谈谈离子水的特征和应用

主要介绍了离子水的制备原理,碱性离子水和酸性离子水的特征及其应用,并展望了离子水的发展前景。     

以离子水合能解释离子选择电极响应机理

用相继切换不同浓度I^-试液的活度阶梯法研究了碘化银基离子选择电极（I^--ISE）的瞬时响应。随电位变化的离子水合自由能△Gh(I^-）显示出|△Gh（I^-）|越小,正活度阶民位跃迁越快而负活度阶梯电位变化越慢。将－△Gh(I^-）看作I（H2O）n^-与I^--ISE表面反应的活化能解释了这个现象。比起传统电位法,活度阶梯法的主要优点是ISEs响应非常快并且更灵敏,有可能实现小体积试液的快速分析。     

关于Fe(OH)3略有两性的实验研究

本文通过实验得到Fe(OH)3略有两性的尺度,解决了Fe(OH)3能溶于多少浓度的强碱中的问题。现行教材中讲Fe(OH)3略有两性,但碱性强于酸性,只有新沉淀出来的Fe(OH)3能溶于浓的强碱溶液中。然而,对初学无机化学的人来说,这略有两性的尺度如何把握呢?Fe(OH)3能部分溶于多少浓度的强碱中呢?为此做了如下的实验。     

苯系物Lewis酸碱性的定量化尝试及估算

TrendMD:     

含氮FAU分子筛的制备、表征及碱催化反应性能

利用脱水氮化法制备了含氮HY分子筛,氮化后分子筛的结晶度和比表面积均得到较好保持.由于氮原子的电负性低于氧原子,氮原子取代氧原子进入HY分子筛的骨架,使其Lewis碱性得到增强.利用氨气吸附红外光谱、二氧化碳吸附红外光谱与二氧化碳程序升温脱附方法对氮化前后的分子筛进行表征.结果表明氮化后HY分子筛的L酸中心数量有所降低,B酸中心数量有所增加,同时生成新的碱性中心.由于新碱性中心的引入,含氮HY分子筛在Knoevenagel缩合碱性探针反应中表现出优异的活性.     

功能离子液体在Michael加成中的应用

离子液体具备不可燃性、低挥发性、良好的溶解性能、可设计性和可重复使用性等特点,因此作为催化剂、促进剂或反应介质被广泛应用于有机合成领域中。本文从不同类型的离子液体角度,分别介绍了近年来酸性、碱性和手性功能离子液体在Michael加成反应中的应用研究,并对功能离子液体的结构特点、催化活性以及可能的催化反应机理方面展开了详细的评述。     

连续流动条件下含氮Beta分子筛催化甲缩醛-异丁烯Prins反应

采用高温氨气氮化法,制备了一系列含氮Beta分子筛样品,并在连续流动条件下,考察了其催化甲缩醛与异丁烯经Prins缩合制异戊二烯的反应性能.利用XRD、 N₂吸附/脱附、元素分析、 ²⁹SiMAS NMR、 NH₃-TPD、 CO₂-TPD和TG等方法对氮化分子筛的结构、酸碱性和反应后积碳进行了表征,研究了反应条件及样品的酸碱性对反应性能的影响.结果表明,以35%甲缩醛水溶液为反应物,在320℃、 2 MPa、异丁烯与甲缩醛摩尔比为7的适宜条件下,铵型Beta为前驱体制备的催化剂对甲缩醛的转化率达99%,异戊二烯的产率达85%.氮化后少量的酸性位和较多的碱性位有利于维持甲缩醛较高的转化率、较高的异戊二烯产率及较低的反应积碳量.催化剂再生6次后仍保持75%异戊二烯产率,样品中Si―N键削弱导致酸碱性变化是再生后反应性能下降的主要原因.     

固相萃取-高效液相色谱法同时测定豆制品中的碱性嫩黄O、酸性橙Ⅱ和碱性橙Ⅱ

建立了一种固相萃取-高效液相色谱法同时测定豆制品中的碱性嫩黄O、酸性橙Ⅱ和碱性橙Ⅱ等3种黄色工业染料的方法。样品经体积分数70%乙醇水溶液(含1.0%氨水)涡旋超声提取后,采用Strata-X-AW固相萃取(SPE)小柱净化,洗脱液用氮气吹至近干后用甲醇溶解并定容,过PTFE滤膜后在Kromasil C18色谱柱上,以V(甲醇):V(20 mmol/L乙酸铵)=65:35的溶液为流动相进行分离,检测波长为450 nm。结果表明,在最优的色谱条件下,各目标化合物的加标回收率在89.0%~94.7%之间,相对标准偏差在2.2%~4.6%之间。3种染料在0.2~20.0 mg/L内呈现良好的线性关系,相关系数r≥0.999,豆制品中碱性嫩黄O、酸性橙Ⅱ和碱性橙Ⅱ的检出限分别为0.06、0.06和0.09 mg/kg。该方法用于实际样品的检测取得了满意的效果。     

电感耦合等离子体原子发射光谱分析中易电离元素的基体干扰及其抑制的研究

选取铝、铜、镁、钙、铁、锰和锌等7种元素的9条谱线,研究电感耦合等离子体原子发射光谱法对其测定时易电离元素钾、钠的基体干扰。结果表明:易电离元素对待测元素具有较明显的干扰作用,而增大射频发射功率及降低雾化器压力可有效地抑制易电离元素对待测元素的干扰。     

Modelling spur chemistry for alkaline and acidic water at high temperatures

The effect of pH and associated ionic strength on the primary yields in the radiolysis of pressurised water has been assessed by diffusion-kinetic calculations for temperatures in the range 100–300°C. Account has been taken for ionic strength I up to 0.1 mol kg⁻¹, assuming that the counter ions of H⁺ in acid solutions and of OH⁻ in base solutions have unit charge. In acid solutions, the H⁺ ions react with e⁻ _aq. The decrease in G(e⁻ _aq) and the increase in G(H) with decreasing pH becomes substantial for [H⁺] ≥ 1 × 10⁻⁴ m, but the primary yields of oxidising species are almost constant. In alkaline solutions, the OH⁻ anions affect the spur chemistry of radiation-generated protons and hydroxyl radicals for [OH⁻] ≥ 1 × 10⁻⁴ m. The scavenging of H atoms and hydrogen peroxide becomes significant for [OH⁻] ≥ 1 × 10⁻² m. The total yields G(OH) + G(O⁻) and G(H₂O₂) + G(HO₂ ⁻) are independent of base concentration below 0.01 m. In more alkaline solutions, G(OH) + G(O⁻) increases, whereas G(H₂O₂) + G(HO₂ ⁻) decreases with increasing [OH⁻]. Calculations showed the substantial yield of the reaction O⁻ + e⁻ _aq in 0.1 m base solution. Spur chemistry in alkaline hydrogenated water is not affected by the presence of H₂ if less than 0.001 m of hydrogen is added.     

Metal Oxide Film Anodes in the Electrolysis of Water or Brine

Metal (M) oxide (M: Ir, Os, Pd, Pt, Rh, Ru) together with MaO₂ and MnO₂ alone, were coated on SnO₂ films and the anode behavior was examined in 1.0 N H₂SO₄, 1.0 N NaOH and 1.0, N NaCl aqueous solutions at 25°. The results are compared with those of DSA and of metallic Pt.     

Defluorination and Mineralization of Difluorophenols in Water by Anodic Contact Glow Discharge Electrolysis

Anodic contact glow discharge electrolysis (CGDE) is a DC-excited atmospheric pressure discharge, in which a steady non-thermal plasma is generated locally between the surface of an electrolytic solution and an anode in contact with it. The I–U characteristics of CGDE were investigated. The plasma temperatures were estimated to be in the range, 1373–2045 K. Hydroxyl radicals and hydrogen peroxide were the main oxidants generated by CGDE. The hydrogen peroxide concentration reached 31.2 mmol/L (mM) in a phosphate buffer solution without organic substrates. During CGDE, the DFPs and the corresponding total organic carbon (TOC) in water were consumed. Most of the fluorine atoms in the DFPs were converted to fluoride ions, and the fluoride concentration increased steadily. An analysis of the hydroxylation of DFPs suggested that the hydroxyl radicals generated by CGDE were the key species responsible for the degradation of DFPs, and the possible mechanistic routes of the mineralization of DFPs are proposed. The disappearance of DFPs and the TOC as well as the defluorination of the DFPs followed first-order kinetics. The rate of TOC disappearance was relatively constant: 1.00 ± 0.05 × 10^?2 min^?1. The order of disappearance of the DFPs was 2,6-DFP > 2,3-DFP > 2,5-DFP > 2,4-DFP > 3,4-DFP > 3,5-DFP. In contrast, the order of defluorination of the DFPs was 2,5-DFP > 2,3-DFP > 2,6-DFP > 2,4-DFP > 3,4-DFP > 3,5-DFP. Overall, the order of the reaction rates for each DFP was k_DFP > k_dF > k_TOC.     

Water absorption in EVOH films and its influence on glass transition temperature

Moisture sorption kinetics of nonoriented ethylene vinyl alcohol copolymer (EVOH) film (EF‐E15) were studied at 25, 35, and 45°C. Anomalous diffusion was observed for the polymeric film at high relative humidities (RH) and higher temperatures. Diffusion and solubility coefficients of water were found to be concentration dependent. The moisture sorption isotherms of three types of EVOH films (EF‐E15, EF‐F15, and EF‐XL15) determined at 25, 35, and 45°C, were well described using the GAB equation. Glass transition temperatures (T_g) of the EVOH films, as influenced by RH, were measured using differential scanning calorimetry. T_g values decreased with increasing RH due to the plasticization effect of water, and were found to be dependent on ethylene content and orientation of the EVOH films. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 691–699, 1999     

Analysis of Phenoxycarboxylic Acids and Other Acidic Compounds in Tap,Ground, Surface and Sewage Water at the Low ng/1 Level

Abstract

Solid-phase extraction with RP-C18 phase has been successfully applied for the determination of more than 30 acidic herbicides and related compounds from environmental water samples. Detection of these contaminants was performed after pentafluorobenzylation at the low ng per liter level using gas chromatography/mass spectrometry. With multiple-component SIM programming simultaneous detection of all compounds in one single gas chromatographic run was possible.

Increased reliability of acidic herbicide analysis from water samples with high matrix content was achieved by using a surrogate as well as an internal standard. 2-(4-chlorophenoxy) butyric acid, being a structural isomer of clofibric acid and mecoprop, was chosen as surrogate standard because cloflbric acid was found to be a widespread contaminant in environmental water samples from the Berlin area. Mecoprop, dichlorprop and 1-naphthylacetic acid were also found in field studies of some of these samples. A few examples of positive findings in tap, ground, surface and sewage water samples are presented.     

雎水流域的水化学特征及其地表水与地下水的相互转化

为了解特定流域的水化学特征及其运移和转化的历史,为水资源科学管理提供依据,分析了小流域雎水河的水化学特征。结果表明:(1)雎水河流域主要是大气降水补给的地矿化度的溶滤水。(2)雎水河全线都是地下水补给地表水。(3)部分泉点矿化度相对较高与SO24-较高有关,可能是因为流经了含煤地层。     

Plasma-Induced Decomposition of Dichlorophenols and Trichlorophenols in Water by Means of Anodic Contact Glow Discharge Electrolysis

Decomposition of aqueous dichlorophenols and trichlorophenols was investigated by means of contact glow discharge electrolysis. With the decay of chlorophenols (CPs), the amount of total organic carbon (TOC) in water also decreased smoothly, indicating that carbon atoms of benzene nucleus could be eventually converted to inorganic carbons. And, it was found that chlorine atoms in the CPs were released as chloride ions. As the by-products, oxalate and formate were formed. The chlorine derivatives of 1,4-hydroquinone and 1,4-benzoquinone were detected as the primary intermediates in the initial stage of decomposition of each of CPs. The decay of both CPs and TOC obeyed the first-order rate law, respectively. The apparent rate constants for the decay of CPs increased with the decrease in pKa values of CPs, while those for the decay of TOC were substantially unaffected.