MIXED-CONVECTION HEAT AND MASS TRANSFER IN A FULLY DEVELOPED HORIZONTAL CHANNEL FLOW

An experimental study of mixed-convection heat and mass transfer flow of a CuS0₄ + H₂S0₄ + H₂O solution in a horizontal channel is performed by using an electrochemical system. Unstable temperature and concentration gradients imposed by a heated cathodic bottom initiate an ascending (secondary) flow of light boundary-layer fluid into the freestream. To visualize the flow, the shadowgraph technique is used. Electrical measurements are used to obtain mass transfer rates and to infer a Sherwood number. The ranges of the parameters studied in the present work for the square channel are Pr = 5-7, Sc = 1,700-2,300, Re = 100-1,000, Gr_m= 1.27 X 10⁶ and Gr_ab = 4.06 × 10⁶-2.4S × 10⁷.     

Electronic energy transfer between dye molecules in structured solutions of H<Subscript>2</Subscript>O and D<Subscript>2</Subscript>O

The structure of H₂O+D₂O solutions was studied by correlation spectroscopy of scattered light. The correlation function and size of scatterers were both found to depend nonmonotonically on the D₂O concentration in the H₂O+D₂O mixture. Processes of transfer of electronic excitation energy between dye molecules of different types in H₂O+D₂O solutions were studied. The efficiency of these processes was found to depend extremally on the concentration of the components of the solution. A fractal distribution of the interacting dye molecules is ascertained from the experimental data. The dependence of the fractal dimensionality of the dye solutions on the D₂O concentration in the D₂O+H₂O mixture is determined.     

An experimental and theoretical kinetic study of t-butyl radical reaction with molecular oxygen

In this work, a unifying picture of the kinetics of the t-C₄H₉ + O₂ reaction is presented by combining the current and previous experimental results with theory. Direct, time-resolved experiments were performed over a wide temperature range (200–500 K) at low pressures (0.3–6 Torr) using a photoionization mass spectrometry method. The kinetic measurements of the t-butyl + O₂ reaction were initiated by laser photolysis of pinacolone at 193 nm or t-butyl bromide at 248 nm to produce t-C₄H₉ radicals. Energies calculated by quantum chemistry at the CCSD(T)/CBS and CASPT2/CBS levels of theory were used in master equation simulations of the kinetics of the t-C₄H₉ + O₂ reaction. The calculations successfully reproduce the pressure and temperature dependencies of both the current low-pressure experiments and literature kinetic data at about atmospheric pressure as well as the literature kinetic data for the overwhelmingly most important bimolecular reaction channel, t-C₄H₉ + O₂ → i-C₄H₈ + HO₂ in the intermediate temperature range. The experimentally constrained master equation model was utilized to simulate the t-C₄H₉ + O₂ reaction kinetics over wide range of conditions. The results of these simulations are provided in ChemKin compatible PLOG format for later use.     

Nitromethane pyrolysis in shock tubes and a micro flow reactor with a controlled temperature profile

Nitromethane has many applications, such as in racing, as a gasoline fuel additive, and as a monopropellant. Despite a large number of studies and the small size of the molecule, the combustion chemistry of nitromethane is still not well understood. To improve models, the pyrolysis of nitromethane (CH₃NO₂) was investigated experimentally in shock tubes and in a micro flow reactor with a controlled temperature profile (MFR), under dilute conditions. Several spectroscopic diagnostics were used in the shock tubes to follow the concentration time histories of CO, H₂O (both using IR laser absorption), and CH₃NO₂ (UV light absorption). A quadrupole mass spectrometer was used to measure CH₃NO₂, NO₂, CH₄, C₂H₄, and C₂H₂ at various temperatures with the MFR. These unique experimental results were compared to modern, detailed kinetics models from the literature, and no mechanism was able to reproduce these data over the wide range of conditions investigated. Predictions for the CO and H₂O levels were generally inaccurate, and the CH₄, C₂H₄, and C₂H₂ predictions were poor in most cases for the MFR data. Importantly, all models largely differ in their predictions. A numerical analysis was performed to identify ways to improve the next generation of nitromethane models. Results indicate that nitromethane decomposition needs to be improved below 1050 K, and that hydrocarbon-NOx interactions still need to be further investigated.     

First direct kinetic measurement of i-C4H5 (CH2CHCCH2) + O2 reaction: Toward quantitative understanding of aromatic ring formation chemistry

The kinetics of the i-C₄H₅ (buta-1,3-dien-2-yl) radical reaction with molecular oxygen has been measured over a wide temperature range (275–852 K) at low pressures (0.8–3 Torr) in direct, time-resolved experiments. The measurements were performed using a laminar flow reactor coupled to photoionization mass spectrometer (PIMS), and laser photolysis of either chloroprene (2-chlorobuta-1,3-diene) or isoprene was used to produce the resonantly stabilized i-C₄H₅ radical. Under the experimental conditions, the measured bimolecular rate coefficient of i-C₄H₅ + O₂ reaction is independent of bath gas density and exhibits weak, negative temperature dependency, and can be described by the expression k₃ = (1.45 ± 0.05) × 10^?12 × (T/298 K)^{?(0.13±0.05)} cm³ s^?1. The measured bimolecular rate coefficient is surprisingly fast for a resonantly stabilized radical. Under combustion conditions, the reactions of i-C₄H₅ radical with ethylene and acetylene are believed to play an important role in forming the first aromatic ring. However, the current measurements show that i-C₄H₅ + O₂ reaction is significantly faster under combustion conditions than previous estimations suggest and, consequently, inhibits the soot forming propensity of i-C₄H₅ radicals. The bimolecular rate coefficient estimates used for the i-C₄H₅ + O₂ reaction in recent combustion simulations show significant variation and are up to two orders of magnitude slower than the current, measured value. All estimates, in contrast to our measurements, predict a positive temperature dependency. The observed products for the i-C₄H₅ + O₂ reaction were formaldehyde and ketene. This is in agreement with the one theoretical study available for i-C₄H₅ + O₂ reaction, which predicts the main bimolecular product channels to be H₂CO + C₂H₃ + CO and H₂CCO + CH₂CHO.     

Nuclear magnetic resonance in [N(CH3)4]2CoCl4 single crystals: transferred hyperfine interaction and spin-lattice relaxation rate

The molecular susceptibility and paramagnetic shift of [N(CH₃)₄]₂CoCl₄ single crystals were measured, and from these experimental results we obtained the transferred hyperfine interaction, H_hf, due to the transfer of spin density from Co²⁺ ions to [N(CH₃)₄]⁺ ions. The transferred hyperfine interaction can be expressed as a linear equation, with H_hf increasing with increasing temperature. The remarkable change in H_hf near T_c5 (=192 K) corresponds to a phase transition. The proton spin-lattice relaxation times of [N(CH₃)₄]₂CoCl₄ single crystals were also investigated, and it was found that the relaxation process can be described by a single exponential function. The variation of the relaxation time with temperature undergoes a remarkable change near T_c5, confirming the presence of a phase transition at that temperature. From the above results, we conclude that the increase in H_hf with increasing temperature is large enough to allow the transfer of spin density between Co²⁺ ions and the nuclear spins of the nonmagnetic [N(CH₃)₄]⁺ ions in the lattice, and thus the increase in the relaxation time with temperature is attributed to an increase in the transferred hyperfine field.     

Concentration and temperature quenching mechanisms of Dy3+ luminescence in BaGd2ZnO5 phosphors

BaGd₂ZnO₅:Dy³⁺ phosphors were synthesized by a traditional solid-state reaction. The crystal structure of the phosphors was characterized by X-ray diffraction (XRD). The blue emission (456 nm) corresponding to ⁴H_15/2→⁶H_15/2 transition was observed at higher sample temperatures, and the population mechanism of ⁴H_15/2 level was assigned to the thermal excitation of ⁴F_9/2 level. The fluorescence concentration quenching of ⁴F_9/2 level was studied based on Van Uitert's model, and that the electric dipole–dipole interaction was confirmed to be the responsible mechanism for the energy transfer between Dy³⁺ ions. Finally, the fluorescence thermal quenching of ⁴F_9/2 level was studied, and the crossover effect was found to be the main physical mechanism for the fluorescence temperature quenching of Dy³⁺.     

EPR Investigation of Exchange Interactions Between Neodymium Ions in {[Nd2(α-C4H3OCOO)6(H2O)2]} n

Electron paramagnetic resonance (EPR) of a new compound {[Nd₂(α-C₄H₃OCOO)₆(H₂O)₂]} _n composed of Nd³⁺–Nd³⁺ dimers is reported. The anisotropy parameters of the spin–spin interaction are determined by fitting experimental and simulated spectra in X- and Q-bands. It is shown that the anisotropy of the exchange interaction gives the main contribution to the anisotropy of the spin–spin interaction. The observed anisotropy disagrees with the expected in the model of the isotropic exchange interaction between real spins. A feature of the EPR spectrum not described by the model of the isolated Nd–Nd dimers and reflecting the magnetization transfer between dimers is detected. The magnetization transfer due to both the relaxation transitions and the interdimer interaction is considered.     

Photoluminescence and energy transfer of Tm doped LiIn (WO4)2 blue phosphors

Room temperature steady and time resolved emission spectra of LiIn_1−xTm_x(WO4)2 (where thulium concentration is 0, 0.5, 1, 5 and 10 at%) blue phosphors, under UV excitation energy have been investigated. The concentration quenching effect on the blue emission, due to the (WO₄)⁻² groups and ¹G₄→³H₆ emission transition of Tm³⁺ were studied. Two energy transfer mechanisms are shown. The first takes place between excited (WO₄)⁻² groups and the ¹G₄ energy level of Tm³⁺, and is mainly analyzed by phonon-assisted energy transfer. The second mechanism is due to an energy transfer from the excited Tm³⁺ ions to the surrounding ground state Tm³⁺ ions. The non-exponential decay curves of the ¹G₄ level observed for higher concentrations are analyzed by the Inokuti–Hirayama model. We think that the quenching effect between Tm³⁺ ions is mainly linked to the dipole–dipole interactions.     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Charge transfer from the ground state of muonic hydrogen to at room temperature

The present status of research of muon transfer from the ground state of muonic protium to ⁴He is reviewed. The analysis of a recent measurement in a triple gas mixture of H₂+⁴He+Ne at 15 bar and room temperature is presented and the result is compared to the existing experimental and theoretical rates. The average muon transfer rate from protium to ⁴He determined from all lifetime measurements is . Received: 22 January 1998 / Revised: 4 March 1998 / Accepted: 31 March 1998     

Pyrolysis of diethyl carbonate: Shock-tube and flow-reactor measurements and modeling

Shock-tube and flow-reactor experiments were used to study the thermal decomposition of diethyl carbonate (C₂H₅OC(O)OC₂H₅; DEC). The formation of CO₂, C₂H₄, and C₂H₅OH was measured with gas chromatography/mass spectrometry (GC/MS) and high-repetition-rate time-of-flight mass spectrometry (HRR-TOF-MS) behind reflected shock waves. The same products were also detected by GC/MS in flow reactor experiments. All experiments combined span a temperature range of 663–1203 K at pressures between 1.0 and 2.0 bar. Time-resolved species concentration profiles from HRR-TOF-MS and product compositions from GC/MS measurements were simulated applying a detailed reaction mechanism for DEC combustion. A master-equation analysis was conducted based on computed energies from G4 calculations. Quantum chemical calculations confirm that DEC primarily decomposes by six-center elimination, C₂H₅OC(O)OC₂H₅ → C₂H₄ + C₂H₅OC(O)OH (1a), followed by rapid decomposition of the alkoxy acid, C₂H₅OC(O)OH → C₂H₅OH + CO₂ (1b). Measured DEC decomposition rate constants k(T) at p ≈ 1.5 bar can be represented by the Arrhenius equation k(T) = 10^13.64±0.12 exp(?204.24±1.95 kJ/mol/RT) s ^{? 1}. Theoretical predictions for k_1a were in good agreement with experimentally derived values. The theoretical analysis also included dipropyl carbonate (C₃H₇OC(O)OC₃H₇; DPC) decomposition and the reactivities of DEC and DPC are compared and discussed in the context of reactivity of dialkyl carbonates under pyrolytic conditions.     

Temperature-dependent photoluminescence spectra of Er-Tm-codoped Al2O3 thin film

Er-Tm-codoped Al₂O₃ thin films with different Tm to Er concentration ratios were synthesized by cosputtering from separated Er, Tm, Si, and Al₂O₃ targets. The temperature dependence of photoluminescence (PL) spectra was studied. A flat and broad emission band was achieved in the 1.4-1.7 μm and the observed 1470, 1533 and 1800 nm emission bands were attributed to the transitions of Tm³⁺: ³H₄ → ³F₄, Er³⁺: ⁴I_13/2 → ⁴I_15/2 and Tm³⁺: ³F₄ → ³H₆, respectively. The temperature dependence is rather complicated. With increasing measuring temperature, the peak intensity related to Er³⁺ ions increases by a factor of five, while the Tm³⁺ PL intensity at 1800 nm decreases by one order of magnitude. This phenomenon is attributed to a complicated energy transfer (ET) processes involving both Er³⁺ and Tm³⁺ and increase of phonon-assisted ET rate with temperature as well. It should be helpful to fully understand ET processes between Er and Tm and achieve flat and broad emission band at different operating temperatures.     

Hydrogen template assisted electrodeposition of sub-micrometer wires composing honeycomb-like porous Pb films

High surface area porous Pb films are electrodeposited using a hydrogen bubble dynamic template. The influence of the experimental parameters on the morphology features such as the pore size, wall thickness, and sub-micrometer size features is investigated. Two structural transformations between sub-micrometer wires and particles obtained by adjusting the HClO₄ concentration are observed. At a low HClO₄ concentration, the growth of sub-micrometer wires is favored. The deposition of particles or wires covered by particles is observed at higher H⁺ concentrations. The addition of sodium citrate as an additive facilitates the preservation of Pb in the form of wires. Adjusting the concentration of Pb(ClO₄)₂·3H₂O influences the mass transfer of Pb and affects its morphology. At low concentrations, the deposition of porous Pb films composed of porous wires is shown. The additional deposition of particles on wires is observed at high concentrations. The formation process of honeycomb-like porous structures is revealed by analysis of films deposited during different deposition time. The influence of the current density on the micro and sub-micrometer scale morphologies is presented.     

Energy transfer from Tb3+ to Nd3+ in glycerol:D2O solution and frozen glass

The mechanism of energy transfer from Tb³⁺ to Nd³⁺ in glycerol:D₂O solution at 280 K, 300 K and in its frozen glass at 80 K, 120 K, 190 K and 250 K has been examined. Analysis of the intensity and lifetime measurements of ⁵D₄ level of Tb³⁺ shows that at 280 K and 300 K in solution the transfer rate varies as the square of the Nd³⁺ concentration. This suggests a dipole-dipole transfer in the glycerol:D₂O solution. However, at lower temperatures up to 190 K, where the solution freezes into a glass, the dependence observed is linear at lower Nd³⁺ concentrations and quadratic at higher concentrations. Moreover, the linear concentration dependence becomes more pronounced as the temperature of the glass is increased. This linear concentration dependence of the transfer rate and its temperature dependence have been ascribed to the migrational transfer accompanying the multipolar transfer. The coefficients of both the interactions at the above temperatures have been calculated.     

Energy transfer in Er:Eu:Yb co-doped tellurite glasses: Yb as enhancer and quencher

Energy transfer has been studied from Er³⁺ to Eu³⁺ ions on excitation with NIR photons (796 and 980 nm) with and without Yb³⁺ ions. It is found that in one case the presence of Yb³⁺ enhances the fluorescence yield (980 nm excitation) whereas in the other case it quenches (796 nm excitation). Energy transfer from Er³⁺ ion's levels ⁴S_3/2 and ²H_11/2 is verified by decay curve analysis in both the cases. The nature of interaction between the donor (Er) and the acceptor (Eu) ions is found to be dipole-dipole. The energy transfer parameters viz. transfer probability, critical distance etc. have been calculated.     

Electronic states of C2H4 ++ from double charge transfer spectroscopy and from SCF-CI calculations

Double ionization potentials of the ethylene molecule corresponding to the formation of the ground state and lower-lying excited states of C₂H₄ ⁺⁺ have been measured by means of double charge transfer spectroscopy. The experimental results are compared with the results of accurate SCF-CI calculations on C₂H₄ ⁺⁺. Very good agreement between the experimental and theoretical double ionization potentials is obtained enabling a full interpretation of the double charge transfer spectrum of C₂H₄ to be given.     

A one-chamber solid electrolyte fuel cell for chemical cogeneration

A one chamber solid oxide fuel cell (SOFC) which works in a flow of a mixture of CH₄ and air has been studied in the present author's laboratory. This new type cell consists of Pt | Solid Electrolyte | Au, in which both electrodes are exposed to the CH₄₊₂ai r mixture with a CH₄/O₂ ratio of 2 at elevated temperatures, and it generates an electric power producing hydrogen and carbon monoxide (synthetic gas) with a H₂/CO ratio of about 2. A large difference in catalytic activity for the partial oxidation of CH₄ between the Pt and Au electrode materials leads to an oxygen concentration cell which can generate an electric power between them. In this paper the author describes such a one-chamber fuel cell with respect to their structural feature, performance as a fuel cell and their component materials citing the experimental results made by his laboratory's group. Paper presented at the 97th Xiangshan Science Conference on New Solid State Fuel Cells, Xiangshan, Beijing, China, June 14–17, 1998.     

The role of radical-radical chain-propagating pathways in the phenyl + propargyl reaction

Well-skipping radical-radical reactions can provide a chain-propagating pathway for formation of polycyclic radicals implicated in soot inception. Here we use controlled pyrolysis in a microreactor to isolate and examine the role of well-skipping channels in the phenyl (C₆H₅) + propargyl (C₃H₃) radical-radical reaction at temperatures of 800–1600 K and pressures near 25 Torr. The temperature and concentration dependence of the closed-shell (C₉H₈) and radical (C₉H₇) products are observed using electron-ionization mass spectrometry. The flow in the reactor is simulated using a boundary layer model employing a chemical mechanism based on recent rate coefficient calculations. Comparison between simulation and experiment shows reasonable agreement, within a factor of 3, while suggesting possible improvements to the model. In contrast, eliminating the well-skipping reactions from the chemistry mechanism causes a much larger discrepancy between simulation and experiment in the temperature dependence of the radical concentration, revealing that the well-skipping pathways, especially to form indenyl radical, are significant at temperatures of 1200 K and higher. While most C₉H₇ forms by well-skipping at 25 Torr, an additional simulation indicates that the well-skipping channels only contribute around 3% of the C₉H_x yield at atmospheric pressure, thus indicating a negligible role of the well-skipping pathways at atmospheric and higher pressures.     

Raman spectroscopic study of a laminar hydrogen diffusion flame in air

Spontaneous Raman spectroscopy has been employed for time-averaged, spatially-resolved measurements of temperature and species concentration in an axisymmetric, laminar hydrogen diffusion flame in quiescent air. Temperatures were obtained from vibrational Q-branch raman spectra of N₂, O₂, and H₂ and the rotational Raman spectra of N₂ and H₂, and concentrations of H₂, and N₂ were determined. The results are compared to existing numerical nonequilibrium calculations for the conditions of this experiment. Significant differences between experimental and predicted temperature and concentration profiles are observed. In particular, the flame is larger in both diameter and length and the flame zone is thicker than predicted. Some possible sources of the discrepancies are discussed.