碘-聚乙烯醇显色法标定硫代硫酸钠溶液

聚乙烯醇和碘能够发生显色反应，在碘量滴定法的一些测定中，可以用聚乙烯醇代替淀粉作指示剂指示终点。分别用碘、碘酸钾作基准试剂，聚乙烯醇、淀粉作指示剂，对硫代硫酸钠溶液进行标定，测定结果基本一致。     

Assessment of the relationships between iodine isotopes (127I, 129I) and atmospheric elements in precipitation from Sweden

In order to assess the relationships between iodine isotopes (¹²⁷I, ¹²⁹I) and atmospheric elements, the concentrations of chlorine and bromine were determined using high resolution inductively coupled plasma mass spectrometry with an X SeriesII ICPMS (Thermal Electron Corporation) machine for precipitation samples collected during the period 2000–2006 at three different stations (Abisko, Uppsala and Kvidinge) in Sweden. For concentration of chlorine, Abisko in the north has the lowest average concentration, 0.6 mg/L, Kvidinge showing a little higher, 1.13 mg/L, and Uppsala exhibits as the highest concentration, 2.93 mg/L. As to bromine, the median concentration was 3.07, 3.43 and 4.73 μg/L for station Abisko, Uppsala and Kvidinge, respectively. Chlorine and bromine show the highest correlation with ¹²⁷I in Kvidinge (r < 0.7) than those in Uppsala and Abisko. The different correlations of ¹²⁷I–Cl and ¹²⁹I–Cl, or ¹²⁷I–Br and ¹²⁹I–Br are attributed to their respective sources to the atmosphere. Furthermore, the results show that iodine isotopes (¹²⁷I, ¹²⁹I) have high correlations with Cl and Br than the other atmospheric elements.     

A sensitive extracto-photometric method for determination of residual chlorine in greywater

A new photometric method for chlorine determination based on the oxidative transformation of iodide to iodine and subsequent extraction in ethyl acetate has been developed. The effects of several chemical variables (pH, ionic strength, and iodide concentration) have been studied. Characteristics of the method were linear range 0-0.6 mg C12/L, limit of detection 5 microg Cl2/L, and coefficient of variation 0.6%. The method has been applied to greywater without previous sample treatment.     

Effect of the molecular weight of poly(vinyl alcohol) on the water stability of a syndiotactic poly(vinyl alcohol)/iodine complex film

To precisely identify the effect of the molecular weight of syndiotactic poly(vinyl alcohol) (s-PVA) on the water stability of a s-PVA/iodine complex film, we prepared four s-PVAs with similar syndiotactic diad (s-diad) contents of about 63% and with different number-average degrees of polymerization, P_n, of 900, 6,000, 10,000, and 17,000, respectively. The desorption behavior of iodine in the s-PVA/iodine complex film in water was investigated in relation to the solubility of s-PVA in water. The degree of solubility of a s-PVA film having different P_n in water at 80 °C was limited to about 0.3-10%, whereas the degrees of solubility of atactic PVA films with P_n of 6,000 and 10,000 were 100% at the same conditions. The degree of iodine desorption of the complex film decreased with increasing P_n of s-PVA. Especially, the degree of iodine desorption of a PVA drawn film having P_n of 17,000 was limited to 2%, regardless of soaking temperature from 40 to 80 °C. The desorption of iodine in water was strongly affected by the dissolution of PVA. In addition, the degree of iodine desorption of the drawn s-PVA/iodine film was larger than that of the undrawn one.     

Iodometric determination of milligram and microgram amounts of levocetirizine in pharmaceuticals

Four simple, selective and sensitive methods are described for the determination of levocetirizine dihydrochloride (LCT) in bulk drug and in tablets. The methods exploit the well-known analytical reaction between iodide and iodate in the presence of acid solution. Iodide present is oxidized by iodate in an amount equivalent to the HCl present in LCT to iodine and the liberated iodine is determined by four different procedures which inturn quantify LCT at varying detection range and sensitiveness. Two direct titrimetric procedures involve titration of iodine by thiosulphate either towards starch end point (method A) or potentiometrically (method B). Both the methods have a reaction stiochiometry of 1: 1 (LCT: liberated iodine) and have quantification ranges of 2–20 mg LCT for method A and method B. The liberated iodine is also measured spectrophotometrically at 350 nm (method C) or the iodine-starch complex measured at 570 nm (method D). In both the methods, the absorbance is found to be linearly dependent on the concentration of iodine which in turn is related to LCT concentration. The calibration curves are linear over 5–40 and 1.25–12.5 mg mL^?1 LCT for method C and method D, respectively. The calculated molar absorptivity and Sandel sensitivity values are 1.0 × 10⁴ L mol^?1 cm^?1 and 0.0435 mg cm^?2, respectively for method C, and their respective values for method D are 2.9 × 10⁴ L mol^?1 cm^?1 and 0.0156 mg cm^?2. The intra-day and inter-day accuracy and precision studies were carried according to the ICH guidelines. The method was successfully applied to the analysis of two brands of tablets LCT. The accuracy was also checked by placebo blank and synthetic mixture analyses besides recovery study via standard addition procedure.     

Eicosapentaenoic acid (EPA) Production byMortierella alpina ATCC 32222

Mortierella alpina ATCC 32222 grew well at 11 degrees C, as well as at 25 degrees C in a liquid medium containing glucose or linseed oil and yeast extract. High Eicosapentaenoic acid (EPA) yield was obtained at 11 degrees C. M. alpina cells did not produce EPA at 25 degrees C in the absence of linseed oil, whereas at 11 degrees C, EPA accumulation was noted in the absence of linseed oil. When grown at 11 degrees C for 10 d in a medium containing 2% linseed oil as carbon source, the mycelium yielded 435 mg/L EPA (20 mg EPA/g dry mycelia) with 5.1% in lipid fraction. By gradually increasing the concentration of linseed oil to 4%, yield of biomass and EPA were increased to 43 g/L and 596 mg/L, respectively.     

Flow-injection potentiometric determination of residual chlorine in water

Residual chlorine is measured in water by using a potentiometric system composed of an iodide-selective electrode and a platinum electrode sensing the iodine-iodide ratio. When the sample is added to acidified iodide solution, the cell response is in a logarithmic relation to the iodine concentration which in turn depends on the concentration of residual chlorine. In the flow injection system evolved, 0.1–5.0 mg l^-1 residual chlorine can be determined at a rate of 40–60 samples per hour. The results of potentiometric determinations of residual chlorine in tap water compared to spectrophotometric results suggest that the presence of various organic substances is responsible for discrepancies between these measurements.     

Differentiation of the halogen content of peat samples using ion chromatography after combustion (TX/TOX-IC)

The proposed method for the differential AOX analysis of water samples was tested for its applicability to differentiate the halogen content of peat samples. For determination of the total and the total organic-bound chlorine, bromine and iodine, peat samples were combusted, and the combustion gases trapped and analyzed by ion chromatography (TX/TOX-IC). The total and the organically bound chlorine, bromine and iodine, respectively, can be determined by two-fold analysis with deviations of around 10%. With respect to chlorine more than a double determination could be required. The limit of quantification is 20 mg kg(-1) for chlorine, 2 mg kg(-1) for bromine and 1 mg kg(-1) for iodine, if 25 mg of peat is combusted. The most crucial step of the analysis is the inorganic halogen removal, which is necessary if the organically bound fraction is determined. However, there are some uncertainties about the complete removal of the inorganic halides from the solid samples. Thus, the values of the organically bound fraction have to be discussed as maximal concentrations. Nevertheless, we suggest that the applied method can be useful as a tool for studying the fate of halogens in soils.     

TMB目视比色法检测水中余氯的改进

为解决GB/T 5750.11-2006生活饮用水标准检验方法中的3,3',5,5'-四甲基联苯胺(TMB)目视比色法检测余氯时出现的评价方法准确性欠佳、TMB显色剂发黄、显色体系偏绿等问题,对TMB目视比色法的评价方法、TMB显色剂的配制条件和水样的检测条件进行了研究。结果表明,次氯酸钠不宜作为余氯标准物质来评价TMB目视比色法的改进效果,而通过检测显色体系的A450和目视比色值相结合的方法来判断方法改进效果更为准确。采用优级纯浓盐酸和无氯纯水室温搅拌溶解,可使显色剂无色透明,从而解决TMB显色剂发黄的问题,符合国标要求。将显色剂配制用酸(盐酸)的浓度由国标中0.1mol/L变更为0.6 mol/L,可解决余氯显色体系偏绿的问题。显色体系pH变化后,显色时间、显色温度、显色剂用量可仍按照国标方法的要求进行操作。通过以上改进措施,进一步提高了余氯检测结果的准确度。     

Rapid Determination of HAAs Formation Potential of the Reaction of Humic Acid with Chlorine or Chlorine Dioxide

On the basis of gas chromatography(GC) coupled with a short capillary column and an electron capture detector(ECD), a simple and rapid method for the determination of five haloacetic acids(HAAs) in drinking water was developed by the optimization of derivation conditions and the modification of gas chromatographic program. HAAs formation potential(HAAFP) of the reaction of humic acid with chlorine was determined via this method. The major advantages of the method are the simplicity of chromatographic temperature program and the short run time of GC. Dichloroacetic acid(DCAA) and Trichloroacetic acid(TCAA), which were detected in the determination of HAAFP, were rapidly formed in the first 72 h of the reaction of humic acid with chlorine. HAAFP of the reaction of humic acid with chlorine increased with the increase in the concentrations of humic acid and chlorine. The average HAAFP of the reaction of humic acid with chlorine was 39.9 μg/mg TOC under the experimental conditions. When the concentration of humic acid was 4 mg/L, the concentration of HAAs, which were produced in the reaction of humic acid with chorine, may exceed MCL of 60 μg/L HAAs as the water quality standards for urban water supply of China and the first stage of US EPA disinfection/disinfection by-products(D/DBP) rule; when the concentration of humic acid was 2 mg/L, the concentration of HAAs may exceed MCL of 30 μg/L HAAs for the second stage of US EPA D/DBP rule. When humic acid was reacted with chlorine dioxide, only DCAA was detected with a maximum concentration of 3.3 μg/L at a humic acid content of 6 mg/L. It was demonstrated that the substitution of chlorine dioxide for chorine may entirely or partly control the formation of HAAs and effectively reduce the health risk associated with disinfected drinking water.     

丹参中3种丹参酮的超临界二氧化碳萃取及液相分析

 用超临界CO2 流体及共溶剂乙醇萃取丹参中的 3种丹参酮 ,分别采用正交设计法和系统法考察了萃取中的主要影响因素 ;采用高效液相法 (HPLC) ,在甲醇 水 (体积比为 80∶2 0 )溶液为流动相和检测波长为 2 80nm的条件下 ,以外标法检测了萃取产物中 3种丹参酮的含量。实验得到的最佳条件为 :萃取压力 2 0MPa ;萃取温度 4 5℃ ;分离温度 35℃ ;共溶剂 95 % (体积分数 )乙醇 ;流量 1 0mL/min。建立的HPLC测定方法简便快捷 ,准确度高 ,重现性良好 ,相关系数r为 0 9994～ 0 9998,相对标准偏差RSD为 2 37%～ 3 4 7%。     

Formation of poly(vinyl alcohol)–iodine complexes in solution

The effect of the dissolved state of poly(vinyl alcohol) (PVA) molecules in water on the color development due to PVA–iodine complexes was investigated at each given PVA and iodine concentration using two kinds of syndiotactic-rich PVA (S-PVA) which are unstable in water because of the formation of intermolecular hydrogen bonds and form the complex easily. In the reaction mixtures prepared by mixing PVA solutions and an iodine solution, the color development was constant and independent of standing time of the PVA solution before the addition of iodine up to a certain time, after which it decreased with the standing time. The color development obtained with use of the PVA solution allowed to stand for a fixed time was higher for S-PVA with a lower s-(diad)%. In the case of the reaction mixture prepared by dissolving PVA in an iodine solution, the color development was higher for S-PVA with a higher s-(diad)%. The initial ratio of the I₅⁻/I₃⁻ and the rate of decrease in the ratio of I₅⁻/I₃⁻ were larger than those in the preceding case. The color development decreased for the PVA with an s-(diad) % of 58, whereas it increased for the PVA an s-(diad) % of 61.3 with increasing propanol content, an inhibitor of gelation. From these results, the aggregates of PVA molecules have been assumed to play an important role in forming the complexes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1701–1709, 1997     

Coulometric titration of antimony with electrogenerated iodine

A method is described for the coulometric titration of tripositive antimony with electrogenerated iodine, in a buffered solution of pH 8. The end-point can be detected either amperometrically, potontiometrically, or (less precisely) visually with starch indicator. Quantities of antimony between 0.06 and 10 mg are titratable with an average error of 0.001 to 0.01 mg.     

Complexation of polyvinyl alcohol with iodine Analytical precision and mechanism

Polyvinyl alcohol (PVA), boric acid and tri-iodide form a characteristic blue complex. For a number of PVA samples, prescribed conditions were used to examine the precision of the formation and spectrophotometry of the complex. The precision of calibration curves was 1-2 % over the range 0-4 mg of PVA per 50 ml of final solution, over which Beer's law holds. Greater deviations can be caused by faulty preparation and aging of individual PVA solutions. The absorbance is independent of the content of residual acetate groups in the PVA for the range 0-15 %. The limit of detection is about 0.01 mg of PVA in 25 ml of sample. A pink colour in the system is due to association of iodine with acetate groups in the PVA. A blue or green colour is due to helical envelopment of iodine molecules by PVA chains stiffened by scattered cyclic groups. The mechanisms of these effects are discussed.     

Chlorine Dioxide–Iodine–Ethyl 2-Chloroacetoacetate Oscillation Reaction Investigated by UV–Vis and Online FTIR Spectrophotometric Methods

In order to study the chemical oscillatory behavior and mechanism of a new chlorine dioxide–iodine–ethyl 2-chloroacetoacetate reaction system, a series of experiments were carried out by using UV–Vis and online FTIR spectrophotometric methods. The initial concentrations of ethyl 2-chloroacetoacetate, chlorine dioxide, iodine, sulfuric acid, and the pH value have great influence on the oscillations observed at wavelength of 585 nm for the starch–triiodide complex ( \( \text{QI}_{3}^{ - } \) ). There is a pre-oscillatory or induction stage, the amplitude and the number of oscillations are associated with the initial concentration of reactants. Equations were obtained for the starch–triiodide complex reaction rate change with reaction time and the initial concentrations in the oscillation stage. The intermediates were detected by the online FTIR analysis. Based upon the experimental data in this work and in the literature, a plausible reaction mechanism was proposed for the oscillation reaction.     

Ultraviolet photodissociation of iodine monochloride (ICl) at 235, 250, and 265 nm

ICl photolysis in the ultraviolet region of the spectrum (235-265 nm) is studied using the Slice Imaging technique. The Cl?((2)P(1/2))/Cl((2)P(3/2)) and the I?((2)P(1/2))/I((2)P(3/2)) branching ratio between the I((2)P(3/2)) + Cl((2)P(3/2))∕Cl?((2)P(1/2)) and I?((2)P(1/2)) + Cl((2)P(3∕/2))∕Cl?((2)P(1/2)) channels is extracted from the respective iodine and chlorine photofragment images. We find that ground state chlorine atoms (Cl((2)P(3/2))) are formed nearly exclusively with excited state iodine atoms (I?((2)P(1/2))), while excited spin-orbit chlorine atoms (Cl?((2)P(1/2))) are concurrently produced only with ground state iodine atoms (I((2)P(3/2))). We conclude that photolysis of ICl in this UV region is a relatively "clean" source of spin-orbit excited chlorine atoms that can be used in crossed molecular beam experiments.     

Combined biologic (anaerobic-aerobic) and chemical treatment of starch industry wastewater

A combined biologic and chemical treatment of high-strength (total chemical oxygen demand [CODtot] up to 20 g/L), strong nitrogenous (total N up to 1 g/L), and phosphoric (total P up to 0.4 g/L) starch industry wastewater was investigated at laboratory-scale level. As a principal step for COD elimination, upflow anaerobic sludge bed reactor performance was investigated at 30 degrees C. Under hydraulic retention times (HRTs) of about 1 d, when the organic loading rates were higher than 15 g of COD/(L.d), the CODtot removal varied between 77 and 93%, giving effluents with a COD/N ratio of 4-5:1, approaching the requirements of subsequent denitrification. The activated sludge reactor operating in aerobic-anoxic regime (HRT of about 4 d, duration of aerobic and anoxic phases of 30 min each) was able to remove up to 90% of total nitrogen and up to 64% of COD tot from the anaerobic effluents under 17-20 degrees C. The coagulation experiments with Fe(III) showed that 1.4 mg of resting hardly biodegradable COD and 0.5 mg of phosphate (as P) could be removed from the aerobic effluents by each milligram of iron added.     

Simple flow injection system for colorimetric determination of iodate in iodized salt

This work presents a flow injection (FI) system that was developed for determination of iodate. The system utilizes the oxidation of iodide by the analyte to iodine, which subsequently forms tri-iodide. In the presence of starch, the blue I₃⁻–starch complex is developed within the sample zone and can be colorimetrically detected at 590 nm. Optimization was carried out to make the system suitable for quantitating iodate added to table salts. To prevent accumulation of the blue complex residue on walls of tubing and the flow cell, a port was placed in the system for injection of 10⁻³ M thiosulfate plug (100 μl). An injection of this cleaning solution after each sample injection is recommended to avoid positive baseline shift. By means of the paired t-test, the amounts of iodine (mg I kg⁻¹) were statistically compared with the results determined by titration and by iodide ion selective electrode. No significant disagreement at 95% confidence was observed. The proposed system is very simple, uses common chemicals and provides rapid analysis (65 injections per h) with high precision (R.S.D.=0.66%, n=10). A detection limit of 2 mg I kg⁻¹ salt can be achieved.     

An extraordinarily rapid polymerization of vinylpentafluorocyclopropane: highly stereo- and regioselective synthesis of unsaturated fluoropolymers

Vinylpentafluorocyclopropane 1 was prepared from the reaction of 1,1,2-trifluoro-4-bromobutene and hexafluoropropylene oxide at 190 degrees C, following by treatment with KOH. 1 is stable at low temperature (-40 degrees C) for 7 years, but it rearranged readily to 2,3,3,4,4-pentafluorocyclopentene-1, 2, at above 80 degrees C (Ea = 28.7 kcal/mol). Under radical conditions, 1 extraordinarily rapidly polymerizes to give highly crystalline Z-fluoropolyolefin (CF2CF2CF=CHCH2)n, 3, which is very useful for cross-linking and grafting but difficult to obtain by other means. The stereochemistry of 3 was further confirmed by radical addition of iodine to 1 to form Z-ICF2CF2CF=CHCH2I, 4, exclusively. The rapid polymerization with high stereoselectivity and regioselectivity could be rationalized by effects of a favorable polar transition state of a high ring strain and electron-deficient pentafluorocyclopropyl and a relative electron-rich double bond of 1.     

Short branching in poly(vinyl alcohol). III. Some properties of model polymers of short-branched poly(vinyl alcohol)

Melting point, the iodine color reaction, and foam fractionation were studied on model poly(vinyl alcohol) (PVA) having short branches of one or two monomer units in length. An increase in the amount of short branching units caused a marked decrease in color intensity of the PVA–iodine reaction and in the melting point. These tendencies were more remarkable when the short branching was two monomer units in length than when it was one monomer unit. It was also found that foam fractionation of an aqueous PVA solution produced PVA fractions with different degree of short branching, the degree increasing with increase in the fraction number. The color intensity of the PVA–iodine reaction has been confirmed to decrease with increase in the fraction number, but this result cannot be explained solely in terms of the short branching. It is concluded that the phenomenon of foam fractionation of PVA and the iodine color reaction of the fraction appear to be governed by many factors such as molecular weight, stereoregularity, and short branching.