低Peclet数下剪切流中气溶胶粒子的传质率

本文研究了低Péclet数下剪切流中气溶胶粒子的传质率。Péclet数(Pe)是物质浓度的对流输送项对分子扩散项的比。它等于Reynolds数(Re)与Schmidt数的(Sc)之积。本文应用奇异扰动方法得到了无因次传质率Nu(Nusselt数)在小Péclet数条件下的四项渐近展式，因而?改进了前人的结果。     

Methoxy formation in the reaction of CH3O2 radicals with NO

Formation of methoxy (CH₃O) radicals in the reaction (1) CH₃O₂+NOCH₃O+NO₂ at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH₃O₂ and CH₃ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k ₁ is (7±2) 10^-12 cm³/molecule · s in good agreement with previous results.     

Electrochemical modelling of self-potential anomalies

An electrochemical model is proposed, which considers the redox conditions and the electrode kinetics at the mineral surface. Advanced modelling of self-potential (SP) anomalies over ore deposits takes into account the course of the redox potential distribution with depth and the oxidation-reduction processes acting at the mineral-electrolyte interface. The application of this model to a SP anomaly in the vicinity of the German Continental Deep Drilling Program (KTB) can explain the surface and borehole data and gives an estimation of the prevailing thermodynamical conditions in the ground.Exclusively, this paper deals with SP anomalies, which are associated with high conductive graphitic layers. It can be concluded that SP-anomalies give an important hint to electronical conducting structures in the earth's crust.     

Autoxidation of N(III), S(IV), and other Species in Frozen Solution – A Possible Pathway for Enhanced Chemical Transformation in Freezing Systems

The chemistry of glycolaldehyde (hydroxyacetaldehyde) relevant to the troposphere has been investigated using UV absorption spectrometry and FTIR absorption spectrometry in an environmental chamber. Quantitative UV absorption spectra have been obtained for the first time. The UV spectrum peaks at 277 nm with a maximum cross section of (5.5± 0.7)×10^–20 cm² molecule^–1. Studies of the ultraviolet photolysis of glycolaldehyde ( = 285 ± 25 nm) indicated that the overall quantum yield is > 0.5 in one bar of air, with the major products being CH₂OH and HCO radicals. Rate coefficients for the reactions of Cl atoms and OH radicals with glycolaldehyde have been determined to be (7.6± 1.5)×10^–11 and (1.1± 0.3)×10^–11 cm³ molecule^–1 s^–1, respectively, in good agreement with the only previous study. The lifetime of glycolaldehyde in the atmosphere is about 1.0 day for reaction with OH, and > 2.5 days for photolysis, although both wet and dry deposition should also be considered in future modeling studies.     

Kinetic study of the hydrocarbon generation from Upper Paleozoic coals in Ordos Basin

When organic matter during geological processes is affected by a variety of factors such as paleotemperature, and time, complicated chemical reactions will occur, finally resulting in the generation of petroleum and natural gas. These reactions leading to…     

二连盆地侏罗系地层热演化史研究

本文应用磷灰石裂变径迹,镜质体动力学模型等方法恢复二连盆地侏罗系地层的热演化史,二连盆地图参１井磷灰石退火浓度为１６００－２７７４ｍ,对应的退火温度为６４－１０２．７℃,图参１井现今温度小于最高古地温,这是由于二连盆地地温梯度逐渐降低及地层发生抬升和剥蚀所致。根据磷灰石裂变径迹分析和镜质体动力学模型模拟图参１井的热演化史,在晚侏罗世时其经受的最高地温梯度分别为７℃／ｈｍ和６℃／ｈｍ。侏罗系地层在晚     

From an initial transient-state to a steady-state in metamorphic reactions: An experimental approach in the system dolomite-quartz-H2O

Abstract We carried out hydrothermal experiments in the system dolomite‐quartz‐H₂O to track the temporal change in reaction rates of simultaneous reactions during the development of reaction zones. Two types of configurations for the starting materials were prepared: dolomite single crystals + quartz powder + water and quartz single crystals + dolomite powder + water, both sealed separately in gold capsules. Runs at 0.1GPa and 600°C with cold seal pressure vessels gave the following results. (i) In short duration (45–71 h) runs metastable layer sequences involving wollastonite and talc occur in the reaction zone, whereas they disappear in longer duration (168–336 h) runs. (ii) The layer sequence of the reaction zones in short duration runs differs from place to place on the dolomite crystal even in the same run. (iii) The diversity of layer sequences in the short duration runs merges into a unique layer sequence in the longer duration runs. (iv) The reaction zone develops locally on the dolomite crystal, but no reaction zone was observed on the quartz crystal in any of the runs. The lines of evidence (i)–(iii) show that the system evolves from an initial transient‐ to a steady‐state and that the kinetic effect is important in the development of reaction zones. A steady diffusion model for the unique layer sequence Qtz/Di/Fo + Cal/Dol + Cal/Dol shows that the Dol + Cal layer cannot be formed by diffusion‐controlled process and that the stability of the layer sequence Qtz/Di/Fo + Cal/Dol depends not only on L‐ratios (a = /L_CaOCaO and b = /L_MgOMgO) but also on the relative rate P = (−2ξ₁ − ξ₂)/(–ξ₁ − 2ξ₂) of competing reactions: Dol + 2Qtz = Di + 2CO₂ (ξ₁) and 2Dol + Qtz = Fo + 2Cal + 2CO₂ (ξ₂). For smaller P the stability field will shift to higher values of a and b. The steady diffusion model also shows that the apparent‐non‐reactivity on the quartz surface can be attributed to void formation in a large volume fraction in the diopside layer.     

Lacustrine basin unconventional resource plays: Key differences

There has been a revival in hydrocarbon source rock characterization and development associated with growing interest in unconventional resources, where these fine-grained organic-rich rocks act as both source and reservoir. To-date, the exploration focus on shale reservoirs has been largely on marine systems. Lacustrine source rocks for conventional resources are geographically important, dominating regions such as China, Indonesia, and Brazil's resource-base. However, they have been generally untested for unconventional resources.There are a number of key differences in the nature of these hydrocarbon systems that should be considered when assessing whether lacustrine systems may represent future unconventional opportunities in areas where the conventional resource-base is dominated by lacustrine-sourced oil. Among the key differences between these depositional systems is the greater sensitivity to high frequency climatic variability within lacustrine systems. Lacustrine systems are highly sensitive to changes in the balance between precipitation and evaporation, which may lead to rapid changes in lake level, potentially exceeding 600 m. These changes in depositional conditions are geologically rapid and may occur over periods of thousands of years. Such changes can reduce the areal extent of potentially thick source rock intervals to only those portions of a basin where a permanent deep lake was present. Thus the core unconventional target area may be geographically limited compared with their marine counterpart. Although potentially areally limited, a review of many lacustrine source rocks suggests that their thicknesses are often significantly greater than marine source rocks. An examination of the more distal portions of lacustrine systems, where better source rock potential is present reveals that there is generally limited connectivity between source and conventional reservoir. In these settings, such as the Wind River basin (Waltman Shale), the hydrocarbons remain trapped within the shales, potentially leading to over-pressured hydrocarbon charged systems. Such conditions suggest that although areally limited, viable unconventional targets may exist, if suitable reservoir conditions are present. Finally, the character of the oils produced is different in these settings, with lacustrine oils being waxy and displaying different hydrocarbon generation and cracking kinetics. High wax oils display distinct flow characteristics, being more viscous, and may offer different production challenges than their non-waxy marine equivalents. Additionally, differences in their cracking kinetics may indicate that the timing of gas generation for shale gas plays may differ significantly from marine systems.     

羟基磷灰石对水溶液中Fe3+的吸附动力学及热力学研究

研究了羟基磷灰石(HAP)对水溶液中Fe3+的吸附动力学及热力学。研究表明,HAP对水溶液中Fe3+的吸附符合Langmiur等温吸附,ct/q=0.006 4 ct+0.018 3;该吸附反应符合一级反应动力学方程,ln CR=-0.043 5 t+4.324 4;吸附反应活化能为Ea=36.26 k J/mol;标准摩尔反应焓为正值表明反应过程吸热;当温度大于285.7 K时,吉布斯自由能小于0,反应可自发进行。     

基于热重分析的菱镁矿分解动力学解析

本文利用热重(TG)分析方法,探讨了菱镁矿的热分解过程。根据热微商(DTG)曲线峰顶温度,结合Kissinger及Ozawa-Doyle方法拟合计算得到菱镁矿热分解的活化能和指前因子(lgA)分别为211.55 kJ/mol和11.07s-1。依次采用单曲线拟合、多元非线性拟合及Malek方法判定得出菱镁矿热分解过程属于三维相界反应模型(R3),其动力学方程为:dα/d T=(1011.07/β)·e-211.55×103/(8.314×T)·3(1-α)2/3。