Thermal lens studies of the reaction of iron(II) with 1,10-phenanthroline at the nanogram level

The determination of iron(II) with 1,10-phenanthroline in aqueous solutions was carried out exemplarily by thermal lens spectrometry. The peculiarities of analytical reactions at the nanogram level of reactants can be studied using this method. Under the conditions of the competing reaction of ligand protonation, the overall stability constant for iron(II) chelate with 1,10-phenanthroline was determined at a level of n × 10^–7 mol L^–1, logβ ₃ = 21.3 ± 0.1. The rates of formation and dissociation of iron(II) tris-(1,10-phenanthrolinate) at a level of n × 10^–8 mol L^–1 were found to be (2.05 ± 0.05) × 10^–2 min^–1 and (3.0 ± 0.1) × 10^–3 min^–1, respectively. The conditions for the determination of iron(II) with 1,10-phenanthroline by thermal lensing were reconsidered, and ascorbic acid was shown to be the best reducing agent, which provided minimum and reproducible sample pretreatment. Changes in the conditions at the nanogram level improved both the selectivity and sensitivity of determination. The optimum measurement conditions for thermal lensing were determined not only by the absorption of the analyte and reagents, but also by the background absorption of the solvent. The limits of detection and quantification of iron(II) at 488.0 nm (excitation beam power 140 mW) are 1 × 10^–9 and 6 × 10^–9 mol L^–1, respectively; the reproducibility RSD for the range n × 10^–8–n × 10^–6 mol L^–1 is 2–5%.     

Investigation of the reaction of copper(I) with 2,9-dimethyl-1,10-phenanthroline at trace level by thermal lensing

The stability constants for copper(I) chelate with 2,9-dimethyl-1,10-phenanthroline are determined by thermal lensing, and the advantages over spectrophotometric determination of stability constants are shown. Changes in the photometric reaction when moving from the microgram to the nanogram level of reactants are discussed. The conditions for the thermal-lens determination of copper are optimized. The limit of detection of copper is 3x10(-8) mol dm(-3), and the linear calibration range 1x10(-7)-1x10(-5) mol dm(-3).     

Investigation of adsorption of nanogram quantities of iron(II) tris-(1,10-phenanthrolinate) on glasses and silica by thermal lens spectrometry

Thermal lens spectrometry is used for studying adsorption equilibria in aqueous solutions at the level of nanogram quantities of iron(II) tris-(1,10-phenanthrolinate) as a model system. The kinetics of the sorption of the chelate on silica is studied and adsorption isotherms are built. Thermal lensing is used as a method for direct determination of the chelate concentration adsorbed on a quartz surface. The detected amount is 4.1×10⁻¹⁵ mol at the area irradiated by the excitation beam. The adsorption of iron(II) tris-(1,10-phenanthrolinate) on laboratory glassware at the nanogram level is characterised by measuring the residual concentration of the sorbate in solution. A procedure for handling and cleaning the laboratory glassware for determining nanogram amounts of iron in aqueous solutions is proposed. The sensitivity of thermal lensing both in measuring adsorption on silica and glass and quartz surfaces is 100-fold higher than diffuse-reflectance measurements under the same conditions.     

High selective determination iron(II) by its enhancement effect on the fluorescence of pyrene-tetramethylpiperidinyl (TEMPO) as a spin fluorescence probe

A novel fluorescence method determination for iron(II) with a high selectivity and sensitivity has been proposed, based on the enhancement of fluorescence signals resulting from specific redox reaction between synthesized spin fluorescence probe pyrene-tetramethylpiperidinyl (TEMPO) and iron(II). Under the experimental conditions, fluorescent probe displayed a rapid and linear response for iron(II) over the concentration range from 2.4 x 10(-7) to 3.6 x 10(-6) mol/L. The limit of detection was 4.0 x 10(-8) mol/L. The relative standard deviation of six replicate measurements was 1.90% for 3.0 x 10(-7) mol/L iron(II). Because of the specific redox reaction between developed spin fluorescence probe and iron(II), there are few interference by other ions, especially in the presence of relative high concentration iron(III). The method has been successfully applied for iron(II) determinations in two different kinds of real samples. Results determined by the proposed method agree favorably with those determined UV-vis spectrometry method with 1,10-phenanthroline.     

Studying the Adsorption of an Iron(II) Complex of 1,10-Phenanthroline on Laboratory Glassware Using Thermal Lens Spectrometry

The adsorption of iron(II) tris(1,10-phenanthroline) on the glass surface of laboratory ware from solutions has been studied by thermal lens spectrometry at a level of nanogram amounts. The effect of glass pretreatment on the fraction of the adsorbed substance has been studied, and the most appropriate variant of the pretreatment has been selected. The kinetics of iron(II) tris(1,10-phenanthroline) adsorption on the surface of laboratory glass has been studied, and an adsorption isotherm has been constructed for nanogram chelate contents of the solution. The process is most closely approximated by the Freundlich equation. Based on the obtained data, a procedure has been proposed for the preparation of solutions for constructing calibration relationships that can be used in thermal lens measurements of trace amounts of analytes. This procedure takes into account the loss of substances at the surface of laboratory glassware.     

Determination of manganese in some medicinal plants and their infusions by a catalytic spectrophotometric method

The catalytic effect of manganese (II) on the oxidation of the azo dye 3-Methyl-6-(2-hydroxyethoxy)-2-[2-methoxy-4-N (N, N diethylamino) phenylazo] benzothiazolium methylsulphate, with potassium periodate in the presence of 1,10-phenanthroline in weakly acidic media was studied. The reaction was followed spectrophotometrically by measuring the decrease in the absorbance of the dye at 560 nm. Under the optimum conditions (4 x 10(-5) mol dm(-3) azo dye, 4 x 10(-4) mol dm(-3) potassium periodate, 1 x 10(-4) mol dm(-3) 1,10-phenanthroline, 0.1 mol dm(-3) buffer--pH 3.0, 70 degrees C, 8 min) manganese (II) in the range 0.1-5 ng cm(-3) could be determined by the fixed-time method with a detection limit of 0.035 ng cm(-3). The developed method is highly sensitive, selective, and simple. The method was applied successfully to the determination of total manganese in some medicinal plants and to analyse their infusions for trace amounts of total manganese and free manganese (II) ions without separation.     

Hexacyanoferrate(III) as a mediator in the determination of total iron in potable waters as iron(II)-1,10-phenanthroline at a single-use screen-printed carbon sensor device

Hexacyanoferrate(III) was used as a mediator in the determination of total iron, as iron(II)-1,10-phenanthroline, at a screen-printed carbon sensor device. Pre-reduction of iron(III) at −0.2 V versus Ag/AgCl (1 M KCl) in the presence of hexacyanoferrate(II) and 1,10-phenanthroline (pH 3.5-4.5), to iron(II)-1,10-phenanthroline, was complete at the unmodified carbon electrode surface. Total iron was then determined voltammetrically by oxidation of the iron(II)-1,10-phenanthroline at +0.82 V, with a detection limit of 10 μg l⁻¹.In potable waters, iron is present in hydrolysed form, and it was found necessary to change the pH to 2.5-2.7 in order to reduce the iron(III) within 30 s. A voltammetric response was not found at lower pH values owing to the non-formation of the iron(II)-1,10-phenanthroline complex below pH 2.5.Attempts to incorporate all the relevant reagents (1,10-phenanthroline, potassium hexacyanoferrate(III), potassium hydrogen sulphate, sodium acetate, and potassium chloride) into a modifying coated PVA film were partially successful. The coated electrode behaved very satisfactorily with freshly-prepared iron(II) and iron(III) solutions but with hydrolysed iron, the iron(III) signal was only 85% that of iron(II).     

Thermal lensing spectrophotometric analysis with ion-pair solvent extraction

Thermal lensing spectrophotometry is applied to the determination of iron(II) with 4,7-diphenyl-1,10-phenanthroline disulfonic acid in aqueous solution, and in chloroform by ion-pair extraction with trioctylmethylammonium chloride. A phase-sensitive detection system with digital processing was used, the optimum modulation frequency being 5–10 Hz. A baseline drift of 0–03% was achieved. In water, the enhancement factor (sensitivity relative to conventional spectrophotometry) was 70 at an exciting power of 800 mW, and 2 × 10^-9 M iron(II) was determined. In chloroform 2 × 10^-10 M iron(II)—complex could be detected, the enhancement factor being 1200.     

Synthesis, structure, and substitution mechanism of new Ru(II) complexes containing 1,4,7-trithiacyclononane and 1,10-phenanthroline ligands

Two new Ru complexes containing the 1,10-phenanthroline (phen) and 1,4,7-trithiacyclononane ([9]aneS3, SCH2CH2SCH2CH2SCH2CH2) ligands of general formula [Ru(phen)(L)([9]aneS3)]2+ (L = MeCN, 3; L = pyridine (py), 4) have been prepared and thoroughly characterized. Structural characterization in the solid state has been performed by means of X-ray diffraction analyses, which show a distorted octahedral environment for a diamagnetic d6 Ru(II), as expected. 1H NMR spectroscopy provides evidence that the same structural arrangement is maintained in solution. Further spectroscopic characterization has been carried out by UV-vis spectroscopy where the higher acceptor capability of MeCN versus the py ligand is manifested in a 9-15-nm blue shift in its MLCT bands. The E1/2 redox potential of the Ru(III)/Ru(II) couple for 3 is anodically shifted with respect to its Ru-py analogue, 4, by 60 mV, which is also in agreement with a higher electron-withdrawing capacity of the former. The mechanism for the reaction Ru-py + MeCN--> Ru-MeCN + py has also been investigated at different temperatures with and without irradiation. In the absence of irradiation at 326 K, the thermal process gives kinetic constants of k2 = 1.4 x 10(-5) s(-1) (DeltaH(++) = 108 +/- 3 kJ mol(-1), DeltaS(++) = -8 +/- 9 J K(-1) mol(-1)) and k-2 = 2.9 x 10(-6) s(-1) (DeltaH(++) = 121 +/- 1 kJ mol(-1), DeltaS(++) = 18 +/- 3 J K(-1) mol(-1)). The phototriggered process is faster and consists of preequilibrium formation of an intermediate that thermally decays to the final Ru-MeCN complex with an apparent rate constant of (k1Khnu)app = 1.8 x 10(-4) s(-1) at 304 K, under the continuous irradiation experimental conditions used.     

Spectrophotometric determination of iron in highly alkaline solution with 4-hydroxy-1,10-phenanthroline

4-Hydroxy-1,10-phenanthroline forms a stable tris-chelate with iron(II) in the range of alkalinity from pH 10 to 2M sodium hydroxide, with molar absorptivity 1.19 x 10(4) l.mole(-1).cm(-1) at 545 nm. The determination of iron is performed by adding the phenanthroline, stannous chloride, and iron-free sodium hydroxide to the sample to give pH > 13; stannite is the active reductant. Beer's law is obeyed over the iron concentration range from 1 x 10(-5) to 8 x 10(-5)M. Advantages over existing methods are the use of stannous chloride instead of sodium dithionite, which avoids the problem of turbidity, and the stability of the iron(II) chelate towards oxidation by air. The conditional reduction potential at pH 11 for the iron(III)/iron(II) complex couple is 0.39 V.     

Speciation of Co(II), Co(III), and Cu(II) in ethylenediamine solutions by capillary electrophoresis

A capillary electrophoretic (CE) method for the speciation of Co(II), Co(III), and Cu(II) in electroless copper-plating baths containing ethylenediamine (En) has been developed. The method is based on the selective pre-capillary derivatization of Co(II) with 1,10-phenanthroline (Phen) followed by CE separation of stable [CoPhen(3)](2+), [CoEn(3)](3+), and [CuEn(2)](2+) chelates. The proposed derivatization procedure protects Co(II) from oxidation by dissolved oxygen and enables rapid determination of all three metal species within a single run. The optimized separations were carried out in a fused silica capillary (57 cmx75-microm I.D.) filled with an ethylenediamine sulfate electrolyte (20 mmol L(-1) H(2)SO(4), pH 7.0 with En, applied voltage +30 kV) using direct UV detection at 214 nm. The detection limits for a signal-to-noise ratio of 3 and 10 s, hydrodynamic injections were 5x10(-6) mol L(-1) for Cu(II), 1x10(-6) mol L(-1) for Co(III), and 4x10(-7) mol L(-1) for Co(II). Application of the method to the speciation of Co(II), Co(III), and Cu(II) in copper-plating bath samples is also demonstrated.     

Spectrophotometric determination of vanadium with 1,10-phenanthroline

A simple and sensitive spectrophotometric method for the determination of vanadium based upon the reaction of vanadate with 1,10-phenanthroline in the presence of sodium dithionite in ammoniacal solution is described. The absorbance of the complex measured at 645 nm follows Beer's law for solutions containing 30-400 microg of vanadium in 100 ml of solution. A 10-fold excess of molybdenum, tungsten, phosphorus or chromium does not interfere. The molar absorptivity is 8.0 x 10(3) 1 mole(-1) cm(-1). The complex is shown to be tris-1,10-phenanthroline vanadium(II). The method has been applied successfully to the determination of vanadium in bauxite.     

Flow-injection determination of copper(II) based on its catalysis on the redox reaction of cysteine with iron(III) in the presence of 1,10-phenanthroline

A redox reaction of cysteine with iron(III) proceeds slowly in the presence of 1,10-phenanthroline (phen). However, this reaction is accelerated in the presence of copper(II) as a catalyst, producing an iron(II)-phen complex (lambda(max)=510 nm). A sensitive spectrophotometric flow-injection method is proposed for the determination of copper(II) based on its catalytic action on this redox reaction. The dynamic range was 0.1-10 ng ml(-1) of copper(II) with a relative standard deviation of 1.0% (n=10) for 1.0 ng ml(-1) of copper(II) at a sampling rate of 30 h(-1). The detection limit (S/N=3) is 0.04 ng ml(-1). The proposed method was successfully applied to the determination of copper in river water as a certified reference material.     

Kinetic determination of traces of manganese in different materials by its catalytic effect on the methylene green-periodate reaction

The oxidation of Methylene Green by sodium periodate is a slow process. A kinetic method based on the catalytic effect of manganese(II) on this reaction in the presence of 1,10-phenanthroline as activator is described. The reaction is followed spectrophotometrically by measuring the decrease in the absorbance of the dye at 620 nm. Under the optimal experimental conditions [4 x 10(-5)M Methylene Green, 0.2M acetate buffer (pH 4), 2 x 10(-3)M 1,10-phenanthroline, 2.5 x 10(-3)M sodium periodate, 35 degrees ], manganese(II) between 0.2 and 30 ng ml is determined by the tangent method. The accuracy of the method and the influence of 44 foreign ions have been studied and an equation for the kinetics of the catalysed reaction is proposed. The procedure has been applied to the determination of manganese in water, milk and beer with excellent results.     

Effects of auxiliary complex-forming agents on the rate of metallochromic indicator colour-change-III: mechanism of the colour change of tac in nickel-edta titrations

The rate of the ligand-substitution reaction of nickel(II)-TAC chelate (NiR(2)) with EDTA (Y) and 1,10-phenanthroline (X) has been determined spectrophotometrically in 20% v v dioxan over the pH range 5.7-6.3 at mu = 0.1 (KNO(3)) and 25 +/- 1 degrees . The substitution reaction with EDTA proceeds through the following two pathways: NiR(2) + H(+) right harpoon over left harpoon NiR(+) + HR, and NiR(2) + H(2)O right harpoon over left harpoon NiR(OH) + HR, The reaction of NiR(+) or NiR(OH) with EDTA is the rate-determining step, and k(1) = 2.1 x 10(3) l .mole(-1) .sec(-1) and k(2) = 7.9 x 10(6) l .mole(-1) .sec(-1).The substitution reaction with 1,10-phenanthroline proceeds as follows: NiR(+) + X right harpoon over left harpoon NiRX(+) At higher concentrations of 1,10-phenanthroline the release of TAC from NiR(2) by hydrogen ion is the rate-determining step, and k(3) = 2.4 x 10(5) l .mole(-1). sec(-1). At lower concentrations of 1,10-phenanthroline -d[NiR(2)]/dt is proportional both to [H(+)] and [X]. The value k(4) = 5.1 x 10(4) l. mole(-1). sec(-1) was calculated by the use of the steady-state approximation for [NiRX(+)]. The substitution with 1,10-phenanthroline proceeds much faster than that with EDTA. By the addition of a small amount of 1,10-phenanthroline, Ni can be titrated with EDTA at 50 degrees, with TAC as an indicator.     

Solvent extraction of anions with metal chelate cations-XVIII Spectrophotometric determination of maleic acid in the presence of fumaric acid by solvent extraction with tris(1,10-phenanthroline)iron(ii) chelate cations

A new colorimetric method is proposed for the determination of maleic acid. Among aliphatic dicarboxylic acids tested, maleic acid was found to be selectively extracted into nitrobenzene as the red ion-association complex (lambda(max) 516 nm) formed between the hydrogen maleate anion and the tris(1,10-phenanthroline)iron(II) cation. At least a 32-fold molar excess of tris(1,10-phenanthroline)iron(II) relative to maleic acid is needed and the optimal pH range is 3-5. A linear relationship is obtained over the concentration range 10(-5)-10(-4)M maleic acid. The relative standard deviation was 1.0 %. The colour intensity of the extract remains constant at room temperature for at least 24 hr. A large amount of fumaric acid, the trans-isomer of maleic add, is not extracted under the same conditions. This makes it possible to determine maleic acid in the presence of fumaric acid.     

New colorimetric methods for the determination of trazodone HCl,famotidine, and diltiazem HCl in their pharmaceutical dosage forms

Two sensitive and simple spectrophotometric methods are developed for the determination of trazodone HCl, famotidine, and diltiazem HCl in pure and pharmaceutical preparations. The methods are based on the oxidation of the cited drugs with iron(III) in acidic medium. The liberated iron(II) reacts with 1,10-phenanthroline (method A) and the ferroin complex is colorimetrically measured at 510 nm against reagent blank. Method B is based on the reaction of the liberated Fe(II) with 2,2-bipyridyl to form a stable colored complex with lambda(max )at 520 nm. Optimization of the experimental conditions was described. Beer's law was obeyed in the concentration range of 1-5, 2-12, and 12-32 microg mL(-1) for trazodone, famotidine, and diltiazem with method A, and 1-10 and 8-16 microg mL(-1) for trazodone and famotidine with method B. The apparent molar absorptivity for method A is 1.06x10(5), 2.9x10(4), 1.2x10(4) and for method B is 9.4x10(4 )and 1.6x10(4), respectively. The suggested procedures could be used for the determination of trazodone, famotidine, and diltiazem, both in pure and dosage forms without interference from common excipients.     

Determination of Adsorbates on the Surface of Polymer with Low Absorption Capacity by Thermal Lens Spectrometry

Thermal lens spectrometry in a coaxial configuration is used for the direct determination of adsorbates on a planar surface of polyethylene terephthalate (PET). A possibility of the direct measurement of the rate of adsorption from solutions and the determination of the parameters of the adsorbed layer is demonstrated by the example of an investigation of the adsorption of iron(II) tris(1,10-phenantrolinate) on a PET surface. The adsorption isotherm of iron(II) tris(1,10-phenantrolinate) on the PET surface is described by the Langmuir equation and is linear in the concentration range in solution from 0.02 to 0.7 mM. The method for calculating the thermal perturbation in surface-absorbing solids was used to interpret the results of the adsorption study, and a possibility of determining iron(II) tris(1,10-phenantrolinate) on the surface at a level smaller than a monolayer was shown. Thermal lens spectrometry enables the determination of the absorption of the surface layer at a level up to 5 × 10^–5 absorbance units, which corresponds to the surface concentration of iron(II) tris(1,10-phenanthrolinate) 2 × 10^–13 mol/cm². Using the example of the adsorption of 4-(2-pyridylazo) resorcinol on the PET surface, it is demonstrated that, in the case of strong absorption of the surface layer, the thermal destruction of substance and the deformation of the substrate may occur. A local increase in temperature in the layer is also confirmed by theoretical calculations.     

Utilization of activating and masking effects by ligands for highly selective catalytic spectrophotometric determination of copper and iron in natural waters

A kinetic–catalytic spectrophotometric method is proposed for the successive determination of nanogram levels of copper and iron, which is based on their catalytic effects on the oxidative coupling of p-anisidine with N,N-dimethylaniline (DMA) to form a colored compound (λ_max=740 nm) in the presence of hydrogen peroxide at pH 3.2. 2,9-Dimethyl-1,10-phenanthroline (neocuproine) acted as an activator for the copper catalysis, and 1,10-phenanthroline (phen) acted as an activator for the iron catalysis. The selectivity was improved in the presence of diphosphate as a masking agent. The determinable ranges were 0.16–10 ppb for copper and 1–100 ppb for iron, respectively. The relative standard deviations of copper and iron were 1.1 and 0.97% for five determinations of 10 ppb copper and 40 ppb iron. The method was successfully applied to the analyses of copper and iron in tap, well, river and pond waters.     

Iron (III) derivatives of 4,7-dihydroxy-1,10-phenanthroline

The chemistry of the iron (III) derivatives of 4,7-dihydroxy-l,10-phenanthroline has been studied in detail. Oxidation of the intensely red tris(4,7-dihydroxy-l,10-phenanthroline) iron (II) ion results in a grey compound, tris(4,7-dihydroxy-l,10-phenanthroline)iron(III), which is stable below pH 10. Above pH 10 the grey compound is partially converted into an amber compound in which the ratio of phenanthroline to iron is 2:1. The amber compound is the conjugate base of a purple 2:1 compound with pK(a) = 9.77. The visible absorption spectra of the three species at various pH values are reported. For 4,7-dihydroxy-1,10-phenanthroline pK(3), as determined by ultraviolet absorptometry, is 12.62 +/- 0.2.