影响混合酸中各组分含量测定的因素及条件

作者曾提出，两种一元弱酸混合酸以及强酸与一元弱酸混合酸中，第一终点ｐＨ〉３．７的情况下，测定各组分酸含量的方法。在此基础上，本文在理论上推导出第一终点ｐＨ值测量误差ΔｐＨ与分析结果的误差ΔＶｅ２／Ｖｅ＾Ｔ之间的关系式，从而明确了影响误差的因素，并提出误差ΔＶｅ２／Ｖｅ＾Ｔ≤１．０％时的测定条件以及第一终点ｐＨ〈３．７时的测定方法。实验结果表明，如果能满足本文提出的条件，可以获得满意的结果。     

半中和点法测定两种一元弱酸混合酸中各组分酸含量

本文根据两种一元弱酸混合物测定各组分酸含量的标准曲线法，在理论上证明标准曲线的斜率（αＡ２－αａ１）值最大时，αＡ２＝１－αＡ１＝αＨＡ１，并提出此时溶液ｐＨ值的测量方法，从而根据Ｖｅ２／Ｖ＾Ｔｅ－１＋αＡ２－１）公式，求出混合酸中各组分酸含量的方法，方法简单，可靠。     

光度法测定甲基橙和二甲基黄在甲醇—水混合溶剂中的离解常数

利用光度法测定了酸碱指示剂甲基橙（ＭＯ）和二甲基黄（ＤＹ）在０％～９０％（Ｖ／Ｖ）和３５％～８４％（Ｖ／Ｖ）甲醇－水混合溶剂中的离散常数ｐＫａ（２５℃，离子强度Ｉ＝０．１ｍｏｌ／ＬＫＣｌ）实验结果表明，随着混合溶剂中甲醇含量的增加，两种指示剂的ｐＫａ均不断减小，当混合溶液中甲醇含量小于７５％时，ｐＫａ同甲醇的摩尔分数Ｘ２之间存在着良好的线性关系。甲醇的加入，指示剂在可见光区的吸收光谱有较明显的改变     

溶剂对螯合物稳定性的影响：镉（Ⅱ）—甘氨酸（苯丙氨酸）—乙醇／…

用ＰＨ－电位滴定法测定了３７℃、Ｉ＝０．１ｍｏｌ．ｄｍ＾－３（ＫＮＯ３）、乙醇／水混合溶剂中配合物Ｃｄ（Ａａ）ｎ（Ａａ－＝甘氨酸、苯丙氨酸，ｎ＝１，２的一、二级稳定常数ｌｇｋ１、ｌｇｋ２及配体Ａａ＾－的酸解离常数ｐｋ１、ｐｋ２。     

示波极谱滴定法测定显影液中米吐尔和对苯二酚含量

用１．５ｍｏｌ／Ｌ乙酸铵－氨（ｐＨ８．２）－无水乙醇（２：１，Ｖ／Ｖ）混合溶液为极谱底液，以Ｋ２ＣｒＯ４与米吐尔和对苯二酚的氧化还原反应为基础，用Ｋ２ＣｒＯ４作为滴定剂，以示波极谱图上ＣｒＯ４＾２－切口出现指示终点，测定显影液中米吐尔和对苯二酚的含量。本法简便易行，灵敏准确，终点直观，应用于Ｄ－７２和Ｄ－７６显影液中米吐尔和对苯二酚的测定，获得满意结果。     

Ga/HZSM-5芳构化催化剂的研究——K、V、B第二组分改性对甲醇、丙烷转化的影响

考察了Ｋ、Ｖ、Ｂ等对Ｇａ／ＨＺＳＭ５催化剂的改性后表面酸性质和Ｇａ组分状态分布的变化以及对甲醇、丙烷芳构化催化作用的异同。结果表明，Ｖ、Ｂ改性后提高了甲醇转化的芳烃选择性，降低了丙烷的芳构化活性。在Ｂ改性催化剂上，甲醇／丙烷偶合转化生成产物中芳烃的选择性低，但低碳烯烃的选择性高。最后提出对不同的催化反应过程，要求不同的强酸中心与活性组分镓相匹配。     

Ga／HZSM—5芳构化催化剂的研究：K,V,B第二组分改性对甲醇,丙烷转…

考察了Ｋ，Ｖ，Ｂ等对Ｇａ／ＨＺＳＭ－５催化剂的入性后表面酸性质和Ｇａ组分状态分布的变化以及对甲醇，丙烷芳构化催化作用的异同。结构表明，Ｖ，Ｂ改性后提高了甲醇转化的芳烃选择性，降低了丙烷的芳构化活性。     

对羟基苯甲酸与对苯二甲酸乙二酯的共聚物研究

对羟基苯甲酸与对苯二甲酸乙二酯的共聚物研究张广利，阎丰琪，李勇，王震，潘景岐，张鸿志（北京大学化学系北京１００８７１）关键词液晶共聚酯，ＰＥＴ／ＰＨＢ共聚脂，序列分布Ｊａｃｂｏｎ和ＫｕｈｆｕＪ’ｌ于７０年代报道了对羟基苯甲酸（ＰＨＢ）一对苯二甲酸乙二...     

异丙基膦酸单(1-已基-4-乙基)辛酯的某些基本常数的测定

用两相滴定法测定异丙基膦酸单（１－己基－４－乙基）辛酯（ＰＴ－２，ＨＬ）在水中的溶解度Ｓ，在水中的解离常数Ｋ在水－正庚烷中的分配常数Ｋｄ及二聚常数Ｋ２，利用ＳＯＬＷＲ计算程序，简单快速地处理两相滴定数据，得到结果为：Ｓ＝３．６８ × １０－５ｍｏｌ／Ｌ，ｐＫａ＝５．４９，ｌｏｇ Ｋ２＝４． ６７，ＩｏｇＫｄ＝ ２． ６７（２５±０． ５℃）．     

高铁酸盐的量气分析法

１引言高铁酸盐经典的铬盐法测定是在高碱度下进行，遇酸必将失败。作者利用高铁酸盐的酸不稳定性，测定它和非还原性稀酸反应的放氧量，来完成对它的分析。样品中高铁酸盐含量α的计算公式：式中：Ｐ与Ｐ’分别为试验环境的大气压（Ｐａ）和温度Ｔ时水的饱和蒸气压（Ｐａ）；Ｔ为反应体系的平衡温度，Ｖ为Ｗ（ｇ）样品参与反应放氧体积（ｍ３）以为高铁酸盐相对分子质量（ｇ）。２实验部分２．１试剂与装置Ｈ２ＳＯ４：２．０ｍｏｌ／Ｌ水溶液；ＨＮＯ３：２．０ｍｏｌ／Ｌ水溶液；镁条：纯度＞９９％；样品Ｋ２ＦｅＯ４、ＢａＦｅＯ４·Ｈ…     

强酸与多元酸混合物中各组分酸含量测定方法研究

各级离解常数均大于10~(-7),而且相邻两级的离解常数之比K_(a1)/K_(a2)只有几十倍的多元酸与强酸混合情况下,提出通过测量多元酸的半中和点,分别测定各组分酸含量的酸碱滴定法。     

Direct oxidation of L-cysteine by [FeIII(bpy)2(CN)2]+ and [FeIII(bpy)(CN)4]-

The oxidation of L-cysteine by the outer-sphere oxidants [Fe(bpy)2(CN)2]+ and [Fe(bpy)(CN)4]- in anaerobic aqueous solution is highly susceptible to catalysis by trace amounts of copper ions. This copper catalysis is effectively inhibited with the addition of 1.0 mM dipicolinic acid for the reduction of [Fe(bpy)2(CN)2]+ and is completely suppressed with the addition of 5.0 mM EDTA (pH<9.00), 10.0 mM EDTA (9.010.0) for the reduction of [Fe(bpy)(CN)4]-. 1H NMR and UV-vis spectra show that the products of the direct (uncatalyzed) reactions are the corresponding Fe(II) complexes and, when no radical scavengers are present, L-cystine, both being formed quantitatively. The two reactions display mild kinetic inhibition by Fe(II), and the inhibition can be suppressed by the free radical scavenger PBN (N-tert-butyl-alpha-phenylnitrone). At 25 degrees C and micro=0.1 M and under conditions where inhibition by Fe(II) is insignificant, the general rate law is -d[Fe(III)]/dt=k[cysteine]tot[Fe(III)], with k={k2Ka1[H+]2+k3Ka1Ka2[H+]+k4Ka1Ka2Ka3{/}[H+]3+Ka1[H+]2+Ka1Ka2[H+]+Ka1Ka2Ka3}, where Ka1, Ka2, and Ka3 are the successive acid dissociation constants of HSCH2CH(NH3+)CO2H. For [Fe(bpy)2(CN)2]+, the kinetics over the pH range of 3-7.9 yields k2=3.4+/-0.6 M(-1) s(-1) and k3=(1.18+/-0.02)x10(6) M(-1) s(-1) (k4 is insignificant in the fitting). For [Fe(bpy)(CN)4]- over the pH range of 6.1-11.9, the rate constants are k3=(2.13+/-0.08)x10(3) M(-1) s(-1) and k4=(1.01+/-0.06)x10(4) M(-1) s(-1) (k2 is insignificant in the fitting). All three terms in the rate law are assigned to rate-limiting electron-transfer reactions in which various thiolate forms of cysteine are reactive. Applying Marcus theory, the self-exchange rate constant of the *SCH2CH(NH2)CO2-/-SCH2CH(NH2)CO2- redox couple was obtained from the oxidation of L-cysteine by [Fe(bpy)(CN)4]-, with k11=4x10(5) M(-1) s(-1). The self-exchange rate constant of the *SCH2CH(NH3+)CO2-/-SCH2CH(NH3+)CO2- redox couple was similarly obtained from the rates with both Fe(III) oxidants, a value of 6x10(6) M(-1) s(-1) for k11 being derived. Both self-exchange rate constants are quite large as is to be expected from the minimal rearrangement that follows conversion of a thiolate to a thiyl radical, and the somewhat lower self-exchange rate constant for the dianionic form of cysteine is ascribed to electrostatic repulsion.     

Microstructure and rheology of stimuli-responsive microgel systems--effect of cross-linked density

The effect of cross-linked density on the rheological behavior of model pH-responsive microgel systems consisting of methacrylic acid-ethyl acrylate (MAA-EA) cross-linked with di-allyl phthalate (DAP) was examined. Neutralization of acid groups increases the osmotic pressure exerted by counter-ions trapped in the polymeric network against the ions in bulk solution, which is responsible for the swelling and increase in viscosity. The viscosity exhibits a maximum at approximately 1 wt.% DAP and it decreases to a steady value at 4 wt.% DAP, which is independent of pH and particle concentrations. Static light scattering results confirmed this optimum density as the critical point where sufficient cross-link points are present to produce permanent junctions that permit optimal swelling of the microgel particles. In addition, the variation of relative swelling with cross-linked densities of our model microgel systems agrees with the theoretical scaling law, Q alpha (yalphaN(x))(3/2) for cross-linked densities beyond this optimum point (Q is the swelling ratio, y is the acidic MAA content, N(x) is the average number of monomer units between two cross-linked points, and alpha is the degree of neutralization). By combining the results from light scattering and rheological measurements, we are able to correlate the microstructural evolution of the colloidal systems with their bulk rheological behavior.     

The Synthesis of α‐Azidoesters and Geminal Triazides

Three simple methods for the synthesis of geminal triazides are described: Starting from 1) 3‐oxocarboxylic acids, 2) iodomethyl ketones, or 3) terminal olefins, a range of triazidomethyl ketones can be constructed under mild oxidative reaction conditions by the use of IBX‐SO₃K, a sulfonylated derivative of 2‐iodoxybenzoic acid (IBX), and NaN₃ as an azide source. This is the first report of representatives of this novel class of triazide compounds: Despite their high nitrogen content, the geminal triazides are easy to handle, even when preparative‐scale syntheses are performed. (Caution: These procedures still require protective measures!) The triazides are now broadly available for further studies regarding their properties and reactivity. Furthermore, we show how the method can be used to provide α‐azidoesters, which are potential building blocks for amino acids.     

Relationships of Acid and water content to proton transport in statistically sulfonated proton exchange membranes: variation of water content via control of relative humidity

An in-depth analysis for proton exchange membranes to examine the effects of acid concentration and effective proton mobility upon proton conductivity as well as their relationship to water content was carried out on two main-chain, statistically sulfonated polymers at 25 degrees C. These polymer systems consisted of poly(ethylenetetrafluoroethylene-graft-polystyrenesulfonic acid) (1) and sulfonated trifluorostyrene (BAM) membrane (2). Nafion (3) was used for comparison. Water content (as represented by Xv, the water volume fraction, where Xv = volume of water in hydrated PEM / volume of hydrated PEM), for each sample was varied by adjusting the relative humidity (RH) of the membrane environment from 50% to 98%. It was found that, at low RH (RH < 70%), the major factor determining proton conductivity is proton mobility. In order to remove the differences in acid strength for the membranes, proton mobility values at infinite dilution (Xv = 1.0) and 25 degrees C were calculated and found to be 2.6 +/- 0.2 x 10-3 (average of 1a-c), 1.6 +/- 0.3 x 10-3 (average of 2a-e), and 2.32 +/- 0.01 x 10-3 cm2 s-1 V-1 (3). These were then compared to the theoretical value for the mobility of a free proton at infinite dilution and to previously reported data. Possible differences in tortuosity and the juxtaposition of acid groups are proposed in order to account for the significant deviations of all samples from the theoretical value.     

Investigations on sample pretreatment for the determination of selected metals and organochlorine compounds in suspended particulate matter of the River Elbe

The River Elbe and some of its tributaries are transporting polluted suspended particulate matter (SPM). Due to the property of SPM to accumulate anthropogenic and nonanthropogenic substances, this matrix is of interest from an analytical point of view. SPM has been collected in 13 sampling devices, placed in monitoring stations along the River Elbe from the Czech border to the North Sea and the embouchures of its tributaries Schwarze Elster, Mulde and Saale. Characterization of the SPM has been carried out by sieving and determining the content of total carbon. Comparative studies with different digestion procedures are presented for the determination of heavy metals and arsenic in the fine grain particle size <20 m of freeze-dried SPM. In a first test the highest concentrations have been found for microwave heating in a closed system when using an acid mixture of HNO₃/HF 3:1. Results of an interlaboratory test show the good practicability of the microwave heating digestion method. The determination of organochlorine compounds in a freeze-dried sample by three different extraction methods including supercritical fluid extraction (SFE) with CO₂ shows that the highest extraction efficiency is found for the conventional Soxhlet method.     

Epoxy acids of the seed oil ofArtemisia absinthium

Summary 1. The seed oil of the Central Asian common wormwood has yielded 1.48% of cis-12,13-epoxyoctadec-cis-9-enoic acid, 5.94% of cis-9,10-epoxyoctadec-cis-12-enoic acid, and traces of 9,10-epoxyoctadecanoic acid, and their structures have been confirmed.2. It is proposed to used the neutralization number of fatty acids to determine the amounts of epoxy acids in their combinations with -hydroxydienic acids.3. The possibility has been shown of determining the amount of ratio of the isomeric epoxy acids using oxidative degradation of the total oxy acids.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 705–710, November–December, 1976.     

Chemiluminescence optosensing implemented with multicommutation: determination of salicylic acid

In this paper we have coupled, for the first time, chemiluminescent detection with multicommuted optosensing principles. This approach has been implemented with the use of a commercial flow cell of 1 mm optical path length filled with an appropriate anionic exchanger gel as chemiluminescence sensing phase. The cell was placed in front of the window of the photosensor module of a home-made luminometer developed in our laboratory and a flat mirror was stuck on the back of the cell. The suitability of using chemiluminescence as detection technique in multicommuted flow-through optosensors has been demonstrated: the determination of salicylic acid by simple oxidation with permanganate on the sensing solid phase was chosen as model reaction. The proposed system allows the determination of salicylic acid in pharmaceuticals, with a sample frequency as high as even 60 samples h⁻¹ and showing a detection limit of 0.30 μg mL⁻¹, the linear response range is 1–30 μg mL⁻¹ and the R.S.D. is 3.1%. Satisfactory results have been obtained when applying the sensor to pharmaceuticals. The accuracy of the proposed methodology has been tested by using a reference method.     

Flow injection spectrophotometric or conductometric determination of ascorbic acid in a vitamin C tablet using permanganate or ammonia

Two simple flow injection (FI) procedures for the determination of ascorbic acid content in a vitamin C tablet are proposed: spectrophotometric involving injection into a stream of acidic potassium permanganate solution and monitoring its color change due to the redox reaction; FI conductometry based on the neutralization of ascorbic acid injected into a flowing ammonia solution yielding a change in conductivity. The procedures have been applied to the analysis of locally commercial vitamin C tablet samples. A through-put of at least 90 injections h⁻¹ can be achieved. The relative standard deviation was found to be 2.5% (for a 50 mg vitamin C tablet; n=7) for both. Results obtained by either procedure agree with a standard titrimetric method.     

柱前衍生毛细管电泳-电致化学发光法测定日用化妆品中的氨甲环酸含量

将氨甲环酸进行N-甲基化衍生反应后，其衍生产物能与联吡啶钌电致化学发光试剂产生强的共发光信号，据此建立了毛细管电泳-电致化学发光法高选择性测定日用化妆品试样中氨甲环酸含量的新方法。实验中发现，添加一种Mg²⁺-海藻糖-SiO₃^2-三元缔合物凝胶至背景电解液中，可极大地改善电泳分离效能。在优化的分析条件下，氨甲环酸和内标物肌氨酸衍生产物的电泳峰可在500 s内达到完全分离，且此两个电泳峰的强度比值与氨甲环酸的初始浓度在10~750 μmol/L的范围内呈良好的线性关系（相关系数r²=0.9993），检出限为3.6 μmol/L（S/N=3）。采用内标法对3种市售牙膏膏体和2种面膜护理液中的氨甲环酸进行了定量测定，测得这些试样中氨甲环酸含量的均值分别为4.05、0.24、6.06 mg/g和51.3、7.98 mg/mL，加标回收率在92.5%~104.0%内，结果令人满意。