通用化学平衡计算和载流床反应器模拟程序的初步研究

Ⅰ.通用化学平衡计算 与热化学数据库相联结,采用进度调整方法编制了多相多元体系的化学平衡计算程序。 本文在选取独立组元的算法上提出了改进,可以减少运算量。另外还扩展了程序的功能,使本程序在以下三种输入条件下都能计算,包括:(1)给定原子矩阵,各组元的标准吉布斯生成自由能及初始摩尔数;(2)给定一组独立化学反应的计量系数矩阵,平衡常数和各组元的初始摩尔数;(3)给定原子矩阵,各组元的标准吉布斯生成自由能和体系的元素组成。     

化学平衡解题通用方法探讨*

对于复杂的化学平衡,平衡时刻浓度、分压、物质的量、转化率之间存在错综复杂的关系,给解题带来了很大难度。提出了“列表-设未知数-计算分压-计算平衡常数-求解”的5步解题通用方法,并利用该方法,结合CASIO计算器独特的解题特色,对近几年化学竞赛中出现的2道化学平衡试题进行了剖析。     

论化学平衡中的独立等量关系

物料平衡等式(MBE)、电荷平衡等式(CBE)和质子平衡等式(PBE)是化学平衡定量解析中的常用等量关系。本文从理论上证明了CBE可以由MBE导出,因此在计算中不是一个必不可少的独立条件。由于H~+来源的多样性,在涉及酸碱的化学平衡中,CBE比MBE的计算效率更高。这些结论与计算实践相一致,即在配位平衡、氧化还原平衡和沉淀平衡的计算中,MBE为主,CBE起辅助作用;在酸碱平衡计算中,CBE为主,MBE为辅。PBE也不是一个独立等量关系,而且仅适用于酸碱平衡,可以完全被效率更高的CBE代替。本研究明确了化学平衡中的独立等量关系,不仅有助于提高化学平衡定量解析的效率,而且使其理论结构更加简洁明晰。     

开发面向分析化学的复杂方程绘图求解软件

化学平衡的精确解析会涉及复杂方程的求解,而分析化学专业人员通常不完全具备相关算法和编程知识。所以,尽管当前硬件发达、编程语言丰富,精确解析仍然难以在分析化学课程中大规模推广。为此,基于Matlab语言,开发了具有针对性的方程求解软件。该软件以简洁的界面、直观的图像和自然的人机交互,实现方程的高效求解;对用户的编程要求非常低。期望通过这种方式,显著降低化学平衡精确解析中的软件使用成本,从而为大规模推广提供进一步的支持。本文介绍了该软件的基本原理和主要特点;通过3个复杂化学平衡实例,详细说明软件的使用方法以及注意事项。另外提供Android系统版本,免费使用。     

化学平衡的多重性、稳定性和重现性

利用动力学方法讨论了非理想的化学反应体系中化学平衡态的多重性、稳定性和实验上的可重现性。分析了实验结果(化学平衡态)与初始条件以及其它动力学过程之间的依赖关系,并简略讨论了化学平衡多重性和稳定性问题在某些实际问题和工程设计中的重要性。     

狭缝孔内甲烷蒸汽重整化学平衡的分子模拟

采用反应蒙特卡罗方法研究了狭缝孔内甲烷蒸汽重整反应的化学平衡. 模拟中将CH4, CO和H2均描述成球形LJ分子, H2O和CO2分子的势能分别采用TIP4P和EMP2模型计算. 狭缝孔壁与LJ点位之间的相互作用采用Steele的10-4-3模型计算. 由于没有狭缝孔内该反应的实验数据, 因此比较了用经典热力学预测与RCMC方法得到的主体相平衡组成. 两种方法得到的结果比较吻合, 表明采用RCMC方法预测孔内的化学平衡是可靠的. 讨论了其它工艺条件对孔内化学平衡的影响.     

一个适用于Huggins常数K′较大的新的一点法特性粘数方程

本文提出了一个适用于Huggins常数较大(0.472≤K＇≤0.825)的聚合物-溶剂体系的新的一点法特性粘数方程[η]=ηsp/Cη~(1/2).并与其它四个一点法方程分别对19种聚合物的27种聚合物-溶剂体系的192个文献数据进行计算比较,发现本方程所得结果是十分满意的.因此,本方程的建立,扩大了用一点法求算聚合物特性粘数方法中K＇值的范围.     

离子选择性电极分析中的多次标准加入法的一种非线性算法

离子选择电极分析的多次标准加入法的实验数据处理通常采用图解法或计算机解法。用计算机求解具有速度快、精度高等优点,目前被广泛采用。1970年Brand提出一种非线性最小二乘法求解C_x、S和E。的Fortran计算程序。其解法是用Taylor级数展开将非线性方程转化为线性法方程,用消元法解法方程,经过迭代计算求得结果。石守衡等人对Bra-ad解法进行改进,提出用共轭斜量法解矛盾方程组,无须形成法方程,从而提高了运算精度     

系统组分数的确定

分析了组分数表达式中各个量的意义,并举例说明组分数的计算。讨论了化学平衡和反应进行到底2种情形对系统组分数的影响:化学平衡中生成物只有1相的,化学平衡考虑与否不会影响组分数;可进行到底的反应,在特定条件下可按照化学平衡来处理。最后总结了快速确定系统组分数的步骤。     

羟基聚丁二烯羟值测定新方法

本文建立了两个相关的∑Aa_i-B_2型凝胶化反应方程,含试样官能团数和重均官能度两个未知数.解联立方程,得到一元二次方程.通过测定该方程的系数,间接测得试样官能团数和重均官能度.该方法用于H_2O_2引发的羟基聚丁二烯羟值测定。其结果比目前国内外通用的经典酰化法高一倍以上.证明新的羟值数据是正确的.     

一种模式分类降维策略及其在复杂化学信息处理中的应用

采用分类相关分析方法处理复杂化学信息的模式分类问题。从高维模式中提取的分类相关成分,它们相互独立,并集中了原有模式的分类信息。提出由相关量份额选择分类相关成分,计算简便,用以替代原模式,可以显著地降维,使问题简化,分类效果良好。该方法应用于天然留兰香油多类判别,结果良好。     

Components and coupling in enzyme-catalyzed reactions

Many enzyme-catalyzed reactions involve coupling of two or more reactions that could otherwise be catalyzed separately. When biochemical reactions are coupled, the equilibrium composition is very different from that when the reactions are not coupled. The number of components in a chemical reaction is equal to the number of independent conservation equations for atoms of elements, but the number of components in an enzyme-catalyzed reaction that is coupled is larger than the number of independent conservation equations for atoms of elements. The investigation of these additional conservation equations by use of linear algebra is complicated by the fact that in dilute aqueous solutions, the activity of water is taken to be unity. This causes an incompatibility of conservation matrices and stoichiometric number matrices that can be avoided by use of the further transformed Gibbs energy G' ' that provides the criterion for spontaneous change and equilibrium when the standard transformed Gibbs energy of water is constant. In the most striking example discussed, the enzyme mechanism of a ligase reaction introduces three constraints in addition to conservation of atoms of elements. This is completely unheard of in chemical reaction thermodynamics.     

Programming the HP 48 Calculator to Control the Lab Works Interface

While the balanced chemical equations for a multireaction system are generally not unique, the minimum number of independent equations, R, is a characteristic property of the system. Deleting one nonspectator species from the system leads to a system with R reduced by one. In this way each system can be reduced to a single-reaction system and ultimately to a no-reaction system. The least number of chemical species that can be deleted to obtain a no-reaction system equals R. Every multireaction system, therefore, can be reduced to a number of single-reaction equations which can be balanced by any one of the standard techniques. Some examples are given where balancing by inspection is employed.     

Chemical Equations for Multireaction Systems

While the balanced chemical equations for a multireaction system are generally not unique, the minimum number of independent equations, R, is a characteristic property of the system. Deleting one nonspectator species from the system leads to a system with R reduced by one. In this way each system can be reduced to a single-reaction system and ultimately to a no-reaction system. The least number of chemical species that can be deleted to obtain a no-reaction system equals R. Every multireaction system, therefore, can be reduced to a number of single-reaction equations which can be balanced by any one of the standard techniques. Some examples are given where balancing by inspection is employed.     

稳态和振荡剪切流动下聚合物共混反应体系演化的格子玻尔兹曼模拟

采用A/B/S三元共混体系为模型体系,其中S由A和B通过可逆的化学反应生成并充当增容剂.我们采用自由能形式的格子玻尔兹曼模拟方法,考察了在稳态及振荡剪切流动下化学反应速率、剪切速率和振荡频率对体系形态结构演化的影响.模拟给出了增容剂平均密度和空间分布随时间的演化,结果表明增容剂S的生成能有效地降低分散相的尺寸,并且通过控制化学反应速率、剪切速率和振荡频率能够有效地调控增容剂在体系中的分布,从而为控制反应共混体系的形态结构提供帮助.     

一种判断电化学/化学反应体系热力学自洽性的新方法

介绍了一种判断电化学/化学反应体系热力学自洽性的新方法-“秩法”。结合 实际例子描述了该方法的原理、计算步骤。该方法充分利用矩阵“秩”的概念,由 反应系数矩阵的“秩”直接判断出其中的独立组分数,并且仅当寻找到依赖反应时 才需对有关方程进行求解。因此,“秩法”概念上清晰、直观,且由于可以直接调 用矩阵变换的子程序,程序实现也极为容易。该方法对于电化学、化学及化工反应 过程的模拟将非常有意义。     

计算导数分光光度法的研究：Ⅰ.钨,钼的同时测定

本文以W、MO-SAF-CTMAB体系为例,选取二阶和三阶导数光谱的2个不同波长下的导数值,采用简单解联立方程组的方法即可同时测定钨和钼。本文从原理和实验上证实了计算导数光度法的可行性,提出了以方程组的系数矩阵条件数来指导测量点的选择。     

A Method to Determine the Dimension of Long-Time Dynamics in Multi-Scale Systems

Modeling reaction kinetics in a homogeneous medium usually leads to stiff systems of ordinary differential equations the dimension of which can be large. The problem of determination of the minimal number of phase variables needed to describe the characteristic behavior of large scale systems is extensively addressed in current chemical kinetics literature from different point of views. Only for a few of these approaches there exists a mathematical justification. In this paper we describe and justify a procedure allowing to determine directly how many and which state variables are essential in a neighborhood of a given point of the extended phase space. This method exploits the wide range of characteristic time-scales in a chemical system and its mathematical justification is based on the theory of invariant manifolds. The procedure helps to get chemical insight into the intrinsic dynamics of a complex chemical process.     

A new regression method based on independent component analysis

Based on independent component analysis (ICA), a new regression method, independent component regression (ICR), was developed to build the model of NIR spectra and the routine components of plant samples. It is found that ICR and principal component regression (PCR) are completely equivalent when they are applied in quantitative prediction. However, independent components (ICs) can give more chemical explanation than principal components (PCs) because independence is a high-order statistic that is a much stronger condition than orthogonality. Three ICs are obtained by ICA from the NIR spectra of plant samples; it is found that they are strongly correlated to the NIR spectra of water, hydrocarbons and organonitrogen compounds, respectively. Therefore, ICA may be a promising tool to retrieve both quantitative and qualitative information from complex chemical data sets.     

A Concise Description of an Old Problem: Application of Matrices to Obtain the Balancing Coefficients of Chemical Equations

It is not difficult to balance chemical equations and thus it is hardly given more thoughts. However, there is a mathematical principle for the balancing of chemical equations and this principle may be used for automation. The balancing of chemical equation is carried out, by formulating a reaction matrix and the latter is used in a matrix equation. The matrix equation is then solved to obtain the balancing coefficients. The conventional matrix inverse method cannot always be used and hence the solution is obtained by row reduced operations. These operations and any matrix manipulation are carried out with Matlab. Further this novel method can be used to classify chemical equations as nonfeasible, unique and nonunique.