神经网络法用于多元混酸同时测定

利用多层神经网络误差反向传播算法处理酸碱电位滴定数据，求得出多元混合酸各组分的浓度，优化了神经网络的结构和参数，测定了三组分有机酸混合样品，结果良好，平均相对偏差ＲＳＤ≤４％。     

小波变换用于电位滴定法测定极弱酸

研究了用小波变换确定电位滴定终点方法测定硼酸和苯酚两种极弱酸,同经典方法及其它数学方法的结果进行比较,说明用小波变换电位滴定法测定极弱酸快速,准确,可为极弱酸的计算机联机测定提供一种新的途径。     

硼酸的电位滴定

讨论了硼酸加甘油的强化电位滴定和直接电位滴定。实验证明 ,对硼酸类的极弱酸可采用两点电位滴定法进行直接电位滴定 ,在终点后测定两组滴定数据 ,用两点法公式计算滴定终点。     

多元弱酸氢离子浓度计算条件的比较

在大学化学教学中,多元弱酸溶液氢离子浓度计算条件在不同的教材中有不同的版本,这给教师和学生的教与学都带来了困惑。由氢离子浓度计算的最简式所要求的相对误差确定了多元弱酸氢离子浓度计算允许的相对误差,通过讨论可忽略二级酸解离产生的氢离子浓度所需的一级和二级酸常数的比值条件,选出了具有相对通用性的计算条件和一种更具普遍适用性的计算策略。     

表面活性剂存在下有机弱酸的自动电位滴定法

有机弱酸普遍存在于医药、农药及食品中，它们的测定方法研究，对生产质量控制、食品安全和环境保护有重要意义。目前，有机弱酸的测定方法主要有固定pH法、双点电位滴定法、单点pH滴定法、线性电位滴定法、直接电位滴定法、非水滴定法、远红外光谱滴定法等，这些方法各有特点，但难尽人意。如多数有机弱酸的水溶性较差，必须在非水介质中进行，增大了测定难度和测量成本。     

多元校正流动注射电位滴定法同时测定苯甲酸和山梨酸

将流动注射应用于酸碱电位滴定分析,建立了一种可同时测定混合有机酸的电位滴定新方法。在该方法中,用氢氧化钠与氯化钾的混合溶液作为滴定剂,在流通池中同时插入pH指示电极和氯离子指示电极,在滴定过程中的任一滴定点,流出液的pH值和酸碱的混合比例可由两个电极的电位测定值同时获得,从而可应用多元校正法由相应的滴定曲线求得混合酸中每一种组分的含量。该方法不仅免去了体积和时间读数,而且减少了试剂和样品的消耗量,分析速度快。应用该方法对混合样品中的苯甲酸和水杨酸进行同时测定,其相对标准偏差分别为0．19％～0．37％,回收率分别为97．3％～102．6％。     

多元弱酸(碱)溶液pH的简易通用计算方法

提出了计算多元弱酸(或碱)溶液pH的新方法.该计算方法具有以下特点:限制条件简单,即多项式中某一项小于最大项的5％即可忽略该项贡献;计算过程和步骤清晰易记;通用性好,一元或多元弱酸(碱)溶液pH计算均可适用.     

酒石酸合成液中有机酸的双检测器离子色谱法测定及计算

为寻找其最佳工艺条件,须及时分析在各种反应条件下各组分的变化及可能产生的副反应。作者曾用电位滴定计算分析法同时测定合成液中的上述反应式中的三种有机酸(分析一个样品需20min),在某些情况下易受副反应产物的干扰。本文探讨了HPICE法分离、检测酒石酸合成液中各有机酸的条件,提出用电导、紫外双检测器法计算处理解决     

配位滴定法同时测定混合液中铜,镉

1 引言 本文将多元统计分析法用于配位滴定法中,提出了金属离子混合液中各组分含量同时测定的方法原理和数学模型,根据电位滴定原理,以EDTA为滴定剂,玻璃电极为指示电极,利用多组标准混合液的滴定数据建立校正模型,然后对合成样品中Cu~(2+)、Cd~(2+)两个离子的浓度进行预报。尽管上述二离子间的logK相差较小,勿需分离或掩蔽,仍能得到满意结果,电极系统也不需严格校正。测定原理简述如下:     

光度法测定有机试剂逐级电离常数及摩尔吸光系数的一种优化计算方法

用光度法测定有机试剂的电离常数及摩尔吸光系数虽然已有数种方法可用,但对于相邻两级电离常数差别较小的二元或多元弱酸,在处理实验数据时往往存在数学模型或数值计算方面的困难。有的方法实际上是近似方法。还没有一种适用于各种情况下     

Flow injection on-line dialysis coupled to high performance liquid chromatography for the determination of some organic acids in wine

A combined system of flow injection on-line dialysis sample pretreatment and high performance liquid chromatographic separation/detection (FID-HPLC) was developed for simultaneous determination of six organic acids (tartaric, malic, lactic, acetic, citric and succinic acids). A sample or mixed standard solution (400 μL) was injected into a donor stream (water) of FID system and was pushed further through a dialysis cell, while an acceptor solution (water) was held in the opposite side of the dialysis membrane. The dialysate containing organic acids in the acceptor solution was then flowed to an injection loop of the HPLC valve, where it was further injected into the HPLC system and analysed under normal HPLC conditions, using a reversed-phase (C₁₈) analytical column and UV detection (210 nm). The order of elution was tartaric, malic, lactic, acetic, citric and succinic acids with the analysis time of 8 min. The FID system could be operated in parallel with HPLC separation, providing sample throughput of 7.5 h⁻¹. Dialysis efficiencies of six organic acids were in range of 4.6-9.5%. Calibration graphs for all the mentioned organic acids were linear over the range of 250-7500 mg L⁻¹. Precisions for all the organic acids were within 5.4%. The proposed system was successfully applied for analysis of some Thai wines. By spiking wine samples with mixed acid standard solutions, the percentage recoveries in range of 84-104 were found. This system has advantages of fast and high degrees of automation for dialysis sample pretreatment, on-line sample separation and dilution, good clean-up for prolongation of life-time of the HPLC column and low consumption of chemicals and materials.     

Determination of various inorganic anions and organic acids in the atmospheric particulate matter using capillary zone electrophoresis with indirect UV detection

Capillary zone electrophoresis with indirect UV detection was developed for the simultaneous analysis of inorganic anions and organic acids using a mixed solution of 2,6-pyridinedicarboxylic acid and cetyltrimethylammonium hydroxide as the background electrolyte (BGE). The parameters which influence the separation, such as indirect UV detection wavelength, BGE conditions, applied voltage and extraction conditions were investigated. Thirteen inorganic anions and organic acids were detected within 20 min. The calibration curves of each analyte were linear with correlation coefficients greater than 0.991. The relative standard deviations (n = 10) of the peak areas ranged from 0.6% to 3.3%. The detection limits for these species ranged from 0.4 to 1.4 mg/L at a signal-to-noise ratio of 3. The recovery rate of each analyte was more than 80% under optimised extraction conditions, except for nitrite. The proposed method was applied towards the analysis of inorganic anions and organic acids in the atmospheric particulate matter using an Andersen sampler. The particle size of the particulate matter was determined, but not the size of the anions.     

Algorithm for calculating the dissociation constants of weak electrolytes and ampholites in water solutions

An algorithm for calculating the dissociation constants of weak organic acids and bases in water solutions is developed on the basis of spectrophotometric data on the UV and visible regions without measuring the рН of the medium or using buffer solutions. The proposed algorithm is tested experimentally for six single-base acids and single-acid bases of different strengths. The relative error in determining the dissociation constants does not exceed 5% and is in agreement with the literature data.     

Palladium‐Mediated Arylation of Lysine in Unprotected Peptides

A mild method for the arylation of lysine in an unprotected peptide is presented. In the presence of a preformed biarylphosphine‐supported palladium(II)–aryl complex and a weak base, lysine amino groups underwent C−N bond formation at room temperature. The process generally exhibited high selectivity for lysine over other amino acids containing nucleophilic side chains and was applicable to the conjugation of a variety of organic compounds, including complex drug molecules, with an array of peptides. Finally, this method was also successfully applied to the formation of cyclic peptides by macrocyclization.     

造纸污水中有机污染物的分布分析

以十七烷酸为内标试剂,用甲基叔丁基醚对水样进行液 液萃取后,用三甲基氯代硅烷和N-O-双-（三甲基硅烷基）三氟乙酰胺进行硅烷化处理,以吡啶为溶剂,用GC-MS仪对造纸厂二次纤维造纸车间的污水样进行定性和相对含量分析,检出约50种有机污染物。 主要是植物原料的小分子溶出物、树脂酸、脂肪酸及各种化学添加剂。 树脂酸在制浆污水中的含量较大,主要来自造纸原料和松香施胶剂;脂肪酸、芳香酸及其衍生物主要存在于澄清白水和混合污水中,主要来源于二次纤维浆、造纸原料与各种添加剂;相对而言,最终进入污水处理厂前的混合污水中有机物质种类最多;真空泵密封水中有机污染物的种类最少,主要是难降解性的芳香类化合物。 讨论了不同生产工段污水中各种有机污染物质的差异和来源及对环境的危害性。     

Analysis of carbonic acid in water samples by ion-exclusion chromatography with pure water as eluent.

A simple, sensitive and rapid ion-exclusion chromatographic method for the simultaneous separation of carbonic acid and short chain organic acids (formic acid, acetic acid, and propionic acid) has been developed. A weakly acidic cation exchange resin column TSKgel OApak-A was used for the separation; pure water, owing to its lower background conductance, was employed as eluent in order to obtain high detection sensitivity. A good separation of these weak acids was achieved in 16 min. The linear range of the peak area calibration curve for carbonic acid was from 3.0 mg/L to 500 mg/L. The conductivity detection limit calculated at S/N = 3 was 0.084 mg/L for carbonic acid. The method developed in this work was successfully applied to the determination of carbonic acid in several environmental water samples without any pretreatment.     

Amperometric titrations of weak acids with ethylenediamine and diethylamine in non-aqueous media

The electrochemical cell : Cu |CuSO(4) + CH(3)OH parallelKNO(3) + CH(3)OH parallelsolution to be titrated Pt was used for the amperometric determination of weak and very weak acids separately and simultaneously present in non-aqueous solvents, with diethylamine and ethylenediamine as titrants. The amperometric measurements were carried out in the presence of pyrogallol as an electrometric indicator and without an externally applied potential. Solvent mixtures such as glycerol and methanol, propanol or isopropanol (1 + 1) have been used for the determination of weak acids such as benzoic, isobutyric and salicyclic. Mixtures of methanol, propanol or isopropanol with 1-3 ml of formamide were used for the determination of very weak acids such as a-naphthol and p-nittophenol.     

Organic acid-assisted soft-templating synthesis of ordered mesoporous carbons

A series of soft-templated ordered mesoporous carbons (OMCs) was synthesized by using resorcinol and formaldehyde as carbon precursors, triblock copolymer Pluronic F127 as a soft-template, and an organic acid (acetic, benzoic, citric, oxalic, or succinic) as a polymerization reaction catalyst. The aforementioned organic acids were strong enough to facilitate the formation of ordered mesophases by the block copolymer template used and to catalyze the polymerization reaction of resorcinol and formaldehyde in this template. The use of weak organic acids instead of strong inorganic acids such as HCl eliminated inorganic anions from the reaction environment and resulted in high surface area OMCs. Basically, the resulting carbons showed the surface areas and pore volumes comparable to those reported for the carbons prepared under similar conditions but in the presence of strong inorganic acids. Electron microscopy analysis proved the presence of ordered mesopores, whereas thermogravimetric analysis showed a good thermal stability of these carbons.     

Continuous chemoselective methylation of functionalized amines and diols with supercritical methanol over solid acid and acid-base bifunctional catalysts

The selective N-methylation of bifunctionalized amines with supercritical methanol (scCH(3)OH) promoted by the conventional solid acids (H-mordenite, beta-zeolite, amorphous silica-alumina) and acid-base bifunctional catalysts (Cs-P-Si mixed oxide and gamma-alumina) was investigated in a continuous-flow, fixed-bed reactor. The use of scCH(3)OH in the reaction of 2-aminoethanol with methanol (amine/CH(3)OH = 1/10.8) over the solid catalysts led to a significant improvement in the chemoselectivity of the N-methylation. Among the catalysts examined, the Cs-P-Si mixed oxide provided the most efficient catalyst performance in terms of selectivity and reactivity at 300 degrees C and 8.2 MPa; the N-methylation selectivity in the products reaching up to 94% at 86% conversion. The present selective methylation was successfully applied to the synthesis of N-methylated amino alcohols and diamines as well as O-methylated ethylene glycol. Noticeably, ethoxyethylamine was less reactive, suggesting that the hydroxy group of the amino alcohols is a crucial structural factor in determining high reactivity and selectivity, possibly because of the tethering effect of another terminus, a hydroxo group, to the catalyst surface. The magic-angle-spinning NMR spectroscopy and X-ray diffraction analysis of the Cs-P-Si mixed oxide catalyst revealed that the acidic and basic sites originate from P(2)O(5)/SiO(2) and Cs/SiO(2), respectively, and the weak acid-base paired sites are attributed to three kinds of cesium phosphates on SiO(2). The weak acid-base sites on the catalyst surface might be responsible for the selective dehydrative methylation.