配位滴定法连续测定铜和锌的新指示剂

对2-（3，5-二氨-2-吡啶偶氮）-5-二甲基苯胺（3，5-diCl-PADMAB）作指示剂络合滴定铜和锌进行了研究。在pH5．0的乙酸-乙酸钠介质中，以3，5-diCl-PADAMAB作指示剂，EDTA为滴定剂连续测定铜和锌，滴定终点颜色变化敏锐，准确度高，铜和锌量各在0～20mg范围内与EDTA量成正比。方法用于合金中铜和锌的测定，分析结果的相对标准偏差为〈0．1％和〈0．4％。     

库仑滴定法测定有机硅样品中的氮含量

本文利用库仑滴定法研究了高分子和低分子硅氮化合物及含氮有机硅样品中氮含量的测定,并研究和讨论了影响测定结果准确性的因素。     

聚乙二醇-硫酸铵双水相萃取次甲基蓝的研究

利用分光光度法研究了次甲基蓝在聚乙二醇-硫酸铵双水相体系的萃取行为,探索了质量配比(mPEc/m(NH4)2SO4)、温度和次甲基蓝的浓度对双水相及次甲基蓝萃取率(Y)的影响.实验表明:(1)在一定的温度和浓度下,随着mPEC/m(NH4)2SO4的减小,分配系数K( cup/clow)增加,萃取率Y略有减小;(2)在一定的质量配比和浓度下,分配系数K(cup/clow)随温度的升高而增大,但萃取率Y却基本保持不变;(3)在一定的质量配比和温度下,随着次甲基蓝浓度的增加,分配系数K(cup/clow)增大;萃取率Y略有增加.在mPEG/m( NH4) 2SO4为1.50∶1,c次甲基蓝=8.915×10-5mol/L、t=30℃的实验条件下,K(cup/clow)=22.14,萃取率(y)可达95.43％.     

碳糊电极阴极吸附伏安法测定橙皮甙

在0.4mol/L的NH4Cl-NH3(pH9.0)缓冲液中,使用JP-303极谱分析仪,橙皮甙在碳糊电极(CPE)上有一灵敏的吸附伏安还原峰,峰电位为-1.2V(vs.SCE).该还原峰的二阶导数峰电流与橙皮甙的浓度在2.0×10-8～1.0×10-6mol/L(富集90s)范围内成良好的线性关系,相关系数为0.9963,检出限为1.0×10-8mol/L(S/N=3,富集110s).探讨了橙皮甙在碳糊电极上的伏安性质和电极反应机理,并且成功应用于中草药桔皮中橙皮甙含量的测定.     

NH3-SCR反应中Fe-ZSM-5的Fe物种分布和酸性位对其水热稳定性及抗硫和抗碳氢性能的影响

以Na+型和H+型ZSM-5为载体制备了Fe-ZSM-5催化剂并用于氨选择性催化还原(NH3-SCR)氮氧化物. Fe-H-ZSM-5在新鲜时和750 oC含10%水的空气中老化后,其SCR活性均优于Fe-Na-ZSM-5.表征结果显示, Fe-H-ZSM-5和Fe-Na-ZSM-5的Fe物种分布和酸性位有所不同.高温水热老化后Fe-H-ZSM-5分子筛骨架的脱铝较Fe-Na-ZSM-5严重.水和硫的存在对Fe-H-ZSM-5和Fe-Na-ZSM-5的SCR活性的影响相似,即降低了低温活性,略提高了高温活性. Fe-Na-ZSM-5表现出比Fe-H-ZSM-5更好的抗碳氢中毒性能.这两种催化剂的SO2和碳氢中毒是可逆的.     

Investigation of efflorescence of inorganic aerosols using fluorescence spectroscopy

The phase transition is one of the most fundamental phenomena affecting the physical and chemical properties of atmospheric aerosols. Efflorescence, in particular, is not well understood, partly because the molecular interactions between the solute and water molecules of saturated or supersaturated solution droplets have not been well characterized. Recently, we developed a technique that combines the use of an electrodynamic balance and a fluorescence dye, 8-hydroxyl-1,3,6-pyrenetrisulfonate (pyranine), to study the distributions of solvated and free water in aqueous droplets (Choi, M. Y.; Chan, C. K.; Zhang, Y. H. J. Phys. Chem. A 2004, 108, 1133). We found that the equality of the amounts of solvated and free water is a necessary but not sufficient condition for efflorescence. For efflorescing compounds such as Na2SO4, (NH4)2SO4, and a mixture of NaCl and Na2SO4, the amount of free water decreases, while that of solvated water is roughly constant in bulk measurements and decreases less dramatically than that of free water in single-particle measurements as the relative humidity (RH) decreases. Efflorescence of the supersaturated droplets of these solutions occurs when the amounts of free and solvated water are equal, which is consistent with our previous observation for NaCl. For nonefflorescing compounds in single-particle levitation experiments such as MgSO4 and Mg(NO3)2, the amounts of free and solvated water are equal at a water-to-solute molar ratio of about 6, at which spectral changes due to the formation of contact ion pairs between magnesium and the anions occur as shown by Raman spectroscopy. Fluorescence imaging shows that the droplets of diluted Mg(NO3)2 (at 80% RH) and MgSO4 are homogeneous but those of NaCl, Na2SO4, (NH4)2SO4, and supersaturated Mg(NO3)2 (at 10% RH) are heterogeneous in terms of the solvated-to-free water distribution. The solvated-to-free water ratios in NaCl, Na2SO4, and (NH4)2SO4 droplets are higher in the outer regions by about half a radius deep than at the center of the droplets.     

Stepwise determination of quaternary ammonium salts and aromatic amines in pharmaceuticals by ion association titration.

A stepwise titrimetric method has been developed for the simultaneous determination of pharmaceutical quaternary ammonium salts (R4N+) and aromatic amines (R3N). The method is based on the solvent extraction of R4N+ and R3NH+ with an ion association reagent. Sodium tetrakis(4-fluorophenyl)borate and sodium tetraphenylborate were used as titrants and potassium tetrabromophenolphthalein ethyl ester (TBPE) was used as an indicator. The ion associate which formed between R4N+ ion and TBPE made a blue color in 1,2-dichloroethane, while the ion associate formed between R3NH+ and TBPE showed a red-violet one. Sample solutions containing quaternary ammonium and/or amine compounds were titrated with sodium tetrakis(4-fluorophenyl)borate or sodium tetraphenylborate. When one drop of excess titrant was added, the color of the organic phase turned from blue or red-violet to yellow at the equivalence point. On the other hand, in the mixture of R4N+ and R3N, the color changed from blue to red-violet at the first equivalence point, and then its color turned to yellow at the second equivalence point. The quaternary ammonium compound and aromatic amine in pharmaceuticals could be simultaneously and successfully determined by the proposed titration method.     

铋系超导体组成分析

本文首次提出了一种离子交换柱分离——滴定法测定Bi系超导体中Bi、Pb、Cu、Ca和Sr含量的方法。研究了进样条件和淋洗方法,特别是Bi~(3+)在微酸性溶液中的亚稳态进样。测定合成样品时,Bi、Pb、Cu、Ca和Sr的相对标准偏差分别为0.7％、1.6％、0.5％、0.4％和0.2％。分析了超导体样品,并测定了其中Cu~(3+)。     

辉光放电等离子体处理阳离子染料结晶紫废水

用辉光放电等离子体技术对结晶紫进行了降解脱色处理,考察了多种因素对结晶紫降解效果的影响。实验发现,提高电解质浓度和增加电压均可提高结晶紫的脱色效果,考虑到电极损耗,辉光放电最佳条件为:电解质浓度为2 g/L Na2SO4,电压为600 V。当改变溶液的初始pH值时,结晶紫的脱色率随溶液的初始pH值升高而增加,加入一定量H2O2能明显地提高结晶紫的脱色效率;若加入0.4 mmol/L Fe2 ,5 min时结晶紫的脱色率由原来的13.64%增加到91.36%。结果表明,辉光放电产生的.OH对结晶紫的降解起重要作用。最佳条件下,40 min内的脱色率达到93%,降解率为74%。     

光波导传感元件在检测酸性气体中的应用

采用旋转甩涂法将甲基紫传感薄膜固定在特制的锡(Sn2+,Sn4+)掺杂玻璃光波导(Sn doped glass slide)表面,研究了该传感薄膜与HCl、H2S、以及SO2作用前后的可见吸收光谱的变化,并在此基础上研制了玻璃光波导酸性气体(HCl、H2S、SO2)传感元件。传感薄膜与酸性气体作用时,薄膜的颜色发生变化,从而降低薄膜对倏逝波的吸收,使传感器的输出光强度(信号)增强。本文采用流动注射法对酸性气体进行了检测。实验结果表明,在室温下,该传感元件对硫化氢气体具有明显的响应,而对相同浓度的其他酸性气体的响应相对较小,对浓度在6×10-4～2.5×10-5(V/V)的硫化氢气体具有良好的线性响应(R=0.9979,n=4),相对标准偏差(RSD)为±3.5%,具有响应快、可逆性和重复性好、容易制备、可以在室温下工作等特点。     

Temperature dependent thermodynamic model of the system H(+)-NH₄(+)-Na(+)-SO₄²⁻-NO₃⁻-Cl⁻-H₂O

A thermodynamic model of the system H(+)-NH?(+)-Na(+)-SO?2?-NO??-Cl?-H?O is parametrized and used to represent activity coefficients, equilibrium partial pressures of H?O, HNO?, HCl, H?SO?, and NH?, and saturation with respect to 26 solid phases (NaCl(s), NaCl·2H?O(s), Na?SO?(s), Na?SO?·10H?O(s), NaNO?·Na?SO?·H?O(s), Na?H(SO?)?(s), NaHSO?(s), NaHSO?·H?O(s), NaNH?SO?·2H?O(s), NaNO?(s), NH?Cl(s), NH?NO?(s), (NH?)?SO?(s), (NH?)?H(SO?)?(s), NH?HSO?(s), (NH?)?SO?·2NH?NO?(s), (NH?)?SO?·3NH?NO?(s), H?SO?·H?O(s), H?SO?·2H?O(s), H?SO?·3H?O(s), H?SO?·4H?O(s), H?SO?·6.5H?O(s), HNO?·H?O(s), HNO?·2H?O(s), HNO?·3H?O(s), and HCl·3H?O(s)). The enthalpy of formation of the complex salts NaNH?SO?·2H?O(s) and Na?SO?·NaNO?·H?O(s) is calculated. The model is valid for temperatures < or approximately 263.15 up to 330 K and concentrations from infinite dilution to saturation with respect to the solid phases. For H?SO?-H?O solutions the degree of dissociation of the HSO?? ion is represented near the experimental uncertainty over wide temperature and concentration ranges. The parametrization of the model for the subsystems H(+)-NH?(+)-NO??-SO?2?-H?O and H(+)-NO??-SO?2?-Cl?-H?O relies on previous studies (Clegg, S. L. et al. J. Phys. Chem. A 1998, 102, 2137-2154; Carslaw, K. S. et al. J. Phys. Chem. 1995, 99, 11557-11574), which are only partly adjusted to new data. For these systems the model is applicable to temperatures below 200 K, dependent upon liquid-phase composition, and for the former system also to supersaturated solutions. Values for the model parameters are determined from literature data for the vapor pressure, osmotic coefficient, emf, degree of dissociation of HSO??, and the dissociation constant of NH? as well as measurements of calorimetric properties of aqueous solutions like enthalpy of dilution, enthalpy of solution, enthalpy of mixing, and heat capacity. The high accuracy of the model is demonstrated by comparisons with experimentally determined mean activity coefficients of HCl in HCl-Na?SO?-H?O solutions, solubility measurements for the quaternary systems H(+)-Na(+)-Cl?-SO?2?-H?O, Na(+)-NH?(+)-Cl?-SO?2?-H?O, and Na(+)-NH?(+)-NO??-SO?2?-H?O as well as vapor pressure measurements of HNO?, HCl, H?SO?, and NH?.     

Applicability of 0.05 mol kg(-1) potassium hydrogen phthalate as reference value pH standard in water-organic solvent mixtures

The applicability of 0.05 mol kg(-1) potassium hydrogen phthalate (KHPh(S), S=the solvent under study) as reference value pH standard (RVS) was studied in water-organic solvent mixtures. Phthalic acid in various aqueous organic solvent mixtures was titrated potentiometrically with Bu(4)NOH (MeOH), using a pH-ISFET and a glass electrode as pH-sensors, and the buffer capacity of the HPh(-) solution was roughly estimated from the difference between the first and second half-neutralization potentials. The influence of potassium ion to the buffer capacity was also studied, titrating KHPh and Et(4)NHPh with CF(3)SO(3)H and Bu(4)NOH (MeOH) and comparing the titration curves. The KHPh solution loses its buffer capacity if the solvent mixture has an aprotic property. For aqueous mixtures of protophilic aprotic solvents (e.g. DMSO and DMF), it is unsuitable as RVS if the water content is less than ca. 40 (v/v)%. The necessity of selecting subsidiary pH standard(s) is suggested for the solvent systems in which KHPh is inapplicable.     

2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺与铱(Ⅲ)显色反应的研究及其应用

研究了新试剂2-(5-碘-2-吡啶偶氮)-5-二甲氨基苯胺(5-I-PADMA)与铱(Ⅲ)的高灵敏显色反应。结果表明,在pH 5.6～7.3的HAc-NaAc缓冲溶液中,铱(Ⅲ)与5-I-PADMA可形成稳定的1：2配合物,其最大吸收峰位于475 nm;铱配合物形成后,当以适量的无机酸(HCl,H2SO4,HClO4,...     

Differential pulse voltammetric indirect determination of aluminium in drinking waters, blood, urine, hair, and medicament samples using L-dopa under alkaline conditions

The differential pulse voltammetric (DPV) indirect determination of aluminium using L-dopa under alkaline conditions on a glassy carbon working electrode was studied. The proposed method relies on the linear decrease of the DPV anodic peak current of L-dopa with increase in the concentration of aluminium added. Under the optimum experimental conditions (pH 8.5, 0.08 M NH4Cl-NH3.H2O buffer solution, and 4 x 10(-4) M L-dopa), the linear range is 2-18 x 10(-7) M AlIII. The detection limit is 7.6 x 10(-8) M and the relative standard deviation for 8 x 10(-7) M AlIII is 3.5% (n = 8). A number of foreign species were examined as potential interferents. The method was applied to the determination of aluminium in drinking waters, synthetic renal dialysate, sodium chloride injection, sucrafate, hydrothorax, blood, urine and hair samples. The physiological significance is discussed.     

The Christiansen effect of brightly colored colloidal dispersion with an amphiphilic polymer

A novel coloration phenomenon in a colloidal dispersion with an amphiphilic polymer was found. The dispersion consists of tetrahydrofuran (THF), an aqueous solution of sodium thiosulfate (Na(2)S(2)O(3).5H(2)O), and hydroxypropylcellulose (HPC). The dispersion was emulsified by HPC as an amphiphilic polymer, so that the aqueous phase was confined in droplets in the THF matrix. It typically appeared bluish violet at room temperature and turned into blue with increasing temperature. In this system, the refractive indices of the inside and outside of the droplet coincided at a certain wavelength at which the light passes through without scattering, which is called the Christiansen effect. The color observed was successfully simulated by Mie's scattering theory in combination with the Christiansen effect.     

葛根素的循环伏安测定及其电化学行为研究

在0.02 mol/L NH4Cl-NH3.H2O(pH8.0)的底液中,采用循环伏安法测定葛根素,得到一良好的氧化峰,峰电位Ep=+0.57V,峰电流Ip与葛根素的浓度在1.046×10-7～5.767×10-5mol/L范围内成线性关系,相关系数r为0.9989,检出限为1.046×10-7mol/L.测定葛根中葛根素的含量,平均回收率在99.8%.并且研究了葛根素在玻碳电极上的电化学行为,结果表明葛根素的电极过程具有吸附性和不可逆性.     

Osteryoung square wave voltammetric determination of lactose in food samples by a derivative procedure

A method for determination of lactose in food samples by Osteryoung square wave voltammetry （OSWV） was developed. It was based on the nucleophilic addition reaction between lactose and aqua ammonia. The carbonyl group of lactose can be changed into imido group, and this increases the electrochemical activity in reduction and the sensitivity. The optimal condition for the nucleophilic addition reaction was investigated and it was found that in NH4C1-NH3 buffer of pH 10.1, the linear range between the peak current and the concentration of lactose was 0.6-8.4 mg L-l, and the detection limits was 0.44 mg L- 1. The proposed method was applied to the ＇determination of lactose in food samples and satisfactory results were obtained.     

Microdetermination of aliphatic diamines and polyamines with cupric ion

The reactions of diamines and polyamines with cupric ion were investigated potentiometrically, using a copper ion-selective indicator electrode and a single-junction reference electrode. In general, cupric ion reacted with 2 mol of vic-diamines or their salts. Tetraaza compounds reacted on an equimolar basis with Cu(II). Both vic-diamines and their salts, as well as tetraaza compounds, could be titrated in the presence of excess ammonia. With cupric ion in ammoniacal solution these compounds yield a characteristic purple/violet color. Diamines separated by more than two methylene groups cannot be determined in the presence of ammonia and yield a blue color. Diamines with more than four methylene groups react with cupric ion on an equimolar basis, also yielding a blue color.     

三次采油耐温抗盐聚合物的合成与评价

以丙烯酰胺(AM)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)和氢氧化钠(Na OH)为原料,采用过硫酸铵[(NH4)2S2O8]、亚硫酸钠(Na2SO3)和四甲基脲[N(CH3)2CON(CH3)2]作为新型复合引发体系,通过共聚后水解工艺,合成了高分子量三元共聚物(AM-AANa-AMPSNa).考察了引发剂用量、单体浓度、p H和引发温度对共聚物黏均分子量的影响.确定最优条件为:引发剂用量0.035%,单体质量浓度为25%,介质p H 7,引发温度0℃.通过红外光谱和核磁碳谱表征了其结构,并系统评价了其理化性能指标、黏弹性、注入性和驱油性能.结果表明,该共聚物较高分子量部分水解聚丙烯酰胺(HPAM)具有更优异的耐温抗盐性能.其黏均相对分子量达到3000万以上,在胜利油田III型盐水中,浓度1500 mg/L,温度85℃条件下,溶液表观黏度达到17.7 m Pa s,岩心驱油实验在水驱采收率51.8%基础上,可再提高15.8%.上述性能表明,该高分子量三元共聚物有望应用在高温高盐油藏三次采油技术中.     

杂多酸水溶液脱除烟气中SO2新方法的研究

在孔板式吸收器（孔板孔径：50μm-70μm）中对杂酸水溶液脱除烟气中SO2的新方法进行了研究。在所考察的几种杂多酸中,H3PW12O40和H2SiW12O40对SO2的脱除率较为接近,H7PMo2W12O49和Na2HPMo12O40对SO2的脱除率相对较高,其中后者对SO2的脱除率最高。杂多酸（HPA）对SO2的脱除率随HPA浓度的提高而增高,随进气中SO2的浓度或吸收温度提高而减低。常温有利于HPA对SO2的脱除。NaCl,NH4VO3,CuSO4及H3PO4这四种添加剂均能提高HPA对SO2的脱除率。复配体系中,以上添加剂对HPA的最优配比为：NaCl/HPA:H3PO4/HPA:NH4VO3/HPA:CuSO4/HPA=1/6:1/8:1/2:1/4。进气中有NOx存在下HPA对SO2的脱除反应式,这些反应式能够很好地说明NOx的作用效果。以上结果表明：HPA水溶液具有很好的烟气脱硫应用前景。