Kinetics and mechanisms of the redox reaction of hexaaquotitanium(III) and the ethylenediamine tetraacetato titanium(III) complex by aqueous solutions of bromine

At 25°C, I = 1.0 M (CF₃SO₃⁻Li⁺+CF₃SO₃H), [H⁺] = 0.034–0.274 M and λ = 453 nm, the rate equation for the oxidation of Ti(H₂O), ₆³⁺ by bromine was found to be: −d/[Br₂]T/dt=kK/[Br₂][Ti^III]/[H⁺]+K+kK/[Br₃⁻][Ti^III]/[H⁺+K, where k = 9.2 × 10⁻³ M ⁻¹ s ⁻¹ and K = 4.5 × 10⁻³ M. At [H⁺] = 1.0 M, [Br⁻] = 0.05–0.4 M, the apparent second-order rate constant decreases as [Br⁻] increases.

The pH-dependence of the oxidation of Ti^III-edta by bromine is interpreted in terms of the change in identity of the Ti^III-edta species as the pH of the reaction medium changes. The second-order rate constants were fitted using a non-linear least-square computer program with (1/k₀^edta)² weighting into an equation of the form: k₀^edta =k₁+k₂K₁[H⁺]⁻¹+k₃K₁K₂[H⁺]^−2/1+K₁[H⁺[H⁺⁻¹+K₁K₂[H⁺]⁻², with K₁ and K₂ fixed as earlier determined at 9.55 × 10⁻³ and 2.29 × 10⁻⁹ M, respectively, for the oxidation of bromine. k₁=k₂=(3.1±0.32)×10³M⁻¹s⁻¹ k₃=(2.3±0.45)×10⁶N⁻¹s⁻¹.

It is proposed that these electron transfer reactions proceed by univalent changes with the production of Br₂^.− as a transient intermediate. An outer-sphere mechanism is proposed for these reactions. The homonuclear exchange rate for Ti^III-edta+Ti^IV-edta is estimated at 32 M⁻¹ s⁻¹.     

Acidity constants of benzidine in aqueous solutions

The acidity constants of benzidine (Bz) in aqueous solutions determined potentiometrically at 25° were K_a1 = (1.11 ± 0.08) × 10⁻⁵, K_a2 = (1.45 ± 0.12) × 10⁻⁴. The apparent mixed constants in 0.1M sodium nitrate are K_a1 = (5.37 ± 0.28) × 10⁻⁶ and K_a2 = (1.14 ± 0.09) × 10⁻⁴. The ultraviolet spectra were recorded as a function of pH and analysed with these constants to obtain the absorption spectra of H₂Bz²⁺, HBz⁺ and Bz; the corresponding wavelengths of maximal absorption are 247, 273 and 278 nm, and molar absorptivities 1.63 × 10⁴, 1.76 × 10⁴ and 2.26 × 10⁴ 1.mole⁻¹.cm⁻¹.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution—10. A potentiometric study of aluminium(III) pyrocatecholates and aluminium(III) hydroxo pyrocatecholates in 0.6 M Na(Cl)

Equilibria between aluminium(III), pyrocatechol (1,2-dihydroxybenzene, H₂L) and OH⁻ were studied in 0.6 M Na(Cl) medium at 25°C. The measurements were performed as emf titrations (glass electrode) within the limits 1.5 ≤ − log[H⁺] ≤ 9; 0.0005 ≤ B ≤ 0.015 M; 0.006 ≤ C ≤ 0.03 M and 2 ≤ C/B ≤ 30 (B and C stand for the total concentrations of aluminium(III) and pyrocatechol respectively). All data can be explained with a main series of complexes: A1L⁺, log β_−2,1,1 = − 6.337 ± 0.005; A1L₂⁻, log β_−4,1,2 = −15.44 ± 0.017 and A1L₃³⁻, log β_−6,1,3 = − 28.62 ± 0.024 together with two minor species: Al(OH)L₂²⁻, log β_−5,1,2 = − 23.45 ± 0.079 and Al₃(OH)₃L₃, log β_−9,3,3 = − 29.91 ± 0.066. Of the two, the latter probably is a type of average composition complex principally occurring at low C/B quotients. The first acidity constant for pyrocatechol as determined in separate experiments is log β_−1,0,1 = − 9.198 ± 0.001. The standard deviations given are 3σ(log β p,q,r). Data were analyzed with the least squares computer program LETAGROPVRID. In a model calculation using kaolinite as solid phase, we compared the complexation ability of this system with that of the system Al³⁺-OH⁻-salicylic acid, reported earlier in this series.     

Simultaneous potentiometric determination of ClO(3)(-)-ClO(2)(-) and ClO(3)(-)-HClO by flow injection analysis using Fe(III)-Fe(II) potential buffer

A rapid potentiometric flow injection technique for the simultaneous determination of oxychlorine species such as ClO₃⁻–ClO₂⁻ and ClO₃⁻–HClO has been developed, using both a redox electrode detector and a Fe(III)–Fe(II) potential buffer solution containing chloride. The analytical method is based on the detection of a large transient potential change of the redox electrode due to chlorine generated via the reaction of the oxychlorine species with chloride in the potential buffer solution. The sensitivities to HClO and ClO₂⁻ obtained by the transient potential change were enhanced 700–800-fold over that using an equilibrium potential. The detection limit of the present method for HClO and ClO₂⁻ is as low as 5×10⁻⁸ M with use of a 5×10⁻⁴ M Fe(III)–1×10⁻³ M Fe(II) buffer containing 0.3 M KCl and 0.5 M H₂SO₄. On the other hand, sensitivity to ClO₃⁻ was low when a potential buffer solution containing 0.5 M H₂SO₄ was used, but could be increased largely by increasing the acidity of the potential buffer. The detection limit for ClO₃⁻ was 2×10⁻⁶ M with the use of a 5×10⁻⁴ M Fe(III)–1×10⁻³ M Fe(II) buffer containing 0.3 M KCl and 9 M H₂SO₄. By utilizing the difference in reactivity of oxychlorine species with chloride in the potential buffer, a simultaneous determination method for a mixed solution of ClO₃⁻–ClO₂⁻ or ClO₃⁻–HClO was designed to detect, in a timely manner, a transient potential change with the use of two streams of potential buffers which contain different concentrations of sulfuric acid. Analytical concentration ranges of oxychlorine species were 2×10⁻⁵–2×10⁻⁴ M for ClO₃⁻, and 1×10⁻⁶–1×10⁻⁵ M for HClO and ClO₂⁻. The reproducibility of the present method was in the range 1.5–2.3%. The reaction mechanism for the transient potential change used in the present method is also discussed, based on the results of batchwise experiments. The simultaneous determination method was applied to the determination of oxychlorine species in a tap water sample, and was found to provide an analytical result for HClO, which was in good agreement with that obtained by the o-tolidine method and to provide a good recovery for ClO₃⁻ added to the sample.     

Spectrophotometric study of complexation equilibria between HCrO4 and Cl ions

The complex equilibria between HCrO₄⁻ and Cl⁻ ions has been studied spectrophotometrically at a constant ionic strength of 3.0 mol dm⁻³ and the data have been analyzed both graphically and numerically by means of the program LETAGROP-SPEFO (L. G. Sillen and B. Warnquist, Arkiv. kemi. 1968, 31, 377). The experimental results can be explained on the basis of the following reaction: HCrO₄⁻+H⁺+Cl⁻ = CrO₃Cl⁻+H₂O (log β₁₁ = 1.37±0.08). Molar absorptivities of HCrO₄⁻ and CrO₃Cl⁻ were also reported.     

New aspects of the reaction of silver(I) cations with the ethylenediaminetetraacetate ion

The highly neutralized ethylenediaminetetraacetate (EDTA) titrant (95–99% as Y⁴⁻ anion) precipitates with Ag⁺ cations to form the Ag₄Y species, in aqueous medium, which is well characterized from conductometric titration, thermal analysis and potentiometric titration of the silver content of the solid. The precipitate dissolves in excess Y⁴⁻ to form a complex, AgY³⁻. Equilibrium studies at 25°C and ionic strength 0.50 M (NaNO₃) have shown from solubility and potentiometric measurements that the formation constant (95% confidence level) β₁ = (1.93 ± 0.07) × 10⁵ M⁻¹ and the solubility products are K_S0 = [Ag +]⁴[Y⁴⁻] = (9.0 ± 0.4) × 10⁻¹⁸ M⁵ and K_S1 = [Ag +]³[AgY³⁻] = (1.74 ± 0.08) × 10⁻¹² M⁴. The presence of Na⁺, rather than ionic strength, markedly affects the equilibrium; the data at ionic strength 0.10 M are: β₁ = (1.19 ± 0.03) × 10⁶ M⁻¹, K_S0 = (1.6 ± 0.4) × 10⁻¹⁹ M⁵ and K_S1 = (1.9 ± 0.5) × 10⁻¹³ M⁴; at ionic strength tending to zero; β₁ = (1.82 ± 0.05) × 10⁷ M⁻¹, K_S0 = (2.6 ± 0.8) × 10⁻²² M⁵ and K_S1 = (5 ± 1) × 10⁻¹⁵ M⁴. The intrinsic solubility is 2.03 mM silver (I) in 0.50 M NaNO₃. Well-defined potentiometric titration curves can be taken in the range 1–2 mM with the Ag indicator electrode. Thermal analysis revealed from differential scanning calorimetry a sharp exothermic peak at 142°C; thermal gravimetry/differential thermal gravimetry has shown mass loss due to silver formation and a brown residue, a water-soluble polymeric acid (decomposition range 135–157°C), tending to pure silver at 600°C, consistent with the original Ag₄Y salt.     

Handling of electronic absorption spectra with a desk-top computer-II: calculation of stability constants from spectrophotometric titrations

A fully automatic system for combined spectrophotometric and pH titrations was described in Part I. Its performance in the titration of weak acids and metal complexes is discussed, along with a computer program for numerical treatment of the data, based on Marquardt's modification of the Newton—Gauss non-linear least-squares method. The deprotonation of p-nitrophenol at concentrations of 4 × 10⁻⁵ and 4 × 10⁻⁶M was studied in order to test the sensitivity. Results identical within the reproducibility of the pH-meter were obtained: pK^H = 7.00 ± 0.01 and 7.02 ± 0.01, respectively. Three complexation reactions were studied: (1) the interaction of SCN⁻ with the Co²⁺ complex of 1,4,8,11-tetramethyl-1,4,8,11-tetra-azacyclotetradecane (TMC); five independent experiments gave pK [CoTMC (SCN)⁺ CoTMC²⁺ + SCN⁻] = 3.099 ± 0.003: (2) the deprotonation of the Cu²⁺ complex of 3,7-diazanonanediamide (DANA); five experiments gave pK (CuDANA²⁺ CuDANAH⁺₋₁ + H⁺) = 7.14 ± 0.01 and pK (CuDANAH⁺₋₁ CuDANAH₋₂ + H⁺) = 8.38 ± 0.01: (3) for the reaction of Cu²⁺ with 1,3,7-triazacyclodecane (L), data from different ligand: metal ratios had to be combined to obtain pK (CuL²⁺ Cu²⁺ + L) = 16.19 ± 0.01, pK (CuL²⁺₂ CuL²⁺ + L) = 10.30 ± 0.01, and pK (Cu₂L₂ (OH)²⁺₂ 2 CuL²⁺ + 2 OH⁻) = 14.58 ± 0.03. Titration curves with a total change in absorbance of as little as 0.03 units could be analysed satisfactorily, extending considerably the useful range of concentrations for spectrophotometric titrations. In combined spectrophotometric/pH titrations the accuracy of the glass electrode is normally the limiting factor. Other equilibrium constants can easily be reproduced with standard errors of less than 0.01 log unit.     

Determination of phosphate in hydroponic nutrient solutions using flow injection potentiometry and a cobalt-wire phosphate ion-selective electrode

The direct flow injection potentiometric (FIP) analysis of phosphate in hydroponic nutrient solution has been carried out using a cobalt-wire ion-selective electrode (ISE). Synthetic hydroponic nutrient solution, commercial hydroponic nutrient solution and working hydroponic farm nutrient solution were analysed for phosphate using the FIP technique. It is shown that FIP results compare favourably to standard methods of analysis such as spectrophotometry and indirect photometric ion-pair chromatography. Reproducible FIP response curves with a slope of −(47.57±0.03) mV per decade and intercept of −(169.7±0.1) mV were obtained for four separate calibrations in the concentration range 5.0×10⁻⁴–1.0×10⁻² M H₂PO₄⁻. Anion corrections for interferences by Cl⁻, NO₃⁻ and SO₄²⁻ were applied to all samples using the selectivity coefficients determined independently using a fixed interference method. Nevertheless, it was found that anion corrections were not necessary, as the deviations fell within the bounds of experimental error for the cobalt-wire ISE technique (i.e.±2–5% R.S.D.). The proposed FIP method enables the direct determination of phosphate in hydroponic nutrient solutions.     

Simultaneous determination of selenium and lead in whole blood samples by differential pulse polarography

The polarographic reduction of lead in the presence of selenite gives rise to an additional peak corresponding to the reduction of lead (Pb) on adsorbed selenium (Se) on mercury at −0.33 V. The selenium and lead content can be determined using this peak by the addition of a known amount of one of these ions first and then the second ion. The linear domain range of lead is 5.0×10⁻⁷–2.0×10⁻⁵ M and for selenium 5.0×10⁻⁷–1.0×10⁻⁵ M. Using this method 4.90×10⁻⁷ M Se(IV) and 1.47×10⁻⁶ M Pb(II) in a synthetic sample could be determined with a relative error of +2.0% and 1.8%, respectively (n=4). A recovery test after acid digestion for a synthetic sample was 97% for selenium and 96.5% for lead. The method was applied to 1 ml of digested blood, and 328±23 μg l⁻¹ Se(IV) and 850±62 μg l⁻¹ Pb(II) could be determined with a 90% (n=5) confidence interval.     

Dual-analyte spectroscopic sensing in sol-gel derived polyelectrolyte-silica composite thin films

Ferrozine (3-(2-pyridyl)-5,6-diphenyl-1,2,4-triazine-p,p′-disulfonic acid, monosodium salt hydrate), an iron indicator, and HTPS (8-hydroxyl-1,3,6-pyrenetrisulfonic acid, trisodium salt), a pH indicator, were immobilized in sol–gel derived PDMDAAC-SiO₂ (where PDMDAAC stands for poly(dimethyldiallylammonium chloride), composite thin films via ion-exchange. The two indicators were immobilized in two adjacent sections of the same PDMDAAC-SiO₂ film which was supported on a glass optical substrate. The spectroscopic response of the film to both Fe²⁺ and H⁺ in solutions was investigated by attenuated total reflection (ATR) spectrometry at two well-separated wavelengths, 562 nm for Fe²⁺ and 460 nm for H⁺. The Ferrozine/HPTS immobilized PDMDAAC-SiO₂ films had the following characteristics: linear range, 2.5×10⁻⁶–5.0×10⁻⁵ M for Fe²⁺, pH 4.1–6.8 for H⁺; sensitivity, 2.2×10⁴ ΔA/M for Fe²⁺, 0.583 ΔA/pH for H⁺.     

PVC membrane based potentiometric sensors for uranium determination

Two novel uranyl PVC matrix membrane sensors responsive to uranyl ion are described. The first sensor incorporates tris(2-ethylhexyl)phosphate (TEHP) as both electroactive material and plasticizer and sodium tetraphenylborate (NaTPB) as an ion discriminator. The sensor displays a rapid and linear response for UO₂²⁺ ions over the concentration range 1×10⁻¹–2×10⁻⁵ mol l⁻¹ UO₂²⁺ with a cationic slope of 25.0±0.2 mV decade⁻¹. The working pH range is 2.8–3.6 and the life span is 4 weeks. The second sensor contains O-(1,2-dihydro-2-oxo-1-pyridyl)-N,N,N′,N′-bis(tetra-methylene)uronium hexafluorophosphate (TPTU) as a sensing material, sodium tetraphenylborate as an ion discriminator and dioctyl phenylphosphonate (DOPP) as a plasticizer. Linear and stable response for 1×10⁻¹–5×10⁻⁵ mol l⁻¹ UO₂²⁺ with near-Nernstian slope of 27.5±0.2 mV decade⁻¹ are obtained. The working pH range is 2.5–3.5 and the life span of the sensor is 6 weeks. Interference from many inorganic cations is negligible for both sensors. However, interference caused by some ions (e.g. Th⁴⁺, Cu²⁺, Fe³⁺) is eliminated by a prior ion exchange or solvent extraction step. Direct potentiometric determination of as little as 5 μg ml⁻¹ uranium in aqueous solutions shows an average recovery of 97.2±1.3%. Application for the determination of uranium at levels of 0.01–1 wt.% in naturally occurring and certified ores gives results with good correlation with data obtained by X-ray fluorescence.     

On the existence of the protonated hydronium dication H4O in sulfolane solution

The enthalpy of solvation in sulfolane of the gaseous protonated hydronium dication is estimated as −628 kcal/mol at 298 K. Using literature data, a value ΔH^o = −212 kcal/mol is calculated for the reaction H₃O⁺ + H⁺→ H₄O²⁺ (in sulfolane), supporting the thermodynamic existence of H₄O²⁺ in sulfolane solution, as characterized previously by potentiometric and conductometric titrations. Some aspects of these results are discussed.     

Manipulation of separation selectivity of inorganic anions in electrostatic ion chromatography by the use of mixed cationic–zwitterionic micelles as the column coating solution

This paper describes an electrostatic ion chromatographic system in which the separation selectivity for inorganic anions, especially for sulfate and phosphate, could be manipulated by altering the molar ratio of the zwitterionic and cationic surfactants in the column coating solution used to prepare the stationary phase. The zwitterionic surfactant used for this study was 3-(N,N-dimethyltetradecylammonio)propanesulfonate (Zwittergent-3-14) and the cationic surfactant was tetradecyltrimethylammonium (TTA). Using a reversed-phase C₁₈ column (250×4.6 mm I.D.) coated with 10/10 (mM/mM) of TTA/Zwittergent-3-14 mixed micelles as the stationary phase and either NaHCO₃ or Na₂CO₃ aqueous solution as the eluent, together with suppressed conductivity detection, baseline separation of seven model inorganic anions was obtained. The elution order for those anions was found to be F⁻4²⁻−4²⁻2⁻−3⁻. Under the same conditions but using 1/10 (mM/mM) of TTA/Zwittergent-3-14 mixed micelles as the column coating solution, the elution order for these model ions was F⁻4²⁻4²⁻−2⁻−3⁻. The early elution of phosphate and sulfate is a unique attribute of this system. Detection limits for F⁻, HPO₄²⁻, Cl⁻, SO₄²⁻, NO₂⁻, Br⁻ and NO₃⁻ (S/N=3, sample injection volume 100 μl) were 0.11, 0.12, 0.12, 0.18, 0.49, 0.49, 0.52 μM, respectively.     

Rate constants for the reaction of OH radicals with CH3CN, C2H5CN AND CH2=CH-CN in the temperature range 298–424 K

Rate constants for the reactions of OH with CH₃CN, CH₃CH₂CN and CH₂=CH-CN have been measured to be 5.86 × 10⁻¹³ exp(−1500 ± 250 cal mole⁻¹/RT), 2.69 × 10⁻¹³ exp(−1590 ± 350 cal mole⁻¹/RT and 4.04 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, respectively in the temperature range 298–424 K. These results are discussed in terms of the atmospheric lifetimes of nitrfles.     

Rates of the reactions CN + H2CO and NCO + H2CO in the temperature range 294–769 K

The rate coefficients of the reactions: (1) CN + H₂CO → products and (2) NCO + H₂CO → products in the temperature range 294–769 K have been determined by means of the laser photolysis-laser induced fluorescence technique. Our measurements show that reaction (1) is rapid: k₁(294 K) = (1.64 ± 0.25) x 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; the Arrhenius relation was determined as k₁ = (6.7 ± 1.0) x 10⁻¹¹ exp[(−412 ± 20)/T] cm³ molecule⁻¹ s⁻¹. Reaction (2) is approximately a tenth as rapid as reaction (1) and the temperature dependence of k₂ does not conform to the Arrhenius form: k₂ = 4.62 x 10⁻¹⁷T^1.71 exp(198/T) cm³ molecule⁻¹ s⁻¹. Our values are in reasonable agreement with the only reported measurement of k₁; the rate coefficients for reaction (2) have not been previously reported.     

Time-resolved vibrational cemiluminescence: Rate constants for the reaction F + HC1 → HF + Cl and for the relaxtion of HF(v = 3) by HCl, CO2, N2O, CO, N2 and O2

The reaction: F + HCl→ HF (v 3) + Cl (1), has been initiated by photolysing F₂ using the fourth-harmonic output at 266 nm from a repetitively pulsed Nd: YAG laser By analysing the time-dependence of the HF(3,0) vibrational chemiluminescence, rate constants have been determined at (296 ± 5) K for reaction (1), k₁ = (7.0 ± 0.5) × 10⁻¹² cm³ molecule⁻¹ s⁻¹, and for the relaxation of HF(v = 3) by HCl, CO₂, N₂O, CO, N₂ and O₂: k_HCl = (1.18 ±0.14) × 10⁻¹¹ k_CO2 = (1.04 ± 0. 13) × 10⁻¹², k_N2O = (1.41 ± 0.13) × 10⁻¹¹ k_CO = (2.9 ± 0.3) × (10⁻¹², k_N2 = (7.1 ± 0.6) × 10⁻¹⁴ and k_O2 = (1.9 ± 0.6) × 10⁻¹⁴ cm³molecule⁻¹s⁻¹.     

Kinetic study of gas-phase Lu(D3/2) with O2, N2O and CO2

The second-order rate constants of gas-phase Lu(²D_3/2) with O₂, N₂O and CO₂ from 348 to 573 K are reported. In all cases, the reactions are relatively fast with small barriers. The disappearance rates are independent of total pressure indicating bimolecular abstraction processes. The bimolecular rate constants (in molecule⁻¹ cm³ s⁻¹) are described in Arrhenius form by k(O₂)=(2.3±0.4)×10⁻¹⁰exp(−3.1±0.7 kJmol⁻¹/RT), k(N₂O)=(2.2±0.4)×10⁻¹⁰exp(−7.1±0.8 kJmol⁻¹/RT), k(CO₂)=(2.0±0.6)×10⁻¹⁰exp(−7.6±1.3 kJmol⁻¹/RT), where the uncertainties are ±2σ.     

Voltammetric determination of glucose based on reduction of copper(II)–glucose complex at lanthanum hydroxide nanowire modified carbon paste electrodes

A novel voltammetric method for the determination of β-d-glucose (GO) is proposed based on the reduction of Cu(II) ion in Cu(II)(NH₃)₄²⁺–GO complex at lanthanum(III) hydroxide nanowires (LNWs) modified carbon paste electrode (LNWs/CPE). In 0.1 mol L⁻¹ NH₃·H₂O–NH₄Cl (pH 9.8) buffer containing 5.0 × 10⁻⁵ mol L⁻¹ Cu(II) ion, the sensitive reduction peak of Cu(II)(NH₃)₄²⁺–GO complex was observed at −0.17 V (versus, SCE), which was mainly ascribed to both the increase of efficient electrode surface and the selective coordination of La(III) in LNW to GO. The increment of peak current obtained by deducting the reduction peak current of the Cu(II) ion from that of the Cu(II)(NH₃)₄²⁺–GO complex was rectilinear with GO concentration in the range of 8.0 × 10⁻⁷ to 2.0 × 10⁻⁵ mol L⁻¹, with a detection limit of 3.5 × 10⁻⁷ mol L⁻¹. A 500-fold of sucrose and amylam, 100-fold of ascorbic acid, 120-fold of uric acid as well as gluconic acid did not interfere with 1.0 × 10⁻⁵ mol L⁻¹ GO determination.     

Simultaneous derivative spectrophotometric determination of thorium and uranium in a micellar medium

Derivative photometric methods for trace analysis of Th(IV) and UO₂(II), and their simultaneous determination in mixtures using 5,8-dihydroxy-1,4-naphthoquinone in a micellar medium are reported. Molar absorptivity and Sandell's sensitivity of 1:2 Th(IV) and 1:1 UO₂(II) complexes at their λ_max, 614.5 nm and 637.0 nm are, 1.19 × 10⁴ 1/mol/cm and 1.12 × 10⁴ 1/mol/cm and 1.95 × 10⁻² μg/cm² and 2.13 × 10⁻² μg/cm² μg/cm², respectively. Calibration graph is linear over the range 9.28 × 10⁻²−18.56 μg/ml of Th(IV) and 9.52 × 10⁻²−19.04 μg/ml of UO₂(II). Though presence of Th(IV) and UO₂(II) causes interference in each others determination, 9.28 × 10⁻¹−9.28 μg/ml Th(IV) and 9.52 × 10⁻¹−9.52 μg/ml UO₂(II) when present together, can be simultaneously determined using derivative spectra.     

Flow injection determination of bismuth in urine by successive retention of Bi(III) and tetrahydroborate(III) on an anion-exchange resin and hydride generation atomic absorption spectrometry

Bismuth as BiCl₄⁻ and BH₄⁻ ware successively retained in a column (150 mm × 4 mm, length × i.d.) packed with Amberlite IRA-410 (strong anion-exchange resin). This was followed by passage of an injected slug of hydrochloric acid resulting in bismuthine generation (BiH₃). BiH₃ was stripped from the eluent solution by the addition of a nitrogen flow and the bulk phases were separated in a gas–liquid separator. Finally, bismutine was atomized in a quartz tube for the subsequent detection of bismuth by atomic absorption spectrometry. Different halide complexes of bismuth (namely, BiBr₄⁻, BiI₄⁻ and BiCl₄⁻) were tested for its pre-concentration, being the chloride complexes which produced the best results. Therefore, a concentration of 0.3 mol l⁻¹ of HCl was added to the samples and calibration solutions. A linear response was obtained between the detection limit (3σ) of 0.225 and 80 μg l⁻¹. The R.S.D.% (n = 10) for a solution containing 50 μg l⁻¹ of Bi was 0.85%. The tolerance of the system to interferences was evaluated by investigating the effect of the following ions: Cu²⁺, Co²⁺, Ni²⁺, Fe³⁺, Cd²⁺, Pb²⁺, Hg²⁺, Zn²⁺, and Mg²⁺. The most severe depression was caused by Hg²⁺, which at 60 mg l⁻¹ caused a 5% depression on the signal. For the other cations, concentrations between 1000 and 10,000 mg l⁻¹ could be tolerated. The system was applied to the determination of Bi in urine of patients under therapy with bismuth subcitrate. The recovery of spikes of 5 and 50 μg l⁻¹ of Bi added to the samples prior to digestion with HNO₃ and H₂O₂ was in satisfactory ranges from 95.0 to 101.0%. The concentrations of bismuth found in six selected samples using this procedure were in good agreement with those obtained by an alternative technique (ETAAS). Finally, the concentration of Bi determined in urine before and after 3 days of treatment were 1.94 ± 1.26 and 9.02 ± 5.82 μg l⁻¹, respectively.