 are separated by ~1.3 yr, which may be the orbital period or a multiple of it, with the neutron star in an eccentric orbit. We also studied a late M-giant long-period variable that we found only 9" from the X-ray position. It has a pulsation period of ~1.5 yr, but is not the companion of the X-ray source.Comment: 6 pages, 7 figures. To appear in The Astrophysical Journa

Terahertz electric-field driven dynamical multiferroicity in SrTiO3_3

The emergence of collective order in matter is among the most fundamental and intriguing phenomena in physics. In recent years, the ultrafast dynamical control and creation of novel ordered states of matter not accessible in thermodynamic equilibrium is receiving much attention. Among those, the theoretical concept of dynamical multiferroicity has been introduced to describe the emergence of magnetization by means of a time-dependent electric polarization in non-ferromagnetic materials. In simple terms, a large amplitude coherent rotating motion of the ions in a crystal induces a magnetic moment along the axis of rotation. However, the experimental verification of this effect is still lacking. Here, we provide evidence of room temperature magnetization in the archetypal paraelectric perovskite SrTiO$_3$ due to this mechanism. To achieve it, we resonantly drive the infrared-active soft phonon mode with intense circularly polarized terahertz electric field, and detect a large magneto-optical Kerr effect. A simple model, which includes two coupled nonlinear oscillators whose forces and couplings are derived with ab-initio calculations using self-consistent phonon theory at a finite temperature, reproduces qualitatively our experimental observations on the temporal and frequency domains. A quantitatively correct magnitude of the effect is obtained when one also considers the phonon analogue of the reciprocal of the Einsten - de Haas effect, also called the Barnett effect, where the total angular momentum from the phonon order is transferred to the electronic one. Our findings show a new path for designing ultrafast magnetic switches by means of coherent control of lattice vibrations with light.Comment: Main text: 10 pages, 4 figures, methods and 8 supplemental figure

Electromagnon dispersion probed by inelastic X-ray scattering in LiCrO2

Inelastic X-ray scattering with meV energy resolution (IXS) is an ideal tool to measure collective excitations in solids and liquids. In non-resonant scattering condition, the cross-section is strongly dominated by lattice vibrations (phonons). However, it is possible to probe additional degrees of freedom such as magnetic fluctuations that are strongly coupled to the phonons. The IXS spectrum of the coupled system contains not only the phonon dispersion but also the so far undetected magnetic correlation function. Here we report the observation of strong magnon-phonon coupling in LiCrO2 that enables the measurement of magnetic correlations throughout the Brillouin zone via IXS. We find electromagnon excitations and electric dipole active two-magnon excitations in the magnetically ordered phase and heavily damped electromagnons in the paramagnetic phase of LiCrO2. We predict that several (frustrated) magnets with dominant direct exchange and non-collinear magnetism show surprisingly large IXS cross-section for magnons and multi-magnon processes

Quasi-2D Heisenberg Antiferromagnets [CuX(pyz)2](BF4) with X = Cl and Br

Two Cu2+ coordination polymers [CuCl(pyz)(2)](BF4) 1 and [CuBr(pyz)(2)]-(BF4) 2 (pyz = pyrazine) were synthesized in the family of quasi two-dimensional (2D) [Cu(pyz)(2)](2+) magnetic networks. The layer connectivity by monatomic halide ligands results in significantly shorter interlayer distances. Structures were determined by single crystal X-ray diffraction. Temperature-dependent X-ray diffraction of 1 revealed rigid [Cu(pyz)(2)](2+) layers that do not expand between 5 K and room temperature, whereas the expansion along the c-axis amounts to 2%. The magnetic susceptibility of 1 and 2 shows a broad maximum at similar to 8 K, indicating antiferromagnetic interactions within the [Cu(pyz)(2)](2+) layers. 2D Heisenberg model fits result in J(parallel to) = 9.4(1) K for 1 and 8.9(1) K for 2. The interlayer coupling is much weaker with vertical bar J(perpendicular to)vertical bar = 0.31(6) K for 1 and 0.52(9) K for 2. The electron density, experimentally determined and calculated by density functional theory, confirms the location of the singly occupied orbital (the magnetic orbital) in the tetragonal plane. The analysis of the spin density reveals a mainly sigma-type exchange through pyrazine. Kinks in the magnetic susceptibility indicate the onset of long-range three-dimensional magnetic order below 4 K. The magnetic structures were determined by neutron diffraction. Magnetic Bragg peaks occur below T-N = 3.9(1) K for 1 and 3.8(1) K for 2. The magnetic unit cell is doubled along the c-axis (k = 0, 0, 0.5). The ordered magnetic moments are located in the tetragonal plane and amount to 0.76(8) mu(B)/Cu2+ for 1 and 0.6(1) mu(B)/Cu2+ for 2 at 1.5 K. The moments are coupled antiferromagnetically both in the ab plane and along the c-axis. The Cu2+ g-tensor was determined from electron spin resonance spectra as g(x) = 2.060(1), g(z) = 2.275(1) for 1 and g(x) = 2.057(1), g(z) = 2.272(1) for 2 at room temperature

Herschel/HIFI observations of interstellar OH+ and H2O+ towards W49N: a probe of diffuse clouds with a small molecular fraction

We report the detection of absorption by interstellar hydroxyl cations and water cations, along the sight-line to the bright continuum source W49N. We have used Herschel's HIFI instrument, in dual beam switch mode, to observe the 972 GHz N = 1 - 0 transition of OH+ and the 1115 GHz 1(11) - 0(00) transition of ortho-H2O+. The resultant spectra show absorption by ortho-H2O+, and strong absorption by OH+, in foreground material at velocities in the range 0 to 70 km/s with respect to the local standard of rest. The inferred OH+/H2O+ abundance ratio ranges from ~ 3 to ~ 15, implying that the observed OH+ arises in clouds of small molecular fraction, in the 2 - 8% range. This conclusion is confirmed by the distribution of OH+ and H2O+ in Doppler velocity space, which is similar to that of atomic hydrogen, as observed by means of 21 cm absorption measurements, and dissimilar from that typical of other molecular tracers. The observed OH+/H abundance ratio of a few E-8 suggests a cosmic ray ionization rate for atomic hydrogen of (0.6 - 2.4) E-16 s-1, in good agreement with estimates inferred previously for diffuse clouds in the Galactic disk from observations of interstellar H3+ and other species.Comment: Accepted for publication in A&A Letter

Detection of interstellar oxidaniumyl: abundant H2O+ towards the star-forming regions DR21, Sgr B2, and NGC6334

We identify a prominent absorption feature at 1115 GHz, detected in first HIFI spectra towards high-mass star-forming regions, and interpret its astrophysical origin. The characteristic hyperfine pattern of the H2O+ ground-state rotational transition, and the lack of other known low-energy transitions in this frequency range, identifies the feature as H2O+ absorption against the dust continuum background and allows us to derive the velocity profile of the absorbing gas. By comparing this velocity profile with velocity profiles of other tracers in the DR21 star-forming region, we constrain the frequency of the transition and the conditions for its formation. In DR21, the velocity distribution of H2O+ matches that of the [CII] line at 158\mu\m and of OH cm-wave absorption, both stemming from the hot and dense clump surfaces facing the HII-region and dynamically affected by the blister outflow. Diffuse foreground gas dominates the absorption towards Sgr B2. The integrated intensity of the absorption line allows us to derive lower limits to the H2O+ column density of 7.2e12 cm^-2 in NGC 6334, 2.3e13 cm^-2 in DR21, and 1.1e15 cm^-2 in Sgr B2.Comment: Accepted for publication in A&

Computational Fluid Dynamics of Catalytic Reactors

Today, the challenge in chemical and material synthesis is not only the development of new catalysts and supports to synthesize a desired product, but also the understanding of the interaction of the catalyst with the surrounding flow field. Computational Fluid Dynamics or CFD is the analysis of fluid flow, heat and mass transfer and chemical reactions by means of computer-based numerical simulations. CFD has matured into a powerful tool with a wide range of applications in industry and academia. From a reaction engineering perspective, main advantages are reduction of time and costs for reactor design and optimization, and the ability to study systems where experiments can hardly be performed, e.g., hazardous conditions or beyond normal operation limits. However, the simulation results will always remain a reflection of the uncertainty in the underlying models and physicochemical parameters so that in general a careful experimental validation is required. This chapter introduces the application of CFD simulations in heterogeneous catalysis. Catalytic reactors can be classified by the geometrical design of the catalyst material (e.g. monoliths, particles, pellets, washcoats). Approaches for modeling and numerical simulation of the various catalyst types are presented. Focus is put on the principal concepts for coupling the physical and chemical processes on different levels of details, and on illustrative applications. Models for surface reaction kinetics and turbulence are described and an overview on available numerical methods and computational tools is provided