Soot formation is one of the most complex phenomena in combustion science and an understanding of the underlying physico-chemical mechanisms is important. This work adopted both experimental and numerical approaches to study soot formation in laminar counterfl ow diffusion flames. As polycyclic aromatic hydrocarbons (PAHs) are the precursors of soot particles, a detailed gas-phase chemical mechanism describing PAH growth upto coronene for fuels with 1 to 4 carbon atoms was validated against laminar premixed and counter- flow diffusion fl ames. Built upon this gas-phase mechanism, a soot model was then developed to describe soot inception and surface growth. This soot model was sub- sequently used to study fuel mixing effect on soot formation in counterfl ow diffusion flames. Simulation results showed that compared to the baseline case of the ethylene flame, the doping of 5% (by volume) propane or ethane in ethylene tends to increase the soot volume fraction and number density while keeping the average soot size almost unchanged. These results are in agreement with experimental observations. Laser light extinction/scattering as well as laser induced fluorescence techniques were used to study the effect of strain rate on soot and PAH formation in counterfl ow diffusion ames. The results showed that as strain rate increased both soot volume fraction and PAH concentrations decreased. The concentrations of larger PAH were more sensitive to strain rate compared to smaller ones. The effect of CO2 addition on soot formation was also studied using similar experimental techniques. Soot loading was reduced with CO2 dilution. Subsequent numerical modeling studies were able to reproduce the experimental trend. In addition, the chemical effect of CO2 addition was analyzed using numerical data. Critical conditions for the onset of soot were systematically studied in counterfl ow diffusion ames for various gaseous hydrocarbon fuels and at different strain rates. A sooting temperature index (STI) and a sooting sensitivity index (SSI) were proposed to present the sooting tendencies of different fuels and their sensitivities to strain rates.

Syngas, a gaseous mixture of H2, CO and diluents such as N2, CO2, is a clean fuel generated via gasification of coal or biomass. Syngas produced via gasification typically has low calorific values due to very high dilution levels (~60% by volume). It has been recognized as an attractive energy source for stationary power generation applications. The present work focuses on experimental and numerical investigation of syngas-air counterflow diffusion flames with varying composition of syngas. Laser-based diagnostic techniques such as Particle Imaging Velocimetry, Rayleigh thermometry and Laser-induced fluorescence have been used to obtain non-intrusive measurements of local extinction strain rates, temperature, quantitative OH and NO concentrations, respectively, for three different compositions of syngas. Complementing the experiments, numerical simulations of the counterflow diffusion flame have been performed to assess the performance of five H2/CO chemical kinetic mechanisms from the literature. The first part of the work involved determination of local extinction strain rates for six H2 /CO mixtures, with H2:CO ratio varying from 1:4 to 1:1. The extinction strain rates were observed to increase from 600 sec-1 to 2400 sec-1 with increasing H2:CO ratio owing to higher diffusivity and reactivity of the H2 molecule. Numerical simulations showed few mechanisms predicting extinction conditions within 5% of the measurements for low H2:CO ratios, however, deviations of 25% were observed for higher H2 :CO ratios. Sensitivity analyses revealed that the chain branching reactions, H+O2 <=>O+OH, O+H2 <=>H+OH and the third body reaction H+O2 +M<=>HO2 +M are the key reactions affecting extinction limits for higher H2:CO mixtures. The second phase of work involved quantitative measurement of OH species concentration in the syngas-air diffusion flames at strain rates varying from 35 sec-1 to 1180 sec-1. Non-intrusive temperature measurements using Rayleigh thermometry were made in order to provide the temperature profile necessary for full quantification of the species concentrations. The [OH] is observed to show a non-monotonous trend with increasing strain rates which is attributed to the competition between the effect of increased concentrations of H2 and O2 in the reaction zone and declining flame temperatures on the overall reaction rate. Although the kinetic mechanisms successfully captured this trend, significant deviations were observed in predictions and measurements in flames with H2:CO ratios of 1:1 and 4:1, at strain rates greater than 800 sec-1 . The key reactions affecting [OH] under these conditions were found to be the same reactions identified earlier during extinction studies, thus implying a need for the refinement of their reaction-rate parameters. Significant disagreements were observed in the predictions made using the chemical kinetic mechanisms from the literature in flames with high H2 content and high strain rate. The final phase of work focused on measurement of nitric oxide (NO) species concentrations followed by a comparison with predictions using various mechanisms. NO levels as high as ~ 48 ppm were observed for flames with moderate to high H2 content and low strain rate. Quantitative reaction pathway diagrams (QRPDs) showed thermal-NO, NNH and prompt-NO pathways to be the major contributors to NO formation at low strain rates, while the NNH pathway was the dominant route for NO formation at high strain rates. The absence of an elaborate CH chemistry in some of the mechanisms has been identified as the reason for underprediction of [NO] in the low strain rate flames. Overall, the quantitative measurements reported in this work serve as a valuable reference for validation of H2/CO chemical kinetic mechanisms, and the detailed numerical studies while providing an insight to the H2:CO kinetics and reaction pathways, have identified key reactions that need further refinement.