New ignition delay time (IDT) measurements for two natural gas (NG) blends composed of C1–C7n-alkanes, NG6 (C1:60.625%, C2:20%, C3:10%, C4:5%, nC5:2.5%, nC6:1.25%, nC7:0.625%) and NG7 (C1:72.635%, C2:10%, C3:6.667%, C4:4.444%, nC5:2.965%, nC6:1.976%, nC7:1.317%) by volume with methane as the major component are presented. The measurements were recorded using a high-pressure shock tube (HPST) for stoichiometric fuel in air mixtures at reflected shock pressures (p5) of 20–30 bar and at temperatures (T5) of 987–1420 K. The current results together with rapid compression machine (RCM) measurements in the literature show that higher concentrations of the higher n-alkanes (C4–C7) ∼1.327% in the NG7 blend compared to the NG6 blend result in the ignition times for NG7 being almost a factor of two faster than those for NG6 at compressed temperatures of (TC) ≤ 1000 K. This is due to the low temperature chain branching reactions that occur for higher alkane oxidation kinetics in this temperature range. On the contrary, at TC > 1000 K, NG6 exhibits ∼20% faster ignition than NG7, primarily because about 12% of the methane in the NG7 blend is primarily replaced by ethane (∼10%) in NG6, which is significantly more reactive than methane at these higher temperatures. The performance of NUIGMech1.2 in simulating these data is assessed, and it can reproduce the experiments within 20% for all the conditions considered in the study. We also investigate the effect of hydrogen addition to the auto-ignition of these NG blends using NUIGMech1.2, which has been validated against the existing literature for natural gas/hydrogen blends. The results demonstrate that hydrogen addition has both an inhibiting and a promoting effect in the low- and high-temperature regimes, respectively. Sensitivity analyses of the hydrogen/NG mixtures are performed to understand the underlying kinetics controlling these opposite ignition effects. At low temperatures, H-atom abstraction byO˙
H radicals from C3 and larger fuels are the key chain-branching reactions consuming the fuel and providing the necessary fuel radicals, which undergo low temperature chemistry (LTC) leading to ignition. However, with the addition of hydrogen to the fuel mixture, the competition by H2 for O˙
H radicals via the reaction H2 +  O˙
H ↔ H˙
 + H2O reduces the progress of the LTC of the higher hydrocarbon fuels thereby inhibiting ignition. At higher temperatures, since H˙
 + O2 ↔ Ö + O˙
H is the most sensitive reaction promoting reactivity, the higher concentrations of H2 in the fuel mixture lead to higher H˙
 atom concentrations leading to faster ignition due to an enhanced rate of the H˙
 + O2 ↔ Ö + O˙
H reaction.

Hydrogen (H2) is known to be the fastest fuel to ignite among all practical combustion fuels. In this study, for the first time, longer ignition delay times (IDTs) for the H2 and H2 blended CH4 mixtures were measured compared to those for pure CH4. This work investigates the ignition characteristics of H2, CH4, and 50% CH4/50% H2 mixtures using a rapid compression machine at pressures ranging from 20 to 50 bar and at equivalence ratios (φ) from 0.5 to 2.0 in air in the temperature range 858–1080 K. The experimental IDTs are simulated using a newly updated kinetic mechanism, NUIGMech1.3, and good agreement is observed. At lower temperatures the IDTs of H2, CH4, and the 50% CH4/50% H2 mixtures are similar to one another, and the IDTs of the 50% CH4/50% H2 mixtures are longer than those for pure CH4 at temperatures below 930 K. At temperatures below 890–925 K, depending on the operating pressure and equivalence ratio, the hydrogen mixtures are the slowest to ignite, with IDTs being 2.5 times longer than those recorded for CH4 at a pressure of 40 bar at 890 K for φ = 1.0, and at 875 K for φ = 2.0. At low temperatures alkyl (Ṙ = ĊH3 and Ḣ) radicals add to O2 producing RȮ2 radicals, which then react with HȮ2 radicals forming ROOH (H2O2 and CH3OOH) and O2. For H2, the self-recombination of HȮ2 radicals leads to chain propagation which inhibits reactivity, whereas for CH4, the reaction between RȮ2 (CH3OȮ) and HȮ2 leads to chain branching, increasing reactivity. Furthermore, CH3OOH decomposes more easily to produce CH3Ȯ and ȮH radicals than does H2O2 to produce two ȮH radicals. Thus, mixtures containing higher H2 concentrations are slower to ignite compared to those with higher CH4 concentrations at low temperatures.

This work presents an experimental and kinetic modeling study of propane oxidation. Ignition delay times of propane were measured in a high-pressure shock tube and in rapid compression machines in the temperature range 689 – 1700 K at equivalence ratios of 0.5, 1.0 and 2.0 in ‘air’, for a wide range of pressures from 20 to 90 bar. CO and H2O mole fraction profiles for propane oxidation were measured in a shock tube behind reflected shock waves in the temperature range 1370–1840 K at equivalence ratios of 0.5, 1.0 and 2.0 and at a pressure of approximately 1.3 atm. Moreover, propane oxidation was studied using a jet-stirred reactor coupled to a synchrotron vacuum ultraviolet photoionization mass spectrometer at low temperatures in the range 565 – 690 K and at a pressure of 1 atm. This wide range of experimental datasets for propane oxidation was used to reoptimize and update our previous kinetic mechanisms, AramcoMech3.0 and NUIGMech1.1. In the current mechanism, NUIGMech1.3, the thermochemical parameters of all species relevant to low-temperature propane oxidation chemistry, including propyl-peroxyl, hydroperoxyl-propyl, hydroperoxyl-propyl-peroxyl, and carbonyl-hydroperoxide radicals, are updated based on newly calculated values at the CCSD(T)-F12/TZ-F12//B2PLYPD3/TZ///B2PLYP-D3/TZ level of theory. The improvements made in the thermochemical values and in the kinetic parameters for the low-temperature propane oxidation reactions in NUIGMech1.3 result in better model agreement with the new IDTs and speciation data, including carbon monoxide, formaldehyde, propene, acetaldehyde and various minor products such as ethylene, acetic acid, acrolein as well as various hydroperoxide and cyclic ether species.

Ammonia is a promising carbon-free alternative fuel for use in combustion systems. The main associated challenges are its relatively low reactivity and high NOx emissions compared to conventional fuels. Therefore, the combustion behaviour of ammonia and ammonia blends still needs to be better understood over a wide range of conditions. To this end, a comprehensive chemical kinetic mechanism C3MechV3.4, which is an update of C3MechV3.3, has been developed for improved predictions of the combustion of ammonia and ammonia blends. C3MechV3.4 has been validated using a wide range of experimental results for pure ammonia and ammonia/hydrogen, ammonia/methanol and ammonia/n-heptane blends. These validations target different data sets including ignition delay times, species profiles measured as a function of time, and/or temperature and laminar flame speeds over a wide range of conditions. The updated developed mechanism gives good predictions for pure ammonia and its blends with hydrogen, methanol and n-heptane. The most important reactions affecting predictions in different regimes for the various ammonia mixtures are discussed.

2,3-Dimethyl-2-butene (TME) is a potential fuel additive with high research octane number (RON) and octane sensitivity (S), which can improve internal combustion engine performance and efficiency. However, the combustion characteristics of TME have not been comprehensively investigated. Thus, it is essential to study the combustion characteristics of TME and construct a detailed chemical kinetic model to describe its combustion. In this paper, two high-pressure shock tubes and a constant-volume reactor are used to measure ignition delay times and laminar flame speeds of TME oxidation. The ignition delay times were measured at equivalence ratios of 0.5, 1.0, and 2.0 in “air”, at pressures of 5 and 10 bar, in the temperature range of 950 – 1500 K. Flame speeds of the TME/ “air” mixtures were measured at atmospheric pressure, at a temperature of 325 K, for equivalence ratios ranging from 0.78 to 1.31. Two detailed kinetic mechanisms were constructed independently using different methodologies; the KAUST TME mechanism was constructed based on NUIGMech1.1, and the MIT TME mechanism was built using the Reaction Mechanism Generator (RMG). Both mechanisms were used to simulate the experimental results using Chemkin Pro. In the present work, reaction flux and sensitivity analyses were performed using the KAUST mechanism to determine the critical reactions controlling TME oxidation at the conditions studied.

This study presents new ignition delay time data for two multi-component natural gas (NG) blends composed of C1–C7 n-alkanes with methane as the major component. New experimental data were recorded using a high-pressure shock tube (HPST) at reflected shock pressures (p5) of 10–30 bar, at temperatures (T5) in the range 770–1480 K, and at equivalence ratios (φ) of 0.5–1.5 in ‘air’. The current results together with published rapid compression machine (RCM) measurements show that higher concentrations of larger molecular weight n-alkanes in the NG blends increase fuel reactivity by more than an order of magnitude with mixtures that have ∼18.75% of C3–C5 components compared to mixtures that have ∼44.4% of C3–C7 components at temperatures below 1000 K. On the contrary, at higher temperatures the effect of increasing reactivity is reduced. NUIGMech1.2 is used to simulate the conditions studied and shows good agreement with the experimental ignition delay time data. A correlation equation is developed through regression analyses using NUIGMech1.2 to predict ignition delay times for a wide range of C1–C7 NG mixtures, in the pressure range 10–50 bar, at temperatures in the range 950–2000 K, and at φ = 0.3–3.0 in air. The proposed correlation expression that employs a traditional Arrhenius form is successfully validated against the new experimental data as well as previously published HPST experimental data.