催化动力学光度法测定痕量钛的研究

在氨性介质中，痕量Ｔｉ（Ⅳ）催化ＫＩＯ４氧化靛红的褪色反应。褪色程度与Ｔｉ（Ⅳ）的浓度在０～８μｇ／Ｌ线性相关；对于靛红褪色反应为零级，对于Ｔｉ（Ⅳ）该反应为一级；测定该反应的表观活化能为７０４５ｋＪ／ｍｏｌ；反应速率关系式是－ｄＣＲ／ｄｔ＝ＫＣＴｉ。基于该反应，建立测定痕量Ｔｉ的方法，其检出限５０５×１０－９ｇ／Ｌ；ＲＳＤ（ｎ＝６）＜５２％，干扰可经伯胺Ｎ１９２３萃取分离消除。方法用于人发样中痕量Ｔｉ（Ⅳ）的测定，结果与极谱法相符。     

镜质体成烃反应动力学模型的标定及其在热史恢复中的应用

镜质体反射率（Ｒｏ）与其生烃率有关，因此，由Ｒｏ应可求取其生烃率；同时，在求取了镜质体成烃反应动力学参数之后，若已知其受热史，则可计算出镜质体的生烃率；反过来，若已知镜质体的生烃率，应可反推其受热史。基于这一基本原理，本文在建立和标定镜质体成烃反应动力学模型的基础上推导了可将其应用于存在着抬升、剥蚀和古地温非线性变化等复杂地质条件下热史恢复的原理模型，结合海拉尔盆地海参７井的实测Ｒｏ值，有效地恢复了其古热史     

不同粒径泥沙共存吸附动力学模式研究

天然水体中泥沙组成具有非恒定性和非均匀性,而不同粒径泥沙的吸附能力差异很大.因此.讨论天然水体中泥沙对重金属污染物的自净能力,必须研究不同粒径泥沙共存(即非均匀沙)的吸附模式.通过系统室内静态试验,研究了不同粒径泥沙共存吸附的吸附动力学模式.它表明,不同粒径泥沙共存吸附体系各粒径之间不存在竞争和干扰,共存体系单位重量泥沙的吸附量等于各粒径泥沙单独存在,在相同条件下单位重量泥沙的吸附量乘以其在共存体系中所占份额的和.这在一定程度上解决了天然河流水体泥沙吸附量的计算问题.     

正定矩阵的三角分解及其在测量平差中的应用

介绍正定矩阵的三角分解方法；讨论利用正定矩阵三角分解，求线性对称方程组中未知数、未知数函数，以及方程组系数矩阵逆阵的方法；给出了相应计算的紧凑格式和在测量平差中的应用实例。     

A crystal-chemical basis for Pb retention and fission-track annealing systematics in U-bearing minerals, with implications for geochronology

This study develops an empirical crystal-chemical framework for systematizing the kinetics of Pb loss and fission-track annealing in U-bearing minerals. Ionic porosity, Z (the fraction of a mineral's unit-cell volume not occupied by ions) potentially accounts for kinetic behavior by monitoring mean metal-oxygen bond length/strength. Various tests of a general kinetics-porosity relationship are presented, based upon diverse mineral data including: (1) Pb diffusion parameters; (2) measured closure temperatures (T_C) for fission-track annealing and (3) retentivities of both Pb and fission tracks, from apparent-age data. Every kinetic parameter (including T_C and mineral age for both the U/Pb and fission-track systems) is inversely correlated with Z within the sub-assemblage: zircon (Z ≈ 29%), titanite ( 34%) and apatite ( 38%). Assuming a diffusional closure model, Pb isotopic transport phenomena are described by a T_C-Z scale “calibrated” with field-based T_C data for titanite (≥ 680 ± 20°C) and apatite ( 500°C). Extrapolation of this scale yields T_C estimates for the following minerals: staurolite (T_C ≥ 1060°C, Z ≈ 25%); garnet (≥ 1010°C, 26.5%); zircon (≥900°C); monazite, xenotime, and epidote (≥ 750°C, 32%); and Ca-clinopyroxene (≥ 670 ± 30°C, 34 ± 1%, depending on composition). These empirical results imply that a (U/)Pb/Pb date for staurolite or garnet records the time of mineral growth, not post-growth isotopic closure, as also concluded in recent field studies. Because Z systematizes fission-track annealing, this recrystallization process, like volume-diffusion, must also be rate-limited by the strength of chemical bonds. The extent to which other recrystallization processes are likewise rate-limited is important to U/Pb geochronology because they potentially compete with diffusion as mechanisms for Pb-isotopic resetting in nature.     

Kinetics of the aromatisation of rearranged ring-C monoaromatic steroid hydrocarbons

The kinetics of the aromatisation of both rearranged and non-rearranged monoaromatics have been investigated in the laboratory under free radical conditions. These studies have indicated that the aromatisation rate constant for the non-rearranged is greater than that for the rearranged isomers at any one particular temperature. Since the members of the rearranged series coelute with their non-rearranged counterparts when both series are present in geological extracts, these results suggest that care needs to be exercised when assessing extents of maturation using monoaromatic and triaromatic steroid hydrocarbons.     

化学动力学在地球化学中的某些应用

化学动力学在地球化学（特别是成矿作用地球化学）研究中有极其重要的作用,其主要应用包括七个方面。本文重点介绍了地球化学中化学动力学的实验研究方法以及碳酸盐、硅酸盐、氧化物和硫化物等矿物的反应动力学实验成果;介绍了Helgeson的质量迁移理论及其研究热液在围岩中的运移方面的应用,并在热力学性质和动力学行为两方面研究了围岩的离解作用、蚀变作用与矿化作用及其相互关系。     

Glaucophane and pyroxene breakdown reactions in the Pennine units of the Eastern Alps

Abstract New occurrences of crossite and jadeitic pyroxene are described from a thick metabasite unit within the upper levels of the Peripheral Schieferhülle in the Tauern Window, Austria. Unusual textures are preserved which provide evidence for the reactions and mechanisms involved in the breakdown of crossite and jadeitic pyroxene. Zones of albite and chlorite, produced by reaction between crossite and paragonite, have been preserved due to sluggish reaction kinetics during decompression from the blueschist to the greenschist facies. The zonal sequence is interpreted in terms of chemical potential gradients in Na, Mg and Al, which have been established by overstepping the equilibrium boundary. Breakdown textures of jadeite-acmite pyroxene to a symplectite of albite + hematite + actinolite, and of crossite to talc and actinolite are also described.
The occurrence of crossite and jadeitic pyroxene at high levels within the Peripheral Schieferhülle implies that even upper levels of the structural sequence have undergone blueschist facies metamorphism with pressures in excess of 8 kbar during the Alpine collisional event.     

ABR反应器基质降解动力学有关参数的试验研究

通过静态模拟实验探讨了厌氧折流板反应器各级基质降解动力学。试验结果表明在25℃条件下,各级有机底物最大比降解速率Vmax和饱和常数Ks分别依次为3.06/d-1、1.52/d-1、0.97/d-1和20157.89mg/L、2947.38mg/L、7007.40mg/L。通过各级Vmax的比较可知,级中微生物活性最大,微生物处于对数增殖期,而、级中微生物处于减速增殖期或内源呼吸期。     

热成因甲烷碳同位素分布的形成机制

很多学者从不同的角度用不同的方法模拟了从有机母质 (包括煤和干酪根等气源 )形成天然气 (甲烷 )时的碳同位素分馏效应 ,建立了碳同位素分馏效应的很多模型 ,同时也讨论了催化作用和成烃后作用对天然气碳同位素的影响。但这些理论模型和模拟实验结果都还不能完全地拟合自然界中热成因甲烷碳同位素的分布 ,也未能从本质上完全阐明其碳同位素的分馏机制。其原因是各种模型的前提假设都未能完全满足复杂的自然界条件。今后工作的重点应放在用化学动力学的方法建立更完善的模型上 ,同时也应当重点考虑催化作用和成烃后作用对天然气同位素的影响。