Li2O·nB2O3(n=4,5)-20%LiCl-H2O过饱溶液20℃结晶动力学研究

采用结晶动力学方法对Li2 O :B2 O3=1 :4和 1 :5在 2 0 %LiCl-H2 O中的过饱的溶液在 2 0℃时的结晶动力学过程进行了研究 ,两种不同Li2 O :B2 O3(摩尔比 )配比的过饱和溶液均析出LiB5O8·5H2 O一种固相 ,通过X -ray粉末衍射、IR光谱和热分析对结晶析出固相进行了表征。同时拟合给出了结晶动力学方程 ,并对结晶反应机理进行了探讨。     

Dehydration of metapelites during high‐P metamorphism: The coupling between fluid sources and fluid sinks

Polymetamorphic metapelites and embedded eclogites share a complex, episodic interplay of dehydration and fluid infiltration at the eclogite type‐locality (Saualpe–Koralpe, Eastern Alps, Austria). The metapelites inherited a fluid content (i.e. mineral‐bound OH expressed in terms of mol.% H₂O) of ～6–7 mol.% H₂O from high‐T–low‐P metamorphism experienced during the Permian. At or near P_max of the subsequent Eoalpine event (～20 kbar and 680^°C), the breakdown of paragonite to Na‐rich clinopyroxene and kyanite in metapelites released a discrete pulse of hydrous fluid. Prior to the dehydration event, the rocks were largely fluid absent, allowing only limited re‐equilibration during the prograde Eoalpine evolution. Similarly, Permian‐aged gabbros have persisted metastably due to the absence of a catalyst prior to fluid‐induced re‐equilibration. The fluid triggered partial to complete eclogitization along a fluid infiltration front partially preserved in metagabbro. Near‐isothermal decompression to ～7.5–10 kbar and 670–690°C took place under fluid‐absent conditions. After decompression, a second breakdown of phengitic white mica and garnet produced muscovite, biotite, plagioclase and ～0.1–0.7 mol.% H₂O that enhanced extensive fluid‐aided re‐equilibration of the metapelites. Potential relicts of high‐P assemblages were largely obliterated and replaced by the recurrent amphibolite facies assemblage garnet+biotite+staurolite+kyanite+muscovite+plagioclase+ilmenite+quartz. The hydrous fluid originating from the metapelites infiltrated the embedded eclogites at these P–T conditions and induced the local breakdown of the peak assemblage omphacite and garnet to fine‐grained symplectites of diopside and plagioclase. Further fluid infiltration led to the formation of hornblende–quartz poikiloblasts at the expense of the symplectites. The metapelites re‐equilibrated until the growth of retrograde staurolite consumed any remaining free fluid, thereby terminating the process. Further re‐equilibration is inhibited by both the lack of a catalytic fluid and H₂O as a reactant essential for rehydration reactions. The interplay between fluid sources and fluid sinks describes a closed cycle for the rocks at the eclogite type‐locality. Final, near‐isobaric cooling is indicated by a slight increase of X_Fe in garnet rims. Post‐decompression dehydration and fluid‐aided re‐equilibration arrested by the introduction of staurolite might explain the apparently homogeneous retrogression conditions as well as the notorious absence of diagnostic high‐P assemblages in metapelites at the eclogite type‐locality.     

砂岩储层中原油微生物降解的模拟实验研究

模拟辽河冷东-雷家地区的砂砾岩储层条件，采用该地区的正常原油，在３０℃恒温和充氧下以及有营养元素的水溶液中，进行了原油喜氧微生物降解实验。实验表明，经微生物降解后，原油的化学组成发生了较大变化，饱和烃含量下降，沥青质、非烃含量上升；水溶液的ｐＨ值下降，并在其中检测出了有机酸，可见在微生物的代谢过程中，原油中的烃类分子被部分转化为水溶性含氧酸性产物。降解实验的油样与取自同一地区的两个重质原油饱和烃气相色谱图比较，两者在组成上极其相近，其结果说明辽河油田的重油成因，是原油遭受了喜氧微生物的降解。实验对微生物降解过程的动力学进行了初步研究。微生物对饱和烃馏分中不同化合物的降解序列为:短链正构烷烃、长链正构烷烃、异构烷烃、环状烷烃。但当各组分间的浓度发生较大变化时，降解序列会有所不同。     

利用生烃动力学和碳同位素生烃动力学探索油气田气体来源

利用气体碳同位素探索油气来源的传统方法由于受源岩类型、源岩成熟度等因素的影响,其实际应用受到很大的限制。生烃动力学和碳同位素动力学结合在这方面具有非常明显的优越性。本文利用热模拟实验,通过生烃动力学和碳同位素动力学计算,表明鄂尔多斯盆地上古生界苏里格气田气体的主要是他源阶段累积气,来源于气田南部高成熟区域、西部的天环坳凹陷气体的贡献比例分别为49%、22%,气田区域的源岩累积气体占29%。     

陆相低成熟烃源岩有机硫与热解成烃动力学关系初探

对陆相低成熟烃源岩（R_o≤ 0.5 %）有机硫与成烃动力学关系进行了研究。结果表明:①有机硫含量与镜质体反射率（R_o）之间呈负相关关系,即有机硫含量随成熟度提高而减少;②源岩的平均活化能（E）有随有机硫含量增大而减小的趋势;③有机硫含量与源岩活化能分布最小值（E_min）和经可溶有机质抽提后的活化能分布最小值（E_min）之间存在正相关关系;④活化能分布范围E_min～ESE_min（ESE_min＞E_min）内的可溶有机质生烃能力与有机硫含量具有一定的相关性;⑤综上结果推断东营凹陷南斜坡东段沙四段（Es₄）源岩中的有机硫在成烃过程中可能起到了一定的作用。     

OPTIMIZATION IN ORGANIC SYNTHESIS.AN APPROACH TO OBTAINING KINETIC INFORMATION BY SEQUENTIAL RESPONSE SURFACE MODELLING.OUTLINE OF THE PRINCIPLES

A method is presented by which it is possible to estimate the initial rate of chemical reactions when theexperimental conditions are varied according to a response surface design.The method is intended as acomplementary method for analysing data obtained from experiments in synthetic chemistry when theobjective is to optimize the yield of the reaction.Data obtained by simulations have been used to develop the method.From the simulated reactions itis shown that sequential analysis of the chemical yield of the reaction makes it possible to estimate modelswhich describe how the parameters of the response surface of the yield vary over time.The derivativesof these time functions of the response surface parameters can be used to define a rate function whichdescribes how the variations in the experimental conditions influence the rate of the reaction.It is shown how such rate functions can be used to afford reasonable estimates of the initial rates ofthe reaction.The initial reaction rates thus estimated can be used to determine the kinetic order of thereactants and also to provide estimates of the activation energy of the reaction.A thorough discussion of how canonical analysis of the rate function may assist in the elucidation ofreaction mechanisms is given.     

Effects of reaction kinetics and fluid drainage on the development of pore pressure excess in a dehydrating system

Fluid is released by dehydration reactions during prograde metamorphism. If the Claperyron slope for the dehydrating reaction is positive, then there is a net decrease in the total solid volume, which implies an irreversible increase in porosity. If the dilation of the pore space is insufficient to provide storage for all the released fluid, then pore pressure excess is generated, and if it becomes sufficiently high, it may lead to brittle fracturing. The time scale for pressure generation and the pore pressure excess can be maintained over long duration hinge on the interplay of reaction kinetics and fluid drainage. Motivated by experimental and microstructural observations, a hydrological model is developed that incorporates dehydration kinetics and its pressure dependence. Analytic solutions were derived for the undrained development of pore pressure. Whether lithostatic pressure may be exceeded hinges on magnitude of the overstep in temperature and corresponding equilibrium pressure. The time scale for development of pore pressure depends on the trade-off between poroelasticity and the pressure sensitivity of reaction rate. A finite difference model was also developed to simulate the progressive development of pore pressure excess, dehydration and porosity development. The model captures the experimental observation in gypsum of a reaction front that progressively propagates from the drained end toward the undrained end of a laboratory sample. It is also in reasonable agreement with experimental data on fluid drainage and porosity production.     

Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

Organotin accumulation in an estuarine food chain: comparing field measurements with model estimations

The bioaccumulation model OMEGA (optimal modelling for ecotoxicological applications) is used to explore accumulation of organotins in the Western Scheldt food chain, consisting of herbi-detritivores, primary and secondary carnivorous fish and a piscivorous bird. Organotins studied are tributyltin (TBT) and triphenyltin (TPT) and the respective di- and mono-organotin metabolites. Empirical elimination rate constants are compared to model predictions for organic substances and metals. It is found that field bioaccumulation ratios are higher than predicted based on elimination kinetics relevant for organic compounds. The results indicate that uptake of organotins mainly occurs via hydrophobic mechanisms, whereas elimination may occur via metal-like kinetics. This results in very low elimination rates, which are comparable to model predictions for metals.