利用同步辐射研究正庚烷火焰燃烧特性

利用同步辐射单光子电离和分子束取样技术并结合飞行时间质谱仪,在低压、预混、燃油当量比为1.0情况下研究正庚烷层流火焰的燃烧特性.共检测出24种中间产物,并计算出其摩尔分数.在燃烧反应前期,主要中间产物是酮、醚类物质.在燃烧反应后期,主要中间产物是碳氢化合物,燃烧反应前期的中间产物在燃烧反应后期继续氧化.乙烯在所有中间产物中摩尔分数最大的.另外,火焰中丙炔与苯有极大的相关性.     

异辛烷/正庚烷混合燃料燃烧中间产物的浓度分布特性

用同步辐射单光子电离和分子束取样技术结合飞行时间质谱仪,在低压预混层流火焰中测量异辛烷/正庚烷混合燃料(体积比9:1)在当量比为1.0时燃烧的主要中间产物.检测出24种主要中间产物,计算各种物质的摩尔分数,对其空间浓度分布进行比较分析,得出不同温度下的物质生成历程.添加金属矿物质可以明显改变热解过程中燃料氮向N2的转化特性.     

正庚烷裂解及乙醇的影响

论文研究乙醇对正庚烷氧化过程的影响.采用同步辐射方法测量当量比为1.0时正庚烷/氧气/氩气,以及正庚烷/乙醇/氧气/氩气低压层流预混火焰中主要成分的浓度.研究结果表明,添加乙醇改变了正庚烷向己烷裂解的路线,促进了庚烷直接裂解成丁烯基的趋向,但丁烷、戊烷都仍是正庚烷的主要裂解产物.添加乙醇,火焰中环已二烯、环戊二烯浓度增加,而且出现了乙烯醇、丁醇.研究结果可作为乙醇燃烧特性进一步研究的参考依据.     

不同燃烧当量比对二甲醚燃烧的影响研究

利用分子束质谱结合真空紫外同步辐射光电离技术研究了低压层流预混二甲醚/氧气/氩气火焰.通过测量火焰物种的离子信号强度随燃烧炉位置的关系曲线,计算了主要火焰物种的摩尔分数曲线.分析了燃料当量比(φ)为0.8,1.0和1.5时主要火焰物种的摩尔分数曲线,阐述了燃烧当量比对低压层流预混二甲醚/氧气/氩气火焰化学结构的影响.研究为进一步认识二甲醚燃烧提供了实验数据.     

正庚烷燃烧反应中间自由基的光谱测量

采用ICCD瞬态光谱探测系统和化学激波管,在点火温度1 408K,点火压力2.0atm,燃料摩尔分数1.0%,当量比1.0的条件下,拍摄了正庚烷燃烧过程中不同时刻的瞬态发射光谱,光谱曝光时间6μs,拍谱范围200～850nm。确认了在所拍光谱范围内主要是OH,CH和C2自由基的特征辐射光谱,表明小自由基OH,CH和C2是正庚烷燃烧过程中重要的反应中间产物。所拍时间分辨光谱显示,在正庚烷燃烧反应中,OH,CH和C2自由基一出现很快就达到其浓度峰值,但CH和C2自由基随着反应的进行迅速减少至消失,OH自由基持续的时间却长很多。实验结果为了解正庚烷燃烧反应微观过程和验证其燃烧反应机理提供了实验依据。     

正庚烷热裂解的反应分子动力学模拟

研究表明正庚烷热裂解的主产物是C₂H₄, H₂, CH₄以及C₃H₆,模拟结果和实验吻合很好. 温度对产物分布具有明显的影响,当温度上升,目标产物乙烯的量会迅速增加. 正庚烷转化率以及主产物的摩尔分数分别通过反应分子动力学和化学动力学模拟计算得到,两种方法模拟结果相吻合. 我们还通过动力学分析研究了正庚烷热裂解反应的动力学参数,反应活化能为47.32 kcal/mol,指前因子为1.78×10¹⁴ s^-1.     

正庚烷高温裂解的温度敏感性

利用ReaxFF分子动力学模拟方法对正庚烷在高温条件下的热解行为进行了研究．细致分析了温度对正庚烷高温裂解过程以及产物分布的影响．结果显示温度对正庚烷的热解过程的影响是分阶段的．高温能加速正庚烷的分解,但是当温度达到一定阶段之后这种影响逐渐变小．正庚烷的热解可以分为三个阶段．主要产物C₂H₄、C3和C4的质量百分数随转化率的变化规律与实验值符合很好．利用一阶动力学模型得到的正庚烷热解的表观活化能和指前因子分别为53.96 kcal/mol和55.34×10¹³ s^-1,与实验值相符．     

正癸烷燃烧反应中OH,CH和C2自由基的瞬态发射光谱

采用ICCD瞬态光谱测量系统和加热激波管,在点火压力2.0atm,点火温度1 100～1 600K,当量比1.0,燃料摩尔分数1.0%条件下,实时测得了正癸烷/氧气/氩气燃烧过程的瞬态发射光谱,光谱范围200～850nm。结果显示燃烧过程中主要发射光谱带归属于小分子中间产物OH,CH和C2自由基,光谱强度的变化反映了燃烧过程中三种自由基浓度的变化历程;正癸烷燃烧过程中光谱强度峰值之比大于同为链烷烃的正庚烷相应OH/CH峰强度之比,揭示出两种链烃燃烧反应机理有较大差异。实验还获得了正癸烷燃烧过程中能显示谱带转动结构的CH和C2高分辨特征发射光谱。实验结果对了解正癸烷燃烧性质和验证正癸烷燃烧反应机理很有意义。     

同步辐射单光子电离技术研究乙醚富燃火焰

本文利用同步辐射单光子电离和分子束质谱技术研究了乙醚在富燃条件下的低压预混火焰.通过测量光电离质谱和扫描光电离效率谱,我们鉴别了该火焰中大部分的燃烧中间体及产物.此外,通过改变燃烧炉的位置测量光电离质谱,得到了各燃烧中间体及产物的摩尔分数曲线.实验结果为深入研究乙醚燃烧动力学并揭示含氧有机化合物在火焰中的反应机理提供了依据.     

同步辐射真空紫外光电离质谱研究乙烯扩散火焰

本文利用探针取样法结合同步辐射真空紫外光电离和分子束质谱技术研究了常压下的乙烯扩散火焰.通过测量光电离质谱和光电离效率谱分辨了该火焰中大部分的燃烧中间体及产物;通过改变探针取样位置以及半定量计算得到了其中部分燃烧中间体及产物的摩尔分数曲线.实验结果为探索多环芳烃和烟尘在扩散火焰中形成的最初阶段的反应机理提供了依据.     

Selective response of DPPV/zeolite composites toward acetone,methanol, and n-heptane vapors

In this work, doped poly(p-phenylene vinylene)/zeolite composites was prepared to detect the three different chemical vapors (acetone, methanol, and n-heptane) and to investigate the effects of zeolite type, chemical vapor type, and vapor concentration based on the electrical conductivity response and selectivity properties of the sensing materials. Before blending with PPV, zeolite Y (Si/Al?=?5.1 and Na⁺), mordenite (Si/Al?=?18 and Na⁺), and 5A (LTA) (Si/Al?=?1.0 and Na⁺) were ion exchanged with Cu²⁺ at 80 % ion exchanged to prepare 80CuNaY, 80CuNaMOR, and 80CuNa5A. 80CuNaY exhibited the highest electrical conductivity response under acetone and methanol exposures while 80CuNaMOR showed the highest response in n-heptane exposure which depended on the adsorption and solubility properties of each porous material. When adding doped poly(p-phenylene vinylene) (dPPV) into the 80CuNaY matrix, the minimum detection vapor concentration decreased in acetone, methanol, and n-heptane vapors. For the selectivity, the composite between 80CuNaY and dPPV responded only in the polar vapors (acetone, methanol) whereas the composite between dPPV and 80CuNaMOR or dPPV_[90]80CuNaMOR responded only in the nonpolar vapor (n-heptane). The interactions between the sensing materials and the chemical vapors were investigated and identified by FTIR and AFM techniques.     

CO_2膨胀液体的分子动力学模拟

采用分子动力学方法,模拟了CO2膨胀甲醇体系、CO2膨胀乙醇体系的热力学性质和输运性质,以及对氯硝基苯在CO2膨胀甲醇体系、苯甲腈在CO2膨胀乙醇体系中的扩散性质。CO2膨胀甲醇体系的密度模拟值略高于实验值,而CO2膨胀乙醇体系的密度模拟值与实验值非常接近。模拟结果表明:CO2使甲醇和乙醇溶液的膨胀非常明显,当CO2的摩尔分数达到0.5时,溶液膨胀约100%;得到了CO2、甲醇、乙醇、对氯硝基苯以及苯甲腈的扩散系数,其中对氯硝基苯和苯甲腈在两种膨胀液体中的扩散系数与实验结果接近;通过扩散系数关联了两种膨胀液体的粘度,计算结果与修正的Wilke-Chang方程得到的体系粘度规律一致。     

Contrasting microscopic interactions determine the properties of water/methanol solutions

Herein we study the different microscopic interactions occurring in water/methanol solutions at different methanol molar fractions, using NMR spctroscopy. Temperature was found to determine which interaction dominates. It was found that the mixing between water and methanol is non-ideal because of the presence of interactions like hydrophobicity and hydrophilicity. These results indicate that the competition between hydrophilic and hydrophobic interactions is different in different thermal regions, and that the physical properties of the solution are determined by the character of the solution itself, which in turn depends on the mole fraction of methanol and on the temperature.     

Hydrogen bonding in different pyrimidine–methanol clusters probed by polarized Raman spectroscopy and DFT calculations

We report on the hydrogen bonding between pyrimidine (Pd) and methanol (M) as H‐donor in this study. Hydrogen bonds between pyrimidine and methanol molecules as well as those between different methanol molecules significantly influence the spectral features at high dilution. The ring‐breathing mode ν₁ of the reference system Pd was chosen as a marker band to probe the degree of hydrogen bonding. Polarized Raman spectra in the region 970–1020 cm⁻¹ for binary mixtures of (pyrimidine + methanol) at 28 different mole fractions were recorded. A Raman line shape analysis of the isotropic Raman line profiles at all concentrations revealed three distinct spectral components at mole fractions of Pd below 0.75. The three components are attributed to three distinct groups of species: ‘free Pd’ (pd), ‘Pd with low methanol content’ (pd1) and ‘Pd with high‐methanol content’ (pd2). The two latter species differ considerably in the pattern and the strengths of the hydrogen bonds. The results of density functional theory calculations on structures and vibrational spectra of neat Pd and eight Pd/M complexes with varying methanol content support our interpretations of the experimental results. A nice spectra–structure correlation for the different cluster subgroups was obtained, similar to earlier results obtained for Pd and water. Apart from N···H and O···H hydrogen bonds between pyrimidine and methanol, O···H hydrogen bonds formed among the methanol molecules in the cluster at high methanol content also play a crucial role in the interpretation of the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

Impact of nitric oxide on n-heptane and n-dodecane autoignition in a new high-pressure and high-temperature chamber

A New One Shot Engine (NOSE) was designed to simulate the thermodynamic conditions at High Pressure-High Temperature like an actual common-rail diesel engine in order to study the compression ignition of spray. The volume of the combustion chamber provided with large optical windows simplified the implementation of various optical diagnostics. The advantage of this kind of set-up in comparison to pre-burn or flue chambers is that the initial gas mixture can be well controlled in terms of species and mole fraction. The purpose of this work was to investigate the impact of nitric oxide (NO) on ignition delay (ID) for two fuels with different cetane numbers: n-heptane, and n-dodecane. In the thermodynamic conditions chosen (60?bar and over 800–900?K), NO had a strong effect on ID, with increases in NO tending to reduce the ignition delay. Results showed that ID and Lift-Off Length (LOL) presented the same trend as a function of temperature and NO concentration. Experimentally, at 900?K the ignition of n-dodecane was promoted by NO up to 100?ppm, whilst higher NO levels did not further promote ignition and a stabilization of the value has been noticed. For n-heptane, stronger promoting effects were observed in the same temperature conditions: the ignition delays were monotonically reduced with up to 200?ppm NO addition. At a lower temperature (800?K) the inhibiting effect was observed for n-dodecane for [NO] greater than 40?ppm, whereas only a promoting effect was observed for n-heptane. The experimental results of LOL showed that NO shortened LOL in almost all cases, and this varied with both the NO concentration and the mixture temperature. Thus, fuels with shorter ignition delays produce shorter lift-off lengths.     

The effect of molecular structures of alkylbenzenes on ignition characteristics of binary n-heptane blends

Alkylbenzenes are major aromatic constituents of real transportation fuels and important surrogate components. In this study, the structural impact of nine alkylbenzenes on their ignition characteristics is experimentally and computationally investigated with particular emphasis on the blending effect with significantly more reactive normal alkanes. Experimental comparisons of mono-alkylbenzenes (toluene, ethylbenzene, n-propylbenzene, iso-propylbenzene) from a modified CFR engine showed that the difference in pure alkylbenzene reactivity significantly diminished when blended with n-heptane, as the strength of the radical scavenging effect of all three alkylbenzenes is similar. Among C₈H₁₀ isomers, the reactivity of pure ethylbenzene and o-xylene and their blends with n-heptane showed a complex competing effect between the difference in CH bond energy and the existence of intermediate/low-temperature chemistry caused by adjacent methyl pairs. A similar structural impact was also observed for C₉H₁₂ isomers and their blends with n-heptane, while the influence of CH bond energy was more noticeable than C₈H₁₀ molecules. Kinetic simulations of the alkylbenzene/n-heptane blends highlighted the effect caused by adjacent methyl pairs that is referred to as the “ortho effect”. Analysis of ethylbenzene and o-xylene showed that o-xylene's intermediate/low-temperature pathways initiated by benzylperoxy radical – benzylhydroperoxide isomerization (RO2 – QOOH) produce additional active radicals such as OH and CH₂O, which accelerates the oxidation chemistry of more reactive n-heptane. This study provides knowledge on the blending effect of alkylbenzene compounds with n-heptane on their ignition characteristics that is useful to develop surrogates that can better mimic the reactivity of real fuels.     

利用OH自由基特征发射谱测量正庚烷的点火延迟时间

在化学激波管中利用反射激波进行点火,采用OH自由基在306.4nm处特征发射谱线强度的急剧变化标志燃料的着火,由光谱单色仪、光电倍增管、压力传感器和示波器组成测量系统,测量了正庚烷/氧气的点火延迟时间,点火压力(1.0±0.1)和(0.75±0.05)atm,点火温度1 170～1 730K,当量比1.0,得到了在此实验条件下正庚烷/氧气点火延迟时间随温度变化的关系式。研究结果表明正庚烷/氧气点火延迟时间随温度的增加呈指数减小,点火压力为0.75atm时,随着点火温度的增加,点火延迟时间的变化率要小于1.0atm条件时。实验结果为建立正庚烷燃烧反应动力学模型,验证正庚烷燃烧反应机理提供了实验依据。     

Magnetic resonance studies of aniline oligomers formed in the reaction of aniline with 1,1-diphenyl-2-picrylhydrazyl

Aniline oligomers, which are formed in the reaction of aniline with 1,1-diphenyl-2-picrylhydrazyl (DPPH) in methanol and chloroform as solvents, are investigated by means of magnetic resonance techniques. The electron paramagnetic resonance (EPR) spectrum of the products of the reaction of aniline with DPPH (mole ratio, 2∶1) in chloroform solution, and of aniline with DPPH (mole ratio, 1∶2) in methanol solution, were recorded as the reaction progressed, and after the reaction was finished. The spectra of the products after reaction were resolved into the spectra of two species. For the acidified methanol solution the spectrum of one of the species shows hyperfine coupling to two nitrogen atoms with a coupling constanta(2·¹⁴N)=5.8 G, in good agreement with previously reported observations for the radical cation of model aniline trimers. A species is observed in the chloroform solution witha(1·¹⁴N)=11.4 G, which suggests the presence of aniline dimers. Both solutions also show a second signal which is attributed to higher oligomer radical cations with unresolved¹⁴N hyperfine structure.¹H nuclear magnetic resonance (NMR) spectra of aniline and aniline-DPPH solutions in CDCl₃ with the peaks due to DPPHH, the product of reduction of DPPH, were observed. The¹H NMR experiments show that only 15% of the available aniline was consumed, in agreement with the theoretical calculations for the formation of polyaniline-emeraldine base salt under these conditions rather than the sole formation of dimers, which would be expected to consume 33% of the available aniline. This is probably due to formation of partially oxidized long-chain aniline oligomers as the main reaction product.