连二硫酸锰的热力学函数测定

用evaporation-temperature法测定了MnS_2O_6·2H_2O和MnS_2O_6·4H_2O的分解压力,关联出这两种水合盐的脱水或分解反应的平衡常数与温度的关系式。并利用这些关系式,计算得到MnS_2O_6·2H_2O的△H°_f,△G°_f,S°分别为-1991.2kJ·mol~(-1)。-1756.0kJ·mol~(-1),388.7J·mol~(-1)·K~(-1),MnS_2O_6·4H_2O的△H°_f,△G°_f,S°分别为-2637.2kJ·mol~(-1),2251.8kJ·mol~(-1),351.5J·mol~(-1)·K~(-1)。     

HPMBP和N_(503)协萃钯(Ⅱ)的研究

研究螫合萃取剂1—苯基—3—甲基—4—苯甲酰吡唑酮—5(HPMBP)与酰胺型革取剂N_(503)氯仿溶液从硝酸介质中协萃钯(Ⅱ)的热力学行为。在30℃、pH=1.70条件下,萃取剂浓度与分配比的关系式可表达为lgD′=2.948lg[HPMBP]_((o)) 6.645,lgD″=0.9809lg[N_(503).HNO_3]_((0)) 2.796。温度与分配比的关系表达为lgD=424.923/T-0.3088。测得协革平衡常数k=34.67,焓变△H=-8.316kJ.mol~(-1),自由能变△G=-8.932kJ.mol~(-1)和熵变△S=2.036J.mol~(-1).K~(-1).     

共价化合物的热力学性质与结构的关系(Ⅸ)——R(CH_2)_nR的气相标准生成焓

考虑到影响R_1CH_2_nR_2的气相标准生成焓△_fH_m~(R_1CH_2_nR_2,g)的各种因素,包括端基,链因子(n)及主链上取代基的支化度等。提出了计算正、异构烷烃(RCH_2_nR)的△_fH_m~(g)的计算模型: △_fH_m~(R_1CH_2_nR_2,g)=-74.4kJ·mol~(-1)-4.9T-20.5n+∑m_ib_i其中:-74.4kJ·mol~(-1)为CH_4的△_fH_m~(g),-4.9为主链上端基(-CH_3)对△_fH_m~(R_1CH_2_nR_2)的贡献,T为端基的数目,n为组成上与CH_2相当的-CH_2-的数目,-20.5为其对△_fH_m~(R_1CH_2_nR_2,g)的贡献,b_i为每类取代基的支化度,m_i为b_i的数目。本文的计算值与实验值很好吻合,相关系数为0.9997。     

水合醋酸铜热解过程动力学研究

为了用醋酸铜取代昂贵难求的醋酸铑作原料,合成在太阳能利用方面很有前途的过渡金属双核络合物光敏荆,用热重(TG)法求得了水合醋酸铜热解过程2个步骤的有关动力学参数:第一步骤对应温度为66～140℃;反应级数n=1;表观活化能E=91.7kJ·mol~(-1);指前因子A=6.65×10~(11)min~(-1).第二步骤对应温度为223～295℃;n=1;E=163kJ.mol~(-1);A=7.95×10~(14)min~(-1).确定了2个步骤的速率常数k对温度T的函数关系式.计算了第二步骤的标准活化熵△_r~≠S_m~(?)=34.2J·mol~(-1)·K~(-1),标准活化焓△_r~≠H_m~(?)=162kJ·mol~(-1).评价了醋酸铜的热稳定性,并确定了用其作原料合成双核铜络合物时的适宜反应温度.     

谷氨酸钠热分解过程的研究

本文采用热重分析法研究了一水合谷氨酸钠的热分解过程。结果表明:一水合谷氨酸钠的热分解过程分为两个阶段,在105℃开始脱去结晶水,在155℃开始分子内脱水。脱结晶水阶段的动力学参数为n=0.2,E_a=102.2 kJ·mol~(-1),A=1.7×10~7S~(-1);分子内脱水阶段的动力学参数为n=3.2,E_a=322.3kJ·mol~(-1),A=1.1×10~(34)S~(-1)。     

热重法研究一水合草酸锶脱水过程的机理与动力学

本文利用等温热重法和非等温热重法,研究了一水合草酸锶脱水过程的机理与动力学.实验测定和理论分析表明:SrC_2O_4·H_2O的脱水过程受A_3机理支配,即属于一种随机成核和晶核随后生长的过程,其活化能E=94.47kJ·mol~(-1),频率因子A=2.59×10~(10)min~(-1).     

关于化学热力学计算中的量纲问题

本文明确地指出了:热化学反应方程式中的计量系数v_i并不是一个无因次量而有单位“mol”;Van′t Hoff等温式△G°=-RTLnK_P中△G°的量纲是J或KJ而不是J·mol~(-1)或KJ·mol~(-1);化学反应的标准焓变△H°和标准嫡变△S°的量纲并不是J·mol~(-1)和J·K~(-1)·mol~(-1),而是J和K~(-1),这样,下列诸式:lnKa=-(△G°)/RT=(-△H°)/RT (△S°)/T=(nF E°)/RT在量纲上才都合理;这里应当指出的是,式中R的量纲已变为J·K~(-1)而不是J.mol~(-1)K~(-1);不论是用动力学方法还是热力学方法导出的化学平衡常数,其单位均为[压力或浓度单位]△v,△v为无因次量.     

镓的高灵敏显色反应(Ga(Ⅲ)-BPR-Tween80-CTAB体系)

本文研究了高灵敏的Ga(Ⅲ)-BPR-Tween80-CTAB体系。该体系的适宜酸度为pH2.87～3.42。最大吸收在528nm。锌量在0.1～1.0μg/25ml范围遵守比耳定律。当Tween80在高浓度(0.8％)时,ε=5.72×10~5l·mol~(-1)·cm~(-1);当Twnne80在低浓度(0.24％)并辅以少量H_2O_2(浓度为4.8×10~(-3)％)时,ε=1.09×10~6l·mol~(-1)·cm~(-1)。镓在6mol/l盐酸介质中用乙酸丁酯萃取分离后,测定了分子筛型催化剂中的镓含量。     

Co(Ⅱ)-NaCl体系在悬汞电极上的还原机理

用恒流计时电位法和循环电位扫描法研究了Co(Ⅱ)-NaCl体系在悬汞电极上的还原动力学,确定了过程存在着前置转化反应,电荷传递为单电子过程.中间价态离子Co(Ⅰ)很不稳定,以岐化反应方式很快分解.前置转化反应的正向速度常数k_1’=2.85dm~3·mol~(-1)·S~(-1),逆向速度常数k’_(-1)=7.15S(-1).过程的动力学参数αn=0.46—0.52,n=1,R_S=1—3×10~(-10)cm·S~(-1).     

O(~3P)原子与环戊酮的二级反应速率常数测定

我们用流动微波放电—化学发光方法首次测定了O(~3p)原子与环戊酮分子在303—503K温度范围内的反应速率常数,反应速率常数与温度关系为k=3.79±1.41×10~(-11)exp(-18.6±1.5kJ·mol~(-1)/RT)cm~3·molecule~(-1)·s~(-1)O(~3p)原子由流动微波放电产生,利用检测其与NO反应生成NO_2~*的化学发光强度的方法来检测O(~3p)浓度。此外,还就这类反应速率常数与环形分子结构关系进行了讨论。     

Markedness and its Interpretation in Language Use

Language markedness is a common phenomenon in languages, and is reflected from hearing, vision and sense, i.e. the variation in the three aspects such as phonology, morphology and semantics. This paper focuses on the interpretation of markedness in language use following the three perspectives, i.e. pragmatic interpretation, psychological interpretation and cognitive interpretation, with an aim to define the function of markedness.     

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.     

低渗透非均质砂岩油藏启动压力梯度研究

理论推导与室内实验相结合,建立了低渗透非均质砂岩油藏启动压力梯度确定方法。首先借助油藏流场与电场相似的原理,推导了非均质砂岩油藏启动压力梯度计算公式。其次基于稳定流实验方法,建立了非均质砂岩油藏启动压力梯度测试方法。结果表明:低渗透非均质砂岩油藏的启动压力梯度确定遵循两个等效原则。平面非均质油藏的启动压力梯度等于各级渗透率段的启动压力梯度关于长度的加权平均;纵向非均质油藏的启动压力梯度等于各渗透率层的启动压力梯度关于渗透率与渗流面积乘积的加权平均。研究成果可用于有效指导低渗透非均质砂岩油藏的合理井距确定,促进该类油藏的高效开发。     

On Tragic Consciousness In The Works By Ernest Hemingway

As an American modern novelist who were famous in the literary world, Hemingway was not a person who always followed the trend but a sharp observer. At the same time, he was a tragedy maestro, he paid great attention on existence, fate and end-result. The dramatis personae's tragedy of his works was an extreme limit by all means tragedy on the meaning of fearless challenge that failed. The beauty of tragedy was not produced on the destruction of life, but now this kind of value was in the impact activity. They performed for the reader about the tragedy on challenging for the limit and the death.     

A computer generator for randomly layered structures

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

An Index mechanism for multi-scale view in spatial databases

There are numerous geometric objects stored in the spatial databases. An importance function in a spatial database is that users can browse the geometric objects as a map efficiently. Thus the spatial database should display the geometric objects users concern about swiftly onto the display window. This process includes two operations:retrieve data from database and then draw them onto screen. Accordingly, to improve the efficiency, we should try to reduce time of both retrieving object and displaying them. The former can be achieved with the aid of spatial index such as R-tree, the latter require to simplify the objects. Simplification means that objects are shown with sufficient but not with unnecessary detail which depend on the scale of browse. So the major problem is how to retrieve data at different detail level efficiently. This paper introduces the implementation of a multi-scale index in the spatial database SISP (Spatial Information Shared Platform) which is generalized from R-tree. The difference between the generalization and the R-tree lies on two facets: One is that every node and geometric object in the generalization is assigned with a importance value which denote the importance of them, and every vertex in the objects are assigned with a importance value,too. The importance value can be use to decide which data should be retrieve from disk in a query. The other difference is that geometric objects in the generalization are divided into one or more sub-blocks, and vertexes are total ordered by their importance value. With the help of the generalized R-tree, one can easily retrieve data at different detail levels.Some experiments are performed on real-life data to evaluate the performance of solutions that separately use normal spatial index and multi-scale spatial index. The results show that the solution using multi-scale index in SISP is satisfying.     

Achieving Unusual States of Matter Under High Pressure

正The periodicity of the elements and the non-reactivity of the inner-shell electrons are two related principles of chemistry,rooted in the atomic shell structure.Within compounds,Group I elements,for example,invariably assume the+1 oxidation state,and their chemical properties differ completely from those of the p-block elements.These general rules govern our understanding of chemical structures and reactions.Using first principles calcula-     

Exchange-Correlation and Electronic Excitation Energies from Pairing Matrix Fluctuations

We have developed an adiabatic connection to formulate the ground-state exchange-correlation energy in terms of pairing matrix linear fluctuations.This formulation of the exchange-correlation energy opens a new channel for density functional approximations based on the many-body perturbation theory.We illustrate the potential of such approaches with an approximation based on the particle-particle Random Phase Approximation(pp-RPA).This re-     

Density Functional Theory for the Response of Periodic Systems to Electric Fields Based on the Vector Potential Approach

正The electronic and nuclear(structural/vibrational)response of 1D-3D nanoscale systems to electric fields gives rise to a host of optical,mechanical,spectral,etc.properties that are of high theoretical and applied interest.Due to the computational difficulty of treating such large systems it is convenient to model them as infinite and periodic(at least,in first approximation).The fundamental theoretical/computational problem in doing so is that     

On the Thermodynamic Limit for Responses to Static Electromagnetic Fields

For molecular systems,the quantum-mechanical treatment of their responses to static electromagnetic fields usually employs a scalar-potential treatment of the electric field and a vector-potential treatment of the magnetic field.Although the potential for each field separately is associated with the choice of an(unphysical)origin,the precise choice of the origin for the electrostatic field has little consequences for the results.This is different for the