电化学监测酸碱滴定法测定(R-H)+·键的异裂自由能

建立一种电化学监测酸碱滴定(EABT)方法, 利用循环伏安(CV)技术直接观测正离子基(RH+*)酸解过程中各物种浓度的变化, 从而得到酸性离解常数(pKRH+*)和键异裂自由能(ΔGhet). 所测吩噻嗪系列在二甲基亚砜和乙腈中的pKRH+*与文献中用间接法得到的pKRH+* 值相当吻合, 证实了本方法的可信度. 由于不需要间接方法所必需的中性母体分子的pKa和负离子氧化电位, 故该方法可适用于难于测定的大量有机体系pKRH+*常数的研究.     

璀璨星云——乙醇凝胶的焰色与变色

以超分子凝胶的制备为基础，结合焰色反应、酸碱指示剂变色和水解平衡移动等原理设计了一个综合性科普实验。实验采用乙酸钙水溶液和乙醇混合的方法制备凝胶，制备过程中加入金属盐(或硼酸)及酸碱指示剂，并调节酸碱性。制得的凝胶在燃烧时，金属盐(或硼酸)使火焰呈现出多彩的焰色，且受热导致凝胶中乙酸盐的水解平衡移动，使凝胶中的酸碱指示剂变色。整体实验效果绚丽多彩，如同璀璨的星云在宇宙中闪耀。本实验涉及知识点丰富，操作安全简便，现象明显，充分展现化学之美，满足不同人群的科普需求。     

酸碱指示剂的胶体误差与蛋白质的探针反应

在有些分析化学教材和参考书中讨论到影响酸碱指示剂变色范围的因素时,除了浓度、温度及溶剂外,都谈到胶体(特别是蛋白质)的影响.Bishop在专著“指示剂”中提出,蛋白质     

混合的单色酸硷指示剂

混合的酸鹼指示剂在分析化学中得到了广泛的普及。但是,到现在由单色酸鹼指示剂所组成的混合指示剂在文献中仍未有所记载。混合的单色酸碱指示剂在各种pH范围能产生无色间隔。例如,我们曾经从六甲氧基红和百里香酚酞,用混合等量体积的0.1％指示剂酒精溶液的方法制得了混合的指示剂。混合的指示剂在下列pH间隔中改变颜色:红色无色蓝色     

萃取过程中羧酸含量的测定

1引言 在羧酸的萃取过程中,处于萃取平衡状态的有机相中酸含量的分析,由于羧酸离解常数小,酸浓度低和指示剂与有机溶剂之间的相互作用会使指示剂变色缓慢,终点难以确定,因此使用常规的酸碱滴定法分析会引起很大的测定误差。一般根据平衡水相中的酸含量测定和体积变化返算平衡有机相中的酸含量,     

活性炭脱色对食醋总酸量的影响

研究活性炭脱色对食醋总酸量的影响。以保宁醋稀释10倍为供试品工作液,利用酸碱滴定法采用酸碱指示剂和酸度计同时监测溶液pH的变化确定终点,通过消耗NaOH体积反映对总酸量的影响,监测在450 nm处吸光度的变化反应脱色效果,研究了加入不同活性炭用量和脱色时间对食醋总酸量和脱色效果的影响,同时研究了活性炭脱色对食醋中可能有的几种无色有机酸的酸量的影响。结果表明：只要用活性炭脱色,测定食醋的总酸量总是偏低,活性炭脱色对几种无色有机酸的酸量有不同程度的影响。不能用活性炭脱色后,用指示剂确定终点酸碱滴定法测定食醋的总酸量。     

（K,Na）ZSM—5的酸碱性质及催化性能

采用红外光谱、程序升温脱附、原子吸收光谱、等离子光谱、Hammett指示剂非水滴定和催化活性测试等方法研究了经不同浓度的KOH溶液交换得到的(K,Na)ZSM-5的酸碱性质。结果表明,(K,Na)ZSM-5具有中等强度的L酸位(K~+,Na~+)及弱碱位(AlO_4~-或骨架O~(2-))和强碱位(OH~-).KOH浓度增大.酸性减弱,碱性增强.所得(K,Na)ZSM-5具有较高的异丙醇脱氢、脱水活性.催化性能与酸碱性密切相关.     

芦丁在酸碱溶液中的紫外光谱研究与应用

芦丁在酸碱溶液中具有不同的紫外吸收光谱.以芦丁的碱性溶液(pH 9.25)为测定液,以等浓度的芦丁酸溶液(pH 2.0)为参比液,用差示法测量其吸光度.结果表明:在405 nm处,当芦丁质量浓度为2.5～25 μg/mL时,吸光度与质量浓度之间存在良好的线性关系,据此建立了差示紫外吸收光度法.并用此法直接测定了芦丁片和槐米中的芦丁,回收率分别为98.8%～102.7%(RSD=1.1%)、97.0%～105.5%(RSD=2.1%).     

胶束对酸碱指示剂离解平衡和变色点及变色范围的影响

探讨了十六烷基三甲基溴化铵(CTMAB),十二烷基硫酸钠(SDS)和TritonX-1003种胶束对酸套指示剂百里香酚蓝和溴百里香酚蓝离解反庆的离解常数的影响,进行了研究了以上3种胶束对指示剂变色点的变以范围的影响,实验结果表明,选择适当的胶束溶液作为滴定介质,不仅可以扩大酸碱指示剂的应用范围,而且还大大提高了测量的准确度.     

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。     

Equivalence-point electromigration acid-base titration via moving neutralization boundary electrophoresis

In this paper, we developed a novel method of acid-base titration, viz. the electromigration acid-base titration (EABT), via a moving neutralization boundary (MNR). With HCl and NaOH as the model strong acid and base, respectively, we conducted the experiments on the EABT via the method of moving neutralization boundary for the first time. The experiments revealed that (i) the concentration of agarose gel, the voltage used and the content of background electrolyte (KCl) had evident influence on the boundary movement; (ii) the movement length was a function of the running time under the constant acid and base concentrations; and (iii) there was a good linearity between the length and natural logarithmic concentration of HCl under the optimized conditions, and the linearity could be used to detect the concentration of acid. The experiments further manifested that (i) the RSD values of intra-day and inter-day runs were less than 1.59 and 3.76%, respectively, indicating similar precision and stability in capillary electrophoresis or HPLC; (ii) the indicators with different pK(a) values had no obvious effect on EABT, distinguishing strong influence on the judgment of equivalence-point titration in the classic one; and (iii) the constant equivalence-point titration always existed in the EABT, rather than the classic volumetric analysis. Additionally, the EABT could be put to good use for the determination of actual acid concentrations. The experimental results achieved herein showed a new general guidance for the development of classic volumetric analysis and element (e.g. nitrogen) content analysis in protein chemistry.     

可视移动中和反应界面离线富集-毛细管电泳法检测电镀废水中痕量重金属离子

建立了一种可视化的、利用移动中和界面离线富集-毛细管电泳检测电镀水中痕量重金属离子的新方法。在该富集系统中,阳极电解液为2.1 mmol/L HCl-98 mmol/L KCl-痕量重金属离子,阴极电解液为4.0 mmol/L NaOH-96 mmol/L KCl,界面向阴极移动,分离电压为180 V,阴极电解液和阳极电解液的流速均为1 mL/min。富集后凝胶中的金属离子浓度用毛细管电泳检测,标准曲线在实验浓度范围内均有良好的线性关系(r≥0.9985),预富集倍数达80～150倍,Cu(II)、Zn(II)、Ni(II)、Mg(II)、Ca(II)、Cr(III)和Fe(III)的检出限分别为0.163、0.256、0.077、0.153、0.203、0.062和0.142 mg/L,均明显低于国家规定标准;日内和日间精密度均小于7.42%。所建方法已成功用于实际电镀废水样品中痕量重金属离子的富集和检测。     

可视化移动反应界面滴定法测定豆浆中蛋白质的含量

利用移动反应界面滴定(moving reaction boundary titration, MRBT)技术可视化快速准确测定豆浆中的总蛋白质含量。在MRBT中,移动反应界面(moving reaction boundary, MRB)是由阴极液中的氢氧根离子和固定在聚丙烯酰胺凝胶(polyacrylamide gel, PAG)中的豆浆蛋白质分子形成,通过酸碱指示剂来指示MRB的移动。利用MRB移动速度(V_MRB)与蛋白质浓度存在的函数关系建立标准曲线。配对t检验MRBT测定结果与凯氏定氮相比在95%的置信区间内无显著性差异。MRBT测定所需时间为10 min左右,线性范围为2.0~14.0 g/L,检出限为0.05 g/L,日内相对标准偏差小于1.90%,日间相对标准偏差小于4.39%,回收率为97.41%~99.91%。此外,三聚氰胺等非蛋白质氮(non-protein nitrogen, NPN)的添加,对豆浆中蛋白质的测定结果影响较小。     

Titration of strong and weak acids by sequential injection analysis technique

A sequential injection analysis (SIA) titration method has been developed for acid-base titrations. Strong and weak acids in different concentration ranges have been titrated with a strong base. The method is based on sequential aspiration of an acidic sample zone and only one zone of the base into a carrier stream of distilled water. On their way to the detector, the sample and the reagent zones are partially mixed due to the dispersion and thereby the base is partially neutralised by the acid. The base zone contains the indicator. An LED-spectrophotometer is used as detector. It senses the colour of the unneutralised base and the signal is recorded as a typical SIA peak. The peak area of the unreacted base was found to be proportional to the logarithm of the acid concentration. Calibration curves with good linearity were obtained for a strong acid in the concentration ranges of 10(-4)-10(-2) and 0.1-3 M. Automatic sample dilution was implemented when sulphuric acid at concentration of 6-13 M was titrated. For a weak acid, i.e. acetic acid, a linear calibration curve was obtained in the range of 3x10(-4)-8x10(-2) M. By changing the volumes of the injected sample and the reagent, different acids as well as different concentration ranges of the acids can be titrated without any other adjustments in the SIA manifold or the titration protocol.     

A stable and convenient protein electrophoresis titration device with bubble removing system

Moving reaction boundary titration (MRBT) has a potential application to immunoassay and protein content analysis with high selectivity. However, air bubbles often impair the accuracy of MRBT, and the leakage of electrolyte greatly decreases the safety and convenience of electrophoretic titration. Addressing these two issues a reliable MRBT device with modified electrolyte chamber of protein titration was designed. Multiphysics computer simulation was conducted for optimization according to two‐phase flow. The single chamber was made of two perpendicular cylinders with different diameters. After placing electrophoretic tube, the resident air in the junction next to the gel could be eliminated by a simple fast electrolyte flow. Removing the electrophoretic tube automatically prevented electrolyte leakage at the junction due to the gravity‐induced negative pressure within the chamber. Moreover, the numerical simulation and experiments showed that the improved MRBT device has following advantages: (i) easy and rapid setup of electrophoretic tube within 20 s; (ii) simple and quick bubble dissipates from the chamber of titration within 2 s; (iii) no electrolyte leakage from the two chambers: and (iv) accurate protein titration and safe instrumental operation. The developed technique and apparatus greatly improves the performance of the previous MRBT device, and providing a new route toward practical application.     

Review on the theory of moving reaction boundary, electromigration reaction methods and applications in isoelectric focusing and sample pre-concentration

Since 1970, a series of systematic investigations have been performed on three modes of moving reaction boundaries (MRBs), viz. moving precipitate boundary (MPB), moving neutralization boundary (MNB) and moving chelation boundary (MCB). So far, there has not been any review on them. Herein, we firstly review the MPB with respect to its velocity, product concentration, elution displacement, stacking effect, separation effect, judgment expressions and related procedures. We then make a review on the MNB about its theory, demonstration, improvement, and uses in isoelectric focusing (IEF), sample stacking, MNB-based stacking mechanisms and relevant computer simulations. We further give a review on the MCB regarding the relevant theory, verifications, and applications in EDTA-based sweeping and computer simulation. Finally, we give an outlook on the MRB study. More than 150 references are cited.     

Isotachophoretic separation of alkylsulfonates and determination of methanesulfonic acid as main component and as trace component in pharmaceutical drug substances

Alkylsulfonates from methanesulfonic acid to decanesulfonic acid were separated by isotachophoresis with conductivity detection in a common electrolyte system at pH 4.8. The electrolyte system consisted of 10 mM HCl buffered with epsilon-aminocaproic acid (pH 4.8) and 0.1% methylhydroxyethylcellulose (MHEC) acting as the leading electrolyte. The terminating electrolyte was 20 mM caproic acid also containing 0.05% MHEC. Current settings of 250 microA for the first and 50 microA for the second capillary were applied. On one hand, the method was applied to the determination of the content of methanesulfonate as the salt forming agent (mesilate) in a recently registered drug substance. The results obtained by ITP were compared with an orthogonal titration method. On the other hand, due to the column-coupling configuration of the electrophoretic instrument, the method could be extended to the trace determination in the ppm range in order to monitor methanesulfonic acid as an impurity in a drug substance. The validation confirmed the linearity of the method between 1 and 10 mg/l, limits of detection and quantification below 1 mg/l, recovery rates from 92.4 to 95.4%, and repeatability with a R.S.D. of 3.8% (six runs with a 4 mg/l spiked sample). Finally, three batches of a newly produced drug substance could be checked for methanesulfonic acid giving results of below 0.0014% (concentration related to the drug substance).     

基于氧化还原反应界面可视化定量检测辣根过氧化物酶

该文建立了一种可视化的、基于氧化还原反应界面移动距离定量检测辣根过氧化物酶（HRP）的方法。比较了隐色结晶紫显色体系和3,3',5,5'-四甲基联苯胺显色体系对HRP的显色效率,并构建了基于3,3',5,5'-四甲基联苯胺显色体系的氧化还原反应电泳滴定模型。同时,文中还设计了适用于该模型的小型化、便携式滴定检测芯片,并对滴定通道凝胶中组分进行了优化。结果表明,界面移动距离与HRP浓度存在对数线性关系,检测灵敏度可达0.002 mg/L,且可在10 min内完成HRP的裸眼检测。该方法不需要配备信号读取装置,用户只需要读取有色界面移动的距离即可实现对待测物的可视化定量检测,对于即时检测具有潜在的应用价值。     

Application of micellar electrokinetic chromatography to the determination of sultamicillin in oral pharmaceutical preparations

A micellar electrokinetic capillary electrophoretic method for determination of sultamicillin in Unasyn oral preparations--tablets and suspension--was evaluated. Phosphate-borate buffer at pH 7.0 containing 1.0% sodium dodecylsulfate was used as a mobile phase. The elaborated method ensures separation of sultamicillin from p-toluenesulfonic acid and the impurities, ampicillin, sulbactam and penicillamine. The method was validated for specificity, reproducibility, precision, accuracy and assay linearity (in a concentration range of sultamicillin of 0.05-1.5 mg/ml). Statistical analysis by Student's t-test showed no significant differences between the results obtained by micellar electrokinetic chromatography and HPLC, t(calculated) 0.519 for suspension assays and 0.284 for tablets assays were smaller then t(tabulated).     

Determination of sulphuric acid in process effluent streams using sequential injection titration

Sulphuric acid in process effluent streams from an electrorefining copper plant was analysed with a sequential injection (SI) titration system using sodium hydroxide as titrant. In the proposed SI titration system a base titrant, acid analyte and base titrant zone were injected sequentially into a distilled water carrier stream in a holding coil and swept by flow reversal through a reaction coil to the detector. The base zones contained bromothymol blue as indicator and the endpoint was monitored spectrophotometrically at 620 nm. The influence of carrier stream flow rate, acid and base zone volumes and titrant concentration on the linear range of the method was studied to obtain an optimum. A linear relationship between peak width and logarithm of the acid concentration was obtained in the range 0.006-0.178 mol l(-1) of H(2)SO(4) for a NaOH concentration of 0.002 mol l(-1). The results obtained for the SI titration of process samples were in good agreement with a standard potentiometric method with an RSD<0.75% and a sample frequency of 23 samples h(-1).