时间参量法(VI)--连续一级反应的热动力学研究

根据化学反应热动力学的基本原理.推导了连续一级反应的积分和微分热动力学方程,建立了连续一级反应热动力学时间参量法的数学模型,通过对己二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学研究,验证了连续一级反应时间参量法的正确性.     

热动力学对比进度法V. 连续一级反应的热动力学研究法

本文导出了连续一级反应动力学和热动力学的对比进度方程, 建立了连续一级反应热动力学的数学模型。根据该模型, 可由一次实验的热谱数据同时解析出两步反应的速率常数和摩尔反应焓。采用热导式热量计研究了己二酸二乙酯皂化反应的热动力学, 实验结果验证了本文热动力学模型的正确性。     

热动力学对比进度法V. 连续一级反应的热动力学研究法

本文导出了连续一级反应动力学和热动力学的对比进度方程, 建立了连续一级反应热动力学的数学模型。根据该模型, 可由一次实验的热谱数据同时解析出两步反应的速率常数和摩尔反应焓。采用热导式热量计研究了己二酸二乙酯皂化反应的热动力学, 实验结果验证了本文热动力学模型的正确性。     

时间参量法（Ⅵ）——连续一级反应的热动力学研究

根据化学反应热动力学的基本原理,推导了连续一反应的积分和微分和微分热动力学方程,建立了连续一级反应热动力学时间参量法的数学模型,通过对已二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学研究,验证了连续一级反应时间参量法的确定性。     

连续一级反应的热动力学研究法: 自函数回归法

根据热动力学基本理论,推导出了热导式量热计测量的连续一级反应的热谱曲线的动力学解析方程,并推出了连续一级反应热动力学的自函数递推方程,由此建立了一种研究连续一级反应的热动力学新方法-自函数回归法。通过对丁二酸二乙酯和邻苯二甲酸二乙酯的皂化反应的热谱曲线分析,验证了自函数回归法的正确性。     

自函数回归法: 连续一级反应的热动力学研究

根据热动力学基本原理,推导出了连续一级反应热动力学自函数递推方程,从而建立了一种新的连续一级反应的热动力学研究法---自函数回归法.应用该法分别研究了丁二酸二乙酯和邻苯二甲酸二乙酯皂化反应的热动力学。     

N-溴代丁二酰亚胺氧化异丙醇反应的热动力学研究

利用Batch型热导式热量计测定了N-溴代丁二酰亚胺(NBS)氧化异丙醇反应的热谱曲线,并分别利用简单级数反应和连续一级反应热动力学特征对比参量法的数学模型计算了反应的动力学参数,计算结果表明:利用连续一级反应热动力学研究法处理得到的动力学参数与文献通过碘量法的测定值是吻合的,因此,在质子性溶剂中的NBS氧化异丙醇反应遵从连续一级反应的动力学规律。     

平行反应的热动力学研究法

根据热动力学基本理论, 推导了平行准一级反应和平行准一二级反应的热动力学方程, 建立了热谱解析平行反应动力学参数的热动力学研究法, 并利用该法研究了两个模拟平行反应体系的热动力学, 实验结果验证了方法的正确性.     

电刷镀含钛合金非晶态镀层的晶化动力学(II)

用热分析仪研究非晶态材料的晶化动力学有两大类方法：等温法和变温法．变温法测定动力学参数的优点是简便，需要的样品量少，能在反应开始到结束的整个温度范围内连续计算动力学参数．晶化反应是一种相变反应．反应前后没有重量的变化，因此，只能采用差热分析法D’fA或差示扫     

热动力学的研究 XV.分数级反应的热动力学法

根据热动力学基础理论和n级反应通用的热动力学方程,本文建立了各种分数级反应的热动力学研究法.应用M-340计算机编制了研究法基本公式中有关无量纲参数的各种函数表,并深入讨论了有关函数的基本性质及其图象.同时将本文建立的分数级反应研究法应用于整数级反应的热动力学研究,所得结果与文献报道的一、二级反应的无量纲参数法基本公式完全相同,该研究法还可用于判断化学反应的级数.     

Kinetic investigation of redox reaction between vitamin C and ferric chloride hexahydrate in acidic medium

The kinetics of the reaction between vitamin C (l-ascorbic acid) and ferric chloride hexahydrate was investigated in acidic medium at pH 3 spectrophotometrically. The order of the reaction was established by applying different methods, such as initial rate method, integration method and half-life method. The results obtained from each method were correlated with each other and consistency in all methods was observed. The order of the reaction with respect to each reactant was found first and the overall second order was recommended for the reaction.     

Study on the reaction kinetics between PBT and epoxy by a novel rheological method

In the present study, the reaction kinetics of polybutylene terephthalate (PBT) and epoxy system was studied by a novel rheological method. The reaction process was determined by rheological test and the results showed that there were three stages in the reaction between PBT and epoxy, which were reaction-controlling stage (stage I), reaction-stagnation stage (stage II) and diffusion-controlling stage (stage III). In addition, the stage I was selected to study the reaction kinetics by the rheological method. The results showed that the reaction between PBT and epoxy could be classified as a pseudo-first-order reaction due to the excessive amount of epoxy group. Furthermore, the reaction apparent activation energy of the stage I determined by the rheological method was 143 kJ/mol. To confirm these results, the reaction kinetics was also evaluated by the endgroup determination method, and the results showed that the reaction could also be classified as a pseudo-first-order reaction. Moreover, the apparent activation energy of the reaction was 116 kJ/mol, which was similar to that of the value obtained by the rheological method.     

固相合成胸腺五肽(TP5)

采用Fmoc固相多肽合成中的活化酯方法和2,6-二氯苯甲酰氯(DCB)混合酸酐法, 对Fmoc-Tyr(t-Bu)-OH与Wang树脂反应中的反应级数和表观活化能进行了研究, 并采用常规方法和微波强化方法分别进行了胸腺五肽的合成. 实验结果表明, 活化酯方法的反应级数为1.855, 表观活化能15.24 kJ/mol, 混合酸酐法的表观活化能为35.14 kJ/mol. 与传统方法相比, 微波将缩合反应速率提高了30倍以上, 氨基酸过量倍数也从传统的三倍降低到两倍.     

测定可逆反应动力学参数的一种新方法

提出了测定一级可逆反应速率常数的新方法,用以测定稀土的偶氮胂Ⅲ络合物与CyDTA交换反应的速率常数,并详细讨论了测定速率常数时动力学数据的选取原则。     

无汞盐密封法测定高氯浓度水样的化学需氧量

提出了一种以重铬酸钾为氧化剂,以6%硫酸银代替硫酸汞作为掩蔽-催化剂消除高氯离子干扰,测定化学需氧量(COD)的无汞密封新方法。研究了反应温度、反应时间和硫酸银浓度等测定条件。该法可以避免汞盐对环境的污染,适合测定多种类型的水样。该法测定结果的相对标准偏差为1.4%(n=8),平均加标回收率为98.5%.     

An improved kinetic determination for creatinine using the Abbott ABA-100

An improved method for the kinetic determination of creatinine on the Abbott ABA-100 is described. By simplex optimization of the picrate and hydroxide reaction concentration a 35% increase in reaction rate, with respect to the Abbott methodology, was obtained. The new method correlated more closely with the Technician AutoAnalyzer Method (N-30) than did the latter method. The percentage CV for the improved method for high and low quality control sera was 2.4 and 3.6%, respectively. The presence of protein in the standards was found to cause a decrease in the reaction rate with respect to aqueous standards.     

A fast, simple colorimetric determination of total urinary estrogen

An improved method for the kinetic determination of creatinine on the Abbott ABA-100 is described. By simplex optimization of the picrate and hydroxide reaction concentration a 35% increase in reaction rate, with respect to the Abbott methodology, was obtained. The new method correlated more closely with the Technician AutoAnalyzer Method (N-30) than did the latter method. The percentage CV for the improved method for high and low quality control sera was 2.4 and 3.6%, respectively. The presence of protein in the standards was found to cause a decrease in the reaction rate with respect to aqueous standards.     

室温固-固反应初期动力学的粉末紫外-可见漫反射光谱研究

以丁二酮肟和水合醋酸镍及无水醋酸镍的反应为模板, 利用反应物与产物之间的颜色差异, 通过粉末紫外-可见漫反射光谱对反应初期产物生成量的变化进行测定, 从而研究其反应动力学. 由于光谱性质与产物的晶型无关, 并且如果反应物与某一产物之间的光谱性质(如颜色)差异较大, 即使在微量产物的情况下也很容易跟踪到产物量的变化. 因此, 该方法对于固-固反应初期的动力学响应非常灵敏, 但当反应进行到一定程度后则不适用.     

Determining optimum conditions for lipase-catalyzed synthesis of triethanolamine (TEA)-based esterquat cationic surfactant by a Taguchi robust design method

A Taguchi robust design method with an L? orthogonal array was implemented to optimize experimental conditions for the biosynthesis of triethanolamine (TEA)-based esterquat cationic surfactants using an enzymatic reaction method. The esterification reaction conversion% was considered as the response. Enzyme amount, reaction time, reaction temperature and molar ratio of substrates, [oleic acid: triethanolamine (OA:TEA)] were chosen as main parameters. As a result of the Taguchi analysis in this study, the molar ratio of substrates was found to be the most influential parameter on the esterification reaction conversion%. The amount of enzyme in the reaction had also a significant effect on reaction conversion%.     

溶剂热法直接合成酞菁铜晶体

以喹啉为溶剂, 在反应釜中将1,3-二异吲哚、钼酸铵和二水乙酸铜在喹啉中反应, 降至室温后得到长10.5 mm针状的酞菁铜单晶, 最佳的反应条件: 以10 mL喹啉为溶剂, 于270 ℃反应8 h, 产率为51.3%.