HCPCF褪色光度法测定微量氧化性阴离子

报道了l，5-二(2-羟基-5-氯苯)-3-氰基甲Ti(HCPCF)在酸性介质中与氧化性阴离子的反应。氧化性阴离子将HCPCF的四氮基转化为无色氧化型而使红色逐渐减褪。利用此褪色反应，探讨了测定NO2^-、BrO3^-、IO3^-、IO4^-、Cr2O7^2-的条件，其表观摩尔吸光系数达l0^4数量级，提出了测定氧化性阴离子的新方法。可用来测定饮用水、池塘水、废水、化学试剂、碘盐及海带中一些氧化性阴离子的含量。     

离子色谱法快速分析饮用水中的四种阴离子

用Dionex DX-120离子色谱仪对饮用水中F^-1、Cl^-1、NO3^-1及SO4^2- 4种阴离子进行测定，分析中采用了Dionex AS14阴离子分离柱对上述4种阴离子进行分离。作者等对Dionex公司所建议的色谱条件作了修改和改进，使方法的分析效能大大提高，达到了快速分析的要求。按改进后的色谱条件，4种离子的分离度达到了3．9的数值，4种阴离子测定结果的相对标准偏差值均小于2．5％，回收率在94％-108%之间。对有标准值的水样用此文的方法和国家标准方法同时进行比较分析，并用卜检验法对两方法的结果的可靠性，以及与标准值的比较，结果表明各离子（Cl^-1、NO3^-1及SO4^2-）的测定结果之间均无显著性差异。     

应用IC-ICP-MS测定胶州湾表层沉积物中的溴酸盐、碘酸盐及亚硒酸盐

建立了离子色谱-电感耦合等离子体质谱联用技术(IC-ICP-MS)测定溴酸盐、碘酸盐及亚硒酸盐的分析方法。该方法对0～1000μg/kg范围内BrO3-、IO3-、SeO23-的线性关系良好(r2=0.9995～0.9999),检出限分别为0.05、0.08、8.15μg/kg;加标回收率为78%～105%;选取经过前处理的BrO3-、IO3-、SeO32-含量分别为85.14、7.20、55.15μg/kg的样品,连续测试7次,其相对标准偏差(RSD)分别为2.5%、1.8%、2.3%。利用该方法初步测定了胶州湾表层沉积物中3种离子形态的含量。结果显示,胶州湾所选8个站位中均检出了3种离子,其中BrO3-含量最高,达2755.58μg/kg,SeO32-次之,IO3-含量最低;BrO3-和SeO23-呈现由西南向东北递增的趋势,离岸低,近岸高,IO3-则呈由中心向南北两侧递减的趋势。该方法具有杂质干扰小、分析速度快、灵敏度高等特点,适用于沉积物中BrO3-、IO3-以及SeO32-的定性定量分析。     

镍电极开路电位测定微量硼氢根离子

实验采用循环伏安法，用镍电极代替铂铑等贵金属电极测定了碱性体系中不同硼氢根离子浓度下的开路电位，得出了研究电极的开路电位（-0．355～-0．280vs.SCE／V）与微量硼氢根离子浓度的对应关系，并用于监测电解偏硼酸钠制备硼氢化钠体系中微量硼氢根离子，同时计算了该方法的误差。结果表明，测量结果的相对标准偏差为2．2％；回收率为98．4％。该法简单、快速，可测定10^-5～10^-3mol／L范围的硼氢根离子浓度。     

碳酸氢铵和食盐制纯碱工业中间产物的分析

研究了由碳酸氢铵和食盐为原料生产纯碱的中控分析方法。生产过程中，中间产物母液中共存的离子有Na^ 、HCO3^-、CO3^2-、NH4^ 、Cl^-，其中Na^ 采用钠离子选择性电极测定，此文主要研究了其余四种离子的滴定分析法。     

微波浓缩-离子法测定饮用水中的痕量溴酸根和高氯酸根

 建立了一种简便的用于浓缩水中痕量BrO3 -和ClO4 -的样品前处理方法。水样经OnGuardAg柱过滤 ,用微波炉在 15min内可浓缩 2 0倍 ,所测离子的回收率均高于 90 %。又采用IonPacAS16型亲水性柱 ,用 15 0 μL定量环 ,以NaOH为流动相、梯度淋洗方式 ,在 35min内测定了包括BrO3 -和ClO4 -在内的 8种离子。BrO3 -和ClO4 -的检测限分别为 0 10 μg/L和 0 2 0 μg/L。该方法在实际应用中有较大的参考价值。     

恒电位氟-铝配位滴定法测定铝的研究

以氟离子溶液作滴定剂,氟离子选择性电极作指示电极,对恒电位配位滴定法测定铝进行了研究,导出了该测定法的计算模型。测定结果的准确度受电位的控制误差对滴定剂体积误差的影响及滴定剂体积的相对误差两个因素影响。在滴定的中间位置,准确度比较高。随着滴定剂体积的增加,测定的灵敏度增加。方法可用于金属铝及锌一铝合金中铝的测定。     

离子色谱法测定啤酒中的F^-、C1^-、SO4^2-、NO3^-和PO4^3-

建立了以AS11—HC型阴离子交换柱分离、NaOH溶液为淋洗液、甲醇为有机改进剂、化学抑制电导检测测定啤酒中的F^-、C1^-、SO4^2-、NO3^-和PO4^3-?A的离子色谱方法。各被测离子的线性关系良好，相关系数为0．9778～0．9991．测定结果的相对标准偏差为0．02％～3．60％，样品回收率为97．88％～103．80％。     

离子色谱法测定油田灌注污水中的CI^—、NO3^—、SO4^2—

采用二氯甲烷萃取、活性炭吸附、Na2CO3/NaHCO3淋洗液储备液沉淀等预处理方法,有效地除去了油田灌注污水样中的有机物质和可能存在的高含量的钙镁离子,进而用离子色谱法同时测定了CI^-、NO3^-、SO4^2-三种离子,相对标准偏差分别为0．06、4．6、2．2,NO3^-、SO4^2-离子的加标回收率分别为97．9％和97．1％。     

加碘食盐中微量碘的离子选择性电极测定

在加碘食盐中加入还原剂将KIO3中的IO3^-还原为I^-,使用碘离子选择性电极技术,采用标准曲线法直接测定了溶液中的I-量.并引入表面活性剂作为增敏剂,降低了检测下限,提高了检测的灵敏度.实际测定3种食盐样品,取得了较好的效果.     

Cyclodextrin-aided determination of iodate and bromate in drinking water by microcolumn ion chromatography with precolumn enrichment.

A selective and simple method for the determination of iodate (IO3-) and bromate (BrO3-) by microcolumn ion chromatography (IC) is presented. In this study, IO3- and BrO3- were determined as IBr2- and tribromide (Br3-), respectively, via a postcolumn reaction with bromide (Br) under acidic conditions with the aid of alpha-cyclodextrin (alpha-CD) in microcolumn IC. IO3- and BrO3- were selectively detected by the present method at a wavelength of 253 or 265 nm. The present system achieved good selectivity for IO3- and BrO3- as well as good repeatability under suitable conditions. Precolumn enrichment improved the detection limit, and allowed the determination of BrO3- in bottled water as low as sub microg L(-1) level in microcolumn IC.     

Determination of iodine and bromine compounds by ion chromatography/dynamic reaction cell inductively coupled plasma mass spectrometry.

An inductively coupled plasma mass spectrometer (ICP-MS) was used as an ion chromatographic detector for the speciation of iodine and bromine. Gradient elution using NH4NO3 at pH 10 allowed the chromatographic separation of ionic iodine (I- and IO3-) and bromine (Br- and BrO3-) species in less than 8 min. Effluents from the ion-exchange column were delivered to the nebulization system of ICP-MS for the determination of I and Br. The potentially interfering 38Ar40ArH+ and 40Ar40ArH+ at the bromine masses m/z 79 and 81 were significantly reduced in intensity (by approximately two orders of magnitude) by using 0.6 mL min(-1) O2 as a reactive cell gas in the dynamic reaction cell (DRC). Moreover, the signal-to-background ratio at iodine mass m/z 127 increased significantly when O2 was used as the reaction gas. The detection limits were in the range of 0.001-0.002 and 0.03-0.04 ng mL(-1) for various I and Br compounds, respectively, based on the peak height. The relative standard deviation of the peak areas for five injections of a 2 ng mL(-1) I-, IO3- and 20 ng mL(-1) Br-, BrO3- mixture was in the range of 3-4%. The concentrations of I and Br compounds have been determined in selected water and urine samples. The spike recoveries were in the range of 94-102% for all of the determinations. This method has also been applied to determine various I and Br compounds in an NIST RM 8435 whole-milk powder reference material and a seaweed sample obtained locally. A microwave-assisted extraction method was used to extract these compounds, which were quantitatively leached with a 10% mass/volume (m/v) tetramethylammonium hydroxide (TMAH) solution in a focused microwave field within a period of 6 min. The major components of I and Br in milk powder and seaweed were I- and Br-.     

New spot-test for silver(I) based on double iodide formation with bismuth(III)

The formation of an intense brownish-maroon or maroon-red product by the interaction of silver(I) and bismuth(III) solution in the presence of iodide forms the basis of a new and specific spot-test procedure for silver. The test is conducted on a spot plate with 2 or 3 drops of 2% potassium iodide solution, 1 drop of 1% bismuth(III) nitrate solution, and 1 drop of test solution. Limit of detection is 0.01 mug; limit of dilution is 1:5 x 10(6). Most cations and anions do not interfere. Only Tl(I), Cs, S(2)O(2-)(3), EDTA, pyridine, excess of thiourea, oxidizing ions (NO(-)(2), IO(-)(3), IO(-)(4), MnO(-)(4), BrO(-)(3), and S(2)O(2-)(8)) and ions such as Cl(-), Br(-), I(-), SCN(-), and N(-)(3) which cause precipitation of silver, interfere. The product formed is most probably Ag(2)BiI(5).     

Polarographic microdetermination of halogens in organic compounds after oxygen flask combustion

A method for the microdetermination of organic compounds containing halogens, by a polarographic finish, is reported. After the combustion of the organic sample in the oxygen flask, the products are absorbed in a suitable absorbent and chemically treated to produce Cl(-), Br(-), BrO(3)(-) or IO(3)(-) ions in solution before the polarography. The method is applicable to partially, highly, and fully halogenated aromatic and aliphatic compounds, whether solid or liquid. The results are generally within the acceptable limits of error.     

Determination of iodine and bromine compounds in foodstuffs by CE-inductively coupled plasma MS

A CE-inductively coupled plasma mass spectrometric (CE-ICP-MS) method for iodine and bromine speciation analysis is described. Samples containing ionic iodine (I(-) and IO(3)(-)) and bromine (Br(-) and BrO(3)(-)) species are subjected to electrophoretic separation before injection into the microconcentric nebulizer (CEI-100). The separation has been achieved in a 50 cm length x 75 microm id fused-silica capillary. The electrophoretic buffer used is 10 mmol/L Tris (pH 8.0), while the applied voltage is set at -8 kV. Detection limits are 1 and 20-50 ng/mL for various I and Br compounds, respectively, based on peak height. The RSD of the peak areas for seven injections of 0.1 microg/mL I(-), IO(3)(-) and 1 microg/mL Br(-), BrO(3)(-) mixture is in the range of 3-5%. This method has been applied to determine various iodine and bromine species in NIST SRM 1573a Tomato Leaves reference material and a salt and seaweed samples obtained locally. A microwave-assisted extraction method is used for the extraction of these compounds. Over 87% of the total iodine and 83% of the total bromine are extracted using a 10% m/v tetramethylammonium hydroxide (TMAH) solution in a focused microwave field within a period of 10 min. The spike recoveries are in the range of 94-105% for all the determinations. The major species of iodine and bromine in tomato leaves, salt, and seaweed are Br(-), IO(3)(-), I(-), and Br(-), respectively.     

流动注射多元校正-络合滴定法同时测定混合金属离子

将流动注射应用于电位络合滴定分析法,建立了一种可同时测定混合金属离子的电位滴定方法。在该方法中,用EDTA与氟化钠的混合溶液作为滴定剂,在流通池中同时插入汞膜电极和氟离子指示电极,在滴定过程中的任一滴定点,流出液的汞电位和反应物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金属离子中每一种组分的含量。应用该方法对混合样品中的Cu2+、Pb2+、Zn2+进行了同时测定,测定结果的相对标准偏差均在0.14%~0.48%(n=5)之间,回收率均在97.3%~103.9%之间。     

Spectrophotometric Method for the Determination of Oxidative IonsWith Decoloring Reaction Using HCPCF

HCPCF is a color reagent for the determination of vanadium, zinc and magnesium, etc. To the best of our knowledge, no work on the decoloring reaction for analytical use of HCPCF for the determination of oxidative anions has been report. In this work, we found that some oxidative anions can oxidize HCPCF in acid medium, forming a colorless product. In addition, surfactant was used in this work, because of the low solubility of HCPCF in aqueous solutions. The purpose of this work is to establish a new, rapid and simple spectrophotometric method for the determination of NO2-, BrO3-,IO3-, IO4-and Cr2O7-based on the reaction between HCPCF and analytes in the presence of emulsion OP.     

Kinetic studies of the reactions of IO,BrO, and ClO with dimethylsulfide

The kinetics of the reactions of IO, BrO, and ClO with DMS have been investigated at 298 K and total pressures of 0.5–6.8 mbar He using the discharge flow-mass spectrometry technique to monitor the halogen oxide radicals. Rate coefficients of (8.8 ± 2.1) × 10^?15, (2.7 ? 0.5) × 10^?13 and (9.5 ± 2.0) × 10^?15 cm³ molecule^?1 s^?1 have been obtained for the reactions of IO, BrO, and ClO with DMS, respectively. The result for IO with DMS is in good agreement with two other recent studies on this reaction but is nearly three orders of magnitude slower than two earlier studies, one of which was from this laboratory. The earlier studies are now thought to be in error because of heterogeneous and secondary chemistry occurring in the systems investigated. The rate coefficient for BrO with DMS is in excellent agreement with a previously reported preliminary value from this laboratory. However, the rate coefficient for ClO with DMS is a factor of 4 lower than our previously determined value. The new data are considered more reliable in view of the much improved experimental technique in the present study. DMSO was detected as a product in all of these reactions. A semi-quantitative determination of the DMSO yield was only possible in the case of the reaction of IO with DMS where a yield of 84 ± 40% was found.     

On the spectroscopic and thermochemical properties of ClO, BrO, IO, and their anions

A coupled cluster composite approach has been used to accurately determine the spectroscopic constants, bond dissociation energies, and heats of formation for the X1(2)II(3/2) states of the halogen oxides ClO, BrO, and IO, as well as their negative ions ClO-, BrO-, and IO-. After determining the frozen core, complete basis set (CBS) limit CCSD(T) values, corrections were added for core-valence correlation, relativistic effects (scalar and spin-orbit), the pseudopotential approximation (BrO and IO), iterative connected triple excitations (CCSDT), and iterative quadruples (CCSDTQ). The final ab initio equilibrium bond lengths and harmonic frequencies for ClO and BrO differ from their accurate experimental values by an average of just 0.0005 A and 0.8 cm-1, respectively. The bond length of IO is overestimated by 0.0047 A, presumably due to an underestimation of molecular spin-orbit coupling effects. Spectroscopic constants for the spin-orbit excited X2(2)III(1/2) states are also reported for each species. The predicted bond lengths and harmonic frequencies for the closed-shell anions are expected to be accurate to within about 0.001 A and 2 cm-1, respectively. The dissociation energies of the radicals have been determined by both direct calculation and through use of negative ion thermochemical cycles, which made use of a small amount of accurate experimental data. The resulting values of D0, 63.5, 55.8, and 54.2 kcal/mol for ClO, BrO, and IO, respectively, are the most accurate ab initio values to date, and those for ClO and BrO differ from their experimental values by just 0.1 kcal/mol. These dissociation energies lead to heats of formation, DeltaH(f) (298 K), of 24.2 +/- 0.3, 29.6 +/- 0.4, and 29.9 +/- 0.6 kcal/mol for ClO, BrO, and IO, respectively. Also, the final calculated electron affinities are all within 0.2 kcal/mol of their experimental values. Improved pseudopotential parameters for the iodine atom are also reported, together with revised correlation consistent basis sets for this atom.     

Photoelectron spectroscopy of higher bromine and iodine oxide anions: electron affinities and electronic structures of BrO(2,3) and IO(2-4) radicals

This report details a photoelectron spectroscopy (PES) and theoretical investigation of electron affinities (EAs) and electronic structures of several atmospherically relevant higher bromine and iodine oxide molecules in the gas phase. PES spectra of BrO(2)(-) and IO(2)(-) were recorded at 12 K and four photon energies--355 nm/3.496 eV, 266 nm/4.661 eV, 193 nm/6.424 eV, and 157 nm/7.867 eV--while BrO(3)(-), IO(3)(-), and IO(4)(-) were only studied at 193 and 157 nm due to their expected high electron binding energies. Spectral features corresponding to transitions from the anionic ground state to the ground and excited states of the neutral are unraveled and resolved for each species. The EAs of these bromine and iodine oxides are experimentally determined for the first time (except for IO(2)) to be 2.515 ± 0.010 (BrO(2)), 2.575 ± 0.010 (IO(2)), 4.60 ± 0.05 (BrO(3)), 4.70 ± 0.05 (IO(3)), and 6.05 ± 0.05 eV (IO(4)). Three low-lying excited states along with their respective excitation energies are obtained for BrO(2) [1.69 (A (2)B(2)), 1.79 (B (2)A(1)), 1.99 eV (C (2)A(2))], BrO(3) [0.7 (A (2)A(2)), 1.6 (B (2)E), 3.1 eV (C (2)E)], and IO(3) [0.60 (A (2)A(2)), 1.20 (B (2)E), ～3.0 eV (C (2)E)], whereas six excited states of IO(2) are determined along with their respective excitation energies of 1.63 (A (2)B(2)), 1.73 (B (2)A(1)), 1.83 (C (2)A(2)), 4.23 (D (2)A(1)), 4.63 (E (2)B(2)), and 5.23 eV (F (2)B(1)). Periodate (IO(4)(-)) possesses a very high electron binding energy. Only one excited state feature with 0.95 eV excitation energy is shown in the 157 nm spectrum. Accompanying theoretical calculations reveal structural changes from the anions to the neutrals, and the calculated EAs are in good agreement with experimentally determined values. Franck-Condon factors simulations nicely reproduce the observed vibrational progressions for BrO(2) and IO(2). The low-lying excited state information is compared with theoretical calculations and discussed with their atmospheric implications.