A shock tube study of H + HNCO → NH2 + CO

The reaction of atomic hydrogen with isocyanic acid (HNCO) to produce the amidogen radical (NH₂) and carbon monoxide, has been studied in shock-heated mixtures of HNCO dilute in argon. Time-histories of the ground-state NH₂ radical were measured behind reflected shock waves using cw, narrowlinewidth laser absorption at 597 nm, and HNCO time-histories were measured using infrared emission from the fundamental v₂-band of HNCO near 5 μm. The second-order rate coefficient of reaction (2(a)) was determined to be: cm³ mol^?1 s^?1, where f and F define the lower and upper uncertainty limits, respectively. An upper limit on the rate coefficient of was determined to be:      

A shock tube study of the pyrolysis of NO2

NO₂ concentration profiles in shock-heated NO₂/Ar mixtures were measured in the temperature range of 1350–2100 K and pressures up to 380 atm using Ar⁺ laser absorption at 472.7 nm, IR emission at 6.25±0.25 μm, and visible emission at 300–600 nm. In the course of this study, the absorption coefficient of NO₂ at 472.7 nm was measured at temperatures from 300 K to 2100 K and pressures up to 75 atm. Rate coefficients for the reactions NO₂+M→NO+O+M (1), NO₂+NO₂→2NO+O₂ (2a), and NO₂+NO₂→NO₃+NO (2b) were derived by comparing the measured and calculated NO₂ profiles. For reaction (1), the following low- and high-pressure limiting rate coefficients were inferred which describe the measured fall-off curves in Lindemann form within 15% [FORMULA] The inferred rate coefficient at the low- pressure limit, k_1o, is in good agreement with previous work at higher temperatures, but the energy of activation is lower by 20 kJ/mol than reported previously. The pressure dependence of k₁ observed in the earlier work of Troe [1] was confirmed. The rate coefficient inferred for the high pressure limit, k_1∞, is higher by a factor of two than Troe's value, but in agreement with data obtained by measuring specific energy-dependent rate coefficients. For the reactions (2a) and (2b), least-squares fits of the present data lead to the following Arrhenius expressions: [FORMULA] For reaction (2), the new data agree with previously recommended values of k_2a and k_2b, although the present study suggests a slightly higher preexponential factor for k_2a. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 483–493, 1997.     

A shock tube and theoretical study on the pyrolysis of 1,4-dioxane

The dissociation of 1, 2 and 4% 1,4-dioxane dilute in krypton was studied in a shock tube using laser schlieren densitometry, LS, for 1550-2100 K with 56 ± 4 and 123 ± 3 Torr. Products were identified by time-of-flight mass spectrometry, TOF-MS. 1,4-dioxane was found to initially dissociate via C-O bond fission followed by nearly equal contributions from pathways involving 2,6 H-atom transfers to either the O or C atom at the scission site. The 'linear' species thus formed (ethylene glycol vinyl ether and 2-ethoxyacetaldehyde) then dissociate by central fission at rates too fast to resolve. The radicals produced in this fission break down further to generate H, CH(3) and OH, driving a chain decomposition and subsequent exothermic recombination. High-level ab initio calculations were used to develop a potential energy surface for the dissociation. These results were incorporated into an 83 reaction mechanism used to simulate the LS profiles with excellent agreement. Simulations of the TOF-MS experiments were also performed with good agreement for consumption of 1,4-dioxane. Rate coefficients for the overall initial dissociation yielded k(123Torr) = (1.58 ± 0.50) × 10(59) × T(-13.63) × exp(-43970/T) s(-1) and k(58Torr) = (3.16 ± 1.10) × 10(79) × T(-19.13) × exp(-51326/T) s(-1) for 1600 < T < 2100 K.     

Detailed kinetics of cyclopentadiene decomposition studied in a shock tube

Mixtures of cyclopentadiene diluted with argon were used to investigate its decomposition pattern in a single pulse shock tube. The temperatures ranged from 1080 to 1550 K and pressures behind the shock were between 1.7–9.6 atm. The cyclopentadiene concentrations ranged from 0.5 to 2%. Gas-chromatographic analysis was used to determine the product distribution. The main products in order of abundance were acetylene, ethylene, methane, allene, propyne, butadiene, propylene, and benzene. The decomposition of cyclopentadiene was simulated with a kinetic scheme containing 44 species and 144 elementary reactions. This was later reduced to only 36 reactions. The ring opening process of the cyclopentadienyl radical was found to be the crucial step in the mechanism. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 505–514, 1997.     

Ab initio study on the mechanism of reaction HNCO+NH_2

Ab initio UMP2 and UQCISD(T) calculations, with 6-311G** basis sets, were performed for the titled reactions. The results show that the reactions have two product channels: NH2+ HNCO→NH3+NCO (1) and NH2+HNCO-N2H3+CO (2), where reaction (1) is a hydrogen abstraction reaction via an H-bonded complex (HBC), lowering the energy by 32.48 kJ/mol relative to reactants. The calculated QCISD(T)//MP2(full) energy barrier is 29.04 kJ/mol, which is in excellent accordance with the experimental value of 29.09 kJ/mol. In the range of reaction temperature 2300-2700 K, transition theory rate constant for reaction (1) is 1.68 × 1011- 3.29 × 1011 mL · mol-1· s-1, which is close to the experimental one of 5.0 ×1011 mL× mol-1· s-1 or less. However, reaction (2) is a stepwise reaction proceeding via two orientation modes, cis and trans, and the energy barriers for the rate-control step at our best calculations are 92.79 kJ/mol (for cis-mode) and 147.43 kJ/mol (for trans-mode), respectively, which is much higher than     

Sensitive detection of NH2 in shock tube experiments using frequency modulation spectroscopy

Frequency modulation detection of NH₂ in shock tube kinetic experiments is demonstrated with sensitivities of 0.5 ppm in a single pass and 0.25 ppm in a double pass configuration (1500 K, 1.3 atm, detection bandwidth 1 MHz, 15 cm shock tube diameter). This corresponds to a minimum detectable absorption of 0.01% and 0.005%, respectively, which represents an improvement of more than a factor of 20 when compared to conventional laser absorption detection. The feasibility of quantitative absolute concentration measurements is demonstrated using CH₃NH₂ as a precursor for the preparation of known NH₂ concentrations. The uncertainty for absolute concentration measurements is estimated to be ±10% if a suitable precursor for direct shock tube calibration measurements can be used, and ±15% if an alternative calibration scheme based on the detection of the signal generated by a scanning etalon in reflective mode is used. FM detection has been applied to determine the rate coefficient of the thermal decomposition of CH₃NH₂: CH₃NH₂ + M → CH₃+NH₂+M over the temperature range 1530–1975 K and at pressures near 1.3 atm. The rate coefficient was found to be: k₁=8.17×10¹⁶ exp(−30710/T) (±20%) [cm³ mol⁻¹ s⁻¹] This is in good agreement with a recent determination using conventional laser absorption detection of the NH₂ radical. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 445–453, 1999     

O原子与HNCO反应机理的量子化学及电子密度拓扑研究

采用MP2(Full),B3LYP,QCISD/MP2和CCSD(T)/MP2方法在6-311G(d,p)水平上对O原子与HNCO反应的微观机理进行了理论研究．采用MP2(Full)和B3LYP对反应位能面上的各驻点进行几何构型的全优化,振动分析和IRC计算证实了中间体和过渡态的真实性和相互连接关系．四种方法计算得到了四个反应通道的反应活化能．研究表明,O原子进攻HNCO中的H原子为反应的主要反应通道,该通道中形成了两个分子复合物,电子密度拓扑分析表明这两个分子复合物均为氢键复合物．     

CH3＋HNCO反应机理的理论研究

在6-311＋＋G**基组水平上,采用UMP2方法对自由基CH3与HNCO反应机理进行了研究，全参数优化了反应通道上各驻点的几何构型.结果表明, 自由基CH3与HNCO分子间反应有三条反应通道,第一为CH3与HNCO分子间经过生成一个稳定化能为4.56 kJ•mol－1的含氢键的分子复合物M后，经过渡态TS生成另一个产物复合物M′，然后分解为甲烷和NCO自由基；第二是CH3与HNCO分子间通过生成稳定反式中间体trans-int，其经过渡态trans-ts分解成产物CH3NH和CO；第三是CH3与HNCO分子间通过生成稳定顺式中间体cis-int，其经过渡态cis-ts分解成产物CH3NH和CO.比较三条反应通道的反应活化能，表明CH3与HNCO反应较易生成CH4＋NCO.     

CH2F自由基与HNCO反应机理的理论研究

The reaction mechanism of CH2F radical with HNCO was investigated by density functional theory (DFT)at the B3LYP/6-311++G(d,p) level. The geometries of the reactants, the intermediates, the transition states and the products were optimized. The transition states were verified through the vibration analysis.The relative energies were calculated at the QCISD(T)/6-311++G**//B3LYP/6-311++G(d,p) level. Seven feasible reaction pathways of the reaction were studied. The results indicate that the pathway (5) is the most favorable to occur, so it is the main pathway of the reaction.     

A shock tube study of the reactions of NH with NO,O2, and O

The reactions of NH(X³Σ⁻) with NO, O₂, and O have been studied in reflected and incident shock wave experiments. The source of NH in all the experiments was the thermal dissociation of isocyanic acid, HNCO. Time-histories of the NH(X³Σ) and OH(X²Π) radicals were measured behind the shock waves using cw, narrow-linewidth laser absorption at 336 nm and 307 nm, respectively. The second-order rate coefficients of the reactions: were determined to be: and cm³ mol⁻¹ s⁻¹, where ƒ and F define the lower and upper uncertainty limits, respectively. The branching fraction of channel defined as k_3b/k_3total, was determined to be 0.19 ± 0.10 over the temperature range of 2940 K to 3040 K.     

The kinetics of tobacco pyrolysis

When tobacco is pyrolysed under non-isothermal flow conditions in an inert atmosphere, variation of the inert gas or its space velocity has only a minor effect on the profiles of formation rate versus temperature for seven product gases. Thus, mass transfer processes between the tobacco surface and the gas phase are very rapid, and the products are formed at an overall rate which is determined entirely by that of the chemical reactions.The effect of radical chain inhibitors (nitrogen oxides) on the pyrolysis is complex because of the resultant oxidation. Nevertheless, no evidence was found for the occurrence of radical chain reactions in the gas phase. A small proportion (less than 10%) of all the gases monitored are formed by homogeneous decomposition of volatile and semi-volatile intermediate products, in the furnace used.At temperatures above about 600°C the reduction of carbon dioxide to carbon monoxide by the carbonaceous tobacco residue becomes increasingly important. However, when tobacco is pyrolysed in an inert atmosphere, only a small amount of carbon dioxide is produced above 600°C and consequently its reduction to carbon monoxide contributes only a small proportion to the total carbon monoxide formed above that temperature. The rate of the tobacco/carbon dioxide reaction is controlled by chemical kinetic rather than mass transfer effects. Carbon monoxide reacts with tobacco to a small extent.When the tobacco is pyrolysed in an atmosphere containing oxygen (9–21% v/v), some oxidation occurs at 200°C. At 250°C the combustion rate is controlled jointly by both kinetic and mass transfer processes, but mass transfer of oxygen in the gas phase becomes increasingly important as the temperature is increased, and it is dominant above 400°C. About 8% of the total carbon monoxide formed by combustion is lost by its further oxidation.The results imply that inside the combustion coal of a burning cigarette the actual reactions occurring are of secondary importance, the rate of supply of oxygen being the dominant factor in determining the combustion rate and heat generation. In contrast, in the region immediately behind the coal, where a large proportion of the products which enter mainstream smoke are formed by thermal decomposition of tobacco constituents, the chemistry of the tobacco substrate is critical, since the decomposition kinetics are controlled by chemical rather than mass transfer effects. tobacco substrate is critical. In addition, the heat release or absorption due to the pyrolytic reactions occurring behind the coal will depend on the chemical composition of the substrate. Thus, together with the differing thermal properties of the tobacco, the temperature gradient behind the coal should depend on the nature of the tobacco.     

HNCO+OH→H2O+NCO的反应机理

采用从头算分子轨道法(UHF/6-31G**水平,并用MP4加以相关能校正)研究了HNCO+OH→H2O+NCO反应机理.同时用Morokuma数值法获得了反应途径即内禀反应坐标(IRC).沿着IRC,运用反应途径哈密顿理论,获得反应途径动态学信息.在此基础上,根据过渡态理论和相应隧道效应校正,计算了在不同温度下的反应速率常数,得到了和实验相一致的结果.计算结果表明,此反应是一步直接型的抽提H反应.     

Reaction chemistry and kinetics of corn stalk pyrolysis without and with Ga/HZSM-5

Journal of Thermal Analysis and Calorimetry - The bifunctional Ga/HZSM-5 catalyst has been proven having the capability to increase the selectivity of aromatics production during catalytic...     

Reaction rate of propene pyrolysis

The reaction rate of propene pyrolysis was investigated based on the elementary reactions proposed in Qu et al., J Comput Chem 2009, 31, 1421. The overall reaction rate was developed with the steady-state approximation and the rate constants of the elementary reactions were determined with the variational transition state theory. For the elementary reaction having transition state, the vibrational frequencies of the selected points along the minimum energy path were calculated with density functional theory at B3PW91/6-311G(d,p) level and the energies were improved with the accurate model chemistry method G3(MP2). For the elementary reaction without transition state, the frequencies were calculated with CASSCF/6-311G(d,p) and the energies were refined with the multireference configuration interaction method MRCISD/6-311G(d,p). The rate constants were evaluated within 200-2000 K and the fitted three-parameter expressions were obtained. The results are consistent with those in the literatures in most cases. For the overall rate, it was found that the logarithm of the rate and the reciprocal temperature have excellent linear relationship above 400 K, predicting that the rate follows a typical first-order law at high temperatures of 800-2000 K, which is also consistent with the experiments. The apparent activation energy in 800-2000 K is 317.3 kJ/mol from the potential energy surface of zero Kelvin. This value is comparable with the energy barriers, 365.4 and 403.7 kJ/mol, of the rate control steps. However, the apparent activation energy, 215.7 kJ/mol, developed with the Gibbs free energy surface at 1200 K is consistent with the most recent experimental result 201.9 ± 0.6 kJ/mol.     

IR laser absorption diagnostic for C2H4 in shock tube kinetics studies

An IR laser absorption diagnostic has been further developed for accurate and sensitive time‐resolved measurements of ethylene in shock tube kinetic experiments. The diagnostic utilizes the P14 line of a tunable CO₂ gas laser at 10.532 μm (the (0 0 1) → (1 0 0) vibrational band) and achieves improved signal‐to‐noise ratio by using IR photovoltaic detectors and accurate identification of the P14 line via an MIR wavemeter. Ethylene absorption cross sections were measured over 643–1959 K and 0.3–18.6 atm behind both incident and reflected shock waves, showing evident exponential decay with temperature. Very weak pressure dependence was observed over the pressure range of 1.2–18.6 atm. By measuring ethylene decomposition time histories at high‐temperature conditions (1519–1895 K, 2.0–2.8 atm) behind reflected shocks, the rate coefficient of the dominant elementary reaction C₂H₄ + M → C₂H₂ + H₂ + M was determined to be k₁ = (2.6 ± 0.5) × 10¹⁶exp(?34,130/T, K) cm³ mol^?1 s^?1 with low data scatter. Ethylene concentration time histories were also measured during the oxidation of 0.5% C₂H₄/O₂/Ar mixtures varying in equivalence ratio from 0.25 to 2. Initial reflected shock conditions ranged from 1267 to 1440 K and 2.95 to 3.45 atm. The measured time histories were compared to the modeled predictions of four ethylene oxidation mechanisms, showing excellent agreement with the Ranzi et al. mechanism (updated in 2011). This diagnostic scheme provides a promising tool for the study and validation of detailed hydrocarbon pyrolysis and oxidation mechanisms of fuel surrogates and realistic fuels. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 423–432, 2012     

Reaction pathways of propene pyrolysis

The gas‐phase reaction pathways in preparing pyrolytic carbon with propene pyrolysis have been investigated in detail with a total number of 110 transition states and 50 intermediates. The structure of the species was determined with density functional theory at B3PW91/6‐311G(d,p) level. The transition states and their linked intermediates were confirmed with frequency and the intrinsic reaction coordinates analyses. The elementary reactions were explored in the pathways of both direct and the radical attacking decompositions. The energy barriers and the reaction energies were determined with accurate model chemistry method at G3(MP2) level after an examination of the nondynamic electronic correlations. The heat capacities and entropies were obtained with statistical thermodynamics. The Gibbs free energies at 298.15 K for all the reaction steps were reported. Those at any temperature can be developed with classical thermodynamics by using the fitted (as a function of temperature) heat capacities. It was found that the most favorable paths are mainly in the radical attacking chain reactions. The chain was proposed with 26 reaction steps including two steps of the initialization of the chain to produce H and CH₃ radicals. For a typical temperature (1200 K) adopted in the experiments, the highest energy barriers were found in the production of C₃ to be 203.4 and 193.7 kJ/mol. The highest energy barriers for the production of C₂ and C were found 174.1 and 181.4 kJ/mol, respectively. These results are comparable with the most recent experimental observation of the apparent activation energy 201.9 ± 0.6 or 137 ± 25 kJ/mol. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Shock tube pyrolysis of 1,2,4,5-hexatetraene

1,2,4,5-Hexatetraene (1245HT) is, according to theory, a key intermediate to benzene from propargyl radicals in a variety of flames; however, it has only been experimentally observed once in previous studies of the C3H3 + C3H3 reaction. To determine if it is indeed an intermediate to benzene formation, 1245HT was synthesized, via a Grignard reaction, and pyrolysized in a single-pulse shock tube at two nominal pressures of 22 and 40 bar over a temperature range from 540 to 1180 K. At temperatures T < 700 K, 1245HT converts efficiently to 3,4-dimethylenecyclobutene (34DMCB) with a rate constant of k = 10(10.16) x exp(-23.4 kcal/RT), which is in good agreement with the one calculated by Miller and Klippenstein. At higher temperatures, various C6H6 isomers were generated, which is consistent with theory and earlier experimental studies. Thus, the current work strongly supports the theory that 1245HT plays a bridging role in forming benzene from propargyl radicals. RRKM modeling of the current data set has also been carried out with the Miller-Klippenstein potential. It was found that the theory gives reasonably good predictions of the experimental observations of 1245HT, 1,5-hexadiyne (15HD), and 34DMCB in the current study and in our earlier studies of 15HD pyrolysis and propargyl recombination; however, there is considerable discrepancy between experiment and theory for the isomerization route of 1,2-hexadien-5-yne (12HD5Y) --> 2-ethynyl-1,3-butadiene (2E13BD) --> fulvene.     

竹材非等温热解动力学

利用热重分析技术对竹材在高纯N2条件下,从室温至1273K进行了非等温热解分析,研究了升温速率(5、10、20和40K/min)对热解过程的影响,探讨了其热解机理。研究表明,竹材非等温热解过程主要分为失水干燥、快速热解和缓慢分解三个阶段组成,其中第二阶段是整个过程的主要阶段,析出大量挥发分造成明显失重。升温速率对热解过程有显著影响,随着升温速率的增加,最大热解速度增大,对应的峰值温度升高,热滞后现象加重,热解各阶段向高温侧移动。热解机理满足一维扩散Parabolic法则,反应机理函数为g(α)=α2。不同升温速率下活化能为75.32-82.99kJ.mol-1,指前因子为1.17×105-1.12×106min-1。     

SiH2自由基与HNCO反应机理的理论研究

采用密度泛函理论B3LYP方法研究了SiH₂自由基与HNCO的反应机理, 并在B3LYP/6-311＋＋G**水平上对反应物、中间体、过渡态进行了全几何参数优化, 通过频率分析和内禀反应坐标(IRC)确定了中间体和过渡态. 为了得到更精确的能量值, 又用QCISD(T)/6-311＋＋G**方法计算了在B3LYP/6-311＋＋G**水平优化后的各个驻点的相对能量. 计算结果表明SiH₂自由基与HNCO的反应有五条反应通道, 其中顺式反应通道SiH₂＋HNCO→IM3→ TS4→IM5→TS5→IM6→SiH₂NH＋CO反应能垒最低, 为主反应通道.     

High-temperature gasification kinetics of biomass pyrolysis

The rate of gas formation from wood pyrolysis has been experimentally measured at temperatures from 300°C to 1000°C. The formation rate of specific product gases has been measured rather than the rate of solid weight loss. Even for very fine particles, the rate becomes heat transfer limited a: high temperatures. The product gases also approach thermodynamic equilibrium rapidly at high temperatures. The results are corrected using the experimental residence time distribution.