A rapid,spatially dispersive frequency comb spectrograph aimed at gas phase chemical reaction kinetics

This New Views article will highlight some recent advances in high sensitivity gas detection using direct infrared absorption frequency comb laser spectroscopy, with a focus on frequency comb use in chemical reaction kinetics and our own contribution to this field. Our recently implemented detection technique uses a combination of a 12.9?GHz free spectral range virtually imaged phased array and diffraction grating to spatially disperse the mid-infrared frequency comb onto a camera. Individual frequencies or ‘comb teeth’ of a 250?MHz repetition-rate frequency comb are able to be resolved. High molecular sensitivity is achieved by increasing the interaction path length using a Herriott multipass cell. High spectral resolution, broadband spectral coverage, and high molecular sensitivity are all achieved on an adjustable 1–50 µs timescale, making this frequency comb apparatus ideal for measuring chemical reaction kinetics where multiple absorbing species can be monitored simultaneously. This New Views article will also discuss some of the challenges and decisions that chemists might face in implementing this advanced physics technology in their own laboratory.

Spatially dispersed 250 MHz mid-infrared frequency comb laser, with absorption of some frequencies by a dilute sample of methane.     

Partitioning of Selected Anisole and Veratrole Derivatives between Water and Anionic Surfactant Micelles

The UV absorption spectra of six structurally related derivatives of anisole and veratrole, i.e., anisaldehyde, (E)-anethole, estragole, veratraldehyde, methyleugenol and (E)-methylisoeugenol, were recorded at various concentrations of the anionic surfactants, either sodium lauryl sulfate (SLS) or sodium lauryl ether sulfate (SLES) at T = 298 K. In addition, conductivity and density measurements were made for the SLS and SLES solutions to determine the volumetric properties of the studied surfactants. Next, using the W. Al-Soufi, L. Pińeiro and M. Novo model (APN model) including the pseudo-phase model for micellar solubilization, the values of micelle-water partition coefficients for each perfume-surfactant system were determined. In addition, the relations between the molecular structures of the solute and the head group of the surfactant and the value of the micelle-water partition coefficient as well as the octanol-water one were discussed.     

Sustainable Drying and Torrefaction Processes of Miscanthus for Use as a Pelletized Solid Biofuel and Biocarbon-Carrier for Fertilizers

Miscanthus is resistant to dry, frosty winters in Poland and most European Union countries. Miscanthus gives higher yields compared to native species. Farmers can produce Miscanthus pellets after drying it for their own heating purposes. From the third year, the most efficient plant development begins, resulting in a yield of 25–30 tons of dry matter from an area of 1 hectare. Laboratory scale tests were carried out on the processes of drying, compacting, and torrefaction of this biomass type. The analysis of the drying process was conducted at three temperature levels of the drying agent (60, 100, and 140 °C). Compaction on a hydraulic press was carried out in the pressure range characteristic of a pressure agglomeration (130.8–457.8 MPa) at different moisture contents of the raw material (0.5% and 10%). The main interest in this part was to assess the influence of drying temperature, moisture content, and compaction pressure on the specific densities (DE) and the mechanical durability of the pellets (DU). In the next step, laboratory analyses of the torrefaction process were carried out, initially using the Thermogravimetric Analysis TGA and Differential Scaning Calorimeter DSC techniques (to assess activation energy (EA)), followed by a flow reactor operating at five temperature levels (225, 250, 275, 300, and 525 °C). A SEM analysis of Miscanthus after torrefaction processes at three different temperatures was performed. Both the parameters of biochar (proximate and ultimate analysis) and the quality of the torgas (volatile organic content (VOC)) were analyzed. The results show that both drying temperature and moisture level will affect the quality of the pellets. Analysis of the torrefaction process shows clearly that the optimum process temperature would be around 300–340 °C from a mass loss ratio and economical perspective.     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

Free convection from horizontal screened plates

Experimental investigations of laminar free convection from horizontal isothermal surfaces screened by cylindrical vertical walls are presented. Screen diameters (D) were equal to the diameter of a heating plate while their heights (H) were varied. Results obtained for several heating fluxes and two different liquids indicate that depending on the (H/D) ratio of cylindrical screens, the heat flux transferred from the heating plate to the liquid varies. Three subranges of screening effect have been distinguished: primary inhibition, intensification and secondary inhibition. For primary inhibition, a theoretical model has been proposed and critical ratio of (H/D) has been predicted. The results of flow visualization are also discussed.

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Freie Konvektion von horizontalen, seitlich abgeschirmten Platten

Zusammenfassung Es werden experimentelle Untersuchungen der laminaren freien Konvektion an horizontalen, isothermen Flächen mit vertikalen zylindrischen Abschirmflächen beschrieben. Die Schirmdurchmesser (D) waren gleich dem einer Heizplatte, während die Schirmhöhen (H) variiert wurden. Die Resultate, welche für mehrere Wärmeflüsse und mit zwei verschiedenen Flüssigkeiten gewonnen wurden, zeigen, daß — abhängig von VerhältnisH/D der zylindrischen Schirme — der von der Heizplatte an das Fluid übergehende Wärmestrom stark variiert. Drei Bereiche konnten bezüglich des Abschirmeffektes unterschieden werden: erste Hemmung, Verstärkung und zweite Hemmung. Für den Fall der ersten Hemmung wird ein theoretisches Modell vorgeschlagen und das kritischeH/D-Verhältnis vorausberechnet. Abschließend erfolgt die Diskussion von Ergebnissen, welche aus der sichtbaren Darstellung des Strömungsfeldes gewonnen wurde.

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Nomenclature a thermal diffusivity [m²/s] - D external diameter of the plate, internal diameter of screens [m] - g gravitational acceleration [m/s²] - H height of screen [m] - Nu= D/ Nusselt number - Nu _(H/D)=0 Nusselt number for plate without screens - Nu _H/D Nusselt number for plate with screen of heightH - Ra=g (T _w1–T _F)D ³/( a) Rayleigh number - Ra _H=g (T _w–T _w1)H ³/( a) Rayleigh number inside screen - q heat flux density [W/m²] - T _w surface temperature of the heating plate [°C] - T _w1 boundary temperature of the motionless liquid [°C] - T _F bulk temperature of the liquid [°C] - heat transfer coefficient [W/(m²·K)] - coefficient of volumetric expansion [1/K] - kinematic viscosity - thermal conductivity [W/(m·K)]     

Laminar free convection heat transfer from a horizontal ring

The analytical solution of laminar free convective heat transfer in an unlimited space from an isothermal horizontal ring with an adiabatic plug is presented. The results of theoretical considerations are presented as relation of the Nusselt and Rayleigh numbers: $$Nu_D = 1.151 \cdot (Ra_D )^{1/5} \cdot \Phi (\phi _0 )$$ \] where Φ(φ₀) is a function of shape coefficient of the ring (φ₀=d/D). The solution presented has been verified experimentally with rings of constant external diameter (D=0.06 [m]) and various internal diameters (d=0, 0.01, 0.02, 0.04 and 0.05 [m]). The fluid tested was glycerin. The theoretical predictions agree well with the experimental results.     

Thermal,spectroscopic, X-ray and theoretical studies of metal complexes (sodium,manganese, copper,nickel, cobalt and zinc) with pyrimidine-5-carboxylic and pyrimidine-2-carboxylic acids

Journal of Thermal Analysis and Calorimetry - The new 3d metal complexes of pyrimidine-2-carboxylic (2PCA) and pyrimidine-5-carboxylic (5PCA) acids were synthesized and characterized using thermal...     

Electrochemical Behavior of Cobaltocene in Ionic Liquids

The electrochemical behavior of cobaltocenium has been studied in a number of room temperature aprotic ionic liquids. Well defined, diffusion controlled, anodic and cathodic peaks were found for the Cc⁺/Cc (cobaltocenium/cobaltocene) reduction/oxidation on gold, platinum and glassy carbon electrodes. Values of the peak separation parameters suggest quasireversibility or even irreversibility for the redox process. The difference between the ferrocene/ferrocenium and cobaltocenium/cobaltocene couples has been evaluated as equal to (1.350 ± 0.020) V. Values of the cobaltocenium (Cc⁺) diffusion coefficients D have been calculated on the basis of the Randles–Sevcik equation.