Effects of nonuniform reactant stoichiometry on thermoacoustic instability in a lean-premixed gas turbine combustor

Detailed experimental investigations of the amplitude dependence of flame describing functions (FDF) were performed using a stratified swirl-stabilized combustor, in order to understand the combustion-acoustic interactions of CH4/air flames propagating into nonhomogeneous reactant stoichiometry. Phase-synchronized OH planar laser induced fluorescence (OH PLIF) measurements were used to investigate local reaction zone structures of forced flames. To determine the amplitude-and frequency-dependent forced flame response, simultaneous measurements of inlet velocity and heat release rate oscillations were made using a constant temperature anemometer and photomultiplier tubes with narrow-band OH*/CH* interference filters. The measurements were made over a wide range of stratification ratios, including inner stream enrichment ( θ o>θ i) and outer stream enrichment ( θ o>θ i)) conditions, and compared to the baseline condition of spatially and temporally homogeneous cases ( θ o=θ i)). Results show that for the inlet conditions investigated, fuel stratification has a significant influence on local and global flame structures of unforced and forced flames. Under stratified conditions, length scales of local contours were found to be much larger than the homogeneous case due to high kinematic viscosities associated with high temperature. Stratification has a remarkable effect on flame-vortex interactions when the flame is subjected to high-amplitude acoustic forcing, leading to different evolution patterns of FDF (amplitude and disturbance convective time) in response to the amplitude of the imposed inlet velocity oscillation. The present experimental investigation reveals that intentional stratification has the potential to eliminate or suppress the occurrence of detrimental combustion instability problems in lean-premixed gas turbine combustion systems. © 2012 Copyright Taylor and Francis Group, LLC.

Effects of nonuniform reactant stoichiometry on combustion instability

This paper analyzes the forced response of swirl-stabilized lean-premixed flames to acoustic forcing in a laboratory-scale stratified burner. The double-swirler, double-channel annular burner was specially designed to generate acoustic velocity oscillations and radial fuel stratification at the inlet of the combustion chamber. Temporal oscillations of equivalence ratio along the axial direction are dissipated over a long distance, and therefore the effects of time-varying fuel/air ratio on the flame response are not considered. Simultaneous measurements of inlet velocity and heat release rate oscillations were made using a hot wire anemometer and photomultiplier tubes with narrowband OH*/CH* interference filters. Time-averaged CH* chemiluminescence intensities were measured using an intensified CCD camera. Results show that flame stabilization mechanisms vary depending on stratification ratio for a constant global equivalence ratio. For a uniformly premixed condition, an enveloped M-shaped flame is observed. For stratified conditions, however, a dihedral V-flame and a detached flame are developed for outer stream and inner stream fuel enrichment cases, respectively. Flame transfer function (FTF) measurement results indicate that a V-shaped flame tends to damp incident flow oscillations, while a detached flame acts as a strong amplifier relative to the uniformly premixed condition. The phase difference of FTF increases in the presence of stratification. More importantly, the dynamic characteristics obtained from the forced stratified flame measurements are well correlated with unsteady flame behavior under limit-cycle pressure oscillations. The results presented in this paper provide insight into the impact of nonuniform reactant stoichiometry on combustion instabilities, which has not been well explored to date. Copyright © 2011 by ASME.

Thermally crosslinkable poly(phenylene sulfide)/poly (ether sulfone)/polymerization of monomer reactant-polyimide blends

The effects of thermally crosslinkable polymerization of monomer reactant-polyimide (POI) on the miscibility, morphology, and crystallization of partially miscible poly(ether sulfone) (PES)/poly(phenylene sulfide) (PPS) blends were investigated with differential scanning calorimetry and scanning electron microscopy. The addition of POI led to a significant reduction in the size of PPS particles, and the interfacial tension between PPS and crosslinked POI was smaller than that between PES and crosslinked POI. During melt blending, crosslinking and grafting reactions of POI with PES and PPS homopolymers were detected; however, the reaction activity of POI with PPS was much higher than that with PES. The crosslinking and grafting reactions were developed further when blends were annealed at higher temperatures. Moreover, POI was an effective nucleation agent of the crystallization of PPS, but crosslinking and grafting hindered the crystallization of PPS. The final effect of POI on the crystallinity of the PPS phase was determined by competition between the two contradictory factors. The crosslinking and grafting reactions between the two components was controlled by the dosage of POI in the blends, the premixing sequence of POI with the two components, the annealing time, and the temperature.

Control of excitation and quenching in multi-colour electrogenerated chemiluminescence systems through choice of co-reactant

We demonstrate a new approach to manipulate the selective emission in mixed electrogenerated chemiluminescence (ECL) systems, where subtle changes in co-reactant properties are exploited to control the relative electron-transfer processes of excitation and quenching. Two closely related tertiary-amine co-reactants, tri-n-propylamine and N,N-diisopropylethylamine, generate remarkably different emission profiles: one provides distinct green and red ECL from [Ir(ppy)3] (ppy=2-phenylpyridinato-C2,N) and a [Ru(bpy)3](2+) (bpy=2,2'-bipyridine) derivative at different applied potentials, whereas the other generates both emissions simultaneously across a wide potential range. These phenomena can be rationalized through the relative exergonicities of electron-transfer quenching of the excited states, in conjunction with the change in concentration of the quenchers over the applied potential range.

Considering the chemical energy requirements of the tri-n-propylamine co-reactant pathways for the judicious design of new electrogenerated chemiluminescence detection systems

The introduction of a 'co-reactant' was a critical step in the evolution of electrogenerated chemiluminescence (ECL) from a laboratory curiosity to a widely utilised detection system. In conjunction with a suitable electrochemiluminophore, the co-reactant enables generation of both the oxidised and reduced precursors to the emitting species at a single electrode potential, under the aqueous conditions required for most analytical applications. The most commonly used co-reactant is tri-n-propylamine (TPrA), which was developed for the classic tris(2,2'-bipyridine)ruthenium(ii) ECL reagent. New electrochemiluminophores such as cyclometalated iridium(iii) complexes are also evaluated with this co-reactant. However, attaining the excited states in these systems can require much greater energy than that of tris(2,2'-bipyridine)ruthenium(ii), which has implications for the co-reactant reaction pathways. In this tutorial review, we describe a simple graphical approach to characterise the energetically feasible ECL pathways with TPrA, as a useful tool for the development of new ECL detection systems.

Electrogenerated chemiluminescence of tris(2,2' bipyridine)ruthenium(ii) using common biological buffers as co-reactant, pH buffer and supporting electrolyte

A series of aliphatic tertiary amines (HEPES, POPSO, EPPS and BIS-TRIS) commonly used to buffer the pH in biological experiments, were examined as alternative, non-toxic co-reactants for the electrogenerated chemiluminescence (ECL) of tris(2,2'-bipyridine)ruthenium(ii) ([Ru(bpy)3](2+)). These were found to be very attractive as "multi-tasking" reagents, serving not only as co-reactants, but also fulfiling the roles of pH buffer and supporting electrolyte within an aqueous environment; thus significantly simplifying the overall ECL analysis. Sub-nanomolar detection limits were obtained for [Ru(bpy)3](2+) in the presence of BIS-TRIS, making this species an valuable option for co-reactant ECL-based bioanalytical applications.

A variable reactant transducer to study the oscillations of a pendulum and the value of local gravity

[EN]We describe a method for studying the classicalexperiment of the simple pendulum, consisting of a body of magnetic material oscillating through a thin conducting coil (magnetic pendulum), which according to Faraday’s law of induction generates a fluctuating current in the coil that can be transferred into a periodic signal in an oscilloscope. The set up described here allows to study the motion of the pendulum beyond what is normally considered in more basic settings, including a detailed analysis of both small and large oscillations, and the determination of the value of the acceleration of gravity.

Molecular Charge-Transfer Cross Sections and Their Correlation with Reactant Ion Structures

Charge-transfer cross sections have been obtained by using time-of-flight techniques, and results correlated with reaction energetics and theoretical structures computed by self-consistent field-molecular orbital methods. Ion recombination energies, structures, heats of formation, reaction energy defects, and 3.0-keV charge-transfer cross sections are presented for reactions of molecular and fragment ions produced by electron bombardment ionization of CH30CH, and CH$l molecules. Relationships between experimental cross sections and reaction energetics involving different ion structures are discussed.

Microfluidic hydrogen generator : featuring passive on-demand gas generation and self-circulated reactant for integration with micro fuel cell

A microfluidic hydrogen generator is presented in this work. Its fabrication, characterization, and integration with a micro proton exchange membrane (PEM) fuel cell are described. Hydrogen gas is generated by the hydrolysis of aqueous ammonia borane. Gas generation, as well as the circulation of ammonia borane from a rechargeable fuel reservoir, is performed without any power consumption. To achieve this, directional growth and selective venting of hydrogen gas is maintained in the microchannels, which results in the circulation of fresh reactant from the fuel reservoir. In addition to this self-circulation mechanism, the hydrogen generator has been demonstrated to self-regulate gas generation to meet demands of a connected micro fuel cell. All of this is done without parasitic power consumption from the fuel cell. Results show its feasibility in applications of high-impedance systems. Lastly, recommendations for improvements and suggestions for future work are described

The importance of reactant positioning in enzyme catalysis: A hybrid quantum mechanics/molecular mechanics study of a haloalkane dehalogenase

Hybrid quantum mechanics/molecular mechanics calculations using Austin Model 1 system-specific parameters were performed to study the SN2 displacement reaction of chloride from 1,2-dichloroethane (DCE) by nucleophilic attack of the carboxylate of acetate in the gas phase and by Asp-124 in the active site of haloalkane dehalogenase from Xanthobacter autotrophicus GJ10. The activation barrier for nucleophilic attack of acetate on DCE depends greatly on the reactants having a geometry resembling that in the enzyme or an optimized gas-phase structure. It was found in the gas-phase calculations that the activation barrier is 9 kcal/mol lower when dihedral constraints are used to restrict the carboxylate nucleophile geometry to that in the enzyme relative to the geometries for the reactants without dihedral constraints. The calculated quantum mechanics/molecular mechanics activation barriers for the enzymatic reaction are 16.2 and 19.4 kcal/mol when the geometry of the reactants is in a near attack conformer from molecular dynamics and in a conformer similar to the crystal structure (DCE is gauche), respectively. This haloalkane dehalogenase lowers the activation barrier for dehalogenation of DCE by 2–4 kcal/mol relative to the single point energies of the enzyme's quantum mechanics atoms in the gas phase. SN2 displacements of this sort in water are infinitely slower than in the gas phase. The modest lowering of the activation barrier by the enzyme relative to the reaction in the gas phase is consistent with mutation experiments.

Experimental investigation of a turbulent reacting plume

An experimental investigation has been made of a round, non-buoyant plume of nitric oxide, NO, in a turbulent grid flow of ozone, 03, using the Turbulent Smog Chamber at the University of Sydney. The measurements have been made at a resolution not previously reported in the literature. The reaction is conducted at non-equilibrium so there is significant interaction between turbulent mixing and chemical reaction. The plume has been characterized by a set of constant initial reactant concentration measurements consisting of radial profiles at various axial locations. Whole plume behaviour can thus be characterized and parameters are selected for a second set of fixed physical location measurements where the effects of varying the initial reactant concentrations are investigated. Careful experiment design and specially developed chemilurninescent analysers, which measure fluctuating concentrations of reactive scalars, ensure that spatial and temporal resolutions are adequate to measure the quantities of interest. Conserved scalar theory is used to define a conserved scalar from the measured reactive scalars and to define frozen, equilibrium and reaction dominated cases for the reactive scalars. Reactive scalar means and the mean reaction rate are bounded by frozen and equilibrium limits but this is not always the case for the reactant variances and covariances. The plume reactant statistics are closer to the equilibrium limit than those for the ambient reactant. The covariance term in the mean reaction rate is found to be negative and significant for all measurements made. The Toor closure was found to overestimate the mean reaction rate by 15 to 65%. Gradient model turbulent diffusivities had significant scatter and were not observed to be affected by reaction. The ratio of turbulent diffusivities for the conserved scalar mean and that for the r.m.s. was found to be approximately 1. Estimates of the ratio of the dissipation timescales of around 2 were found downstream. Estimates of the correlation coefficient between the conserved scalar and its dissipation (parallel to the mean flow) were found to be between 0.25 and the significant value of 0.5. Scalar dissipations for non-reactive and reactive scalars were found to be significantly different. Conditional statistics are found to be a useful way of investigating the reactive behaviour of the plume, effectively decoupling the interaction of chemical reaction and turbulent mixing. It is found that conditional reactive scalar means lack significant transverse dependence as has previously been found theoretically by Klimenko (1995). It is also found that conditional variance around the conditional reactive scalar means is relatively small, simplifying the closure for the conditional reaction rate. These properties are important for the Conditional Moment Closure (CMC) model for turbulent reacting flows recently proposed by Klimenko (1990) and Bilger (1993). Preliminary CMC model calculations are carried out for this flow using a simple model for the conditional scalar dissipation. Model predictions and measured conditional reactive scalar means compare favorably. The reaction dominated limit is found to indicate the maximum reactedness of a reactive scalar and is a limiting case of the CMC model. Conventional (unconditional) reactive scalar means obtained from the preliminary CMC predictions using the conserved scalar p.d.f. compare favorably with those found from experiment except where measuring position is relatively far upstream of the stoichiometric distance. Recommendations include applying a full CMC model to the flow and investigations both of the less significant terms in the conditional mean species equation and the small variation of the conditional mean with radius. Forms for the p.d.f.s, in addition to those found from experiments, could be useful for extending the CMC model to reactive flows in the atmosphere.

Look before you leap : a confidence-based method for selecting species criticality while avoiding negative populations in τ-leaping

The stochastic simulation algorithm was introduced by Gillespie and in a different form by Kurtz. There have been many attempts at accelerating the algorithm without deviating from the behavior of the simulated system. The crux of the explicit τ-leaping procedure is the use of Poisson random variables to approximate the number of occurrences of each type of reaction event during a carefully selected time period, τ. This method is acceptable providing the leap condition, that no propensity function changes “significantly” during any time-step, is met. Using this method there is a possibility that species numbers can, artificially, become negative. Several recent papers have demonstrated methods that avoid this situation. One such method classifies, as critical, those reactions in danger of sending species populations negative. At most, one of these critical reactions is allowed to occur in the next time-step. We argue that the criticality of a reactant species and its dependent reaction channels should be related to the probability of the species number becoming negative. This way only reactions that, if fired, produce a high probability of driving a reactant population negative are labeled critical. The number of firings of more reaction channels can be approximated using Poisson random variables thus speeding up the simulation while maintaining the accuracy. In implementing this revised method of criticality selection we make use of the probability distribution from which the random variable describing the change in species number is drawn. We give several numerical examples to demonstrate the effectiveness of our new method.

An experimental study of a reactive plume in grid turbulence

Experimental results for a reactive non-buoyant plume of nitric oxide (NO) in a turbulent grid flow doped with ozone (O3) are presented. The Damkohler number (Nd) for the experiment is of order unity indicating the turbulence and chemistry have similar timescales and both affect the chemical reaction rate. Continuous measurements of two components of velocity using hot-wire anemometry and the two reactants using chemiluminescent analysers have been made. A spatial resolution for the reactants of four Kolmogorov scales has been possible because of the novel design of the experiment. Measurements at this resolution for a reactive plume are not found in the literature. The experiment has been conducted relatively close to the grid in the region where self-similarity of the plume has not yet developed. Statistics of a conserved scalar, deduced from both reactive and non-reactive scalars by conserved scalar theory, are used to establish the mixing field of the plume, which is found to be consistent with theoretical considerations and with those found by other investigators in non-reative flows. Where appropriate the reactive species means and higher moments, probability density functions, joint statistics and spectra are compared with their respective frozen, equilibrium and reaction-dominated limits deduced from conserved scalar theory. The theoretical limits bracket reactive scalar statistics where this should be so according to conserved scalar theory. Both reactants approach their equilibrium limits with greater distance downstream. In the region of measurement, the plume reactant behaves as the reactant not in excess and the ambient reactant behaves as the reactant in excess. The reactant covariance lies outside its frozen and equilibrium limits for this value of Vd. The reaction rate closure of Toor (1969) is compared with the measured reaction rate. The gradient model is used to obtain turbulent diffusivities from turbulent fluxes. Diffusivity of a non-reactive scalar is found to be close to that measured in non-reactive flows by others.