弹道明胶老化初级阶段的模型

用流变震荡模式研究了10 wt%浓度的弹道明胶在冷却和等温下的老化行为.对明胶从sol-gel点冷却到某个目标温度的过程,通过不同冷却速率的实验,建了一个弹性模量与温度的线性关系.不同温度下明胶的等温老化实验表明,弹性模量-时间曲线具有相似的形状.依据Normand提出的二级反应动力学模型,引入一个表征明胶老化行为的速率常数,构建了一个预测弹道明胶在老化初级阶段的弹性模量演化的模型.该模型中模量-温度关系在初始和无穷大时是直线,其他模量-温度线是近似直线,并交于sol-gel点.老化速率常数和过冷度之间符合Flory-Weaver方程.对弹性模量和老化时间进行归一化处理,可将不同温度下的老化曲线叠加成一条主曲线.     

利用数字化手持技术探究“电解池阳极与原电池负极金属腐蚀速率”的大小

引入数字化手持技术设计6个实验,将金属腐蚀速率问题转换为金属腐蚀过程气体产生速率问题,进而转换为一定时间内密闭体系压强变化问题。实验关键是用气压传感器测定一定时间密闭体系气压变化,得到压强-时间曲线,根据曲线斜率分析反应速率,进而解决"金属腐蚀速率"问题。同时,还从"宏观-曲线-微观-符号"四重表征角度深入分析实验,有助于学生深入理解实验过程与反应原理。本实验研究结论是:(1)同一电解质溶液中,电解原理引起的腐蚀速率大于原电池原理引起的腐蚀速率;(2)对同种电解质溶液,在一定浓度范围内,电解质溶液浓度越大,腐蚀越快。     

数码成像比色法探究反应物浓度对化学反应速率的影响

利用数码成像比色法探究反应物浓度对化学反应速率的影响,采用紫红色溶液互补光"绿"通道的亮度值-时间的曲线变化表征反应物浓度与化学反应速率的关系。同时也利用分光光度计研究反应物浓度与反应速率的关系,测出透光率-时间的曲线变化。从实验结果比较分析,用数码成像比色法探究反应物浓度对化学反应速率的影响是非常简便可行的方法,同时让学生使用随身所带的电子产品开展实验研究,不仅使实验教学具有趣味性和科学性,而且能更好地培养学生的创新潜质。     

巧用二组分金属固液相图的测绘实验讲授Origin软件入门

二组分金属固液相图测绘实验是大学物理化学实验课程中的一个重要实验，通常绘制步冷曲线用时较长，在此过程当中仅讲授实验原理及实验步骤会显得枯燥乏味。鉴于此，拟在实验间隙讲授Origin软件的操作，以提高学生的数据处理能力。Origin作为一款重要的数据分析、处理与绘图软件，在科学研究过程中，使用率极高，因此提前让学生在本科阶段接触Origin软件入门级数据处理和绘图功能，掌握实验数据的简单处理，由此增加学生在实验过程中的投入度，从而提高学习效果，同时为日后数据分析处理与绘图工作打下坚实的基础。     

利用手持技术探究加热过程中石棉网上表面的温度

利用手持技术实时精确测量加热中石棉网上表面不同位置的温度，采用独立样本t检验比较石棉网上表面无铁丝点和有铁丝点间的温度差异与温差差异，通过回归分析探究石棉网上表面温度与其主要影响因素间的关系。研究表明：同等条件下加热中的石棉网上表面无铁丝点与有铁丝点存在显著温度差异，而无铁丝点间的单位距离温差与有铁丝点间的单位距离温差无显著差异；石棉网升温阶段上表面温度与时间、位置的关系可拟合为二元一次线性方程，恒温阶段上表面温度与位置的关系可拟合为一元三次曲线方程；石棉网上表面温度从中心向边缘小幅递减，均匀分布，最大温差小于玻璃仪器的耐热骤变温差。研究结果为化学教育实践中科学使用石棉网以及化学实验教材的编写提供参考依据。     

拐点法计算气体在高分子中的扩散系数

根据Fick扩散的基本假定,推导了从微分渗透曲线上的拐点值计算气体在高分子薄膜中扩散系数的公式。此法不需要达到稳态扩散,因此,可成倍地缩短实验时间。 用气体色谱仪测定丙烯气体在聚酰胺1010和聚酰胺1010/聚乙烯/聚乙烯与马来酸酐接枝共聚物的共混物的扩散系数,由本法计算的结果与滞后时间法、t_(1/2)法相一致,也符合实验值。     

基于手机录像功能的相变类观察实验改进

建立了一种基于手机录像的简便观察方法，可以用于毛细管法测定熔点、毛细管法测定沸点、氯化铵的结晶等相变类实验的改进。该方法一方面可以明显提高相变类实验的观察效果，便于学生清晰准确地捕捉记录相变过程；另一方面可以反复回放实验过程，便于学生撰写实验报告和教师的检查指导。该方法对提高学生的实验积极性和实验效果具有较大的帮助，并为实验的设计提供了更多的可能性。     

基于气相色谱技术研究黑色中性笔字迹中3种溶剂随书写时间的变化规律

基于溶剂挥发原理,采用气相色谱-质谱法(GC-MS)和气相色谱法-氢火焰离子检测器(GC-FID)对黑色中性笔历时性字迹样本中的甘油、二甘醇、三甘醇溶剂含量进行测定,并绘制了3种溶剂的含量随书写时间变化的关系曲线(字迹的老化曲线)。利用GC-MS从196种市购黑色中性笔中筛选出分别以甘油、二甘醇、三甘醇为主要溶剂的9支黑色中性笔,比照直尺在A4纸上画线,每只笔制作3个样本,每个月制作一次样本,连续收集21个月的样本,室温保存在封闭抽屉中。用直径为0.5 mm的打孔器在每张A4纸上取10个墨迹点,用含5 mg·L~(-1)苯甲酸乙酯(内标物)的甲醇溶液提取其中的溶剂,提取液进入GC-FID,吸附在DB-FFAP色谱柱上的溶剂在程序升温条件下分离,用FID测定。配制50 mg·L~(-1)混合标准溶液用于单点法定量,以书写时间为横坐标,其对应的单位书写长度中的溶剂的质量为纵坐标绘制字迹的老化曲线。结果显示,每个中性笔字迹中溶剂的初始含量各不相同,但每种溶剂含量随书写时间变化的拐点基本相同,甘油、二甘醇、三甘醇的含量分别在第7个月、第3个月、第9个月左右出现拐点,拐点之后溶剂含量趋于13,3,7 ng·mm~(-1)。方法用于一起实际案例(收条真伪鉴定)的分析,在涉及的2张收条中分别检出了20,34 ng·mm~(-1)的甘油,表明2张收条都是近期伪造的。     

酸碱滴定曲线拐点的理论探讨

酸碱滴定曲线中各拐点的情况,特别是突跃点与等当点之间的关系问题,历来引起人们的兴趣。一般认为,强碱-强酸滴定的突跃点与等当点是完全一致的,而强碱一元弱酸滴定的突跃点在等当点之前。但是在作这样的推断时,往往忽略了滴定过程中体系体积的增大,因此这只是一种近似处理。Me-ites指出,如果考虑体积的改变,则由于稀释作用,被滴定物质的分析浓度不可能是常数。此时强碱-强     

Origin用于物理化学实验数据的非线性拟合

在物理化学实验数据处理中应用Origin软件对数据进行非线性拟合,介绍用Origin求得实验曲线的非线性拟合参数的方法。结果表明,使用该软件能降低数据处理的随意性,减少处理误差,并且快捷方便,使实验结果更合理。     

Fitting and Analyzing pH Titration Curves on a Graphing Calculator

The pH titration curve is a well-known figure in chemistry. It is easy to plot this graph from experimental data by measuring pH as a function volume of added titrant; however, there is no simple mathematical equation of expressing pH as a function of titrant volume. The logistic function has been suggested but, as discussed in this paper, it is inadequate for modeling titration curves. Developed in this paper is a piecewise continuous function (with chemically meaningful parameters) of pH versus volume. A program has been written to display this function on a graphing calculator. This program can be used by students (1) to analyze the characteristics of pH titration curves, for example, the derivative and the presence of two inflection points, and (2) to interactively fit experimental titration data that they have collected.     

A numerical method of finding potentiometric titration end-points by use of approximative spline functions

A new numerical method of determining potentiometric titration end-points is presented. It consists in calculating the coefficients of approximative spline functions describing the experimental data (e.m.f., volume of titrant added). The end-point (the inflection point of the curve) is determined by calculating zero points of the second derivative of the approximative spline function. This spline function, unlike rational spline functions, is free from oscillations and its course is largely independent of random errors in e.m.f. measurements. The proposed method is useful for direct analysis of titration data and especially as a basis for construction of microcomputer-controlled automatic titrators.     

Electron spin resonance investigation of molecular motions in oil-extended styrene–butadiene–styrene block copolymers. I. The temperature dependence of resonance spectra: Glass,narrowing, and inflection temperatures

Spin-probe research into nanometer-scale molecular motions occurring in oil-extended styrene–butadiene–styrene diblock copolymers within the glass-transition range is reported. Complex resonance spectra are deconvoluted, and their intricate temperature dependence, resulting from the convolution of individual spectra due to nitroxide molecules located in different phases of the block copolymers, is analyzed. It is proved that a Boltzmann sigmoid accurately describes the temperature dependence of outer line separation. The characteristic inflection point of each sigmoid is used to assign an inflection temperature to each phase of the block copolymers. The inflection temperature coincides with the narrowing temperatures, within the experimental error. It is concluded that the inflection temperature is estimated with a higher accuracy than the narrowing temperature and that it allows a more profound analysis of molecular motions. The anomalous dependence of the glass, narrowing, and inflection temperatures for spin probes immobilized within the hard phase on the oil content has been assigned to morphological modifications, on the nanometer scale, induced by oil molecules added to the block copolymers. The experimental data demonstrate the sensitivity of spin-probe data to modifications of the nanometer-size architecture of block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1960–1971, 2004     

Characteristic Events in Free Radical Polymerization of Lower n-alkyl Methacrylates

It is well known that the free radical bulk polymerization of lower n-alkyl methacrylates is characterized by autoacceleration after definite conversions of the monomers. The conversion vs.time curves of polymerization have a typical 'S' shape. There are several characteristic points in these curves: the onset of autoacceleration (point M), the maximum in the polymerization rate (point S) and the end of the polymerization (point K). We have observed points P and R (maximum and minimum of autoacceleration) as inflection points in the derived polymerization rate vs. time curve. In this work, the free radical bulk polymerizations of methyl, ethyl and butyl methacrylates were investigated by differential scanning calorimetry. The effects of the polymerization temperature and the alkyl group length in the esters on the monomer conversions at the points M, P, S, R and K were studied. By regression analysis of the experimental results, relations were developed with which it is possible to predict the positions of the characteristic points, depending on the polymerization temperature and the alkyl group length. This revised version was published online in July 2006 with corrections to the Cover Date.     

分析化学有效数字教学中常见问题及分析

Analytical chemistry often involves a large amount of experimental data, and the reliability and accuracy of the experimental results are related to whether the original data can be properly recorded and calculated. In this paper, starting from the importance of significant figures, analyzing the frequently encountered problems related to the significant figures in teaching process, and giving some solutions, we try to help students to learn and master the concept of significant figures, rounding off numerical values, rule of operation and data processing.     

On the spline approximation of low-temperature calorimetry data

An algorithm for the spline approximation of heat capacity taking into account the Debye or Tarasov asymptotes in extrapolation from the first experimental temperature to 0 K was developed. The possibility of applying other boundary conditions that do not contradict the modern concepts of the behavior of heat capacity as a function of temperature is considered. A procedure for selecting the smoothing parameter based on a priori specifying the number of inflection points in the smoothing dependence is suggested. Possibilities for estimating the accuracy of approximation with the use of the orthogonal functions are discussed.     

溶液表面吸附实验的再讨论

In the solution adsorption experiment, different adsorption mode has been observed for aqueous ethanol and aqueous n-butanol, respectively. However, it is difficult to make an adjustment by the profiles of σ-c relationship. Choosing the experimental conditions improperly will give wrong results. Since there is no consistency between the Gibbs adsorption isotherm and Langmuir adsorption isotherm, the experimental data should not be fitted by using any algebraic equations or physical models. The data fitting for this experiment should be carried out according to the following steps:fitting the σ-lnc curve manually, making it monotonic and smooth; retrieving more data from this fitting curve, and re-plotting the σ-lnc curve; calculating the first derivatives at these data points (i.e., (∂σ/∂lnc)_T); calculating surface adsorptions by Gibbs adsorption isotherm, Γ=-(∂σ/∂lnc)_T/RT. As for the calculation of the cross-section area for the solute molecule, the effect of concentration of bulk solution (i.e., c) on the surface molecular density should be taken into account.     

Two trends of sample dispersion variation with carrier flow rate in a single flow-injection manifold

Two trends of sample dispersion variation with carrier flow rate in a single flow-injection manifold are completely revealed for the first time and an inflection point in the dispersion coefficient (D) vs. flow rate (q) curve is discovered. With the increase of the flow rate, the value of D increases before the inflection point but decreases after the inflection point. The value of the carrier flow rate at the inflection point (q_m) is independent of the sample injection volume, the tube length, the tube coil radius and the tube inner diameter. It is only affected by the substance diffusion coefficient (D_m) of the analysis. The value of q_m decreases as D_m increases. Therefore, the value of D_m for a sample can be estimated according to the D_m vs. q_m curve.     

Role of azeotropy in true-boiling-point distillation of complex mixtures of aliphatics,aromatics and 1-butanol

In true-boiling-point (TBP) distillation, the complex mixture is assumed to be separated into its components according to their boiling points. Plotting the head temperature of the column versus the mass fraction distilled, the TBP curve is obtained. Usually, the TBP curve may be considered to be an integral distribution function with respect to the normal boiling-point temperature characterizing the composition of the complex mixture. However, if there are azeotropes, this assumption is no longer correct.In a previous paper, we studied the role of azeotropy for mixtures consisting of an aliphatic petroleum fraction and of alcohols both experimentally and by continuous thermodynamics. We verified the TBP curve to be essentially influenced by azeotropy. Particularly, azeotropic influence is expressed by the occurrence of a temperature jump in the TBP curve.Real petroleum fractions often contain large amounts of aromatics. Therefore, in this paper, we expand the investigation of azeotropic effects to more complex mixtures consisting of aliphatics, aromatics and of 1-butanol. We show how to calculate TBP curves, and corresponding to that, we present experimental data. For the calculation, continuous thermodynamics is applied. In this, both the aliphatics and the aromatics are described by continuous distributions functions except for toluene which is treated as a separate component. The calculated TBP curves agree reasonably well with the measured data.     

Redox Titrations-II Location of inflection points of titration curves for homogeneous redox reactions

The relative positions of the inflection points and equivalence point of a homogeneous redox reaction have been studied by using the redox buffer capacity to derive an equation for the titration curve. The position of the inflection point corresponding to the maximum slope of the titration curve relative to the equivalence point depends on the electron transfers of the analyte and the titrant (the stoichiometric coefficients of the reaction equation) and on the difference between the formal potentials of the redox couples in a more complicated way than has been described previously.