单柱离子色谱同时分析有机酸和无机阴离子的研究

本实验以邻苯二甲酸为淋洗液，用阴离子交换柱，直接电导检测，探索了同时分析乙酸，琥珀酸，苹果酸，苯甲酸，柠檬酸，酒石酸，Ｃｌ＾－，ＮＯ２＾－，Ｉ＾－，Ｈ２ＰＯ４＾－及ＳＯ４＾２－等有机酸和无机阴离子的条件。研究了淋洗液的ＰＨ值和浓度对保留时间的影响。当浓度为０．７５ｍｍｏｌ．Ｌ＾－１，ｐＨ为４．２５时，分离良好，并进行了果品和饮料等样品的测定。     

铝镁混合金属氢氧化物溶胶阴离子交换性能研究

本文研究了电解质对铝镁混合金属氢氧化物（Ａｌ－ＭｇＭＭＨ）溶胶粒子中Ｃｌ－和ＯＨ－的阴离子交换性能。在所研究的电解质ＮａＮＯ３，ＨＣＯＯＮａ，ＣＨ３ＣＯＯＮａ，Ｎａ２ＣＯ３，Ｎａ２ＳＯ４和Ｎａ３ＰＯ４中，发现高价阴离子的交换能力大于低价阴离子的交换能力，无机阴离子的交换能力大于有机阴离子的交换能力。所研究Ａｌ－ＭｇＭＭＨ溶胶粒子的阴离子交换容量为２．８２ｍｍｏｌ／ｇ，比粘土粒子的阳离子交换容量大得多。     

有机酸在阴离子交换树脂上的保留行为及其机理

研究了有机酸在阴离子交换树脂上的保留行为。首次报道了有机酸在阴离子交换色谱过程中的“多峰现象”,即一种有机酸有两个或两个以上的色谱峰流出色谱柱。对这种“多峰现象”形成的机理进行了初步探讨,提出了有机酸离解后的不同价数阴离子在阴离子交换树脂上同时保留的机理。研究中还发现离解很弱的有机酸的保留行为不完全符合离子交换机理。     

钠化合物洗提钨及混合洗提中共存反离子的加速效应

研究了在季胺Ⅰ型强碱性阴离子交换树脂上用ＮａＯＨ、ＮａＮＯ３、ＮａＣｌ和ＮＨ４Ｃｌ洗提及洗提后的吸附特性。给出了洗提曲线、穿透曲线和工作交换容量。采用ＮａＣｌ和ＮａＯＨ混合洗提的工艺，获得了钨浓度高而过剩洗提剂含量低的洗出液。为由洗出液蒸发结晶制取高纯Ｎａ２ＷＯ４·２Ｈ２Ｏ开辟了途径。混合洗提的宏观结果表明：由于反离子的存在，Ｃｌ－、ＯＨ－和在溶液相或交换剂中的扩散系数发生改变，→Ｃｌ－及→ＯＨ－的交换速度加快了。     

风化煤腐植酸与Ca(H2PO4)2相互作用机理的研究

采用化学法及ＩＲ、ＸＲＤ、ＸＰＳ等综合解析手段,研究了风化煤腐植酸（ＨＡ）、腐植酸钾（ＨＡ－Ｋ）与磷酸一钙「Ｃａ（Ｈ２ＰＯ４）２」之间的反应特征,探讨了二者的反应机理。结果表明,磷酸一钙与ＨＡ基本未发生反应,而与ＨＡ－Ｋ反应后生成ＫＨ２ＰＯ４以及ＨＡ与ＣａＨＰＯ４的有机－无机复合物,但该复合物不太稳定,在水溶液中易水解生成腐植酸钙（ＨＡ－Ｃａ）和Ｃａ（Ｈ２ＰＯ４）２。本研究将为研制以煤炭腐植酸为基     

间接光度高效液相色谱法分析无机阴离子的研究

报导了间接光度高效液相色谱法测定了无机阴离子的新方法，在自己研制的硅基键合阴离子交换柱上，用１．０ｍｍｏｌ／Ｌ苯甲酸钠和０．６ｍｍｏｌ／Ｌ柠檬酸钠为洗脱液，可在１５ｍｉｎ内对Ｈ２ＰＯ４、Ｃｌ，ＮＯ２，ＮＯ３，ＳＯ４等六种阴离子得到较好的分离，对Ｃｌ的最小检测限为４．０ｎｇ。     

用混合床离子色谱柱同时测定阴阳离子

将阴离子交换树脂和阳离子交换换树脂混合后填充在一根色谱柱中，即所谓阴阳离子混合床柱。研究了阴阳离子在此混合柱上的保留行为并探讨了其保留机理。     

环戊烷选择性氧化用VPO催化剂的合成新方法

研究了ＶＰＯ催化剂时还原溶剂对ＶＰＯ的结构及催化性能的影响,ＶＰＯ的合成方法如下：（１）Ｖ２Ｏ５与Ｈ３ＰＯ４反应生成磷酸钒;（２）用不同的还原溶剂还原磷酸钒得到ＶＰＯ催化剂前身;（３）活化ＶＰＯ催化剂前身,研究的还原溶剂有;异丁醇,异丁醇－苯甲醇,异丁醇－石油醚和正己醇。结果表明,使用异丁醇－石油醚作还原溶剂,只能生成ＶＯＨＰＯ４．０．５Ｈ２Ｏ晶体;使用其它溶剂则会生成ＶＯ（Ｈ２ＰＯ４）２和ＶＯＨ     

钯(0)/离子交换树脂对有机锡试剂和有机卤化物偶联反应的催化性能和结构表征

制备了强碱阴离子交换树脂（Ｐ－－ＣＨ２＾＋（ＣＨ３）３ＯＨ＾－，Ｄ７１７）负载钯（０）催化剂，发现它对有机锡试剂和有机卤化物的偶联反应有很高的催化活性，分离容易，可重复使用。起催化作用的是金属态钯。ＸＰＳ等实验结果表明，在催化剂中钯作为桥将功能基－Ｎ＾＋（ＣＨ３）３与ＯＨ＾－联结起来。催化剂中的钯可以看作是两配位的和配位不饱和的，经过氧化加成、金属交换、还原消除过程完成催化反应。     

羧酸型聚乙二醇聚氨酯离聚物及其导电性能

以聚环氧乙烷（ＰＥＯ）为软段，与４，４’－二苯甲烷二异氰酸酯（ＭＤＩ）预聚，以２，２’－二羟甲基丙酸（ＤＭＰＡ）扩链合成了含羧酸基团的聚氨酯，并经中和形成了含不同金属离子的离聚物．测定了样品的热分析数据和力学性能，利用交流阻抗分析仪测定了样品的阻抗谱，由此计算出样品的离子电导率．这类样品由于阴离子（－ＣＯＯ－）固定在聚合物分子链上，因此只有单一阳离子迁移．结果表明，羧酸型聚氨酯离聚物既有较高的单一离子电导率又具有优良的力学性能．讨论了不同软段分子量、硬段含量和金属抗衡离子对离子电导性能的影响     

离子交换与离子排斥色谱柱串联体系中阳离子的多峰现象及其机理

研究了串联柱体系中阳离子的“多峰现象”。在阳离子交换柱后面接上阴离子分析用的离子排斥柱构成一个串联柱体系,当以酒石酸（ＴＡ）和吡啶二羧酸（ＰＤＣ）的混合溶液作淋洗液时,每一种阳离子同时出现３个色谱峰。这是因为从阳离子交换柱流出的阳离子与有络合作用的两种淋洗剂阴离子形成络合物,使流动相中淋洗剂阴离子浓度减少以及两种淋洗剂阴离子在离子排斥柱中被保留且保留值不同。     

含氧阴离子的离子色谱法研究

 在含有阴、阳离子双官能团的色谱柱上 ,用两种浓度的Na2 HPO4洗脱液分别同时分离了 5种和 7种含氧阴离子 ,并且实现了元素不同价态的分析。 7.5mmol/LNa2 HPO4( pH 9.3)适于同时分离SeO32 - ,HAsO42 - ,SeO42 - ,WO42 - ,MoO42 - ,GeO32 - 和CrO42 - ;0 .75mmol/LNa2 HPO4(pH 9.3)适于同时分离IO3- ,H2 AsO3- ,BrO3- ,NO2 - 和NO3- ;检测波长为 2 0 4nm。另外 ,选择其它 4种阴离子色谱柱进行比较 ,对分离机理进行了初步的研究。     

Preparation and ion chromatographic properties of a new core-shell chromatographic support Al2O3/SiO2-10

A new stationary phase Al₂O₃/SiO₂-10 was prepared and characterized by XPS, XRD, SEM and surface analysis. The anion exchanger properties of this new stationary phase were investigated by the separation of inorganic anions in ion chromatography (IC). pH of the mobile phase, concentration and strength of the Lewis base of the elute, and the organic modifier of the mobile phase strongly affect the separation of inorganic anions, and anion exchange selectivities of the analyte on the new support are significantly different from quaternary ammonium styrene based anion exchangers. The result of separation of inorganic anions shows that the new stationary phase provides excellent column efficiency, well-defined chromatographic peaks and favorable retention times.     

A novel ion chromatographic method based on cation-exchange and acid-base interactions for the simultaneous determination of total alkalinity and monovalent cations in samples of microliter volume

An ion chromatographic (IC) method based on the use of titrant (strong acid) as the stationary phase was developed for simultaneous determination of total alkalinity (TA) and monovalent cations. The titrant used in this study was obtained by initially loading lithium dodecylsulfate (Li-DS) onto a reversed-phase material and then conditioning the column with a slightly acidified aqueous LiCl solution (a mixture of 50.0 mM LiCl and 0.1 mM H2SO4). When a small amount of a basic sample was injected onto a column prepared in this way, the basic species (Bn-) reacted predominantly with H+ on the stationary phase and the reaction with the eluent phase was negligible due to the very low concentration of eluent H+ (in the eluent, a molar ratio of [Li+]/[H+] = 250:1 applied). The stationary phase H+ consumed in the acid-base reaction was then re-supplied by H+ from the eluent. By monitoring the conductance of the eluent using conductivity, an induced peak resulting from the basic species was observed. Calibration graphs of peak areas vs. molar concentration of the basic species for OH-, HCO3- and H2PO4- were found to be identical. CO3(2-), HPO4(2-), and B4O7(2-) also gave identical calibration curves but their slope values were twice those for HCO3-. The detection limit for HCO3- was less than 3.2 microM and the calibration curve was linear up to 12.3 mM (injection volume, 100 microL). Seawater was directly analyzed and its total alkalinity was found to be 2.87 mM (RSD 0.53%, n = 5), which was in good agreement with the result of 2.88 mM (RSD 3.2%, n = 5) obtained using auto-potentiometric titration. Na+ and K+ were determined simultaneously and the concentrations were 481.6 and 10.6 mM, respectively.     

Interpretation of solute retention of some monovalent inorganic anions in anion-exchange chromatography using a dicarboxylic Acid as an eluent.

In single-column anion-exchange chromatography, the retention volume of some monovalent inorganic anions (Cl(-), Br(-), NO(3)(-), NCS(-) and NO(2)(-)) were observed as a function of the pH of a mobile phase at a fixed concentration of 2-phenylmalonic acid or 1,4-benzenediacetic acid used as an eluent. The experimental retention volume of such an anion was decreased with an increase in the pH of a mobile phase, and was able to be described by the following equation taking account of anion-exchange equilibria of a sample anion with a hydrogen dicarboxylate ion (HE(-)) and with a dicarboxylate ion (E(2-)): alpha(1s)/V(R)'[HE(-)] = 1/m(T)wK(ex1) + (2K(a2)/m(T)w(2)K(ex2))(V(R)'/alpha(1s)[H(+)]), where V(R)', m(T), w, K(a2), K(ex1) and K(ex2) are the adjusted retention volume of a given sample anion, the capacity for the anion-exchange of column packings and the weight of column packings packed into a separating column, the second acid-dissociation constant of the dicarboxylic acid used as an eluent, and equilibrium constants for the anion exchange of a sample anion with a monovalent hydrogen dicarboxylate ion and with a divalent dicarboxylate ion, respectively. The term alpha(1s), defined as K(as)/([H(+)] + K(as)), where K(as) is the acid-dissociation constant of HX, is the mole fraction of a sample anion, X(-), and is equal to 1 when using a strong acid anion as a sample anion.     

对二甲氨基苯甲酸的阴离子识别应用研究

采用紫外分光光度法和荧光分光光度法研究了主体分子对二甲氨基苯甲酸与HPO42-、SO42-、H2PO4-、ClO4-、HSO4-、NO3-、BF4-、PF6-、F-、Cl-和Br-等11种阴离子客体的识别作用.发现在乙腈溶液中,该主体分子对二价阴离子HPO42-和SO42-表现了强亲和力和高选择性;并对一价阴离子F-和H2PO4- 具有一定的响应能力;而与一价阴离子ClO4-、HSO4-、NO3-、BF4-、PF6-、Cl-和Br-几乎没有作用.结果表明主客体分子本身的酸碱性和阴离子的负电荷数目是影响主体分子对阴离子识别性能的主要因素.     

Determination of inorganic acids by ion chromatography with n-tetradecylphosphocholine (zwitterionic surfactant) as the stationary phase and pure water as the mobile phase

A new ion chromatographic (IC) system, in which n-tetradecylphosphocholine (TDPC, a phosphobetaine type of zwitterionic surfactant) was used as the stationary phase, pure water as the mobile phase, and conductivity as the method of detection, has been developed for the determination of inorganic acids. Five model acids, HCl, HNO3, HClO4, H2SO4, and H3PO4, were separated to baseline and eluted in the order H3PO4 > HCl > HNO3 > H2SO4 > HClO4. When peak areas were plotted against the concentrations of the acids in samples, linear calibration curves were obtained. Ultimate determination limits were approximately 1 mmol L(-1), but the discrimination of the method between solutions of different concentration was better than 10 micromol L(-1) for those model analytes. Salts of divalent cations could also be separated, but they were eluted faster than the acids. No separation was observed for the salts of monovalent cations. This newly proposed approach is applicable to the simultaneous determination of the inorganic acids (produced by reactions of NOx, SOx, and HCl with water) in aerosols.     

亲水作用色谱柱与阳离子交换树脂柱结合分离无机离子（英文）

A combination of hydrophilic interaction chromatographic(HILIC) column and a weakly acidic cation-exchange resin(WCX) column was used for simultaneous separation of inorganic anions and cations by ion chromatography(IC).Firstly,the capability of HILIC column for the separation of analyte ions was evaluated under acidic eluent conditions.The columns used were SeQuant ZIC-HILIC(ZIC-HILIC) with a sulfobetaine-zwitterion stationary phase(ZIC-HILIC) and Acclaim HILIC-10 with a diol stationary phase(HILIC-10).When using tartaric acid as the eluent,the HILIC columns indicated strong retentions for anions,based on ion-pair interaction.Especially,HILIC-10 could strongly retain anions compared with ZIC-HILIC.The selectivity for analyte anions of HILIC-10 with 5 mmol/L tartaric acid eluent was in the order of I-> NO-3 > Br-> Cl-> H2PO-4.However,since HILIC-10 could not separate analyte cations,a WCX column(TSKgel Super IC-A/C) was connected after the HILIC column in series.The combination column system of HILIC and WCX columns could successfully separate ten ions(Na+,NH+4,K+,Mg2+,Ca2+,H2PO-4,Cl-,Br-,NO-3 and I-) with elution of 4 mmol/L tartaric acid plus 8 mmol/L 18-crown-6.The relative standard deviations(RSDs) of analyte ions by the system were in the ranges of 0.02%-0.05% in retention times and 0.18%-5.3% in peak areas through three-time successive injections.The limits of detection at signal-to-noise ratio of 3 were 0.24-0.30 μmol/L for the cations and 0.31-1.2 μmol/L for the anions.This system was applied for the simultaneous determination of the cations and the anions in a vegetable juice sample with satisfactory results.     

离子色谱法分离弱酸阴离子保留值规律的研究

 研究了离子色谱弱酸阴离子分析中以氢氧化钠作淋洗液时 ,弱酸阴离子的调整保留时间随淋洗液中氢氧化钠浓度变化的规律 ,建立了二者关系的非线性函数模型。将一元非线性问题转化为多元线性问题求解 ,磷酸根的调整保留值与淋洗液中氢氧化钠浓度关系回归方程的相关系数在 0 99以上。用该数学模型预测磷酸根阴离子的保留值 ,相对误差小于 5 % 。