碳氧化反应速率常数与温度特殊关系的理论解释

对于碳氧化反应,在不同温度范围内,温度对反应速率常数的影响呈现不同规律的现象进行了讨论。指出第一阶段主要由氧气在碳表面化学吸附平衡受温度的影响决定。第二阶段则由碳在二氧化碳中发生气化反应,特别是其中的酮基脱附步骤决定。对已有的反应机理进行了比较,提出了新的简化机理,并采用速率控制步骤近似和平衡近似对机理进行了近似处理,得出的第二阶段动力学方程可以较好地解释相关实验规律。     

二(乙酰丙酮根)合铜(Ⅱ)热分解动力学研究

金属有机化合物气相化学沉积(OMCTD)形成铜膜常用的母体化合物是铜(Ⅱ)的β-二酮类配合.本文首次采用CW二氧化碳激光研究二(乙酰丙酮根)合铜(Ⅱ)[Cu相似文献   

二(乙酰丙酮根)合铜(Ⅱ)热分解动力学研究

金属有机化合物气相化学沉积(OMCTD)形成铜膜常用的母体化合物是铜(Ⅱ)的β-二酮类配合.本文首次采用CW二氧化碳激光研究二(乙酰丙酮根)合铜(Ⅱ)[Cu相似文献   

过渡金属团簇M+2(M=Fe、Co、Ni)与CO的化学反应

利用离子讲质谱计和激光溅射技术相结合,研究了Fe2＋、CO2＋、Ni2＋与CO气体的吸附反应,比较了它们的反应活性,给出了化学反应的速率常数及随反应气体压强的变化关系,并从理论上模拟了化学反应过程,测量结果与已有的实验值符合较好．     

2%Mn2O3-5%Na2WO4/SiO2催化剂上的甲烷氧化偶联反应动力学

在Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ２催化剂上的甲烷氧化偶联反应可用Ｒｉｄｅａｌ－ｒｅｄｏｘ机理描述，它包括均相及多相两个步骤。甲基自由基的生成是一个多相过程，Ｃ２烃的生成是一个均相过程。催化剂的活性同氧化速率和ＣＨ４与表面氧种的反应速率有关，Ｃ２烃的选择性与甲基自由基氧化速率常数和甲基自由基偶联速率常数的比值有关，这些常数均可从实验中求得。     

HCF(~1A'''')+SO_2反应的动力学研究

用激光光解-激光诱导荧光方法研究了室温下(T=293K)HCF(X%A′)自由基与SO2分子的反应动力学.实验中1HCF(X%A′)自由基是由213nm激光光解HCFBr2产生的,用激光诱导荧光(LIF)检测HCF(X%A′)自由基的相对浓度随着11反应时间的变化,得到此反应的二级反应速率常数为:k=(1.81±0.15)×10-12cm3?molecule-1?s-1,体系总压为1862Pa.高精度理论计算表明,HCF(X%A′)和SO2分子反应的机理是典型的加成-消除反应.我们运用RRKM-TST理论计算了1此二级反应速率常数的温度效应和压力效应,计算结果和室温下测定的二级反应速率常数符合得较好.     

2％Mn_2O_3－5％Na_2WO_4／SiO_2催化剂上的甲烷氧化偶联反应动力学

在Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ４催化剂上的甲烷氧化偶联反应可用Ｒｉｄｅａｌ－ｒｅｄｏｘ机理描述，它包括均相及多相两个步骤．甲基自由基的生成是一个多相过程（表面反应），Ｃ２烃的生成是一个均相过程（气相反应）．催化剂的活性同氧化速率（ｋ１）和ＣＨ４与表面氧种的反应速率（ｋ２）有关，Ｃ２烃的选择性与甲基自由基氧化速率常数和甲基自由基偶联速率常数的比值（ｋ／ｋ４）有关，这些常数均可从实验中求得．     

反应(Cl+HBr→HCl+Br和Cl+HBr→BrCl+H)机理和速率的密度泛函理论研究

用密度泛函理论(DFT)B3LYP方法,在6-311G**基组下,计算研究了反应Cl+HBr→HCl+Br和Cl+HBr→BrCl+H的机理,求得的各过渡态均通过振动分析加以确认.运用求得的反应活化能,以及不同温度下过渡态和反应络合物的配分函数,借助绝对反应速率理论求得50～1500K的反应速率常数.     

N－甲基咪唑与氯高铁血红素取代反应动力学

本文用停流法和分光光度法研究了［Ｆｅ（ｐｏｒ）Ｃｌ］（ｐｏｒ＝原卟啉（ｐｐ）或对应的二甲酯（ｐｐｄｍｅ））与Ｎ－甲基咪唑（Ｎ—ＭｅＩｍ）的亲核取代反应动力学，讨论了反应机理，求得前置平衡的平衡常数（Ｋ）和基元步骤的速率常数（ｋ１），研究了温度对反应动力学的影响，得到平衡步骤的和基元步骤的活化参数     

用于大气化学反应和二次有机气溶胶研究的实验室烟雾箱系统的搭建、测试与初步实验

为了从本质上认识和了解大气氧化反应进程以及二次有机气溶胶的形成机制,设计并搭建了一套实验室模拟烟雾箱系统．将质子转移反应质谱、同步辐射光电离质谱及气溶胶激光飞行时间质谱等特色质谱检测系统与烟雾箱结合,用于大气氧化反应气相和粒子相产物的定量与定性分析．通过一系列表征实验获得了该系统的基本参数,如烟雾箱内温度和光强特征,气体化合物和颗粒物的壁损耗速率,零空气的背景反应性及实验结果的可重复性．臭氧氧化α-蒎烯定量化实验和OH启动异戊二烯光氧化反应的定性检测结果进一步表明了该系统能够满足大气化学反应过程中气相和粒子相化学成分的定性分析及二次有机气溶胶的定量化研究的需要.     

Real-time,single-particle measurements of ambient aerosols in Shanghai

As one of the major components of the earth’s atmosphere, airborne particulate matter (or aerosol) has strong effects on air quality, regional and global climate, and human health. In ambient atmosphere, the different sources and complex evolutionary history of aerosol particles make the study of their chemical and physical properties extremely challenging. The invention of an online single-particle aerosol mass spectrometer provides a powerful technique to determine the size and chemical composition of individual aerosol particles in real time. We deployed an aerosol time-of-flight mass spectrometer (ATOFMS) to carry out single particle measurement in the urban area of Shanghai in the past few years. In this review paper, we summarize our recent work on the identification of particle type, mixing state and aging process, and the application of the individual particle information to the source apportionment of primary aerosol, and the investigation of the formation mechanism of secondary aerosol in Shanghai. The special capabilities of single particle mass spectrometry are proven essential to these studies. Multi-functional technique combinations of ATOFMS with other state-of-art aerosol instruments are also discussed for future studies.     

二次有机气溶胶的气体/粒子分配理论

本文重点评述了二次有机气溶胶形成的气体/粒子分配理论,简要介绍了它的发展和可能的应用.在大气中,气体有机物种的氧化可以产生半挥发性的有机化合物,二次有机气溶胶的形成可以用气体/粒子分配的吸收模型来评估.气体/粒子分配过程决定于半挥发性化合物的成分、浓度和蒸气压,以及吸收性材料的浓度和成分.在气体/粒子分配理论的基础上,人们又研究和开发出二次有机气溶胶的分子组分的气体/粒子分配的热力学模型,它可以用来预估气溶胶中液态水的含量、无机物的分布、亲水性和疏水性有机物的分布.二次有机气溶胶形成的化学机理和气体/粒子分配的热力学模型与加利福尼亚工学院三维都市/区域性大气模型相结合,可以用于气相和气溶胶相模拟.     

Analytical advances to study the air – water interfacial chemistry in the atmosphere

Formation of aqueous secondary organic aerosol (aqSOA) at the air – liquid interface recently has attracted a lot of attention in atmospheric chemistry. The discrepancies in mass distributions, aerosol oxidative capacity, liquid water content, hygroscopic growth of aerosols, and formation of clouds and fogs suggest that interfacial chemistry play a more important role than previously deemed. However, detailed mechanisms at the air–water interface remain unclear owing to the lack of comprehensive understanding that underpins complicated interfacial phenomena, which are not easily measurable from field campaigns, laboratory measurements, or computational simulations. This review highlights relevant and recent technical advancement employed to study aqSOA encompassing spectroscopy and mass spectrometry. The current knowledge on the aqSOA processes is digested with an emphasis on recent research of interfacial aqSOA formation including laboratory studies and model simulations. Finally, future directions of the interfacial chemistry are recommended for field and laboratory studies as well as theoretical efforts to resolve interfacial challenges in atmospheric chemistry.     

Communication: quantitative Fourier-transform infrared data for competitive loading of small cages during all-vapor instantaneous formation of gas-hydrate aerosols

A simple method has been developed for the measurement of high quality FTIR spectra of aerosols of gas-hydrate nanoparticles. The application of this method enables quantitative observation of gas hydrates that form on subsecond timescales using our all-vapor approach that includes an ether catalyst rather than high pressures to promote hydrate formation. The sampling method is versatile allowing routine studies at temperatures ranging from 120 to 210 K of either a single gas or the competitive uptake of different gas molecules in small cages of the hydrates. The present study emphasizes hydrate aerosols formed by pulsing vapor mixtures into a cold chamber held at 160 or 180 K. We emphasize aerosol spectra from 6 scans recorded an average of 8 s after "instantaneous" hydrate formation as well as of the gas hydrates as they evolve with time. Quantitative aerosol data are reported and analyzed for single small-cage guests and for mixed hydrates of CO(2), CH(4), C(2)H(2), N(2)O, N(2), and air. The approach, combined with the instant formation of gas hydrates from vapors only, offers promise with respect to optimization of methods for the formation and control of gas hydrates.     

气溶胶粒子通过填充柱的保留时间分布测定

采用亚微米单分散聚苯乙烯球形硬气溶胶粒子和脉冲进样技术,测定了气溶胶粒子通过无规则石英砂填充柱的保留时间分布,从保留时间分布曲线得到了气溶胶粒子在填充柱中的平均保留时间和穿透率.研究了平均保留时间和穿透率与流体流速、填充柱的长度、填料粒度和气溶胶粒子大小之间的关系.研究发现,流速越大,保留时间分布曲线越尖锐,流速越小,保留时间分布曲线越平坦;气溶胶粒子的穿透率随着柱长的增加而降低,随流速、气溶胶粒子粒径和石英砂颗粒大小的减小而减小;平均保留时间随柱长增加而增大,随流速增大而减小,随气溶胶粒子粒径减小而减小,而与石英砂颗粒大小几乎无关.     

Photo-oxidation of Isoprene with Organic Seed: Estimates of Aerosol Size Distributions Evolution and Formation Rates

ondary organic aerosol (SOA) formation from OH-initiated photo-oxidation of isoprene in the presence of organic seed aerosol. The dependence of the size distributions of SOA on both the level of pre-existing particles generated in situ from the photo-oxidation of trace hydrocarbons of indoor atmosphere and the concentration of precursor, has been investi-gated. It was shown that in the presence of high-level seed aerosol and low-level isoprene (typical urban atmospheric conditions), particle growth due to condensation of secondary organic products on pre-existing particles dominated; while in the presence of low-level seed aerosol and comparatively high-level isoprene (typical atmospheric conditions in rural re-gion), bimodal structures appeared in the size distributions of SOA, which corresponded to new particle formation resulting from homogeneous nucleation and particle growth due to condensation of secondary organic products on the per-existing particles respectively. The effects of concentrations of organic seed particles on SOA were also investigated. The particle size distributions evolutions as well as the corresponding formation rates of new particles indifferent conditions were also estimated.     

Spectrofluorimetric Evidence of the Transport of Marine Organic Matter in Antarctic Snow Via Air-Sea Interaction

Abstract

This paper considers the importance of marine aerosol in the atmosphere. As a consequence of its peculiar generation mechanism, it is also considered as a possible contributor to the transport of man-made microcomponents via air-sea interaction, especially in remote sites.

In view of future marine aerosol studies, the dominant presence of marine aerosol components in coastal Antarctic snow is discussed the presence of fluorescent marine organic matter in Antarctic snow is shown. Its “marum” nature is evidenced.

We give a tentative interpretation of the experimental data, and make a hypothesis concerning the variations in marine aerosol composition in correspondence to various altitudes.     

Experimental studies of the vapor phase nucleation of refractory compounds. VI. The condensation of sodium

In this paper we discuss the condensation of sodium vapor and the formation of a sodium aerosol as it occurs in a gas evaporation condensation chamber. A one-dimensional model describing the vapor transport to the vapor/aerosol interface was employed to determine the onset supersaturation, in which we assume the observed location of the interface is coincident with a nucleation rate maximum. We then present and discuss the resulting nucleation onset supersaturation data within the context of nucleation theory based on the liquid droplet model. Nucleation results appear to be consistent with a cesium vapor-to-liquid nucleation study performed in a thermal diffusion cloud chamber.     

Particle formation and surface processes on atmospheric aerosols: A review of applied quantum chemical calculations

Aerosols significantly influence atmospheric processes such as cloud nucleation, heterogeneous chemistry, and heavy-metal transport in the troposphere. The chemical and physical complexity of atmospheric aerosols results in large uncertainties in their climate and health effects. In this article, we review recent advances in scientific understanding of aerosol processes achieved by the application of quantum chemical calculations. In particular, we emphasize recent work in two areas: new particle formation and heterogeneous processes. Details in quantum chemical methods are provided, elaborating on computational models for prenucleation, secondary organic aerosol formation, and aerosol interface phenomena. Modeling of relative humidity effects, aerosol surfaces, and chemical kinetics of reaction pathways is discussed. Because of their relevance, quantum chemical calculations and field and laboratory experiments are compared. In addition to describing the atmospheric relevance of the computational models, this article also presents future challenges in quantum chemical calculations applied to aerosols.