偶氮二甲酰胺热分解机理及氧化锌对其分解的影响

采用TG-MS联用仪表征了不同温度下偶氮二甲酰胺热分解的气体种类,红外光谱表征了偶氮二甲酰胺在不同温度下的分解残留物,探讨了偶氮二甲酰胺的热分解机理以及氧化锌对其分解的影响。研究表明,偶氮二甲酰胺热分解过程分为3个阶段：第一阶段的气相产物为N₂、CO、HNCO,固体残留物为联二脲等;第二阶段的气相产物为NH₃、HNCO;第三阶段的气相产物为NH₃、CO₂,固体残留物为尿唑等。ZnO的加入使得偶氮二甲酰胺热分解的第一阶段反应提前,第二阶段反应和第三阶段反应滞后。     

替硝唑的非等温热分解动力学及热稳定性研究

报道了用热重法(TG)研究替硝唑（Tinidazole,TNZ）原药及片剂中替硝唑热分解非等温动力学以及药物的稳定性,并对用热重分析仪测定片剂含量的方法进行了探讨.推断出原药热分解过程为零级反应,其动力学方程为dα/dt=Ae-(Ea)/(RT),热分解反应活化能Ea为99.7kJmol-1,指前因子A为3.60×107s-1;片剂中替硝唑的热分解过程为三维扩散级反应,其动力学方程为dα/dt=Ae-(Ea)/(RT)3/2(1+α)2/3/［(1+α)1/3-1］,活化能Ea为105.1kJmol-1,指前因子A为1.08×106s-1.实验表明替硝唑原药具有较高的热解活化能,热稳定性较好;在片剂中热分解机理和分解活化能发生改变,说明赋形剂对药物的热稳定性有一定影响.根据得到的热分解反应的机理函数和动力学参数,得到片剂有效存贮期与贮存温度的关系曲线,估算出在室温（25℃）下,分解率为10%时药物的存贮期为26.7年,分解率为5%时所需要的时间约为6.9年.     

含石蜡燃料热分解特性研究

采用差示扫描量热法(DSC)和热重法(TGA)对HTPB燃料、石蜡及含石蜡燃料的热分解过程进行了分析。研究了石蜡含量、碳粉含量和不同升温速率对含石蜡燃料热分解过程的影响。实验结果表明:石蜡热分解过程可以分为低温分解阶段和高温分解阶段。含石蜡燃料的热分解主要分为四个阶段;随着石蜡含量的增加,样品的初始分解反应放热峰温和第三反应放热峰温不断提前,放热量不断增大,而对其第二分解放热峰和镁粉氧化放热峰基本无影响;随着升温速率的增大,含石蜡燃料各分解反应的放热峰温不断提高,第二、第三分解反应的放热量增大;计算出了4#含石蜡燃料的第一、第二、第三热分解反应的活化能E和指前因子A。     

硫代双乙醇的超临界水热分解过程

在等温管式平推流反应器中研究了超临界水中硫代双乙醇 (TDG)的水热分解反应 ,反应温度为 42 5～ 5 2 5℃ ,压力为 2 2～ 30 MPa,反应停留时间为 0 .6～ 6 3.2 s。结果表明 ,TDG可在超临界水中快速、彻底分解。TDG分解产物为甲烷、一氧化碳、二氧化碳、乙烯、氢气、乙醇、乙醛、硫化氢和单质硫。 TDG转化率随停留时间增加而增大。随温度和压力升高 ,TDG分解速率加快。分析表明 ,TDG的水热分解过程是通过水解和热解两条反应路径进行的     

碘海醇注射液的热分解反应动力学

测定了碘海醇注射液在60°C、80°C下因受热分解而产生的碘离子浓度随时间的变化,研究了碘海醇注射液的热分解反应动力学。结果表明:碘海醇注射液的热分解反应为一级反应,在60°C和80°C时,热分解速度常数分别为5.9×10-6d-1和7.2×10-5d-1,碘海醇的分解活化能Ea=122.1kJ/mol,热分解速度常数与温度的关系为k=3.51×1013e-14716/T。     

过硫酸根离子在硫酸溶液中的热分解动力学和机理

本义比较详细地研究了过硫酸鲫在1.25N和0.1144N硫酸中的热分解动力学和机理,在较广的硫酸浓度范围内以及在中性和碱性介质中测定了分解速度常数,计算了相应的活化能,分解是一级反应,但在1.25N硫酸中观察到的是假一级反应,这时k随硫酸浓度的增大而增加。H+离子催化S_2O_8=离子热分解的反应只能在一定浓度的酸溶液中发生,超过限度酸对热分解起阻碍作用,硫酸浓度增加速度常数降低。酸催化分解反应的活化能较低,所得数值与文献值一致,且有且盐效应;酸阻化反应的活化能则较高,没有盐效应,随着酸浓度的增加发生了从H+离子催化的反应机理到未催化反应机理的过渡。一些合氮杂坏化合物如吡啶,β-和-γ甲基呲啶以及異菸酸显著地阻化S_2O_8=离子在硫酸溶液中的热分解。忽为阻化作用在于阻化剂加速了生成动力学上比较稳定的Caro酸的链终止过程。第一次在实验上发现了作为链反应特征的诱导期。根据实验结果,特别是诱导期和阻化作用,重新提出并完善了过硫酸盐热分解的自由基链反应机理。通过对于热分解过程中生成酸Caro酸量的测定和把阻化反应的速度常数分解为未阻化反应的速度常数,得出几点结论:(1)在某种酸浓度下,S_2O_8=离子的热分解和水解以可相比拟的速度同时进行,这时Caro酸的生成和存在不影响热分解的动力学级数但使分解速度相当地降低。阻化作用随着生成Caro酸的速度的增大而加强。(2)在一定酸浓度下,S_2O_8=离子因热分解和水解生成Caro酸而消失的总反应(称为未阻化反应)服从一极速度定律,且其速度常数k_0为定值。(3)在γ-甲基吡啶存在下,热分解受到了阻化而转化生成Caro酸的反应却得到了加速,S_2O_8=根消失的总速度则不变,因而k_0也不变。     

ZrxCe1-xO2的制备及其氢氧化物前驱体的热分解过程研究

采用共沉淀法制备了不同铈锆比的ZrxCe1-xO2(x=0,0.1,0.3,0.5,0.7,0.9,1.0)固溶体.利用热分析方法研究了Zrx(OH)4x.Ce1-x(OH)4(1-x)体系的热分解过程,并运用XRD对其热分解产物进行了表征.实验表明Zrx(OH)4x.Ce1-x(OH)4(1-x)在空气中的热分解是一步完成的,随着锆含量的增加分解温度逐渐提高.应用微分法和积分法相结合对该分解过程的分解机理进行了推测,得出了一系列分解反应的表观活化能E和指前因子A.发现其热分解反应遵循Zhuralev-Lesokin-Tempelman三维扩散机理,其动力学方程为:f(α)=3/2(1-α)4/3[(1-α)-1/3-1]-1;g(α)=[(1-α)-1/3-1]2,其表观活化能大小与样品中的锆含量有关.     

六氟丙烷热分解性能及机理研究

在管式反应器中对六氟丙烷进行热分解,用气相色谱-质谱仪、气相色谱仪和化学滴定法对热分解气体进行分析。结果发现:六氟丙烷在600~800℃热分解时主要发生脱氟化氢(HF)反应,随着反应温度和停留时间的增加,六氟丙烷分解程度提高。根据均裂的化学键类型提出六氟丙烷热分解的5个初级反应路径,通过密度泛函理论DFT-(U)B3LYP/6-31G*计算六氟丙烷各化学键离解能,发现H转移反应所需活化能最低,C—C键断裂反应次之,分别为282.74和381.88 kJ/mol,表明六氟丙烷热分解过程中最易发生H转移反应脱去HF。在高温热分解气体中还检测到微量CF4、CHF3、CF2CHF等多种产物,分析是由H转移反应产物与C—C键断裂产生的自由基相互结合或者分解再结合形成。     

固体热分解动力学机制的研究

利用热失重技术,以碳酸钙为模型物质,进行了样品质量为2.52～18.37mg、升温速率为2～20℃/min的不同条件下的非等温热分解研究。对改进的积分法和Coats-Redfern方法的计算结果进行了对比。确定了碳酸钙热分解速率受相界反应控制的机制,热分解的活化能为250～370kJ/mol,频率因子为2.65×10~(10)～3.49×10~(19)。研究了升温速率和样品质量对碳酸钙热分解的影响以及热分解过程的补偿效应规律。     

刘伟1 刘中星2 王建龙1* 曹端林1 陈丽珍1

为了研究3,4-二硝基吡唑(DNP)的热分解性能和热稳定性,采用绝热加速量热仪(ARC)对其在绝热条件下的热分解进行了研究,得到了DNP绝热分解的温度、压力、温升速率等随时间及温度的变化曲线。结果表明：DNP的绝热分解分为四个阶段,后两个阶段为其主要热分解阶段,主要的热分解从245.5℃开始,绝热分解整体是较为缓慢的,没有自催化现象发生,证明DNP具有良好的热稳定性;根据温升速率方程及Arrhenius公式对这后两个阶段进行了动力学计算,两个阶段的热分解反应级数为0.5和1,活化能分别为218.4 kJ/mol、331.1 kJ/mol,指前因子分别为7.9×10₁₈min_-1、6.9×10₂₈ min_-1,并得到了DNP绝热分解温升速率随温度变化的数据模型。     

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.