Visual MINTEQ软件在大学化学教学中的应用

介绍了水文地球化学软件Visual MINTEQ的基本功能和特点,并结合大学化学课程中化学平衡章节的教学内容,举例说明了该软件在缓冲溶液pH计算、酸碱滴定过程模拟、配合物分布曲线绘制以及沉淀溶解平衡预测等应用实例中的使用方法.Visual MINTEQ程序在大学化学课堂中的应用不仅丰富了教学形式,还加强了学生对相关理论知识的理解和掌握,从而为其创新实践能力及科学研究方法的培养奠定了良好的基础.     

计算机在分析化学中的应用——分析化学中的数值方法(Ⅱ)

这一讲介绍在分析化学计算中经常用到的求解高次方程的数值法,着重讨论了简单迭代法、牛顿法和二分法的解题过程、收敛条件及方法特点等。文中叙述了络合物溶液中各物种浓度、多元酸碱溶液的pH及其中各物种浓度、酸碱滴定曲线等的计算方法,给出了程序和计算实例。     

关于酸碱滴定教学中的一些问题

酸碱滴定是基础分析化学中最重要的内容之一。通过酸碱滴定的教学,不仅有利于学生掌握滴定分析法的基本原理,而且为比较严谨地处理分析化学中各种化学平衡问题打下牢固的基础。因此,新编分析化学教材对酸碱滴定一章有所加强,与过去的教材相比,内容的改变也较大,而变化最大的是用酸碱质子理论来定量处理酸碱平衡问题。其他如溶液中各种酸碱组分的分布、溶液pH值的精确计算、缓冲容量、终点误差和非水滴定等内容,也有所加强。本文拟对用质子理论处理酸碱平衡和终点误差     

化学平衡制图软件HYDRA/MEDUSA在大学化学教学中的应用

介绍化学平衡制图软件HYDRA/MEDUSA的基本功能与特点。结合大学化学课程在化学平衡教学方面的内容,分别给出了沉淀-溶解平衡、酸碱平衡、配位平衡与氧化还原平衡的应用实例,充分显示了该软件有利于学习大学化学课程中复杂的平衡计算,帮助认识各化学形态之间的化学反应和控制条件,也为涉及到化学平衡体系计算与形态分布的化学研究提供帮助。     

利用手持技术探究不同酸碱环境下生物体pH变化的规律

利用手持技术数字化实验新手段做经典实验,通过pH传感器实时监测了去离子水、磷酸盐缓冲溶液、碳酸盐缓冲溶液、猪肝研磨液（新鲜和变质）和生菜研磨液（新鲜和变质）等溶液分别在酸、碱滴定过程中pH的变化,依据实验曲线和数据并结合相关生物化学知识,定量分析和比较了各物质滴定结果,从而证明在不同酸碱环境下生物体能够在一定范围内维持pH稳定并解释了其原因。     

分布分数计算式推导及应用中的对应性和规律性问题探讨

酸碱体系中各组分平衡浓度的计算是分析化学教学中的重要知识点之一,其教学效果取决于对分布分数(δ)计算式推导、应用和计算式中各项潜在含义的掌握。在教学中作为重点,其推导和应用既是花费时间又是繁琐复杂的内容。δ在溶液pH、酸碱体系和络合体系中各物种浓度、缓冲容量及滴定误差等的计算方面均有很好的应用。本文探讨在推导和应用过程中启发学生善于发现其中的对应性和规律性,掌握n元酸碱溶液中各物种δ计算式的快速推导和简便应用的方法,可达到激发学生兴趣、加深认知和牢固掌握的教学目的。     

络合滴定中由副反应系数Igα_(L(H))计算pH的新方法

本文根据溶液中酸碱组分的对数浓度与pH的关系,提出了由副反应系数计算溶液pH值的新方法。它使一个一元高次方程的求解简化为加减运算,为确定络合滴定的适宜酸度提供了一个简便的方法。     

强碱滴定弱酸的信息化教学软件及其教学实践*

基于酸碱滴定中的离子平衡现行教学中存在的问题,研发了一款以强碱滴定弱酸为例的离子平衡知识学习与习题检验的软件工具。该软件以可视化的技术,用曲线、柱状图等形式展示滴定过程中的动态变化,便于学生从滴定过程中的离子反应、图像和数据中获取信息并进行推理,从而认知酸碱滴定中的离子平衡的内在原理。该软件不仅能用于离子平衡中各概念的教学,也能为相关习题课的讲解创设必要的教学情境。     

酸碱滴定中指示剂浓度的影响

从理论计算和实验两方面对酸碱滴定指示剂浓度的影响进行讨论。通过酸碱滴定通式计算了溴百里酚蓝和酚酞在氢氧化钠滴定盐酸过程中pH的变化情况。结果表明指示剂的浓度过高或过低均不利于判定滴定终点。必须采用合适的指示剂浓度才能实现好的变色和好的准确度。     

通用酸碱滴定曲线方程式及BASIC计算程序

酸碱平衡和酸碱滴定问题的计算机处理已有不少报道。本文以滴定过程中溶液体系始终满足电荷平衡关系为依据,导出通用酸碱滴定曲线方程式(以下简称通式),用BASIC语言编制出计算程序,结构简单,功能较全,通用性强。一、通用酸碱滴定曲线方程式在通式推导过程中,把被滴定溶液体系中的强酸(强碱)看成是离解常数K_a(K-b)》1(用程序计算时,取1×10~4)的弱酸(弱碱):把盐看成是组成盐的相应酸     

酸碱滴定终点误差的快速估算法——基于CurTiPot酸碱滴定曲线的快速绘制

利用CurTiPot软件快速绘制酸碱滴定曲线,并在相对误差概念的基础上,实现了酸碱滴定终点误差的快速计算。     

Trace analysis of acids and bases by conductometric titration with multiparametric non-linear regression

A chemometric method for analysis of conductometric titration data was introduced to extend its applicability to lower concentrations and more complex acid-base systems. Auxiliary pH measurements were made during the titration to assist the calculation of the distribution of protonable species on base of known or guessed equilibrium constants. Conductivity values of each ionized or ionizable species possibly present in the sample were introduced in a general equation where the only unknown parameters were the total concentrations of (conjugated) bases and of strong electrolytes not involved in acid-base equilibria. All these concentrations were adjusted by a multiparametric nonlinear regression (NLR) method, based on the Levenberg-Marquardt algorithm. This first conductometric titration method with NLR analysis (CT-NLR) was successfully applied to simulated conductometric titration data and to synthetic samples with multiple components at concentrations as low as those found in rainwater (∼10 μmol L⁻¹). It was possible to resolve and quantify mixtures containing a strong acid, formic acid, acetic acid, ammonium ion, bicarbonate and inert electrolyte with accuracy of 5% or better.     

虚拟实验在大学基础化学实验教学中的探索与应用

针对复杂酸碱体系的滴定问题和氯化铅溶度积常数测定两个典型基础化学实验进行了虚拟实验设计与建设。借助于软件平台创建的虚拟实验交互系统涵盖了大量的基本理论、实验仪器与设备等信息,提供了各种反应条件下的组合实验、实验数据的计算结果与检验等,满足了学生不同层次的学习要求。     

Acid-base chemistry of red wine: analytical multi-technique characterisation and equilibrium-based chemical modelling

In this paper an attempt is made to model the alkalimetric titration trend (pH<7) of a series of red wines on the basis of an equilibrium-based calculation involving as input the chemical equilibria of the acid-base active substances, whose analytical concentration was determined in each wine under consideration. The chemical model (14 acid-base active substances and 22 protonation equilibria were considered) has been built in reliable conditions with respect to the chemical environment of the fluids under study, in order to describe the acid-base properties at a thermodynamic level using specific professional software. In this connection, protonation constant values of the substances involved were necessary, paying attention to: solvent composition, background salt, ionic strength and temperature. A series of synthetic solutions (based on mixed ethanol/water solvents at known ionic strength) was then pH-metrically titrated (25 °C) in order to refine suitable protonation constant values.Analytical measurements of carboxylic acids, amino acids, inorganic anions and metals were executed to know the concentration of a series of acid-base active reactants (pH<7) and the ionic strength state of each wine. Finally, a comparison between the experimental trend of the alkalimetric titration of each wine and the calculated one via the chemical model tested by means of a computer-assisted simulation has been performed. As an overall check of our job, the charge balance principle was adopted. During the alkalimetric titrations of each wine conductometric detection was performed as well, with the aim of confirming the values of ionic strength calculated using both analytical and equilibrium concentrations. The agreement we found when comparing the calculated values of ionic strength with varying pH with the trend of the conductometric signal can be considered as a significant validation of the chemical model proposed. The jump from the analytical to the equilibrium composition may allow the prediction of the effect on red wines consequent to chemical actions (addition of substances) or natural phenomena.     

Study of acid-base properties of fulvic acids using fluorescence spectrometry and multivariate curve resolution methods

Samples of fulvic acids obtained from cultivated calcareous soils are analyzed using acid-base titrations with spectrofluorimetric detection. Observed changes in both synchronous and emission spectra of fulvic acids when pH is changed are explained in terms of a limited number of fluorescent contributions each defined by its specific fluorescent spectrum and a concentration profile (species distribution) recovered from the multivariate curve resolution analysis of experimental data. Information on equilibrium is estimated from concentrations of the acid-base species.     

A digital image-based method for determining of total acidity in red wines using acid-base titration without indicator

This work proposes the use of digital image-based method for determination of total acidity in red wines by means of acid-base titration without using an external indicator or any pre-treatment of the sample. Digital images present the colour of the emergent radiation which is complementary to the radiation absorbed by anthocyanines present in wines. Anthocyanines change colour depending on the pH of the medium, and from the variation of colour in the images obtained during titration, the end point can be localized with accuracy and precision. RGB-based values were employed to build titration curves, and end points were localized by second derivative curves. The official method recommends potentiometric titration with a NaOH standard solution, and sample dilution until the pH reaches 8.2-8.4. In order to illustrate the feasibility of the proposed method, titrations of ten red wines were carried out. Results were compared with the reference method, and no statistically significant difference was observed between the results by applying the paired t-test at the 95% confidence level. The proposed method yielded more precise results than the official method. This is due to the trivariate nature of the measurements (RGB), associated with digital images.     

Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium

Various samples of aminopropyl-functionalized silica (APS) have been prepared by grafting an organosilane precursor 3-aminopropyl-triethoxysilane (APTES) onto the surface of silica gel. The amine group content of the materials has been adjusted by varying the amount of APTES in the reaction medium (toluene). The grafted APS solids have been characterized with using several analytical techniques (N₂ adsorption, X-ray photoelectron spectroscopy, infrared spectrometry) to determine their physico-chemical properties. Their reactivity in aqueous solutions was studied by acid-base titration, via protonation of the amine groups, and by way of complexation of these groups by Hg^II species. APS stability in aqueous medium was investigated at various pH and as a function of time, by the quantitative analysis of soluble Si- or amine-containing species that have been leached in solution upon degradation of APS. The chemical stability was found to increase when decreasing pH below the pK_a value corresponding to the RNH₃⁺/RNH₂ couple, but very low pH values were necessary to get long-term stability because of the high local concentration of the amine groups in the APS materials. Adsorption of mercury(II) ions on APS was also performed to confirm the long-term stability of the grafted solid in acidic medium. Relationship between solution pH and APS stability was discussed. For sake of comparison, the stability of APS in ethanol and that of mercaptopropyl-grafted silica (MPS) in water have been briefly considered and discussed with respect to practical applications of silica-based organic–inorganic hybrids, e.g., in separation science or in the field of electrochemical sensors.     

测定固体催化剂表面酸碱分布新方法的研究

酸碱催化是一类很重要的催化反应,酸碱强度分布和酸碱反应类型之间有着对应关系,因此,对表面酸碱的测定具有重要的意义。 固体表面酸碱的测定方法很多,常用的是Hammett指示剂酸碱滴定法,但这种方法不能用于测定有色催化剂,神保等研究的Al_2O_3和硅铝上苯酚的升温脱附曲线表明,Al_2O_3上有较强的碱性吸附点。Webb用HF-Al_2O_3吸附NH_3后再脱附并计算表面吸附的NH_3量,认为表面吸附的NH_3多,则表面酸也强,Shirasaki在SiO_2-Al_2O_3上吸附吡啶等气体后,以吸附量x对da/dx(s为吸附热)作图,得到酸碱分布图,Zetllemoyey用吸附热对吸附量的倒数作