New ionic liquids with the bis[bis(pentafluoroethyl)phosphinyl]imide anion, [(C2F5)2P(O)]2N—Synthesis and characterization

A new series of low melting and hydrophobic ionic liquids (ILs) containing the bis[bis(pentafluoroethyl)phosphinyl]imide anion, [(C₂F₅)₂P(O)]₂N⁻ (FPI), and ammonium, phosphonium, imidazolium, pyridinium or pyrrolidinium cations were prepared and characterized. Their density, viscosity, melting point, glass transition temperature, decomposition temperature and conductivity are discussed. Many of these ionic liquids are liquids at room temperature with melting points below 15 °C, viscosities below 110 mm² s⁻¹ and thermal stabilities above 300 °C.     

3-(Aryl)-2-sulfanylpropenoates of mercury(II) and phenylmercury(II)

Compounds [HQ]₂[Hg(L)₂] and [HQ][PhHg(L)] [where HQ = diisopropylammonium cation; L = pspa, fspa, tspa, where p = 3-(phenyl), f = 3-(2-furyl), t = 3-(2-thienyl), and spa = 2-sulfanylpropenoato] have been prepared by the reaction of mercury(II) acetate or phenylmercury(II) acetate with the corresponding acid in the presence of diisopropylamine in ethanol. The compounds have been characterized by elemental analysis, FAB mass spectrometry and IR and NMR (¹H, ¹³C) spectroscopy. The crystal structures of the [HQ]₂[Hg(L)₂] compounds show the presence of diisopropylammonium cations and [Hg(L)₂]²⁻ anions. In each anion the Hg atom is in an HgO₂S₂ environment and this can be described as nido-tbp. The crystal structures of the [HQ][PhHg(L)] compounds show the presence of diisopropylammonium cations and [PhHg(L)]⁻ anions in which the Hg atom adopts an HgCOS distorted T-environment. The NMR data suggest that the coordination mode of the ligand L²⁻ determined by X-ray diffractometry in the solid remains in solution.     

Ambient temperature imidazolium-based ionic liquids with tetrachloronickelate(II) anions

Deep blue tetrachloronickelate(II) salts of 1-alkyl-3-methylimidazolium cations [C_nmim]⁺ with intermediate chain lengths (n = 5, 7, 8 and an n = 4/6 mixture) have been prepared from imidazolium chlorides and NiCl₂. They are liquid at ambient temperatures (ca. 20 °C) and above, and display viscosities and thermal stability comparable to related [BF₄]⁻ compounds. The similarities may reflect the compensating effects of the dinegative charge of the [NiCl₄]²⁻ ion and its larger size.     

Response of halogenated compounds in ion mobility spectrometry depending on their structural features

Ion mobility spectrometry (IMS) with handheld and transportable devices permits the sensitive detection of chlorinated compounds which are important in environmental monitoring. The ion mobility spectra in negative measuring modus mostly show one product ion peak [(H₂O)_nCl⁻] due to dissociative electron attachments. In this paper, we investigated relevant chlorinated compounds (R-Cl) where R represents allyl-, benzyl-, phenyl-, alkyl- and vinyl-groups. These groups cause differences in the R-Cl bond strength and differences in the cleavage of chlorine can therefore be expected. All chlorinated substances investigated provide the same product ion peak at 2.75 cm² Vs⁻¹ independent on the different C-Cl bond strength. However, distinct influences of structural features on the peak intensities of the (H₂O)_nCl⁻ product ion peak were established. Generally, increasing sensitivities were obtained in the order chlorobenzenes < vinyl- < allyl- < alkyl compounds < benzylchlorides. Sensitivities and limits of detection (LODs) of aromatic compounds depend on the nature and position of second substituent. Electron-withdrawing substituents (chlorine, fluorine, nitrile) enhance sensitivity while electron-repelling substituents decrease it. A dependence of sensitivity on the chain length or ring size can be observed for alkyl compounds. Additional influences of intramolecular interactions on the sensitivity were found for di-halogenated compounds. Therefore, the quantification of negative product ion peaks of chlorinated compounds requires a consideration of structural features of analytes.     

Insight into the cation–anion interaction in 1,1,3,3-tetramethylguanidinium lactate ionic liquid

In order to deepen the understanding of cation–anion interaction in ionic liquids (ILs), the structure and interionic interaction of 1,1,3,3-tetramethylguanidinium lactate ([tmg][L]) ion pair, including stable configuration, hydrogen bond, frontier molecular orbital, electron density, ion interaction energy and charge transfer, are studied by using ab initio calculations. It is found that more charge-localized character of [tmg][L], especially the C1 carbocation on [tmg]⁺, and the intermolecular –NH₂-associated hydrogen bonds can substantially increase the cation–anion interaction, the interaction energy is 65.3–109.3 kJ/mol higher than that of 1-n-butyl-3-methylimidazolium-based ILs. It is also found that the frontier molecular orbitals, i.e., the HOMO, HOMO + 1 of [L]⁻ and the LUMO, LUMO + 1 of [tmg]⁺, can effectively interact and more charges are transferred between cation and anion. Based on the above results, the physical property of ILs is discussed.     

The structure of N-meso-(6,8,8,14,16,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,13-diene)nickel(II) chloro(isothiocyanato)zincate(II)

A yellow compound which was crystallised from a solution of (6,8,8,14,16,16-hexamethyl-1,5,9,13-tetraazacyclohexadeca-5,13-diene)bis(isothiocyanato)nickel(II) in aqueous zinc(II) chloride has cations with singlet ground state nickel(II) in square-planar coordination by the nitrogen atoms of the macrocycle. The asymmetric unit has two similar cations. The N₄ group of one cation is near coplanar (r.m.s. displacements ±0.009(1) Å, with Ni displaced by 0.048(1) Å from this plane) while the other cation has significant tetrahedral twisting of the N₄ group (r.m.s. displacements of N atoms ±0.126(2) Å, with Ni displaced by 0.027(2) Å from this plane). The mean Ni–N distances are Ni–N_amine = 1.950(6) and Ni–N_imine = 1.897(6) Å. Both cations have N-meso configurations with saddle conformations, with the substituted chelate rings in boat conformations tilted to one side of the NiN₄ ‘plane’ and the unsubstituted chelate rings tilted to the other side, one in a boat conformation and the other with the central methylene group disordered, the components forming boat {s.o.f. 0.70(1) and 0.74(1) for the two cations} and chair conformation chelate rings. The counter-ions have tetrahedrally coordinated zinc(II) ions, one as [ZnCl₂(NCS)₂]²⁻ ions and the other with one ligand site with disordered Cl⁻ {s.o.f. 0.78(1)} and NCS⁻ ligands, i.e. with disordered [ZnCl₂(NCS)₂]²⁻ and [ZnCl(NCS)₃]²⁻ ions, with an overall composition of [Ni(trans-Me₆[16]diene)][ZnCl_1.9(NCS)_2.1].     

Use of ion mobility spectroscopy with an ultraviolet ionization source as a vanguard screening system for the detection and determination of acetone in urine as a biomarker for cow and human diseases

An ion mobility spectrometer equipped with an ultraviolet lamp was used for the qualitative and quantitative determination of acetone in urine samples. This analyte can be used as a biomarker for some fat metabolism-related diseases in humans and cows. Samples require no pretreatment other than warming at 80 °C for 5 min, after which an N₂ stream is used to drive volatile analytes to the ion mobility spectrometer. The precision of the ensuing method, expressed as relative standard deviation (%RSD), is better in all cases than 6.7% for peak height and calculated at three levels of concentration. The analyte concentration range studied was from 5 to 80 mg L⁻¹, its limit of detection in the aqueous matrix 3 mg L⁻¹ and recoveries from spiked urine samples 109 ± 3%. The calculated reduced mobility for acetone in the urine samples, 1.75 ± 0.04 cm² V⁻¹ s⁻¹, was similar to previously reported values. Also, the results were consistent with those provided by test strips used for reference. The proposed method provides a new vanguard screening system for determining acetone in urine samples.     

Cu22Bi12S21Cl16—A mixed conductor with fast one-dimensional copper(I) ion transport

Melting reactions of Cu, CuCl, S, and Bi₂S₃ yield black, shiny needles of Cu₂₂₍₁₎Bi₁₂S₂₁₍₁₎Cl₁₆₍₁₎. The compound decomposes peritectically at 649(5) K. Oxidation state +I of the copper atoms is supported by Cu-K-XANES. The compound crystallizes in the hexagonal space group P6/m with a=2116.7(7) pm and c=395.17(5) pm. Seven anions coordinate each of the two independent bismuth cations in the shape of mono-capped trigonal prisms. These polyhedra share edges and faces to form trigonal and hexagonal tubes running along [0 0 1]. The hexagonal tubes are centered by chloride ions, which are surrounded by disordered copper cations. The majority of copper cations are distributed over numerous sites between the tubes. The Joint Probability Density Function (JPDF) reveals a continuous pathway along [0 0 1]. The high mobility of the copper cations along [0 0 1] was demonstrated by impedance spectroscopy and DC polarization measurements on single crystals. The ionic conductivity at 450 K is about σ_ion=0.06 S cm⁻¹, and the activation energy for Cu⁺ ion conduction is E_a=0.44 eV. The chemical diffusion coefficient of copper is in the order of D_cu^δ=10¹⁹ cm⁻³ at 420 K. The electronic band gap (p-type conductor) was determined as E_g=0.06 eV. At room temperature the thermal conductivity of a pressed pellet is about κ=0.3 W K⁻¹ m⁻¹ and the Seebeck coefficient is S=43 μV K⁻¹.     

(27)Al NMR and Raman spectroscopic studies of alkaline aluminate solutions with extremely high caustic content - Does the octahedral species Al(OH)(6)(3-) exist in solution?

²⁷Al NMR and Raman spectra of alkaline aluminate solutions with 0.005 M ≤ [Al(III)]_T ≤ 3 M in various M′OH solutions (M′⁺ = Na⁺, K⁺ and Li⁺) were recorded and analysed. Caustic concentrations up to 20 M were used to explore whether higher aluminium hydroxo complexes are formed at extremely high concentrations of hydroxide. A single peak was observed on the ²⁷Al NMR spectrum of each solution. The chemical shift of this peak shifts significantly upfield with increasing [M′OH]_T in solutions with [Al(III)]_T < 0.8 M. This variation shows a strong dependence on the cation of the solution and practically disappears in systems with [Al(III)]_T ≥ 0.8 M. For Raman spectra of solutions with [Al(III)]_T = 0.8 M and [NaOH]_T ≥ 10 M, the peak maximum of the symmetric ν₁-AlO₄ stretching of Al(OH)₄⁻ shifted progressively from ∼620 to ∼625 cm⁻¹ and decreased in intensity with increasing [NaOH]_T. In parallel, modes centred at ∼720 and ∼555 cm⁻¹ (cf. ∼705 and ∼535 cm⁻¹ at lower [NaOH]_T, ascribed to a dimeric aluminate species appeared, and their intensities increased with increasing [NaOH]_T. These variations in the ²⁷Al NMR and Raman spectra can be interpreted in terms of contact ion-pairs formed between the cation of the medium and the well-established Al(OH)₄⁻ or the dimeric aluminate species. Assumption of higher aluminium hydroxo complex species (e.g., Al(OH)₆³⁻) is not necessary to explain the spectroscopic effects observed.     

Flow injection fluorimetric determination of chromium(VI) in electroplating baths by luminescence quenching of tris(2,2'-bipyridyl) ruthenium(II)

A sensitive and selective luminescence quenching method is developed and used for manual and flow injection analysis (FIA) of chromium(VI) by reaction with [Ru(bpy)₃]²⁺. The emission peak of ruthenium(II) at 595 nm is linearly decreased as a function of Cr(VI) concentration. This permits determination of chromium(VI) ion over the concentration range 0.1-20 μg ml⁻¹ with a detection limit of 33 ng ml⁻¹. The quenching process is due to an electron transfer from the luminescent [Ru(bpy)₃]²⁺ complex ion to Cr(VI) resulting in the formation of the non-luminescent [Ru(bpy)₃]³⁺ complex ion. Selectivity for Cr(VI) over many anions and transition, alkali and alkaline earth metal cations is demonstrated. High concentration levels of sulphate, chloride, borate, acetate, phosphate, nitrate, cyanide, Pb²⁺, Zn²⁺, Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺ and Mn²⁺ ions are tolerated. The effects of solution pH and [Ru(bpy)₃]²⁺ reagent concentration are examined and the reaction conditions are optimized. Validation of the method according to the quality assurance standards show suitability of the proposed method for use in the quality control assessment of Cr(VI) in complex matrices without prior treatment. The method is successfully applied to determine chromium(VI) in electroplating baths using flow injection analysis. Results with a mean standard deviation of ±0.6% are obtained which compare fairly well with data obtained using atomic absorption spectrometry.     

Oxygen/nitrogen ordering in lanthanum new phase (La3Si8N11O4)

High-resolution ¹⁷O NMR spectra have been collected for crystalline samples of lanthanum new phase, La₃Si₈N₁₁O₄. In conjunction with previously published ²⁹Si and ¹⁵N spectra obtained for this phase, and in the light of the high-quality crystal structure data reported recently, a more detailed interpretation of the NMR spectra is presented than was possible in previous studies. The non-bridging oxygens in the structure are responsible for the single sharp peak seen in the ¹⁷O spectrum at 188 ppm; the remaining oxygens, occupying bridging sites shared with nitrogen, show up only weakly on the ¹⁷O spectrum as a broad diffuse band centered around zero ppm. The peak at −57.3 ppm on the ²⁹Si spectrum is believed to correspond to an overlap of [SiN₄] and [SiON₃] environments, with the −68.2 ppm peak corresponding to an [SiO₂N₂] environment.     

Potentiometric membrane sensor based on 6-(4-nitrophenyl)-2,4-diphenyl-3,5-diaza-bicyclo[3.1.0]hex-2-ene for detection of Sn(II) in real samples

A Sn²⁺ ion-selective electrode which was prepared with a polymeric membrane based on 6-(4-nitrophenyl)-2,4-diphenyl-3,5-diaza-bicyclo[3.1.0]hex-2-ene (NDDBH) as a ionophore. Effects of experimental parameters such as membrane composition, nature and amount of plasticizer, the amount of additive and concentration of internal solution on the potential response of Sn²⁺ sensor were investigated. The electrode exhibited a Nernstian slope of 28.8 ± 1.1 mV/decade of Sn²⁺ over a concentration range of 1.0 × 10⁻⁵ to 1.0 × 10⁻¹ M of Sn²⁺ in an acidic solution (pH 1). The limit of detection was 4.0 × 10⁻⁶ M. The results show that this electrode can be used in ethanol media until 20% (v/v) concentration without interference. It can be used for more than 6 weeks without any considerable divergence in the potentials. The proposed membrane electrode revealed very good selectivity for Sn(II) ions over a wide variety of other cations and could be used in acidic media. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode. The stability constant (log K_s) of the Sn(II)-ionophore complex was determined at 25 °C by potentiometric titration in mixed aqueous solution. It was used as indicator electrode in potentiometric determination of Sn(II) ion in real samples.     

Electrochemical determination of iodide on a vanadium oxide-polypropylene carbonate coated glassy carbon electrode

A vanadium oxide-modified glassy carbon electrode was simply and conveniently fabricated by casting vanadium tri(isoproxide) oxide (VO(OC₃H₇)₃) and poly(propylene carbonate) (PPC) onto the glassy carbon electrode surface. The electrochemical properties of iodide at the VO(OC₃H₇)₃-PPC film-modified glassy carbon electrode were investigated by cyclic voltammetry, and an anodic peak was observed at approximately +0.71 V (vs. SCE). Based on this, a sensitive and convenient electrochemical method was proposed for the determination of iodide. Flow injection amperometry (FIA) exhibited a good linear relationship with the concentration of iodide in the range of 5 × 10⁻⁷ mol L⁻¹ and 1 × 10⁻³ mol L⁻¹, and the detection limit was 1 × 10⁻⁷ mol L⁻¹. Quantitative recovery of iodide in synthetic samples has been obtained and the interferences from different cations and anions have been studied. The method has been successfully applied to the determination of iodide in dry edible seaweed. The concentrations of iodide measured by this method are in good agreement with those obtained by spectrophotometric method.     

Oxidation of glyoxylic acid by a mononuclear manganese(IV) complex of 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane: A kinetics and mechanistic study

The oxidation of glyoxylic acid (HGl) by Mn^IVL {L⁴⁻ = tetra deprotonated 1,8-bis(2-hydroxybenzamido)-3,6-diazaoctane} was investigated in the pH range 1.67-10.18, at 25-45 °C and 0.5 M ionic strength. The reaction exhibited biphasic kinetics with Mn^IIIL⁻ as the reactive intermediate. Mn^IV was reduced to Mn^II. The products of oxidation of HGl were identified as formic acid and CO₂ in acidic medium, and oxalate in basic medium, consistent with the stoichiometry: −Δ[Mn^IV]/−Δ[HGl] = 1. In acidic medium, both Mn^IVL and Mn^IIIL⁻ formed outer-sphere adducts with the neutral HGl {HC(OH)₂COOH} molecule, with an association constant Q_av of 28 and 70 M⁻¹, respectively. A similar adduct formation was not observed for the glyoxylate mono anion {Gl⁻, CH(OH)₂(CO₂⁻)} and glyoxylate dianion {Gl²⁻, CH(OH)(O⁻)CO₂⁻}. The rate and activation parameters for the various paths are reported and an outer-sphere electron transfer mechanism is suggested.     

A novel uranyl membrane sensor with potentiometric anionic response

A novel potentiometric uranyl membrane sensor with a divalent anionic response is developed, characterized and used for determination of uranyl ion. The sensor incorporates triethylenetetramine (TETA) as an ionophore in poly(vinyl chloride) matrix membrane (PVC) plasticized with o-nitrophenyloctyl ether (o-NPOE). In strong sulphate test solutions, UO₂²⁺ ion forms a highly stable [UO₂(SO₄)₂]²⁻ anion, extractable in TETA as {(2TETAH)²⁺ [UO₂(SO₄)₂]²⁻} complex. Formation of the complex is confirmed and characterized by elemental analysis, mass spectrometry and infrared spectrometry. Sensor based on this system displays at pH 2.5-3.8 a linear response over the concentration range of 1.0 × 10⁻¹-3.5 × 10⁻⁵ mol l⁻¹ uranium with a near-Nernstian calibration slope of −26.5 ± 0.3 mV decade⁻¹. The lower limit of detection is ∼5 μg ml⁻¹, the lifetime is 12 weeks and negligible interferences are caused by most common cations. Validation of the assay method reveals excellent performance characteristics in terms of sensitivity, selectivity, fast response and potential stability. The sensor is used for the determination of 0.01-7.09 wt% uranium in naturally occurring and certified ore samples. The results show an average recovery of 97.6% and compare fairly well with data obtained using X-ray fluorescence technique.     

Synthesis of novel pyrene discotics for potential electronic applications

Novel pyrene discotics, 6,7,15,16-tetrakis(alkylthio)quinoxalino[2′,3′:9,10]phenanthro[4,5-abc]phenazines, TQPP-[SR]₄, were synthesized efficiently. The HOMO and LUMO energy levels of TQPP-[SR]₄ were estimated to be 5.57 eV and 2.97 eV, respectively. The average saturation hole mobility of TQPP-[C₁₂H₂₅]₄ was ∼10⁻³ cm² V⁻¹ s⁻¹.     

Basic study on the determination of total boron by conversion to tetrafluoroborate ion (BF4) followed by ion chromatography

The basic study on the determination of tetrafluoroborate ion (BF₄⁻) by ion chromatography, and total boron by conversion of boric acid to BF₄⁻ followed by ion chromatography of BF₄⁻ has been carried out. The results of thermodynamic calculations for the system of boric acid (H₃BO₃)-F⁻-H⁺ showed that the mole fraction of BF₄⁻ was higher than 99% at pH lower than 3.5 and 4.5 when the total free fluoride concentration (2[H₂F₂] + 2[HF₂⁻] + [HF] + [F⁻]) was as high as 0.1 and 1.0 M, respectively. The fraction of BF₄⁻ increased with increasing total free fluoride concentration. BF₄⁻ fraction values were higher than 99% at pH 0.75 and at total free fluoride concentration of 0.05 M or higher. BF₄⁻ was hardly formed at pH > 7 even when the total free fluoride concentration was as high as 1.0 M. According to the experimental results, the fraction of BF₄⁻ at pH 0.7-0.8 was 51.2, 95.6 and 96.7% when the total fluoride concentration (2[H₂F₂] + 2[HF₂⁻] + [HF] + [F⁻] + 3[BF₃OH⁻] + 4[BF₄⁻]) was 0.2, 1.0 and 3.3 M, respectively. The formation reaction of BF₄⁻ from boric acid reached an equilibrium state within 20 min regardless of reaction temperature, in the range of 20-50 °C, when the total boron and total fluoride concentrations were 66.7 mM and 1.0 M, respectively. Although BF₄⁻ was formed only under acidic conditions, BF₄⁻, once formed, was very stable under alkaline conditions at least for several hours. We have concluded that BF₄⁻ could be analyzed by ion chromatography using sodium hydroxide solution as an eluent because BF₄⁻ was stable under chromatographic conditions. BF₄⁻ solution prepared from boric acid could be used as a standard solution in the ion chromatographic analysis of BF₄⁻ instead of the sodium tetrafluoroborate (NaBF₄) reagent available commercially, if a discrepancy of about 4-5% was allowed.     

Mixed-ligand ternary complexes of potentially pentadentate but functionally tridentate Schiff base chelates

The potentially pentadentate chelate 2,6-diacetylpyridine-bis(N-methyl-S-methyldithiocarbazate) (Nmedapsme) has been synthesized and structurally characterized by X-ray diffraction. Its reactions with nickel(II) salts did not lead to pentadentate coordinated ligand complexes but ternary complexes of general formula, [Ni(Nmedapsme)(nmesme)L]X·H₂O (L = Br⁻, I⁻; X = I⁻, BF₄⁻) where Nmedapsme binds as a tridentate and nmesme = N-methyl-S-methyldithiocarbazate. The related ternary nickel(II) complexes of formula, Ni(Nmedapsme)(nmetsc)Br₂ has also been prepared and characterized. X-ray crystal structures of [Ni(Nmedapsme)(nmesme)I]I·H₂O and [Ni(Nmedapsme)(nmesme)Br]BF₄·H₂O revealed that, in these complexes, the Nmedapsme ligand acts as a tridentate NNN donor while the distal S-donors are not coordinated. The bidentate (NS) ligand, nmesme coordinates to the nickel(II) ion via the amino nitrogen and the thione sulfur atoms, the sixth coordination site is occupied by an anion. In both complexes, the nickel(II) ion adopts a distorted octahedral configuration. The complex [Cu(nmesme)₂(ONO₂)]NO₃ was obtained from an unsuccessful attempt to complex copper(II) with Nmedapsme. Hydrolysis of the parent Schiff base Nmedapsme occurred during complexation. An X-ray crystallographic structure analysis shows that the complex, [Cu(nmesme)₂(ONO₂)]NO₃ has an approximately square-pyramidal geometry with the two nmesme ligands coordinated to the copper(II) ion as NS bidentate chelating agents via the amino nitrogen and thione sulfur atoms and the fifth coordination position of copper(II) is occupied by a monodentate nitrate ligand.     

Selection of entrainers in the 1-hexene/n-hexane system with a limited solubility

Vapor-liquid equilibria (VLE) have been measured for five 1-hexene/n-hexane/ionic liquid systems and 1-hexene/n-hexane/NMP (N-methyl-2-pyrrolidone) system with a headspace-gas chromatography (HSGC) apparatus at 333.15 K. The ionic liquids investigated were 1,3-dimethylimidazolium tetrafluoroborate [C₂MIM]⁺[BF₄]⁻, 1-butyl-3-methylimidazolium tetrafluoroborate [C₄MIM]⁺[BF₄]⁻, 1-methyl-3-octylimidazolium tetrafluoroborate [C₈MIM]⁺[BF₄]⁻, 1,3-dimethylimidazolium dicyanamide [C₂MIM]⁺[N(CN)₂]⁻ and 1-octylquinolinium bis(trifluoromethylsulfonyl)amide [C₈Chin]⁺[BTA]⁻. It was found that at low feeding concentration of 1-hexene and n-hexane, the separation ability of ionic liquids is in the order of [C₂MIM]⁺[BF₄]⁻ > [C₄MIM]⁺[BF₄]⁻ ≈ [C₂MIM]⁺[N(CN)₂]⁻ > [C₈MIM]⁺[BF₄]⁻ > [C₈Chin]⁺[BTA]⁻, which is consistent with the priori prediction of the COSMO-RS (conductor-like screening model for real solvents) model. But at high feeding concentration, the separation ability of ionic liquids is in the order of [C₂MIM]⁺[BF₄]⁻ < [C₄MIM]⁺[BF₄]⁻ ≈ [C₂MIM]⁺[N(CN)₂]⁻ < [C₈MIM]⁺[BF₄]⁻ < [C₈Chin]⁺[BTA]⁻. The liquid demixing effect should be taken into account. The activity coefficients of 1-hexene and n-hexane at infinite dilution calculated with the COSMO-RS model were correlated using the NRTL, Wilson and UNIQUAC model. In this work the predictive results from the COSMO-RS model and UNIFAC model for the 1-hexene/n-hexane and 1-hexene/n-hexane/NMP systems were compared. The UNIFAC model is one of the most important academic contributions by Prof. Jürgen Gmehling.     

Determination of adrenaline by using inhibited Ru(bpy)3 electrochemiluminescence

Adrenaline was found to inhibit strongly the electrochemiluminescence (ECL) from the Ru(bpy)₃²⁺/tripropylamine system when a working Pt electrode was maintained at 1.05 V (versus Ag/AgCl) in pH 8.0 phosphate buffer. On this basis, a flow injection (FI) procedure with inhibited electrochemiluminescence detection has been developed for determination of adrenaline. The method exhibited a good reproducibility, sensitivity, and stability with a detection limit (signal-to-noise ratio = 3) of 7.0×10⁻⁹ mol l⁻¹ and dynamic concentration range of 2×10⁻⁸ to 1×10⁻⁴ mol l⁻¹. The relative standard deviation was 2.2% for 1.0×10⁻⁶ mol l⁻¹ adrenaline (n=11). The method was successfully applied to the determination of adrenaline in pharmaceutical samples. Moreover, ECL emission spectra, UV-Vis absorption spectra and cyclic voltammograms of Ru(bpy)₃²⁺/tripropylamine/adrenaline were studied. The inhibition mechanism has been proposed as the interaction of electrogenerated Ru(bpy)₃^2+* and the o-benzoquinone derivatives, adrenochrome and adrenalinequinone, at the electrode surface.