First-stage Ignition Delay Times Research Articles

Chemical insights into the two-stage ignition behavior of NH3/H2 mixtures in an RCM

This study investigated the two-stage ignition behavior of NH3/H2 mixtures using a rapid compression machine (RCM). The ignition delay times and first-stage ignition delay times of NH3/H2 blends were measured at temperatures ranging from 881 to 1127 K, pressures of 15 and 25 bar, and equivalence ratios (ϕ) of 1.0 and 1.5. Experimental results showed that H2 had a significant promotional effect on the ignition of NH3, and two-stage ignition behavior was observed in some test mixtures. Time-resolved species concentrations were recorded using the gas chromatography (GC) method during the single- and two-stage ignition process. Species evolution suggested that the consumption of NH3 and H2 separated during the two-stage ignition process. The oxidation of H2 primarily occurred at the first-stage ignition point, while NH3 oxidation occurred at the total ignition point. A kinetic model was developed to predict the two-stage ignition behavior of NH3/H2 and the species profiles. Model analysis showed that H2 played a key role in initiating the oxidation process and contributed to the early heat release. When H2 content was high (e.g. 50%), its oxidation led to the simultaneous total oxidation of NH3, resulting in single-stage ignition characteristics. However, when a small amount of H2 was present (e.g. 10%), its oxidation only partially consumed NH3, leading to the two-stage ignition behavior. Sensitivity analyses indicated that the co-oxidation of fuels during the first-stage ignition was primarily dominated by H2 oxidation chemistry, while NH3 oxidation became dominant during the following total ignition stage as H2 was completely consumed. Additional model simulations revealed that the ignition behavior of NH3/H2 mixtures is strongly influenced by temperature and pressure. A distinct threshold for temperature and pressure was identified, demarcating the transition between single-stage and two-stage ignition phenomena. Moreover, the fraction of H2 in the mixture had a significant impact on the ignition behavior, with higher fractions leading to increased intensity of the first-stage ignition and closer proximity to the total ignition point. However, when the H2 fraction exceeds a certain threshold, two-stage ignition behavior disappears.

Low-temperature oxidation of n-octane and n-decane in shock tubes: Differences in time histories of key intermediates

The impact of chain length on the time histories of key intermediate species that form upon first-stage ignition was studied experimentally in a shock tube using multi-color laser absorption diagnostics. CO, CH2O, OH, and composite time histories of heavier carbonyls were measured simultaneously during the low temperature oxidation of n-octane & n-decane in the temperature range of 720–860 K, and pressure range of 4.1–5.8 atm. The test mixtures were 0.64% & 0.6% fuel in oxygen, respectively. A two-color diagnostic was also developed and used in tandem with other diagnostics to quantify the evolution of temperature during oxidation. To our knowledge, this work reports the first measurement of CH2O, OH, and temperature during oxidation of C8 or heavier hydrocarbon fuels at low temperatures. The measured time histories were also compared against the predictions of two recent detailed kinetic models. Significant differences in the measured and predicted first-stage ignition delay times, absolute concentration of species post-ignition and the maximum rate of formation of species were observed. Our measurements will serve as targets for further refinement of these detailed kinetic models and in the development of rate rules for similar classes of fuels. The measurements also revealed significant differences in the relative reactivity of n-octane and n-decane. Taken together with previous speciation studies conducted in n-heptane, we observe a strong correlation between the species time histories, reactivity, and chain length of straight chain alkanes. This observation lends further support to the selection of CO and CH2O as target species for development of Low-Temperature Hybrid Chemistry (HyChem) models for real transportation and aviation fuels in future.

An experimental and modeling study on auto-ignition of ammonia in an RCM with N2O and H2 addition

Deep insights into the combustion kinetics of ammonia (NH3) can facilitate its application as a promising carbon-free fuel. Due to the low reactivity of NH3, experimental data of NH3 combustion can only be obtained within a limited range. In this work, nitrous oxide (N2O) and hydrogen (H2) were used as additives to investigate NH3 auto-ignition in a rapid compression machine (RCM). Ignition delay times for NH3, NH3/N2O blends, and NH3/H2 blends were measured at 30 bar, temperatures from 950 to 1437 K. The addition of N2O and H2 ranged from 0 to 50% and 0 to 25% of NH3 mole fraction, respectively. Time-resolved species profiles were recorded during the auto-ignition process using a fast sampling system combined with a gas chromatograph (GC). An NH3 combustion model was developed, in which the rate constants of key reactions were constrained by current experimental data. The addition of N2O affected the ignition of NH3 primarily through the decomposition of N2O (N2O (+M) = N2 + O (+M), R1) and direct reaction between N2O and NH2 (N2H2 + NO = NH2 + N2O, R2). The rate constant of R2 was constrained effectively by experimental data of NH3/N2O mixtures. Two-stage ignition behaviors were observed for NH3/H2 mixtures, and the corresponding first-stage ignition delay times were reported for the first time. Experimental species profiles suggested the first-stage ignition resulted from the consumption of H2. The oxidation of H2 provided extra HO2 radicals, which promoted the production of OH radicals and initiated first-stage ignition. Reactions between HO2 radicals and NH3/NH2 dominated the first-ignition delay times of NH3/H2 mixtures. Moreover, the first-stage ignition led to the fast production of NO2, which acted as a key intermediate and affected the following total ignition. Consequently, the reaction NH2 + NO2 = H2NO + NO (R3) was constrained by total ignition delay times.

Prospects and Limitations of Predicting Fuel Ignition Properties from Low-Temperature Speciation Data

Using chemical kinetic modeling and statistical analysis, we investigate the possibility of correlating key chemical “markers”─typically small molecules─formed during very lean (ϕ ∼ 0.001) oxidation experiments with near-stoichiometric (ϕ ∼ 1) fuel ignition properties. One goal of this work is to evaluate the feasibility of designing a fuel-screening platform, based on small laboratory reactors that operate at low temperatures and use minimal fuel volume. Buras et al. [Combust. Flame 2020, 216, 472–484] have shown that convolutional neural net (CNN) fitting can be used to correlate first-stage ignition delay times (IDTs) with OH/HO2 measurements during very lean oxidation in low-T flow reactors with better than factor-of-2 accuracy. In this work, we test the limits of applying this correlation-based approach to predict the low-temperature heat release (LTHR) and total IDT, including the sensitivity of total IDT to the equivalence ratio, ϕ. We demonstrate that first-stage IDT can be reliably correlated with very lean oxidation measurements using compressed sensing (CS), which is simpler to implement than CNN fitting. LTHR can also be predicted via CS analysis, although the correlation quality is somewhat lower than for first-stage IDT. In contrast, the accuracy of total IDT prediction at ϕ = 1 is significantly lower (within a factor of 4 or worse). These results can be rationalized by the fact that the first-stage IDT and LTHR are primarily determined by low-temperature chemistry, whereas total IDT depends on low-, intermediate-, and high-temperature chemistry. Oxidation reactions are most important at low temperatures, and therefore, measurements of universal molecular markers of oxidation do not capture the full chemical complexity required to accurately predict the total IDT even at a single equivalence ratio. As a result, we find that ϕ-sensitivity of ignition delay cannot be predicted at all using solely correlation with lean low-T chemical speciation measurements.

Auto-ignition characteristics of a near-term light surrogate fuel for marine diesel: An experimental and modeling study

Autoignition characteristics of a four-component surrogate fuel(M2) were investigated in a heated rapid compression machine over a wide range of conditions. The near-term light surrogate M2 developed for marine diesel fuel was formulated in our previous study containing 17.3% n-hexadecane, 5.93% 2,2,4,4,6,8,8-heptamethylnonane, 30% decalin and 46.77% 1-methylnaphthalene by mole fraction. Ignition delay times (IDTs) of gas-phase M2/N2/O2 mixture were measured at pressures of 7, 10, 15 and 20 bar over the temperature range from 675 K to 914 K for the equivalence ratios (ER) of 0.5, 1 and 1.5. NTC behaviours within the temperature of 730–850 K and two-stage ignition phenomena were observed. The effects of operating conditions such as pressure, equivalence ratio and oxygen content were systematically studied, and correlations of total IDTs and first-stage IDTs were performed to further quantitatively reveal the IDTs dependence on the above parameters. Reasonable modifications were made to a literature mechanism to improve its predicting quality. The simulation results using the modified model could satisfactorily reproduce the IDTs under the test conditions, and the model is also able to capture the ignition delay dependence on pressure and fuel/oxygen content. A brute force sensitivity analysis at the low temperature (680 K) and the NTC temperature (780 K) was carried out to identify the key reactions that govern the ignition event of surrogate M2.

Thermal-pyrolysis induced over-driven flame and its potential role in the negative-temperature dependence of iso-octane flame speed at elevated temperatures

Recently, high-temperature flame speed measurement up to 900 K has been successfully realized at Stanford University using a conventional shock tube, assisted by laser ignition and chemiluminescence image systems. For a near stoichiometric iso-octane/O2/N2/He mixture at atmospheric pressure, their results show that while flame speed increases with increasing unburnt temperature in the low and high-temperature range, it decreases with increasing unburnt temperature in the intermediate temperature regime (750–800 K). The measurement time for the flame initiation and propagation is orders of magnitude shorter than the first-stage ignition delay time, implying that the unburnt mixture upstream of the flame is largely chemically frozen. Therefore, such non-monotonic behavior in the flame speed is unlikely to be induced by autoignition chemistry. To understand this interesting phenomenon, 1-D transient simulation of spherical flame initiation and propagation with different ignition energy has been performed and compared with the experiment data. It is shown that for the relatively low ignition energy 7.5 mJ, an over-driven flame regime characterized by flame speeds and stretch rates well above the steady-state values occurs in the intermediate temperature range. The chemical structure of an over-driven flame involves substantial fuel thermal decomposition in the preheat zone, followed by C1-C4 oxidation in the reaction zone. It is found that the non-monotonicity in the observed flame speed is strongly correlated with the occurrence of over-driven flames in simulations. These results demonstrate a new flame structure which can potentially explain the observed non-monotonic flame speed for iso-octane at high temperatures. Higher ignition energy or smaller ignition kernel is suggested in future experiments to mitigate such over-driven effects.

Studies of autoignition-assisted nonpremixed cool flames

Autoignition-assisted nonpremixed cool flames of diethyl ether (DEE) are investigated in both laminar counterflow and turbulent jet flame configurations. First, the ignition and extinction limits of laminar nonpremixed cool flames of diluted DEE are measured and simulated using detailed kinetic models. The laminar flame measurements are used to validate the kinetic models and guide the turbulent flame measurements. The results show that, below a critical mixture condition, for elevated temperature and dilute mixtures, the cool flame extinction limit and the low-temperature ignition limit merge, leading to autoignition-assisted cool flame stabilization without hysteresis. Based on the findings from the laminar flame experiments, autoignition-assisted turbulent lifted cool flames are established using a Co-flow Axisymmetric Reactor-Assisted Turbulent (CARAT) burner. The lift-off heights of the turbulent cool flames are quantified using formaldehyde planar laser-induced fluorescence. Based on an analogy with autoignition-assisted lifted hot flames, a correlation is proposed such that the autoignition-assisted cool flame lift-off height scales with the product of the flow velocity and the square of the first-stage ignition delay time. Using this scaling, we demonstrate that the kinetic mechanism that most accurately predicts the laminar flame ignition and extinction limits also best predicts the turbulent cool flame lift-off height.

Autoignition of CRC diesel surrogates at low temperature combustion conditions: Rapid compression machine experiments and modeling

As federal programs require increasingly stringent engine emissions and fuel economy standards, these ambitions can only be met if next-generation combustion technology is developed focusing on high-efficiency and low-emissions engines. Recent research has indicated the need to operate engines at higher compression ratios and with low temperature combustion (LTC) to achieve the needed gains in engine efficiency and reductions in emissions. Because there is a lack of understanding of the chemistry of diesel fuel components and their mixtures at these LTC conditions, this limits the ability to develop predictive chemical kinetic models that can be used to optimize engine combustion. The current study aims to fill in gaps in fundamental combustion data on surrogate fuel mixtures relevant to diesel fuels. Specifically, four multicomponent diesel surrogates formulated by the Coordinating Research Council (CRC) to emulate an ultra-low-sulfur research-grade #2 certification diesel fuel (CFA), namely V0a (4 components), V0b (5 components), V1 (8 components), and V2 (9 components), have been investigated in a rapid compression machine (RCM) through determination of total and first-stage ignition delay times. Autoignition characteristics of lean to rich fuel/O2/N2 mixtures, for the four CRC surrogates and CFA, have been measured using an RCM at LTC relevant pressures and temperatures, in the ranges of 10–20 bar and 650–1000 K, respectively. The equivalence ratios have been varied by independently changing the oxygen mole fraction and the fuel mole fraction in the test mixtures, thereby illustrating the individual effects of oxygen concentration and fuel loading on diesel autoignition. Autoignition results of these four CRC surrogates are compared among them and with those of CFA. Some degree of agreement in autoignition response between each CRC surrogate and CFA is observed, while discrepancies are also identified and discussed. In addition, a detailed chemical kinetic model for diesel surrogates has been developed and validated against these newly-acquired RCM data. This model shows reasonable agreement with the overall ignition delay time results of the current RCM experiments. Chemical kinetic analyses of the developed model were further conducted to help identify the reactions controlling the autoignition processes and the consumption of fuel components in CRC surrogates.

The effect of ammonia addition on the low-temperature autoignition of n-heptane: An experimental and modeling study

Ammonia (NH3) is receiving increasing attention as an alternative engine fuel due to its carbon-free nature. However, its fundamental combustion characteristics, such as higher autoignition temperature and lower burning velocity compared to conventional hydrocarbons, limit its direct use in traditional engines. To confront this dilemma, hydrocarbon/NH3 blending fuels are seen as one of the most appropriate ways to exploit its advantage and offset its weaknesses. Using n-heptane as a representative of hydrocarbons, this study investigated the effect of NH3 addition on the low-temperature autoignition of n-heptane. The ignition delay times of five n-heptane/NH3 mixtures with NH3 fractions of 0%, 20%, and 40% were measured in a rapid compression machine at temperatures of 635–945 K, pressures of 10 and 15 bar, and equivalence ratios of 1.0 and 2.0. Experimental results show that the n-heptane/NH3 blending fuels exhibit pronounced low-temperature reactivity, and both the total and the first-stage ignition delay times increase with the increase of NH3 fraction. A blending mechanism of n-heptane/NH3 was compiled based on the existing n-heptane mechanism and NH3 mechanism. It is found that the blending mechanism is capable to predict the inhibition effect of NH3 addition on n-heptane autoignition and qualitatively capture the dependence of ignition delay time on equivalence ratio and oxygen mole fraction. Nevertheless, there are significant discrepancies between the experiments and the simulation. Furthermore, kinetic analyses, including species evolution, rate of production and sensitivity of OH radical were conducted sequentially to reveal the autoignition kinetics of NH3/n-heptane blends and the interaction between n-heptane and NH3. Suggestions are provided for the further development of the blending mechanism.

An experimental and modeling study of n-hexadecane autoignition under low-to-intermediate temperatures

N-hexadecane is a potential candidate of diesel surrogate fuels and is also the largest linear alkane (n-alkanes) with known chemical kinetic models. The objective of this study is to investigate the autoignition characteristics of n-hexadecane in the low-to-intermediate temperature region and to validate the existing kinetic models. In this study, the ignition delay times (IDTs) of n-hexadecane were measured using a heated rapid compression machine (RCM) at two pressures of 7 and 10 bar, and over equivalence ratios ranging from 0.5 to 1.3. Two-stage ignition characteristic and the negative temperature coefficient (NTC) behavior of total ignition delay time were experimentally captured. This study paid special attention to the influence of pressure, equivalence ratio, and oxygen content on the IDTs of n-hexadecane. It is observed that both the total IDTs and the first-stage IDTs decrease with the rise of those parameters. It is worth noting that the first-stage IDT is found to show a greater dependence on temperature but a weaker dependence on other parameters compared to the total IDT. The observed IDT dependence in the low-temperature region (LTR) were quantitatively described by ignition delay time correlations. The newly measured IDTs were then validated against two kinetic models (LLNL and CRECK). Simulation results show that both models underpredict the first-stage IDT but generally capture the temperature dependence. The CRECK model well predicts the total IDTs of n-hexadecane while the LLNL model significantly underpredicts the total IDTs at most investigated conditions. To the best of our knowledge, this study is the first investigation on n-hexadecane autoignition under low-to-intermediate temperatures, which deepens the understanding of large n-alkane oxidation and contributes to the improvement of the existing kinetic models.

Significance of reaction CH3 + NO = H2CN + OH in two-stage ignition of nitromethane

Two-stage ignition of nitromethane diluted in Ar is investigated at various equivalence ratios (0.2–0.5), dilution levels (93%–97%), and pressures (4–16 atm) with a heated shock tube apparatus. OH* emission profiles are used to determine ignition delay times. The second-stage ignition delay time increases with increasing equivalence ratio or dilution level, but is insensitive to pressure especially at high dilution levels. The first-stage ignition delay time is unaffected by the present experimental parameters above 1150 K, below which it decreases with increasing equivalence ratio or pressure. An updated model reconsidering reaction CH3 + NO = H2CN + OH is examined against the experimental measurements from present work and literature, including ignition delay times, laminar burning velocities, and species mole fraction profiles. At fuel-rich condition, this reaction has a significant contribution to the formation of OH radical during the second-stage ignition. The two-stage ignition and intensity evolution of OH peaks are well predicted and explained kinetically by the updated model.

Experimental and modeling validation of a large diesel surrogate: Autoignition in heated rapid compression machine and oxidation in flow reactor

Autoignition and oxidation characteristics of a three-component diesel surrogate fuel were studied in a heated rapid compression machine (RCM) and a flow reactor (FR) over a wide range of conditions. The surrogate components, n-cetane, 2,2,4,4,6,8,8-heptamethylnonane (HMN), and 1-methylnaphthalene (1-MN), all fall within the C10–C20 range of real diesel fuel. The RCM-measured ignition delay times (IDTs) and FR oxidation data of the surrogate fuel were then compared with those of the target diesel. It is found that the diesel surrogate fuel is in good agreement with the target diesel in total ignition delay time and FR speciation data over the whole temperature range, reflecting the success of the surrogate fuel construction. A semi-detailed kinetic model was used to predict the autoignition and oxidation behavior of the surrogate fuel in RCM and FR experiments. Results show that the kinetic model captures well the measured total IDTs and the mole fractions of O2, H2, CO2, and small hydrocarbons under all investigated conditions. To deepen the understanding of low-temperature reaction scheme, rate of production (ROP) analysis of OH and HO2 radicals was carried out during the first-stage ignition to explore the causes of low-temperature and negative temperature coefficient (NTC) reactivity. A brute force sensitivity analysis of first-stage ignition delay time was also conducted to further identify the controlling reactions in the first-stage ignition of the surrogate fuel.

Shock tube study of normal heptane first-stage ignition near 3.5 atm

Shock tube ignition delay times and species time history measurements for Primary Reference Fuels (PRFs) such as normal heptane provide targets for the validation of combustion models, which in turn are used to develop more fuel-efficient engines that have smaller environmental footprints. However, a review of the literature has revealed that most of the shock tube ignition delay time and species measurement data for normal heptane have been obtained at elevated pressures, rather than at relatively low pressures where many other important experimental techniques such as jet-stirred reactors and flow reactors can provide corroborating results. One central problem preventing previous shock tube studies from examining first-stage ignition at these lower pressures was that ignition times were too long under these conditions to be measured within the available shock tube test times. To address this issue, recent advances in shock tube techniques for achieving long uniform test times have been applied in order to measure low-pressure first-stage ignition times of normal heptane together with normal heptane fuel time-history records at times up to about 30 ms. These measurements were performed in the Negative Temperature Coefficient (NTC) region (T=664−792 K) in lean mixtures (21%O2/Ar, equivalence ratio ϕ=0.5) at pressures of roughly P=3.5 atm using both the conventional and Constrained Reaction Volume (CRV) shock tube filling strategies. The data have been used to evaluate the performance of several combustion models, have been compared with other higher-pressure shock tube first-stage ignition times in n-heptane/20–21%O2 mixtures found in the literature, and have been fit using a two-zone Arrhenius model for first-stage ignition delay times. The results showed that some combustion models yield ignition delay time predictions that differ from the experimental results by as much as an order of magnitude, that under these conditions n-heptane first-stage ignition times scale by roughly P−0.71 but are insensitive to ϕ, and that the fraction of fuel remaining after first-stage ignition increases with increasing initial experimental temperature.

A comparison of sensitivity metrics for two-stage ignition behavior in rapid compression machines

A rapid compression machine (RCM) multi-zone model is used to simulate the ignition of primary reference fuel (PRF) mixtures that exhibit two-stage ignition behavior. Sensitivity coefficients for each reaction in the PRF mechanism are calculated from four different metrics: (1) first-stage energy release, (2) first-stage pressure rise, (3) first-stage ignition delay time, and (4) total ignition delay time. The sensitivity coefficients are used to provide four unique rankings, and the rankings are compared using Spearman’s rank correlation coefficient. Special emphasis is given to comparing the rankings based on first-stage energy release and total ignition delay time. The level of agreement between these two rankings is shown to depend on the reaction conditions. Simulation cases with high peak heat release rates during the first stage of ignition tend to exhibit disagreement in the rankings, indicating that new kinetic information can be obtained by studying first stage energy release in addition to total ignition delay time. Simulations show that the high peak heat release rates are associated with energy release across a broad range of temperatures (range can be in excess of 100K even for lean conditions). This distribution leads to a discrepancy between sensitivity coefficients calculated for the total ignition delay time and the first-stage energy release. Sensitivity coefficients for the total ignition delay time are characterized by reactivity at the highest temperatures in the RCM, while sensitivity coefficients for the first-stage energy release are characterized by reactivity across the full range of temperatures in the RCM.

A direct numerical simulation of cool-flame affected autoignition in diesel engine-relevant conditions

In diesel engines, combustion is initiated by a two-staged autoignition that includes both low- and high-temperature chemistry. The location and timing of both stages of autoignition are important parameters that influence the development and stabilisation of the flame. In this study, a two-dimensional direct numerical simulation (DNS) is conducted to provide a fully resolved description of ignition at diesel engine-relevant conditions. The DNS is performed at a pressure of 40 atmospheres and at an ambient temperature of 900 K using dimethyl ether (DME) as the fuel, with a 30 species reduced chemical mechanism. At these conditions, similar to diesel fuel, DME exhibits two-stage ignition. The focus of this study is on the behaviour of the low-temperature chemistry (LTC) and the way in which it influences the high-temperature ignition. The results show that the LTC develops as a “spotty” first-stage autoignition in lean regions which transitions to a diffusively supported cool-flame and then propagates up the local mixture fraction gradient towards richer regions. The cool-flame speed is much faster than can be attributed to spatial gradients in first-stage ignition delay time in homogeneous reactors. The cool-flame causes a shortening of the second-stage ignition delay times compared to a homogeneous reactor and the shortening becomes more pronounced at richer mixtures. Multiple high-temperature ignition kernels are observed over a range of rich mixtures that are much richer than the homogeneous most reactive mixture and most kernels form much earlier than suggested by the homogeneous ignition delay time of the corresponding local mixture. Overall, the results suggest that LTC can strongly influence both the timing and location in composition space of the high-temperature ignition.

Time-resolved carbon monoxide measurements during the low- to intermediate-temperature oxidation of n-heptane, n-decane, and n-dodecane

Time-resolved mid-infrared laser absorption measurements of carbon monoxide were carried out during the low- and intermediate-temperature oxidation of n-heptane, n-decane, and n-dodecane in a shock tube. Dilute mixtures of n-alkane/O2/Ar were shock heated, initiating oxidation and resulting in CO formation and heat release with time scales of 1 to 10ms. Experiments are reported in two temperature and oxygen concentration ranges, 686–797K at 5% O2 and 1121–1290K at 0.5% O2, for pressures around 10atm. For measurements in the lower temperature range, first-stage ignition was observed and found to exhibit negative-temperature-coefficient behavior. The low-temperature reactivity was found to increase with increasing n-alkane chain length and first-stage ignition delay to be well correlated with literature derived cetane numbers. The time-resolved CO measurements and first-stage ignition delay times provide quantitative targets for kinetic models that are sensitive to important low-temperature ignition chemistry; comparisons are made with n-alkane kinetic models from the literature.

Constrained reaction volume shock tube study of n-heptane oxidation: Ignition delay times and time-histories of multiple species and temperature

Ignition delay times of normal heptane have been measured at temperatures ranging from 651 to 823K and at pressures between 6.1 and 7.4atm at an equivalence ratio of 0.75 in 15%O2/5%CO2/Ar and in 15%O2/Ar mixtures behind reflected shock waves in a shock tube. Time-history measurements of fuel, OH, aldehydes (mostly CH2O), CO2, H2O, and temperature were also measured under these conditions. These time-histories provide critically needed kinetic targets to test and refine large reaction mechanisms. Measurements were acquired using a novel constrained reaction volume approach, wherein a sliding gate valve confined the reactant mixture to a region near the endwall of the shock tube. A staged-driver gas filling strategy, combined with driver section extensions, driver inserts, and driver gas tailoring, was used to obtain constant-pressure test times of up to 55ms, allowing observations of the chemistry in the Negative Temperature Coefficient (NTC) region. Experiments with conventional shock tube filling were also performed, showing similar overall ignition behavior. Comparisons between current data and simulations using the Mehl et al. n-Heptane mechanism (2011) are provided, revealing that the mechanism generally under-predicts first-stage ignition delay times in the NTC region, and that at low temperatures it over-predicts the extent of fuel decomposition during first stage ignition.