FT-IR Study of the Kinetics and Products of the Reactions of Dimethylsulphide, Dimethylsulphoxide and Dimethylsulphone with Br and BrO   总被引：3，自引：0，他引：3  

B. Ballesteros  N. R. Jensen  J. Hjorth 《Journal of Atmospheric Chemistry》2002,43(2):135-150

Kinetics and products of the gas-phase reactions of dimethylsulphide (DMS), dimethylsulphoxide (DMSO) and dimethylsulphone (DMSO₂) with Br atoms and BrO radicals in air have beeninvestigated using on-line Fourier Transform Infrared Spectroscopy (FT-IR) as analytical technique at 740 ± 5 Torr total pressure and at 296 ± 3 K in a480 L reaction chamber. Using a relative rate method for determining the rate constants; the following values (expressed in cm³molecule^–1 s^–1) were found: k_DMS+Br = (4.9 ±1.0) ×10^–14, k_DMSO + Br < 6 × 10^–14,k_{DMSO 2} + Br 1 × 10^–15,k_DMSO + BrO = (1.0 ± 0.3) × 10^–14 andk_{DMSO 2} + BrO 3 × 10^–15 (allvalues are given with one on the experimental data). DMSO, SO₂, COS, CH₃SBr andCH₃SO₂Br were identified as the main sulphur containing products of the oxidation of DMS by Br atoms. From the reaction between DMSO and Br atoms, DMSO₂and CH₃SO₂Br were the only sulphur containing products thatwere identified. DMSO, DMSO₂ and SO₂ were identified as themain sulphur containing products of the reaction between DMS and BrO.DMSO₂ was found to be the only product of the reaction between DMSO and BrO. For the reactions of DMSO₂ with Br and BrO no products were identified because the reactions were too slow.The implications of these results for atmospheric chemistry are discussed.  相似文献   

The ultra‐high pressure coronitic and pseudomorphous reactions in a metagranodiorite from the Brossasco‐Isasca Unit,Dora‐Maira Massif,western Italian Alps: a petrographic study and equilibrium thermodynamic modelling     

M. Bruno  R. Compagnoni  M. Rubbo 《Journal of Metamorphic Geology》2001,19(1):33-43

Metagranodiorite samples from the Brossasco‐Isasca Unit, Dora‐Maira Massif, western Alps, show pseudomorphous and coronitic textures where igneous minerals were partially replaced by ultra‐high pressure (UHP) metamorphic assemblages. The original magmatic paragenesis consisted of quartz, plagioclase, K‐feldspar, biotite and minor phases. During UHP metamorphism, the plagioclase (site P) was replaced by zoisite, jadeite, quartz, K‐feldspar and kyanite, and coronitic reactions developed between biotite and adjacent minerals. At the original igneous biotite–quartz contact (site A), a single corona of poorly zoned garnet is developed, whereas at the biotite–K‐feldspar (site B) and biotite–plagioclase (site C) contacts, composite coronas are formed. Integration of results from petrographic observations, calculations of mineral stoichiometry and thermodynamic calculations of mineral stability has allowed the determination of the metamorphic reactions involved and the estimation of the metamorphic conditions, which reached as high as 24 kbar and 650 °C. Accurate microanalysis by energy‐dispersive spectroscopy (EDS) and statistical analysis of the data allowed us to identify, for the first time in a natural Na‐pyroxene of metagranitoid rocks, the end‐member Ca‐Eskola.  相似文献   

Estimation and inference in inverse methods for kinetic models of hydrocarbon generation     

David R. Fox 《Mathematical Geology》1995,27(8):923-938

Procedures based on ordinary and generalized least of squares for the estimation of kinetic parameters in laboratory pyrolysis experiments are compared. When the data consist of measurements on the degree of chemical reaction through time for a number of temperatures, a single regression procedure is preferred to the two-stage regression alternative. Methods are developed for the construction of confidence intervals for calibration curves used to infer formation temperature on the basis of the unreacted fraction of source material.  相似文献   

Inverse methods and kinetic models of hydrocarbon generation. II. Case histories for residual kerogen analysis     

Jianchang Liu  I. Lerche 《Mathematical Geology》1990,22(8):989-1009

Using the results of the first paper in this series, which dealt with an inverse procedure for hydrocarbon generation, this paper focuses on case histories and numerical implementation of the model. Experimental data on residual kerogen analysis have been used with the inverse procedure to examine the applicability of the model to hydrocarbon generation directly from the degradation of kerogen, and to derive the kinetic parameters for the construction of a prediction equation. Energy-dependent channeling probability distributions are used to exhibit the stability of the model in describing the processes of kerogen degradation. The numerical methods for the solution of the inverse procedure and a sensitivity analysis are also discussed.  相似文献   

氯化钠和硫酸钾晶体生长动力学研究     

周利民刘峙嵘  许文苑 《华东地质学院学报》2005,28(3):266-269

研究了不同添加剂对晶体生长的影响,对NaCl和K2SO4晶体在流化床中的动态生长行为及单个晶体在溶液中的静态生长行为进行了研究.实验中还考虑了晶体表面的完整程度对晶体生长的影响,并对上述晶体的生长机理进行了分析.此外,对存在添加剂及纯溶液中NaCl和K2SO4晶体的溶解过程进行了研究.结果表明,本实验所选用的添加剂在低浓度下即能有效抑制NaCl和K2SO4晶体生长.  相似文献   

The Vale de Abrutiga uranium phosphates mine, central Portugal     

Marina M.S. Cabral Pinto  Maria M.V.G. Silva 《Chemie der Erde / Geochemistry》2007,67(3):251-252

A brief summary about the composition and origins of the U deposit is present. The mineralization is composed by secondary uranium phosphates (saleeite and meta-saleeite). The precipitation was probably the main responsible factor for U retention within the quartz veins leading to the uranium phosphate mineralization of Vale de Abrutiga.  相似文献   

硅酸盐体系的化学平衡:(3)反应动力学     

马鸿文  戚洪彬  王蕾  聂轶苗  靳昕  王英滨  苏双青 《现代地质》2006,20(4):647-656

通过具体实例,简要介绍了矿物材料学研究中有关反应动力学研究的基本原理,给出了对硅酸盐体系若干典型过程的反应动力学研究结果,包括:(1)高铝粉煤灰-Na2CO3体系的中温烧结反应和钾长石-石膏-碳酸钙体系钾长石的热分解反应;(2)KA lS i3O8-Ca(OH)2-H2O体系钾长石水热分解-雪硅钙石晶化反应;(3)S iO2-A l2O3-CaO体系微晶玻璃的β硅灰石晶化反应;(4)13X微孔分子筛和MCM-41介孔分子筛对Hg2+的吸附反应。反应动力学研究成果可望对矿物材料制备实验方案优化、工业生产过程的条件控制以及改进矿物材料性能提供理论指导。  相似文献   

生烃动力学、同位素动力学方法在烃源岩研究中的应用     

刘大永彭平安  林会喜林玉祥 刘华 《地质通报》2006,25(9):1201-1204

生烃动力学、同位素动力学常用于烃源岩评价、油气源对比研究中.生烃动力学参数结合盆地热史,可恢复烃源岩在任一时代的生烃史,对构造复杂盆地的二次生烃研究具有独特的优势.利用生烃动力学方法可以实现有机质总量的恢复,在此基础上对高-过成熟样品原始有机质丰度是否有必要恢复进行了讨论;而基于生烃动力学的油气源对比综合考虑热史、成藏期次、成藏过程等各种地质参数对烃源岩生烃的影响,是一种动态的研究方法.  相似文献   

Shrinking Sphere Kinetics for Batch Dissolution of Mixed Particles of a Single Substance at High Under-Saturation: Validation with Sodium Chloride, but with Biogenic Silica in Mind     

Victor W. Truesdale 《Aquatic Geochemistry》2008,14(4):359-379

The cubic equation recently derived for the increase in concentration of a solute with time, as the solid dissolves in batch according to the shrinking sphere model at high under-saturation, is extended to dissolutions of mixtures of differently sized particles. This problem needs to be solved if batch dissolutions are to play their part in the proposed amelioration of global warming and associated climate change by accelerated ‘re-burial’ of excess CO₂ in ocean sediment. The upgraded model was tested using sodium chloride dissolved in 50% aqueous propanone, whence the model fitted two separate runs with 500 and 212 μm, and 212 and 38 μm, diameter crystals, respectively. The key to simulating dissolution in this way lies in the dissolutions being independent of each other. It is further shown that although this condition was implicit in the recent derivation of the cubic equation, it was not recognised at the time. The work should be applicable to any batch dissolution of mixed particles at high under-saturation, and hence, may find use in many industrial and laboratory dissolutions. Simulations show how agglomerated mixtures can yield a straight line on the plot of ln(1 − C/C _T) versus time, as was reported to occur recently with sodium chloride taken ‘straight from the bottle’. It is shown that this probably explains why exponential dissolutions may have seemed appropriate to the dissolution of biogenic silica in earlier literature. This study suggests that a new round of biogenic silica dissolutions, but with sieved samples, would be worthwhile, with the likelihood that shrinking sphere behaviour might well be found to characterise the kinetics. The opportunity is taken to investigate a number of aspects of the shrinking sphere model not generally discussed before, e.g. the graph for the change in surface area with time. The limitations of using cubic salt crystals with the shrinking sphere model are discussed.  相似文献   

苯并[a]芘在脊尾白虾（Exopalaemon carinicauda）体内富集的动力学研究     

李磊  蒋玫  沈新强  吴庆元  牛俊翔  许高鹏 《台湾海峡》2014,(4):481-485

通过室内实验模拟了脊尾白虾（Exopalaemon carinicauda）对苯并[a]芘（benzo[a]pyrene,Ba P）的生物富集,通过非线性曲线拟合获得脊尾白虾对Ba P的富集动力学参数（吸收速率常数k1、释放速率常数k2、生物富集因子BCF、平衡状态下脊尾白虾体内Ba P含量CAmax、生物学半衰期B1/2）.各动力学参数分别为：k1范围为12.34～24.96,平均值为18.80,k2范围为0.06～0.10,平均值为0.08,BCF范围为208.41～248.03,平均值为228.02、CAmax范围为12.40～93.79 ng/g,平均值为46.78 ng/g,B1/2范围为6.89～11.71 d,平均为8.95 d.脊尾白虾对Ba P的吸收速率常数k1、释放速率常数k2、BCF均随外部水体中Ba P浓度的增大而减少,CAmax、B1/2随外部水体中Ba P浓度的增大而增大.  相似文献