Stability of underexpanded supersonic jet flames burning H2-CO mixtures

It has been established experimentally that both natural gas and hydrogen discharges, through circular orifices larger than a critical diameter, sustain stable lifted flames irrespective of the reservoir pressure driving the release. At smaller diameters, however, stable burning will only be achieved at operating pressures higher than a particular, diameter-dependent, threshold. This latter is strongly fuel-type dependent but empirical correlations have been developed to describe such behaviour. Given the wide disparity of critical diameters depending upon the fuel type considered, the behaviour of multi-component gaseous mixtures involving hydrogen is much less predictable than the correlations for pure fuels might indicate. A series of experiments has been undertaken in which H₂-CO mixtures are discharged from a high pressure reservoir to ambient through convergent circular nozzles, varying in diameter from 1.3 to 5 mm. A wide range of driving pressures has been investigated, from 3 to 50 bar, embracing fuel mixtures containing up to 20% CO by volume. Stability curves have been derived that identify the region where stable burning is sustained relative to the pressure ratio (reservoir pressure/ambient pressure) and the CO concentration in the fuel mixture. The present experimental data are compared with existing correlations (Kalghatgi 1981), derived from subsonic releases, and Birch et al. (1988a), applied to underexpanded supersonic methane jet flames. Although these correlations reproduce the general trend observed experimentally, they appear to significantly over-estimate the stability region. Furthermore, they do not account for the high sensitivity of the diluent concentration on the blowout stability. A thorough investigation is carried out in order to determine the source of discrepancies observed between the empirical correlations and the present measurements. Differential diffusion between the fuel components is shown to be negligible. The introduction of additional information on the turbulent flowfield from numerical simulation of the isothermal underexpanded jet, immediately upstream of the flame stabilisation region, does not appear to yield discriminating evidence for incipient blow-off instability. The maximum burning velocity alone, a widely employed characterising parameter, does not appear to describe accurately the complex interactions between the turbulent flowfield and the chemical kinetics.     

The identification of two distinct laminar to turbulent transition modes in pipe flows accelerated from rest

A study was undertaken to investigate transition in a pipe flow accelerated from rest. Experiments were carried out on a vertical tube under a constant head of liquid: flow was initiated by opening a solenoid valve. A wall shear stress probe used in the role of an event recorder identified two transition events, separated by the passage of a turbulent to laminar front and a period of laminar flow. Evidence suggests that the first comprises a laminar to turbulent interface arising from a natural stable/unstable front moving up the tube as local conditions become met, while the second is consequent upon the formation of a continuous turbulent structure carried down the tube from the inlet by the bulk flow. The paper provides a formal explanation of a phenomenon which is typical of that which is observed in starting pipe flows with a disturbed inlet.     

Neutral palladium(II) complexes with P,N Schiff-base ligands: Synthesis, characterization and catalytic oligomerisation of ethylene

New N-functionalised 2-phosphinobenzaldimino (P^N) ligands bearing 3-picolyl, furfuryl, thiophene-2-methyl, thiophene-2-ethyl, and benzyl groups have been prepared in good yield. The 2-phosphinobenzaldimino ligands were reacted with PdCl₂(COD) to give the corresponding metal complexes of the type Pd(L)Cl₂ (L = 2-phosphinobenzaldimino (P^N) ligand). All compounds were fully characterized using spectroscopic and analytical techniques, including ¹H, ¹³C, and ³¹P NMR and IR spectroscopies, mass spectrometry and elemental analysis. Selected neutral palladium complexes were evaluated as catalyst precursors in ethylene oligomerisation reactions, after activation with a co-catalyst (MMAO, EtAlCl₂, or Et₂AlCl).     

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of low-energy electrons by doubly charged ions in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H₂PO₄ radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations and H- atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations.     

Thermolysis studies on platinacycloalkane complexes

Thermal decomposition studies on platinacycloalkanes of the type Pt(CH₂)_mL₂ (where m = 6,7,8,10 and L₂ = dppp {1,3-bis(diphenylphosphino)propane}, dppe {1,2-bis(diphenylphosphino)ethane} or L = PPh₃, ^tBu₃P) are described. The results reveal that the organic product distribution depends on various factors such as the nature of ligand, the metal system, the mode of decomposition, the ring size and the temperature. Possible mechanistic pathways for the formation of various products are discussed. These platinacycloalkanes can be used as models for metallacycloalkane intermediates in catalytic reactions.     

Transient innermolecular carbene-hemicarcerand complex of fluorophenylcarbene

Laser flash photolysis of fluorophenyldiazirine incarcerated in hemicarcerand 2 affords incarcerated fluorophenylcarbene [2⊙3], which forms a metastable, innermolecular π-complex with aryl moieties of 2. This carbene complex can be observed spectroscopically. Extensive computational studies provide insights into the structure, spectroscopy, energetics, and kinetics of the 2⊙3 carbene complex.     

Isotope effects in electron spin resonance: the negative ion of cyclo-octatetraene-1-d

Replacement of one hydrogen atom by deuterium in the negative ion of cyclo-octatetraene, makes no significant difference to the electron spin densities at the hydrogen nuclei. This result contrasts with a recent observation that mono-deuteration produces a measurable change in the spin distribution in the benzene negative ion. The difference between the two systems is interpreted in terms of the Jahn-Teller effect.     

Higgs boson cosmology

The discovery of the Standard Model Higgs boson opens up a range of speculative cosmological scenarios, from the formation of structure in the early universe immediately after the big bang, to relics from the electroweak phase transition one nanosecond after the big bang, on to the end of the present-day universe through vacuum decay. Higgs physics is wide ranging, and gives an impetus to go beyond the Standard Models of particle physics and cosmology to explore the physics of ultra-high energies and quantum gravity.     

Ultrahigh pressure equation of state of tantalum to 310 GPa

ABSTRACT

The isothermal compression of transition metal tantalum (Ta) was studied in a diamond anvil cell by X-ray diffraction utilizing rhenium (Re) and gold (Au) as internal X-ray pressure standards. The Re pressure marker was employed during non-hydrostatic compression to pressures up to 310?GPa while the Au pressure marker was used during quasi-hydrostatic compression in a neon pressure-transmitting medium to 80?GPa. Two ultra-high pressure experiments were conducted on Ta and Re mixtures utilizing focused-ion beam machined toroidal diamond anvils with central flats varying from 8 microns to 16 microns in diameter. The Ta metal was observed to be stable in the body-centered-cubic phase to a volume compression V/V₀?=?0.581. The measured equations of state (EOS) of Ta using two different calibrations of the Re pressure marker are compared with the ambient temperature isotherm derived from shock compression data. We provide a detailed analysis of EOS fit parameters for Ta under quasi-hydrostatic and non-hydrostatic conditions.     

A laser scanning system for the measurement of facial surface morphology

A no contact system based on laser scanning, which records 20 000 facial surface coordinates with a dynamic resolution of approximately 0·9mm in 30s, has been developed for the study of facial changes following facial reconstructive surgery. Individual profiles are recorded with a resolution better than 0·5mm. The system is based on the analysis of the output from a video camera which obliquely views a laser line projected vertically onto the face. In order to sample the whole face, the subject sits on a chair which rotates at six degrees per second under computer control. Examples of applications of the system are given.