4氯化铜对聚氯乙烯燃烧产物的催化作用

用现代色谱分析技术确定了在不同炉温条件下,掺杂有CuCl~2的聚氯乙烯燃烧过程中二噁英和多环芳烃的生成量,研究了氯化铜用量对其生成量的影响。结果表? 鞯ゴ康木勐纫蚁┤忌詹罅康亩嗷贩继蜕倭康亩f英,氯化铜的加入可大大增加二噁英的生成量,并能抑制多环芳烃的产生。金属氯化物可能是促使聚氯乙? ┤忌詹f英的主要因素之一。     

The determination of hydrogen chloride in ambient air with diffusion/denuder tubes

A manual method for the determination of hydrogen chloride in air, based on diffusion/denuder tube separation from particulate chloride aerosol is described. When air is drawn through a tube coated with a selective absorbent (sodium fluoride), separation is achieved because gaseous hydrogen chloride diffuses much more rapidly to the tube walls than particulate chloride aerosol, which passes through virtually unabsorbed. After the sampling period (the length of which depends on the concentration of gaseous hydrogen chloride expected), the sorbed hydrogen chloride is washed from the tube and measured with a highly sensitive chloride ion-selective electrode with a mercury (I) chloride membrane. The method is examined theoretically and experimentally. The experimentally derived absorption efficiencies of the diffusion/denuder tubes were > 90% and the standard deviation of the method was 0.023 μg m^?3 for hydrogen chloride concentrations of 0.16–0.55 μg m^?3. Interference from particulate chloride salts was negligible; this was confirmed by tests with artificially generated aerosol particles from an aerosol generator. The diffusion/denuder tubes have high capacity; level as high as 330 μg m^?3 hydrogen chloride can be sampled for 60 min without affecting performance. A detection limit of (50/t) μg m^?3 can be achieved, where t is the sampling rime (min); e.g., 1μg m^?3 hydrogen chloride can be detected with a sampling period of 50 min.     

Pyridine and triphenylphosphine oxide activation of sulfonyl chlorides in the syntheses of (E) alk-1-enyl sulfones

This paper describes efficient and new approaches to (E) alk-1-enyl sulfones, starting from sulfonyl chloride/pyridine or sulfonyl chloride/triphenylphosphine complexes in the presence of (E) di-iso-butyl alk-1-enyl alanes.The use of CuCl in the presence of sulfonyl chloride/pyridine complexes or pyridine in the presence of sulfonyl chloride/triphenylphosphine complexes, respectively, results in a remarkable increase in the yields and conversions.     

Synthesis and characterization of benzyl and benzoyl substituted oxime-phosphazenes

Two oxime-cyclophosphazenes were prepared from hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (7). The reactions of these oximes with benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride were studied. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with benzyl chloride (4) and benzoyl chloride, respectively. However, the oxime groups on 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride. Hexasubstituted compounds were also obtained from the reactions of hexakis(4-[(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) with benzoyl chloride (10), 4-methoxybenzoyl chloride (11) and 2-chlorobenzoyl chloride (12). A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride (9). All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR, ¹H, ¹³C and ³¹P NMR spectroscopy.     

氯化铕对大黄愈伤组织生长及超微结构的影响

以掌叶大黄的愈伤组织为材料，研究了不同浓度氯化铕对其生长的影响，并利用透射电镜技术研究了氯化铕对大黄细胞超微结构的影响。实验结果表明，低浓度氯化铕促进愈伤组织生长，高浓度则抑制生长，浓度达到１００ｍｇ／Ｌ则可导致大黄外植体全部死亡。氯化铕对大黄的促进作用可被钙调蛋白的拮抗剂氯丙嗪抑制。１０ｍｇ／Ｌ氯化铕可使大黄愈伤组织的细胞形态发生明显变异。     

S(N)2 Mechanism for Alcoholysis, Aminolysis, and Hydrolysis of Acetyl Chloride

First-order solvolysis rate constants are reported for solvolyses of acetyl chloride in methanol and MeOD, and in binary aqueous mixtures with acetone, acetonitrile, ethanol, methanol, and trifluoroethanol at 0 degrees C. Product selectivities (S = [MeCOOR]/[MeCOOH] x [water]/[alcohol]) are reported for solvolyses in ethanol/ and methanol/water at 0 degrees C. Solvolyses of acetyl chloride show a high sensitivity to changes in solvent ionizing power, consistent with C-Cl bond cleavage. As the solvent is varied from pure ethanol (or methanol) to water, S values and rate-rate profiles show no evidence for the change in reaction channel observed for solvolyses of benzoyl and trimethylacetyl chlorides. However, using rate ratios in 40% ethanol/water and 97% trifluoroethanol/water (solvents of similar ionizing power but different nucleophilicities) to compare sensitivities to nucleophilic attack, solvolyses of acetyl chloride are over 20-fold more sensitive to nucleophilic attack than benzoyl chloride. The solvent isotope effect of 1.29 (MeOH/MeOD) for acetyl chloride is similar to that for p-methoxybenzoyl chloride (1.22) and is lower than for benzoyl chloride (1.55). Second-order rate constants for aminolyses of acetyl chloride with m-nitroaniline in methanol at 0 degrees C show that acetyl chloride behaves similarly to p-methoxybenzoyl chloride, whereas benzoyl chloride is 40-fold more sensitive to the added amine. The results indicate mechanistic differences between solvolyses of acetyl and benzoyl chlorides, and an S(N)2 mechanism is proposed for solvolyses and aminolyses by m-nitroaniline of acetyl chloride (i.e. these reactions are probably not carbonyl additions, but a strong sensitivity to nucleophilic attack accounts for their high rates).     

Synergistic effect of ferric chloride and silicon mixtures on the thermal stabilization enhancement of ABS

A previous study from this laboratory has shown that Lewis acid-type transition metal chlorides (NiCl₂, CoCl₂, ZnCl₂, and FeCl₃) are effective char forming catalysts for ABS terpolymer in an inert atmosphere [Jang J, Kim JH, Bae JY. Polym Degrad Stab 2005;88(2):324.]. However, transition metal chloride catalysed char formation (and flame-retardance enhancement) of ABS in air was unsuccessful due to the oxidative degradation of the char at a higher temperature. In order to overcome these undesirable phenomena, we incorporated silicon with transition metal chlorides as co-catalyst and a series of ABS/transition metal chloride/silicon compounds were made from them and their flame retardancy was evaluated by measuring the limiting oxygen index (LOI) values. Our results showed that among various transition metal chloride/silicon catalyst systems the incorporated mixture of ferric chloride and silicon is very effective in enhancing the thermal stabilization of ABS and LOI value as high as 33 is obtained. The reason for this synergistic effect by ferric chloride and silicon was postulated to come from the interaction between ferric chloride and silicon at elevated temperatures, probably generating silicon tetrachloride and hydrogen chloride.     

离子色谱法测定“地沟油”中钠离子和氯离子的含量及其比例关系

采用离子色谱法测定“地沟油”样品中钠离子和氯离子的含量,通过计算两者的比例关系确定样品中是否含有“地沟油”。使用去离子水提取“地沟油”样品中钠离子和氯离子。氯离子以20 nmol/L KOH溶液为淋洗液,AS19分离柱(250 mm×4 mm)分离,抑制器电流112 mA;钠离子以20 nmol/L甲基磺酸(MSA)为淋洗液,CS12分离柱(250 mm×4 mm)分离,抑制器电流59 mA;两者分离采用的其他相同色谱条件为: 柱温、检测器温度30 ℃,电导检测器检测,进样量25 μL,流量1 mL/min,峰面积定量。氯离子的检出限为0.005 mg/L,在0～5 mg/L范围内有良好的线性关系（r2=0.999988）;钠离子的检出限为0.001 mg/L,在0～5 mg/L范围内有良好的线性关系（r2=0.999926）。氯离子平均加标回收率为94.2%,相对标准偏差(RSD)为2.4%;钠离子平均加标回收率为92.5%, RSD为2.7%。经测定、计算,正常食用油中钠离子和氯离子的物质的量比约为1,而“地沟油”中钠离子与氯离子的物质的量比高于4。“地沟油”中钠离子和氯离子的含量及其比例关系可作为判断“地沟油”的重要依据。     

Evaluation of gas chromatography coupled with ion mobility spectrometry for monitoring vinyl chloride and other chlorinated and aromatic compounds in air samples

The objective of this research was to evaluate, in the laboratory, the potential of gas chromatography/ion mobility spectrometry (GC/IMS) for monitoring vinyl chloride and other organic compounds in air samples in the field. It was determined that GC/IMS has the potential to directly detect vinyl chloride in air at the 2 ppbv level, and when concentrated on an adsorbent trap from a 1 L sample of air, detection could be lowered to the 0.02 ppbv level. From a comparative investigation of 18 EPA priority pollutants and 34 common vapor-phase organic compounds, many compounds were found to provide a more sensitive response in IMS than vinyl chloride, indicating that GC/IMS would be broadly applicable to the direct detection of vapor-phase organics in air. Operating parameters including drift gas, spectrometer temperature, and sample-inlet position were evaluated and discussed with respect to sensitivity and resolution. High temperature dramatically increased sensitivity to vinyl chloride. Vinyl chloride was shown to produce both negative and positive ion mobility spectra, with the negative-mode spectra resulting from electron-capture dissociation of the vinyl chloride. The limit of detection for vinyl chloride was found to be 7 pg/s. Limits of detection for 18 EPA priority pollutants were determined and compared to vinyl chloride. The responses of 34 other vapor-phase organic compounds were also compared to that of vinyl chloride. Non-selective, positive-ion detection of 30 of the 34 compounds was demonstrated along with selective, electron-capture-type detection of 29 of them. Chloride-specific and bromide-specific detection illustrated the advantages of selected-ion monitoring in IMS.     

顶空气相法测定氯乙烯生产过程产生的盐酸溶液中的乙炔和氯乙烯

 采用顶空气相法测定了氯乙烯生产过程产生的盐酸溶液中的乙炔和氯乙烯。使用氢氧化钠将试样中的氯化氢中和 ,从而消除其在气相分析乙炔和氯乙烯中的影响。顶空平衡温度为 35℃ ,平衡时间为 4 5min ,柱为填充了GDX 2 0 2固定相的 2m× 3mmi d 不锈钢柱 ,柱温 14 0℃。顶空气体进样量为 1mL。以外标法定量 ,乙炔含量测定结果的相对标准偏差为 0 85 % ;当其含量为 30 0 μg/g～ 15 0 μg/g时 ,回收率为 98 9%～10 3%。氯乙烯含量测定结果的相对标准偏差为 1 4 % ;当其含量为 2 0 0 μg/g～ 10 0 μg/g时 ,回收率为 98 8%～10 2 %。     

Quantitative analysis of chloride in brackish water: an application to the hyperchromic effect of copper(II) ion with chloride ion.

A new modified method was applied to the determination of chloride anion in brackish water by using a common copper(II) sulfate solution and a spectrophotometer. The result of the quantitative analysis demonstrated that chloride concentrations were 1.61% w/v and 1.74% w/v at ebb tide and flood tide, respectively, of the Muya River. On the other hand, chloride concentrations were 1.17% w/v at ebb tide and 1.65% w/v at flood tide of the Yoshino River. The new method proved that chloride concentration corresponded well with results from Mohr and conductive methods. Therefore, the newly developed method can be exploited as common means to measure chloride concentration in aqueous solutions. Moreover, it is also valuable for application to other types of environmental samples.     

Plasmonic photocatalytic system using silver chloride/silver nanostructures under visible light

Plasmonic photocatalytic nanostructured system was investigated on silver chloride/silver nanoparticles under visible light. Silver chloride/silver nanoparticles were readily prepared using dispersing agent and light irradiation. The d-spacing analysis, high resolution-transmission electron microscopy, X-ray diffraction analysis and diffuse-reflectance spectroscopy demonstrated that silver nanoparticles were introduced on the surface of silver chloride nanoparticles and then silver chloride/silver nanostructured photocatalytic materials were successfully synthesized. The as-synthesized plasmonic photocatalysts exhibited the enhanced photocatalytic performance over nitrogen-doped titania nanomaterials. The improved catalytic activity was originated from the enhanced adsorption for visible light, electron–hole separation, and the formation of chloride atoms in silver chloride/silver nanostructured materials.     

Capillary electrophoresis determinations of trace concentrations of inorganic ions in large excess of chloride: soft modelling using artificial neural networks for optimisation of electrolyte composition

In this work, using a combination of experimental design (ED) and artificial neural networks (ANN), the composition of a triethanolamine-buffered chromate electrolyte was optimised for determination of sulphate anions in the presence of high chloride excess. The optimal electrolyte, allowing a baseline-resolved separation of sulphate from chloride present in a 1500 multiple excess in less than 170 s, consists of 10 mmol/L CrO(3), 2 mmol/L hexamethonium hydroxide, 10% methanol, and triethanolamine added to adjust the pH to 8.0. The method is suitable to a wide concentration range of chloride (4-1757 mg/L) and sulphate (4-590 mg/L) with linear calibration plots (R(2) = 0.9937-0.9999). Relative standard deviations are less than 2.0% for both anions for migration times and peak areas. The detection limits (hydrodynamic injection of 1 s) were 0.6 mg/L for sulphate and 0.5 mg/L for chloride. The method was successfully applied to determination of sulphate in mineral waters containing a high chloride concentration and to determination of sulphate traces in an anticancer drug injection preparation containing a physiological level of chloride. It was shown that alpha-cyclodextrin as an electrolyte additive has a significant potential for further increasing the separation selectivity for inorganic anions.     

THERMOLUMINESCENCE EVIDENCE FOR CHLORIDE REQUIREMENT IN THE S2→S3 TRANSITION OF THE WATER-SPLITTING SYSTEM

Abstract— The role of chloride in photosynthetic oxygen evolution was investigated by means of thermoluminescence measurements. It was found that chloride depletion in isolated chloroplasts almost completely abolished the B₁ thermoluminescence band (S₃Q_B⁻ recombination) but diminished only slightly the amplitude of the B₂ band (S₂Q_B⁻ recombination). The B₂ band could be excited to full intensity by the first flash of a flash series and subsequent flashes caused no further change in the amplitude of the band. These observations suggest a block in the S₂→S₃ transition of the water-splitting system in chloride-depleted chloroplasts. Readdition of chloride provided evidence that the inhibitory effect of chloride removal is reversible.     

Friedel–Crafts polymerization of fluorene with methylene chloride,methoxyacetyl chloride,and chloromethyl methyl ether

The polymerization of fluorene with various chloromethylating reagents (methylene chloride, methoxyacetyl chloride, and chloromethyl methyl ether) in the presence of aluminum chloride was studied. The products that were obtained were insoluble, infusible, colored powders which contain a low concentration of aromatic radicals. Each of the polymers is composed predominantly of fluorene nuclei bridged at the 2 and 7 positions by methylene groups. In addition, the materials possess varying amounts of crosslinked and ring-fused moieties. Based on physical and spectral properties and reaction stoichiometry, the fluorene/methylene chloride polymer is the most highly crosslinked of the three. The fluorene/methoxyacetyl chloride and fluorene/chloromethyl methyl ether polymers are similar to each other in most respects.     

Arylation of Quintones with Aryl Mercuryl Chloride Catalyzed by Lithium Palladium Chloride

Treatment of benzoquinone/naphthoquinone with aryl mercury chloride in the presence of palladium chloride and lithium chloride gives the corresponding aryl substituted benzoquinone/naphthoquinone at the quinonoid position.     

聚二烯丙基甲基苄基氯化铵的合成及粘度行为

以甲胺、烯丙基氯、NaOH、氯化苄和偶氮二异丙基咪唑啉盐酸盐为原料,合成了聚二烯丙基甲基苄基氯化铵(PDAMABC),采用FT IR、1H NMR和元素分析对其结构进行表征,并考察了其在氯化钠、氯化钾、溴化钾、氯化钙、氯化镁、硫酸镁和硫酸钠溶液中的粘度行为。 将所得水相和低沸点馏分回用,二烯丙基甲基胺的收率从72.79%提高至83.41%;以水与乙醇为混合溶剂（V（H2O）∶V（C2H5OH）为1∶3~2∶3）,合成的二烯丙基甲基苄基氯化铵收率较高且水溶性好。 PDAMABC的比浓粘度随外加盐浓度增加而降低。 在0.1 mol/L NaCl溶液中,当其质量浓度低于0.031 25 g/L时,表现为聚电解质行为;质量浓度大于0.125 g/L时,表现为中性聚合物的粘度行为。 外加盐对比浓粘度的影响顺序为：Na2SO4＜NaCl＜KCl＜MgSO4＜MgCl2＜CaCl2＜KBr。 阴离子的屏蔽作用是导致比浓粘度降低的主要原因。     

Repetitive determination of chloride using the circulation of the reagent solution in closed flow-through system

The precipitation reaction of silver chloride (AgCl) is carried out in a large amount of ammonia (NH₃). This makes possible to adopt a closed-loop flow injection (FI) system and to determine chloride repetitively. A solution of 30 mmol l⁻¹ silver nitrate and 80 mmol l⁻¹ NH₃ in a single reservoir (250 ml) is continuously circulated through the flow cell at a flow rate of 2.0 ml ml⁻¹. The chloride containing sample (100 μl) was introduced into this reagent solution by means of six-way valve. AgCl precipitates formed in the sample zone are monitored spectrophotometrically (at 500 nm) in the flow system. After passing through the flow cell, the excess NH₃ in the circulating reagent solution dissolves AgCl precipitates and the stream then returns to the reservoir. Various variables of the FI system were optimized and a study of interfering ions was also carried out. A linear calibration graph was obtained from 3.0 to 30 mg l⁻¹ chloride. Two hundred repetitive injections of 5.0 mg l⁻¹ chloride into the circulating reagent solution have shown unchanged base-line and good reproducibility. The method was successfully applied to the determination of chloride in tap, natural and the reference waters.     

Chlorinated Organic Compound Removal by Gas Phase Pulsed Streamer Corona Electrical Discharge with Reticulated Vitreous Carbon Electrodes

Trichloroethylene (TCE) and vinyl chloride (VC) removal by gas phase pulsed corona discharge was investigated with attention to energy efficiency and byproduct identification. Approximately 50–95% removal of TCE and vinyl chloride was observed, depending on the energy density applied to the gas. Water vapor reduced TCE removal in some experiments. Evidence was found for post-corona reactions leading to removal of vinyl chloride downstream of the plasma discharge, while significant post-corona removal of TCE was not observed. Removal efficiencies of 100–900 g/kW-hr in the case of 1000 ppm feed of TCE, and of 2–24 g/kW-hr for a 100 ppm feed of vinyl chloride were found. In the TCE experiments, the formation of dichloroacetyl chloride was observed, while an unknown byproduct was found with vinyl chloride. The addition of a platinum-rhodium coated electrode was found to reduce the post-corona removal of vinyl chloride at low energy density.     

pH/Cl-复合探针技术对钢筋混凝土电化学除氯的原位检测

采用恒电流法电化学除氯处理受氯离子污染的钢筋混凝土试样,并用pH/Cl^-复合探针原位检测电化学除氯过程钢筋混凝土不同位置孔隙液的氯离子含量与pH值分布,同时用线性极化曲线和交流阻抗谱图等电化学技术考察钢筋的腐蚀性能,探讨电化学除氯过程的混凝土微环境和钢筋腐蚀速率. 研究结果表明：在电化学除氯过程,混凝土孔隙液的氯离子浓度逐降,而pH值在初期略有升高,随之其pH值略降;电化学除氯施加的阴极电流,使钢筋处于阴极极化状态而得到保护;除氯停止（即退极化）后钢筋的腐蚀电位明显正移,腐蚀电流降低,极化电阻升高,表明电化学除氯能改善钢筋的腐蚀环境,降低钢筋的腐蚀速率.