对-叔丁基杯[4]的热力学和热分析动力学

用热重TG和DSC对杯芳烃对-叔丁基杯[4]热分解过程进行了研究,用多升温速率法和单升温速率法相结合的方法推断出了对-叔丁基杯[4]热分解的可能过程,并推断出了其可能的裂解反应动力学方程及热分析动力学参数;得出了结论脱包结甲苯的过程为23号机理函数,为三级反应过程,动力学方程为dα/dt=Ae-(E)/(RT)(1)/(2)(1-α)3;;表观活化能E为166.97 kJ*mol-1,指前因子A为1.67×1016 s-1;自身热分解脱去叔丁基的过程为1号机理函数,反应过程为一维扩散,动力学方程为dα/dt=Ae-(E)/(RT)(1)/(2)α;活化能E为248.89 kJ*mol-1,指前因子A为42.89 s-1.     

催化动力学褪色光度法测定痕量铀(Ⅵ)的研究

在稀硝酸介质中,铀能催化过氧化氢氧化罗丹明B褪色的反应,据此建立了催化动力学光度法测定痕量铀的新方法.实验测得反应体系的最大吸收波长λmax为556nm,并求得反应体系的表观活化能Ea=21.76 kJ/mol,表观速度常数K=6.07×10-4S-1,摩尔吸光系数ε=2.47×105L.mol-1.cm-1.方法的线性范围为1.7~12.0 ug/25mL,检出限为2.95×10-8g/mL.应用该方法测定了合成废水中的铀,结果满意.     

多升温速率等温法的动力学分析在一水草酸钙脱水反应中的应用

用一种新的方法求算热分析动力学的三因子 :(1)用迭代的等转化率法求出较为可靠的 Ea;(2 )用多升温速率等温法判定出可能的机理函数 ,并在 Ea和的基础上计算出 A.用该法对一水草酸钙 (Ca C2 O4· H2 O)脱水反应的热分析动力学三因子进行研究 ,得出其对应的机理函数的方程为 ;f (a) =n(1-a) 1- 1/n;Ea为 82 .83 k J· mol- 1;A为 1.14 2× 10 5～ 1.2 3 5× 10 5s- 1     

过氧化二异丙苯在空气中的非等温热分解动力学

采用热重-微分热重(TG-DTG)技术,研究过氧化二异丙苯在动态空气气氛中的热分解过程.运用Starink法,Madhusudanan-Krishnan-Ninan(MKN)法和Achar-Brindley-Sharp-Wendworth(ABSW)法分析非等温动力学数据,推断出过氧化二异丙苯热分解动力学模式为收缩球状R3模型,得到其反应的动力学方程为dα/dt=Aexp(-E/RT)×3(1-α)2/3,热分解反应的活化能E为117.32 kJ.mol-1,活化自由能ΔG≠为123.12 kJ.mol-1,活化焓ΔH≠为113.69 kJ.mol-1,活化熵ΔS≠为-21.41 J.(mol.K)-1.     

树脂D301M吸附草甘膦的热力学及动力学

通过静态吸附实验,研究了树脂D301M对草甘膦水溶液的吸附热力学和吸附动力学特性.测定了303.15～318.15K的等温吸附线和吸附动力学数据,并分别用Langmuir,Freundlich,Temkin模型拟合了树脂D301M吸附草甘膦水溶液的实验数据.结果表明,树脂D301M对水溶液中草甘膦的吸附符合Langmuir等温吸附方程,并根据热力学原理,计算出吸附热力学参数,其吸附焓值ΔH=58.42kJ.mol-1,ΔG0,ΔS0.树脂D301M的吸附过程符合准二阶动力学方程;采用Arrhenius方程计算出吸附的表观活化能Ea=165.22kJ.mol-1.     

无水醋酸锌与无水草酸固相反应动力学的研究

用等温热重法研究了无水醋酸锌与无水草酸的固相化学反应,反应分2步进行,通过对转化率数据α进行动力学拟合得到了反应的动力学方程.转化率α较低时发生第一步反应,动力学方程(1－α)－1/2=Ae－E/RTt式中E=70.72kJ/mol、A=4.43×108min－1;转化率α较高时发生第二步反应,动力学方程(1－2α/3)－(1－α)2/3=Ae－E/RTt式中E=122.7kJ/mol、A=9.81×1014min－1.     

在Cu(Ⅱ)催化下,对氯苯酚和苯酚钾反应的动力学研究

借助于高效液相色谱技术(HPLC),研究了在Cu(Ⅱ)催化下,对氯苯酚和苯酚钾合成对苯氧基苯酚的反应动力学。结果表明:此合成反应对于对氯苯酚和苯酚钾的浓度分别为一级。总反应的表观活化能Ea=1.07.0 kJ/mol,指前因子A0=2.147×1010kg·mol-1·min-1, 反应的速度方程为: -(d[p-ClC6H4OH]/dt)=2.147 ×1010×exp((107.0×103)/RT)·[p-ClC6H4OH][C6H5OK]。     

过碳酸钠分解等温动力学研究

本文利用热重分析仪 ,采用等温热重法 ,在 91～ 1 0 2℃范围内 ,研究了过碳酸钠在氮气氛围中的分解动力学。在氮气氛围中 ,过碳酸钠的分解为自催化模型。以最优化法 ,求得样品不同温度下的动力学模型参数。过碳酸钠分解的活化能 Ea=1 50 .89KJ· mol- 1 ,频率因子 A0 =5.6× 1 0 1 8。     

稀土多元配合物的热力学函数的计算与讨论

本文通过应用微量热法对轻稀土多元配合物的热化学性质研究发现,在该组内稀土元素配合物的标准摩尔生成焓与原子序数基本呈线性关系,从而线性拟合计算出稀土配合物Pr(TCA)3.3H2O(s),Pr(TCA)(C9H6NO)2(s)的标准摩尔生成焓分别为:-3056.65 kJ.mol-1,-1362.24 kJ.mol-1;并且利用文献数据计算出稀土配合物Ce(Gly)2(Ala)3Cl3.3H2O(s),Nd(Gly)2(Ala)3Cl3.3H2O(s),Sm(Gly)2(Ala)3Cl3.3H2O(s)的晶格能分别为:-4960.8±4.32kJ.mol-1,-5026.7±4.32 kJ.mol-1,-5109.9±4.32 kJ.mol-1,结果符合镧系收缩规律.     

锰酸锂合成的动力学研究(Ⅰ)──氧气气氛

用热分析仪测试不同升温速率下,氢氧化锂和二氧化锰在氧气气氛中的差热分析曲线,结合DoyleOzawa法和Kissinger法研究锰酸锂合成的动力学;计算各反应阶段的表观活化能,依次为59462kJ·mol-1,92672kJ·mol-1,163271kJ·mol-1和107524kJ·mol-1·并确定反应级数,频率因子,速率常数,推导出每个反应阶段的动力学方程·为制备尖晶石型锰酸锂提供理论依据,进一步优化工艺条件·     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

A computer generator for randomly layered structures

AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…     

海南岛地体及其毗邻陆缘晚中生代—新生代古地磁研究和构造演化

本文叙述了对海南岛及其毗邻大陆边缘白垩纪到第四纪地层岩石进行古地磁研究的全部工作过程。通过分析岩石中剩余磁矢量的磁偏角及磁倾角的变化,提出海南岛白垩纪以来经历的构造演化模式如下:早期伴随顺时针旋转而向南迁移,后期伴随逆时针转动并向北运移。联系该地区及邻区的地质、地球物理资料,对海南岛上述的构造地体运动提出以下认识:北部湾内早期有一拉张作用,主要是该作用使湾内地壳显著伸长减薄,形成北部湾盆地。从而导致了海南岛的早期构造运动,而海南岛后期的构造运动则主要是受南海海底扩张的影响。海南地体运动规律的阐明对于了解北部湾油气盆地的形成演化有重要的理论和实际意义。     

Exciton Seebeck in Molecular Systems

Various applications relevant to the exciton dynamics,such as the organic solar cell,the large-area organic light-emitting diodes and the thermoelectricity,are operating under temperature gradient.The potential abnormal behavior of the exicton dynamics driven by the temperature difference may affect the efficiency and performance of the corresponding devices.In the above situations,the exciton dynamics under temperature difference is mixed with     

Achieving Unusual States of Matter Under High Pressure

The elongation method,originally proposed by Imamura was further developed for many years in our group.As a method towards O(N)with high efficiency and high accuracy for any dimensional systems.This treatment designed for one-dimensional(ID)polymers is now available for three-dimensional(3D)systems,but geometry optimization is now possible only for 1D-systems.As an approach toward post-Hartree-Fock,it was also extended to     

《Chinese Science Bulletin》SUBJECT INDEX TO VOLUME 59(2014)

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An on-line scaling method for improving scalability of a database cluster

The explosive growth of the Internet and database applications has driven database to be more scalable and available, and able to support on-line scaling without interrupting service. To support more client's queries without downtime and degrading the response time, more nodes have to be scaled up while the database is running. This paper presents the overview of scalable and available database that satisfies the above characteristics. And we propose a novel on-line scaling method. Our method improves the existing on-line scaling method for fast response time and higher throughputs. Our proposed method reduces unnecessary network use, i.e. , we decrease the number of data copy by reusing the backup data. Also, our on-line scaling operation can be processed parallel by selecting adequate nodes as new node. Our performance study shows that our method results in significant reduction in data copy time.     

An improved R-tree based on childnode''s probability

R-Tree is a good structure for spatial searching. But in this indexing structure,either the sequence of nodes in the same level or sequence of traveling these nodes when queries are made is random. Since the possibility that the object appears in different MBR which have the same parents node is different, if we make the subnode who has the most possibility be traveled first, the time cost will be decreased in most of the cases. In some case, the possibility of a point belong to a rectangle will shows direct proportion with the size of the rectangle. But this conclusion is based on an assumption that the objects are symmetrically distributing in the area and this assumption is not always coming into existence. Now we found a more direct parameter to scale the possibility and made a little change on the structure of R-tree, to increase the possibility of founding the satisfying answer in the front sub trees. We names this structure probability based arranged R-tree (PBAR-tree).     

Integrating GIS Web services based on mediating architecture

The geographic information service is enabled by the advancements in general Web service technology and the focused efforts of the OGC in defining XML-based Web GIS service. Based on these models, this paper addresses the issue of services chaining,the process of combining or pipelining results from several interoperable GIS Web Services to create a customized solution. This paper presents a mediated chaining architecture in which a specific service takes responsibility for performing the process that describes a service chain. We designed the Spatial Information Process Language (SIPL) for dynamic modeling and describing the service chain, also a prototype of the Spatial Information Process Execution Engine (SIPEE) is implemented for executing processes written in SIPL. Discussion of measures to improve the functionality and performance of such system will be included.     

Tracking data management using topology of moving object database system for moving object constrained trajectory in LBS application

Advances in wireless technologies and positioning technologies and spread of wireless devices, an interest in LBS (Location Based Service) is arising. To provide location based service, tracking data should have been stored in moving object database management system (called MODBMS) with proper policies and managed efficiently. So the methods which acquire the location information at regular time intervals then, store and manage have been studied. In this paper, we suggest tracking data management techniques using topology that is corresponding to the moving path of moving object. In our techniques, we update the MODBMS when moving object arrived at a street intersection or a curved road which is represented as the node in topology and predict the location at past and future with attribute of topology and linear function. In this technique, location data that are corresponding to the node in topology are stored, thus reduce the number of update and amount of data. Also in case predicting the location,because topology are used as well as existing location information, accuracy for prediction is increased than applying linear function or spline function.