Simultaneous determination of three chloroacetic acids,three herbicides,and 12 anions in water by ion chromatography

An ion chromatography method was developed for the simultaneous detection of three soluble herbicides (glyphosate, bentazone and picloram), three chlorine disinfection byproducts (monochloroacetic acid, dichloroacetic acid and trichloroacetic acid) and 12 anions in water (Cl^–, Br^–, SO₄^2–, CO₃^2–, ClO₃^–, ClO₄^–, BrO₃^–, PO₄^3–, NO₂^–, NO₃^–, CH₃COO^– and COO^–). High linearity (r² > 0.996) was observed for all target analytes for each respective concentration range. The limit of detection and limit of quantitation were between 0.21–0.85 and 0.06–25.46 μg/L, respectively. However, the interference effect of Cl^–, NO₃^–, SO₄^2– and CO₃^2– on some target analytes must be considered during the analysis. Sample pre‐treatment by a hydrogen column (H‐column) required to reduce the negative effect of CO₃^2–. Additionally, sample pre‐treatment by a sliver–hydrogen column (Ag–H‐column) is required when Cl^– > 100 mg/L and SO₄^2– < 50 mg/L, and pre‐treatment by both a barium column (Ba‐column) and an H‐column is required when Cl^– > 100 mg/L and SO₄^2– > 50 mg/L. When Cl^– > 100 mg/L, SO₄^2– > 50 mg/L and CO₃^2– > 20 mg/L, the sample pre‐treatment by either an Ag–H–Ba‐column or an Ag–H‐column and Ba‐column is required to minimize interference.     

Screening of seized cocaine samples using electrophoresis microchips with integrated contactless conductivity detection

This study describes the development of a new analytical method for the separation and detection of cocaine (COC) and its adulterants, or cutting agents, using microchip electrophoresis (ME) devices coupled with capacitively coupled contactless conductivity detection (C⁴D). All the experiments were carried out using a glass commercial ME device containing two pairs of integrated sensing electrodes. The running buffer composed of 20 mmol/L amino‐2‐(hydroxymethyl) propane‐1,3‐diol and 10 mmol/L 3,4‐dimethoxycinnamic acid provided the best separation conditions for COC and its adulterants with baseline resolution (R > 1.6), separation efficiencies ranging from (2.9 ± 0.1) to (3.2 ± 0.2) × 10⁵ plates/m, and estimated LOD values between 40 and 150 μmol/L. The quantification of COC was successfully performed in four samples seized by the Brazilian Federal Police Department and all predicted values agree with values estimated by the reference method. Some other interfering species were detected in the seized samples during the screening procedure on ME–C⁴D devices. While lidocaine was detected in sample 3, the presence of levamisole was observed in samples 2 and 4. However, their concentrations were estimated to be below the LOQ. ME–C⁴D devices have proved to be quite efficient for the identification and quantification of COC with errors lower than 10% when compared to the data obtained by a reference method. The approach herein reported offers great potential to be used for on‐site COC screening in seized samples.     

Ion Chromatographic Determination of Anions in Environmental Samples

Abstract

The use of ion-exchange chromatography with an IonPac AS 14 column, 3.5 mM Na₂CO₃/1.0 mM NaHCO₃ eluent and suppressed conductivity detection provides a simple, cost-effective, fast, accurate, and highly sensitive method for the determination of F^?, Cl^?, NO₂ ^?, Br^?, NO₃ ^?, PO₄ ^2?, SO₄ ^2?, and C₂O₄ ^2? at low μ/L levels in environmental samples. Data on sensitivity, selectivity, accuracy, and % relative standard deviation are described. The method is suitable for many environmental applications including atmospheric aerosols (exposed on cellulose, glass fiber, and quartz filters), rainwater, cloud water, potable- and non-potable waters, and carbonated waters. Dominant components of the aerosol were SO₄ ^2?, NO₃ ^?, and Cl^?. Rainwater, on the other hand, has relatively very low concentrations of these three species. The wide-spread concentration range for Cl^? in variety of water samples and the high concentrations for SO₄ ^2? in drinking water are striking. Determination of the anionic composition of carbonated waters revealed a considerable variation of the individual anions.     

Visible Light Excitable SCN− Selective Fluorescence Probe Derived from Thiophene

An efficient fluorescence probe, 4‐methyl‐2,6‐bis((thiophen‐2‐ylmethylimino)methyl)phenol (DFPTMA) and its SCN^? adduct has been synthesized and characterized by different spectroscopic techniques like ¹H NMR,¹³C NMR, QTOF‐MS ES⁺, UV‐Vis and FTIR spectroscopy. Single crystal X‐ray structure of DFPTMA is reported. In presence of SCN^?, DFPTMA exhibits significant fluorescence enhancement (λ_Ex, 455 nm, λ_Em, 504 nm) in aqueous methanol (water‐methanol, 1:4, V/V, 0.1 mol/L HEPES buffer, pH 7.4). Common bio‐relevant anions viz. CH₃COO^?, NO₂^?, NO₃^?, Cl^?, Br^?, I^?, SO₄^2?, HSO₄^?, N₃^?, HAsO₄^2?, Cr₂O₇^2?, H₂PO₄^?, ClO₄^?, NCO^?, CN^?, CO₃^2?, F^?, PO₄^3?, S^2?, HS^? do not interfere in the recognition of SCN^?. Lowest detection limit for SCN^? is 0.88 µmol/L with response time <5 min. The SCN^? assisted enhancement in emission intensity may be attributed to the formation of H‐bond which enhances the rigidity of the molecular assembly.     

Rapid Determination of Trifluoromethanesulfonate and p-Toluenesulfonate by Ion-Pair Chromatography Using a Reversed-Phase Silica-Based Monolithic Column: Application to the Analysis of Ionic Liquids

A method of ion-pair chromatography was developed on a reversed-phase silica-based monolithic column for the fast and simultaneous determination of trifluoromethanesulfonate (CF₃SO₃ ^?) and p-toluenesulfonate (C₇H₇SO₃ ^?). The analysis was performed using a mobile phase of tetrabutylammonium hydroxide?+?citric acid?+?acetonitrile on the Chromolith Speed ROD RP-18e column with direct conductivity detection. The effects of the eluent, column temperature and flow rate on the retention of the anions were investigated. The experimental phenomenon was discussed according to hydrophobic interaction and ion-exchange mechanism in the separation. The optimized chromatographic conditions were selected. The optimized eluent for the separation consisted of 0.2?mmol?L^?1 tetrabutylammonium hydroxide?+?0.10?mmol?L^?1 citric acid?+?9% acetonitrile (pH 5.5). The flow rate was set at 6.0?mL?min^?1. The column temperature was 25???C. Under the optimal conditions, the better separation of CF₃SO₃ ^? and C₇H₇SO₃ ^? was achieved without any interference by other anions (Cl^?, Br^?, I^?, NO₃ ^?, SO₄ ^2?, ClO₃ ^?, BF₄ ^? and PF₆ ^?). The detection limit (S/N?=?3) was 0.28 and 0.71?mg?L^?1 for CF₃SO₃ ^? and C₇H₇SO₃ ^?, respectively. The method has been applied to the determination of CF₃SO₃ ^? and C₇H₇SO₃ ^? in ionic liquids. The spiked recoveries of CF₃SO₃ ^? and C₇H₇SO₃ ^? were 101.1 and 100.2%, respectively.     

A Series of Amino Acid Functionalized Tripodal Hexaamide Anion Receptors: Ion‐Pair‐Assisted Capped‐Cleft Formation by a Pentafluorophenyl‐Functionalized Amide

A new series of tris(2‐aminoethyl)amine (tren)‐based L ‐alanine amino acid backboned tripodal hexaamide receptors (L1–L5) with various attached moieties based on electron‐withdrawing fluoro groups and lipophilicity have been synthesized and characterized. Detailed binding studies of L1–L5 with different anions, such as halides (F^?, Cl^?, Br^?, and I^?) and oxyanions (AcO^?, BzO^? (Bz=benzoyl), NO₃^?, H₂PO₄^?, and HSO₄^?), have been carried out by isothermal titration calorimetric (ITC) experiments in acetonitrile/dimethylsulfoxide (99.5:0.5 v/v) at 298 K. ITC titration experiments have clearly shown that receptors L1–L4 invariably form 1:1 complexes with Cl^?, AcO^?, BzO^?, and HSO₄^?, whereas L5 forms a 1:1 complex only with AcO^?. In the case of Br^?, I^?, and NO₃^?, no appreciable heat change is observed owing to weak interactions between these anions and receptors; this is further confirmed by ¹H NMR spectroscopy. The ITC binding studies of F^? and H₂PO₄^? do not fit well for a 1:1 binding model. Furthermore, ITC binding studies also revealed slightly higher selectivity of this series of receptors towards AcO^? over Cl^?, BzO^?, and HSO₄^?. Solid‐state structural evidence for the recognition of Cl^? by this new category of receptor was confirmed by single‐crystal X‐ray structural analysis of the complex of tetrabutylammonium chloride (TBACl) and L1. Single‐crystal X‐ray diffraction clearly showed that the pentafluorophenyl‐functionalized amide receptor (L1) encapsulated Cl^? in its cavity by hydrogen bonds from amides, and the cavity of L1 was capped with a TBA cation through hydrogen bonding and ion‐pair interactions to form a capped‐cleft orientation. To understand the role of the cationic counterpart in solution‐state Cl^? binding processes with this series of receptors (L1–L4), a detailed Cl^? binding study was carried out with three different tetraalkylammonium (Me₄N⁺, Et₄N⁺, and Bu₄N⁺) salts of Cl^?. The binding affinities of these receptors with different tetralkylammonium salts of Cl^? gave binding constants with the TBA cation in the following order: butyl>ethyl>methyl. This study further supports the role of the TBA countercation in ion‐pair recognition by this series of receptors.     

Anion‐Templated Assembly and Magnetocaloric Properties of a Nanoscale {Gd38} Cage versus a {Gd48} Barrel

The comprehensive study reported herein provides compelling evidence that anion templates are the main driving force in the formation of two novel nanoscale lanthanide hydroxide clusters, {Gd₃₈(ClO₄)₆} ( 1 ) and {Gd₄₈Cl₂(NO₃)} ( 2 ), characterized by single‐crystal X‐ray crystallography, infrared spectroscopy, and magnetic measurements. {Gd₃₈(ClO₄)₆}, encapsulating six ClO₄^? ions, features a cage core composed of twelve vertex‐sharing {Gd₄} tetrahedrons and one Gd???Gd pillar. When Cl^? and NO₃^? were incorporated in the reaction instead of ClO₄^?, {Gd₄₈Cl₂(NO₃)} is obtained with a barrel shape constituted by twelve vertex‐sharing {Gd₄} tetrahedrons and six {Gd₅} pyramids. What is more, the cage‐like {Gd₃₈} can be dynamically converted into the barrel‐shaped {Gd₄₈} upon Cl^? and NO₃^? stimulus. To our knowledge, it is the first time that the linear M‐O‐M′ fashion and the unique μ₈‐ClO₄^? mode have been crystallized in pure lanthanide complex, and complex 2 represents the largest gadolinium cluster. Both of the complexes display large magnetocaloric effect in units of J kg^?1 K^?1 and mJ cm^?3 K^?1 on account of the weak antiferromagnetic exchange, the high N_Gd/M_W ratio (magnetic density), and the relatively compact crystal lattice (mass density).     

Cost‐Efficient Graphitic Carbon Nitride as an Effective Photocatalyst for Antibiotic Degradation: An Insight into the Effects of Different Precursors and Coexisting Ions,and Photocatalytic Mechanism

In this study, the photocatalytic activity of graphitic carbon nitride (g‐C₃N₄) synthesized via different precursors (urea, thiourea, and dicyandiamide) is investigated in the degradation process of tetracycline. Owing to the efficient charge separation and transfer, prolonged radiative lifetime of charge, large surface area, and nanosheet morphology, the urea‐derived g‐C₃N₄ exhibits superior photocatalytic activity for tetracycline degradation under visible‐light irradiation. This performance can compare with that of most reported g‐C₃N₄‐based composite photocatalysts. Through the time‐circle degradation experiment, the urea‐derived g‐C₃N₄ is found to have an excellent photocatalytic stability. The presence of NO₃^?, CH₃COO^?, Cl^? and SO₄^2? ions with the concentration of 10 mm inhibits the photocatalytic activity of urea‐derived g‐C₃N₄, where this inhibitory effect is more obvious for Cl^? and SO₄^2? ions. For the coexisting Cu²⁺, Ca²⁺, and Zn²⁺ ions, the Cu²⁺ ion exhibits a significantly higher inhibitory effect than Ca²⁺ and Zn²⁺ ions for tetracycline degradation. However, both the inhibitory and facilitating effects are observed in the presence of Fe³⁺ ion with different concentration. The h⁺, ^.OH and ^.O₂^? radicals are confirmed as major oxidation species and a possible photocatalytic mechanism is proposed in a urea‐derived g‐C₃N₄ reaction system. This study is of important significance to promote the large‐scale application of g‐C₃N₄ photocatalysts in antibiotic wastewater purification.     

Highly Selective Thiocyanate Electrode Based on Bis‐bebzion Schiff Base Binuclear Copper(II) Complex as Neutral Carrier

Abstract

A highly selective polyvinyl chloride (PVC) membrane electrode, based on N,N′‐(aminoethyl)ethylenediamide bis(2‐benzoideneimine) binuclear copper(II) complex [Cu(II)‐AEBB] as neutral carrier, was prepared for thiocyanate (SCN^?) determination, which displays an anti‐Hofmeister selectivity sequence for a series of anions in the following order: SCN^?>ClO₄ ^?>Sal^? > I^?>NO₃ ^?>Br^?> Cl^?>NO₂ ^?>SO₃ ^2?>F^?>H₂PO₄ ^?>SO₄ ^2?. The electrode exhibited near‐Nernst response for SCN^? with a slope of –59.0 mV/decade over a wide concentration range (8.5×10^?7～6.8×10^?1 mol/L) with a detection limit of –5.0×10^?7 mol/L in pH 5.0 phosphate buffer solution at 25°C. Alternating current (AC) impedance and equivalent circuits were used to investigate the thiocyanate response mechanism of the membrane doped with [Cu(II)‐AEBB].     

Counter‐Anion‐Regulated Mixed‐Valency of Cobalt(II/III) Centers in a Metallosupramolecular Framework

A diamagnetic Au^I₄Co^III₂ hexanuclear complex, [Au₄Co₂(dppe)₂(l ‐nmc)₄]²⁺ ([ 1_{L ‐ nmc} ]²⁺; dppe=1,2‐bis(diphenylphosphino)ethane, l ‐H₂nmc=N‐methyl‐l ‐cysteine), was newly synthesized by the reaction of [Co(l ‐nmc)₂]^? with [Au₂Cl₂(dppe)] and crystallized with different inorganic anions (X=ClO₄^?, NO₃^?, Cl^?, SO₄^2?) to produce ionic solids ([ 1_{L ‐ nmc} ]X_n). Single‐crystal X‐ray analysis revealed that all the solids crystallize in the chiral space group F432 with a face‐centered‐cubic lattice structure consisting of supramolecular octahedra of complex cations. The paramagnetic nature of all the solids was evidenced by magnetic susceptibility measurements, showing the variation of the oxidation states of two cobalt centers in [ 1_{L ‐ nmc} ]ⁿ⁺ from Co^II_1.00Co^III_1.00 for X=ClO₄^? or NO₃^? to Co^II_0.67Co^III_1.33 for X=Cl^?, via Co^II_0.83Co^III_1.17 for X=SO₄^2?. The difference in the Co^II/III mixed‐valences was explained by the difference in sizes and charges of counter anions accommodated in lattice interstices with a fixed volume.     

Selective permeation of plutonium(IV) through supported liquid membrane containing 2-ethylhexyl 2-ethylhexyl phosphonic acid as ion carrier

The selective transport of plutonium across supported liquid membrane using an indigenously synthesized 2-ethylhexyl 2-ethylhexyl phosphonic acid (KSM-17, equivalent to PC 88A) dissolved in dodecane as carrier has been investigated in this work. Laminar type polypropylene hydrophobic microporous membranes were used as solid supports. Transport experiments were carried out to evaluate the effect of varied hydrodynamic and chemical compositions of the system, i.e., stirring speed, carrier concentration, anionic composition (e.g. SO²⁻₄, NO⁻₃, PO³⁻₄, ClO⁻₄, Cl⁻) and acidity of source phase (SP) solution. Transport rates of plutonium from SP solutions of different anionic composition followed the order: ClO⁻₄>NO⁻₃>Cl⁻>SO²⁻₄>PO³⁻₄. Selective permeability of plutonium was observed in the presence of several cationic impurities such as Al, B, Be, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Si, Zn, Ce, Dy, Eu, Gd and Sm. Using this technique, separation of plutonium from laboratory analytical waste was accomplished with an average flux 8.94×10⁻⁶ mol m⁻² s⁻¹ and with an enrichment factor greater than 2. The product solution obtained from this process was in oxalate medium with negligible contamination from other cationic and anionic impurities. From this solution, plutonium was precipitated as Pu-oxalate for further processing. Reusability of the membrane support was found to be satisfactory.     

Naked Eye Detection of Carbonate,Hydroxide, and Cyanide Ions with 1,4′‐Diazaflavonium Bromides: A Simple Spectrophotometric Method for Cyanide Determination

Anion sensor properties of N‐alkyl‐substituted 1,4′‐diazaflavonium bromides in methanol–water were evaluated by UV–vis spectrometry. Pronounced changes were observed in the absorption spectra of all compounds for only OH^?, CO₃^2?, and CN^? among F^?, Cl^?, Br^?, I^?, OH^?, CO₃^2?, NO₃^?, PO₄^3?, CN^?, SO₄^2?, HSO₄^?, HCO₃^?, SCN^?, NO₂^?, and P₂O₇^2? ions. Two new absorption bands at 385 and 685 nm accompanying the distinct color change for OH^?, CO₃^2?, and CN^? ions were observed in case of all compounds. The color changes were from pink to blue for CO₃^2? and OH^? ions and from pink to purple for CN^? ion. Thanks to the distinct color change, the compounds can be used as selective colorimetric anion sensors. Linear changes of absorbance of N‐heptyl‐substituted compound at 385 nm as a function of the ion concentration were used to determine CN^? ion in water samples. Detection and quantification limits of the proposed method were 0.94 and 2.82 mg/L, respectively.     

The Hofmeister Anion Effect on Ionophore‐based Ion‐selective Nanospheres Containing Solvatochromic Dyes

Recently reported ionophore‐based ion‐selective nanospheres contained pH‐independent and positively charged solvatochromic dyes. Here, we evaluate systematically the effect of anions to the fluorescence response of the nanospheres. The anion interference was found significant for anion concentrations above 10 mM. The sensor responses in the presence of various anion background was studied. While target ion (K⁺) causes the fluorescence of the nanospheres to decrease, increasing anion background also leads to lower fluorescence intensity. Lipophilic anions such as ClO₄^?, SCN^?, and I^? exhibited much more interference than hydrophilic anions (e. g., NO₃^?, Cl^?, F^?, SO₄^2?). The trend of the anion interference followed the Hofmeister series. A theoretical model was also demonstrated based on anion adsorption on the surface of the nanospheres.     

Influence of Anions on Electrochemical Properties of Polypyrrole-Modified Electrodes

The influence of anions ClO₄ ^–, NO₃ ^–, Cl^–, SO₄ ^2–, and DDS^– (dodecyl sulfate) on the cyclic voltammetric response of polypyrrole-modified electrodes is studied. The change in the film composition is examined by electron probe microanalysis. It is established that essential changes in the shape of voltammograms take place during cycling if the anions are not sufficiently freely mobile in the polymer film and insertion of cations from the solution is necessary to guarantee electroneutrality of the system. Some differences between the mobility of Cl^– ions and ClO₄ ^– or NO₃ ^– ions are in good agreement with the results of semi-empirical quantum chemical calculations showing that the interaction of Cl^– and Br^– ions with pyrrole oligomers is stronger than that of NO₃ ^– or ClO₄ ^– ions. Nevertheless, it is established that the peak current determined from voltammograms increases linearly with the increase of the scan rate with very high correlation coefficient. It means that it is possible to describe the behavior of ClO₄ ^–, NO₃ ^– and Cl^– ions in the framework of the model of free ions. The redox behavior of the PPy films doped with anions of low mobility such as SO₄ ^2– and DDS^– depends essentially on the nature of cations in the test solution. It is found that the mobility of cations increases in the row Li⁺ < Na⁺ < K⁺ < Cs⁺. The mobility of DDS^– ions in the PPy in ethanolic solution is significantly higher and their electrochemical properties are quite similar to PPy|Cl or NO₃ ^– film in aqueous solution.     

Aroyleneimidazophenazine: A Sensitive Probe for Detecting CN− Anion and its Solvatochromism Effect

A novel electron‐deficient heteroacene 15H‐pyrazino[2″,3″:3′,4′]pyrrolo[1′,2′:1,2]imidazo[4,5‐b]phenazin‐15‐one ( 1 ) has been successfully synthesized and characterized. Compound 1 can selectively recognize CN^? and F^? over other 10 anions including BF₄^?, PF₆^?, Cl^?, SO₄^2?, NO₃^?, I^?, H₂PO₄^?, ClO₄^?, Ac^?, and Br^? in CHCl₃/DMF mixed solvents with dual responses, including absorption signals and fluorescent “turn‐off” effects. CN^? and F^? can be distinguished by the completely quenched fluorescence (for CN^?) and partially reduced fluorescence (for F^?). Especially, compound 1 exhibits higher sensitivity to CN^? than F^? with the response concentration as low as 5.0 × 10^?6 mol/L. Moreover, compound 1 shows very interesting solvatochromism effect, and the CHCl₃ solution of compound 1 is sensitive to triethylamine, and its emission could change from green to red upon the addition of triethylamine, which is attributed to the n–π intermolecular charge‐transfer interaction.     

Use of Ionenes as Capillary Modifiers in the Simultaneous Determination of Azide, Chlorate, and Perchlorate Ions by Capillary Electrophoresis

It was demonstrated that Cl^–, SO₄ ^2-, NO₃ ^-, N₃ ^-, ClO₃ ^–, and ClO₄ ^– ions can be simultaneously and selectively determined by capillary electrophoresis using 2,4-ionene as a capillary modifier. The effect of n-butanol additives to the buffer electrolyte on the migration times of ions was shown. The optimum buffer electrolyte contained 0.5 mM Na₂CrO₄, 0.05% 2,4-ionene, 10%n-butanol, and 7% methanol. It was shown that azide can be identified in wash solutions obtained at the place of lead azide explosion. The detection limit for azide was 1–3 mg/L.     

Extraction-photometric selective determination of trace perchlorates in potable waters

A method is proposed for the selective photometry determination of perchlorates in potable water with a detection limit of 2×10^?3 mg/L is proposed based on the extraction of its ion pair with the astrafloxin cation and absorbance measurements at 540 nm. The following ratios of matrix ions are acceptable (in parentheses): ClO^?, ClO ₂ ^? , ClO ₃ ^? , BrO ₃ ^? (500); I^? (1000); IO ₃ ^? (7000); HCO ₃ ^? , Cl^?,SO ₄ ^2? , NO ₃ ^? , Br^?, Na⁺, K⁺, Ca²⁺, Mg²⁺ (10000). The relative error of determination for ClO ₄ ^? is 20% in the range 4 × 10^-3-1 × 10^?2 mg/L and 10% in the range 1 × 10^-2–5 × 10^?2 mg/L.     

Lattice Effects on the Spin‐Crossover Profile of a Mononuclear Manganese(III) Cation

Six solvated salts of a mononuclear manganese(III) complex with a chelating hexadentate Schiff base ligand are reported. One member of the series, [MnL]PF₆^.0.5 CH₃OH ( 1 ), shows a rare low‐spin (LS) electronic configuration between 10–300 K. The remaining five salts, [MnL]NO₃? C₂H₅OH ( 2 ), [MnL]BF₄?C₂H₅OH ( 3 ), [MnL]CF₃SO₃?C₂H₅OH ( 4 ), [MnL]ClO₄?C₂H₅OH ( 5 ) and [MnL]ClO₄?0.5 CH₃CN ( 6 ), all show gradual incomplete spin‐crossover (SCO) behaviour. The structures of all were determined at 100 K, and also at 293 K in the case of 3 – 6 . The LS salt [MnL]PF₆^.0.5 CH₃OH is the only member of the series that does not exhibit strong hydrogen bonding. At 100 K two of the four SCO complexes ( 2 and 4 ) assemble into 1D hydrogen‐bonded chains, which weaken or rupture on warming. The remaining SCO complexes 3 , 5 and 6 do not form 1D hydrogen‐bonded chains, but instead exhibit discrete hydrogen bonding between cation/counterion, cation/solvent or counterion/solvent and show no significant change on warming.     

Determination of chlorine species by capillary electrophoresis – mass spectrometry

The applicability of CZE with mass spectrometric detection for the determination of four chlorine species, namely chloride and three stable chlorine oxyanions, was studied. The main aspects of the proper selection of BGE and sheath liquid for the CE‐MS determinations of anions with high mobility were demonstrated, pointing out the importance of pH and the mobility of the anion in the BGE. The possibility of using uncoated fused silica capillary and common electrolytes for the separation was shown and the advantage of using extra pressure at the inlet capillary end was also presented. The linear range was found to be 1–100 µg/mL for ClO₃^? and ClO₄^?, 5–500 µg/mL for ClO₂^?, and 25–500 µg/mL for Cl^?, but the sensitivity can be greatly improved if larger sample volume is injected and electrostacking effect is utilized. The LOD for ClO₃^? in drinking water was 6 ng/mL, when very large sample volume was injected (10 000 mbar·s was applied).     

Effect of anions on the dissolution of Al in acid solutions

The effect of Cl^?, Br^?, I^?, ClO₄^?, NO₃^?, HSO₄^?, HCrO₄^? and H₂PO₄^? on the of Al in 2 M HCl is studied by the thermometric method. Three sets of experiments are carried out, which allow the variation of the concentration of the various species in a programmed manner. Dissolution promotion is noted in solutions to which HCl, HBr and H₂CrO₄ are added. The way of action of each of these anions is discussed. Additions of HI, HClO₄, H₂SO₄ and H₃PO₄, on the other hand, first retard and later enhance the dissolution of Al in 2 M HCl, as their concentration in solution is increased. This is related to anion adsorption, which is counterbalanced by increase in acidity. HNO₃ differs from the other tested acids in causing only dissolution retardation. Experiments in which LaCl₃ is added to the test solution indicate that the NO₃^? is adsorbed as such on Al₂O₃. The ability of the various anions to retard the dissolution of Al in 2 M HCl decreases in the succession: NO₃^? (strong)>I^?>HSO₄^?>H₂PO₄^?>Br^?, ClO₄^? (weak)