直流电弧放电中的高温化学反应     

胡斌  江祖成 《岩矿测试》1991,10(1):50-55

本文对近年来国内外关于直流电弧放电中的高温化学反应的应用进展进行了综述。附参考文献72篇。  相似文献   

中国城市经济区划分的初步研究   总被引：34，自引：8，他引：34  

顾朝林 《地理学报》1991,(2)

本文建立了城市经济区划分的理论与方法——d△系和R_d链法,应用33个指标对全国434个城市进行了综合实力的R型因子分析评价,并进行了不同层次d系的划分和Ⅰ、Ⅱ、Ⅲ级d△系和R_d链组建,提出了我国两大经济发展地带、三条经济开发轴线、九大城市经济区和33个Ⅱ级城市经济区的城市经济区区划体系设想。  相似文献   

Oxidation of sulphur compounds in the atmosphere: I. Rate constants of OH radical reactions with sulphur dioxide,hydrogen sulphide,aliphatic thiols and thiophenol     

Barnes  I.  Bastian  V.  Becker  K. H.  Fink  E. H.  Nelsen  W. 《Journal of Atmospheric Chemistry》1986,4(4):445-466

The reactions of OH radicals with SO₂, H₂S, thiophenol, and a series of aliphatic thiols (1–5 C-atoms) have been investigated in 201 and 381 reaction chambers at 1 atm total pressure and 300 K using a competitive kinetic technique. Initially, OH radicals were produced by photolysis of CH₃ONO/NO mixtures in air. Applying this OH source rate constants for OH with SO₂, H₂S, and thiophenol in synthetic air were determined to be (1.1±0.2)×10^-12, (5.5±0.8)×10^-12 and (1.1±0.2)×10^-11 cm³ s^-1, respectively. However, when this method was applied to the aliphatic thiols the rate constants obtained were found to be dependent on the partial pressures of O₂ and NO. These effects have been attributed to the built-up of a radical species, not yet identified, which leads to uncontrolled chain reactions in the system. Using the photolysis of H₂O₂ at wavelengths greater than 260 nm as the OH source in 1 atm N₂, rate constants for the 1–5 aliphatic thiols in the range 2.9 to 5.6×10^-11 cm³ s^-1 were obtained. The rate constants obtained in the present study are compared with recent literature values.  相似文献   

The photo-oxidations of propyl acetates in synthetic air-HONO-NO x mixtures: Product formation studies and proposed kinetic mechanisms     

J. Alistair Kerr  David W. Stocker 《Journal of Atmospheric Chemistry》1986,4(2):263-276

The formation of products following the hydroxyl radical initiated photo-oxidations of n-and isopropyl acetates has been studied. Mixtures of synthetic air containing a few ppm of nitrous acid, nitric oxide, nitrogen dioxide and one of the propyl acetates were irradiated with sunlamps in a Teflon bag smog chamber. The decay of reactants and the formation of products was monitored by chemiluminescent analysis or by gas chromatography. The major primary products from the photo-oxidation of n-propyl acetate are acetaldehyde and propionaldehyde while from isopropyl acetate they are acetone and methyl nitrate. It was not possible to analyse for formaldehyde, an expected primary product in these systems. The nature and distribution of products indicate that a significant fraction of primary products arise from decomposition reactions of the alkoxy-type radicals generated following the initial attack of hydroxyl radicals on the esters. The derived reaction stoichiometries (molecules of NO oxidised per molecule of ester reacted) are also consistent with the proposed mechanisms.  相似文献   

长江三角洲南通地区第四纪地层马尔柯夫链综合分析   总被引：2，自引：0，他引：2  

李仁平  匡有为 《地球科学》1989,14(2):213-219

本文简要论述了马尔柯夫链的基本方法,并试图利用此法对长江三角洲地区第四纪地层剖面作综合分析。文中以南通地区两个有代表性的钻孔剖面为例,采用马尔柯夫链极限概率分析、置换分析、熵分析、旋回类型分析和地层模拟,对两钻孔剖面作了综合对比分析。结果表明,马尔柯夫链分析方法是该区第四纪地层分析的一种行之有效的方法。  相似文献   

污灌土壤中有机氮的矿化速率及其影响因素   总被引：1，自引：0，他引：1  

蒋景诚  陈金秀 《地球科学》1989,14(6):627-633

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The Reaction of Unsaturated Aliphatic Oxygenates with Ozone   总被引：1，自引：0，他引：1  

Eric Grosjean  Daniel Grosjean 《Journal of Atmospheric Chemistry》1999,32(2):205-232

The reaction of ozone with unsaturated aliphatic oxygenates has been studied at ambient T (287–297 K) and p = 1 atm. of air (RH = 55 ± 10%) with sufficient cyclohexane added to scavenge the hydroxyl radical. Reaction rate constants, in units of 10-18 cm3 molecule-1 s-1, are 10.7 ± 1.4 for methyl trans-3-methoxy acrylate, 63.7 ± 9.9 for 4-hexen-3-one (predominantly the trans isomer), 125 ± 17 for trans-4-methoxy-3-buten-2-one, 148 ± 13 for cis-4-heptenal, 439 ± 37 for 3- methyl-2-buten-1-ol and 585 ± 132 for (cis + trans)-ethyl 1-propenyl ether. The influence of the oxygen-containing substituents on reactivity toward ozone is examined. Unsaturated ethers react with ozone faster than their alkene structural homologues; the reverse is observed for unsaturated esters and unsaturated carbonyls. Major reaction products have been identified by liquid chromatography with ultraviolet detection (LC-UV), particle beam-mass spectrometry (PB- MS) and gas chromatography-mass spectrometry (GC-MS) and are methyl formate and methyl glyoxylate from methyl trans-3-methoxy acrylate, acetaldehyde and 2-oxobutanal from 4-hexen-3-one, propanal and succinic dialdehyde from cis-4-heptenal, hydroxyacetaldehyde and acetone from 3-methyl-2-buten-1-ol, and ethyl formate and acetaldehyde from (cis + trans)-ethyl 1-propenyl ether. PB-MS and GC- MS were also employed to identify new reaction products and to confirm the structure of products tentatively identified in a previous study of the reaction of ozone with five unsaturated oxygenates (Grosjean and Grosjean, 1997a): formic acid and methyl glyoxylate from methyl acrylate, formic acid and formic acetic anhydride from vinyl acetate, 2-oxoethyl acetate and 3-oxopropyl acetate from cis-3-hexenyl acetate, ethyl formate and formic acid from ethyl vinyl ether, and methyl formate from trans-4-methoxy-3- buten-2-one. The nature and formation yields of the reaction products are consistent with (and supportive of) the reaction mechanism: O3 + R1R2C=CR3X (R1COR2 + R3C(X)OO) + (1 - )(R3COX + R1C(R2)OO), where R1, R2 and R3 = H or alkyl, X is the oxygen-containing substituent, R1COR2 and R3COX are the primary products and R1C(R2)OO and R3C(X)OO are the carbonyl oxide biradicals. The variations of the coefficient , which ranges from 0.25 to 0.61, are discussed in terms of the number and nature of alkyl and oxygen-containing substituents. Subsequent reactions of the alkyl-substituted biradicals R1C(R2)OO and of the biradicals R3C(X)OO that bear the oxygen-containing substituent are discussed. For the biradical CH3CHOO, the ratio ka/kb for the competing pathways of rearrangement to acetic acid (CH3CHOO CH3C(O)OH, reaction (a) and formation of an unsaturated hydroperoxide (CH3CHOO CH2=CH(OOH), reaction (b) is <0.25 for ethyl 1-propenyl ether and <0.27 for 4-hexen-3-one. Concentrations measured in co- located samples, one downstream of a water impinger and the other without water impinger, show the uptake in water impingers to be high (from 83.2 to >99.9%) and comparable to that for formaldehyde (98.4%) for formic acetic anhydride and for difunctional oxygenated compounds. Uptake in water impingers was lower (19–78%) for monofunctional aldehydes and ketones.  相似文献   

The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)     

Mikhail Yu. Gershenzon  Sergeid. Il'in  Nikolai G. Fedotov  Yulii M. Gershenzon  Elena V. Aparina  Vladislav V. Zelenov 《Journal of Atmospheric Chemistry》1999,34(1):119-135

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.  相似文献   

变质流体对变质反应温度缓冲作用实例研究及意义     

赵国春  刘树文  孙德有 《吉林大学学报(地球科学版)》1996,(1)

有关闽北麻源群、浙西南陈蔡群、冀东麻粒岩和冀西南阜平群变质流体与变质反应温度关系实例研究表明，在变质作用过程中，变质流体对变质反应温度存在着明显的缓冲效应，缓冲的温度范围可超过某些变质相或变质带之间的温度差。因此，变质流体同变质温度、压力一样，是划分变质相带一个独立参数。本文从热力学理论上解释了变质流体对变质反应温度缓冲作用的机制，并对缓冲强度进行了估算，据此阐述了变质流体在变质相带研究中的重要意义。  相似文献   

新疆阿尔泰阿拉尔花岗岩多维矿物相-水氧同位素交换反应动力学   总被引：6，自引：0，他引：6  

刘伟  贺伯初  陈振胜 《地质学报》1996,70(2):129-141,T001

新疆阿尔泰阿拉尔花岗岩中共生石英、长石、黑云母的δ~(18)O值具有宽广的变化范围,3者表现出显著的~(18)O/~(16)O不平衡关系,尤其是石英、长石具有倒转△~(18)O_(石英-长石)关系(△~(18)O_(石英-长石)<0)。上述关系清楚地表明在花岗岩-水之间发生了~(18)O/~(16)O交换反应。根据质量平衡约束关系对岩石与外来流体的初始δ~(18)O值作了估计。由于花岗岩的初始δ~(18)O值被大大地改变了,简单运用全岩或者单矿物样品的δ~(18)O值判断岩浆来源的方法是不可靠的。水-岩之间的~(18)O/~(16)O交换反应并不伴随着岩石矿物学上的强烈蚀变效应,这种脱藕关系暗示着交换反应发生于较高温度即岩浆次固相-岩浆期后冷凝过程中。交换机制主要为扩散控制。定量模拟表明:阿拉尔岩体具有高流体流动速率(3×10~(-14)mol/s)、长水-岩反应时限(0.8-6Ma)、高水/岩值(0.79-6.14)。在造山带岩浆弧环境的中部地壳层次下,变质流体流动和环流是非常强烈的。  相似文献