Flow-injection catalytic spectrophotometic determination of molybdenum(VI) in plants using bromate oxidative coupling of p-hydrazinobensenesulfonic acid with N-(1-naphthyl)ethylenediamine

A novel flow-injection spectrophotometry has been developed for the determination of molybdenum(VI) at nanograms per milliliter levels. The method is based on the catalytic effect of molybdenum(VI) on the bromate oxidative coupling of p-hydrazinobenzenesulfonic acid with N-(1-naphthyl)ethylenediamine to form an azo dye (λ_max = 530 nm). Chromotropic acid (4,5-dihydroxy-2,7-naphthalenedisulfonic acid) acted as an effective activator for the molybdenum(VI)-catalyzed reaction and increased the sensitivity of the method. The reaction was monitored by measuring the change in absorbance of the dye produced. The proposed method allowed the determination of molybdenum(VI) in the range 1.0-20 ng mL⁻¹ with sample throughput of 15 h⁻¹. The limit of detection was 0.5 ng mL⁻¹ and a relative standard deviation for 10 ng mL⁻¹ molybdenum(VI) (n = 10) was 2.5%. The interfering ions were eliminated by using the combination of a masking agent and on-line minicolumn packed with cation exchanger. The present method was successfully applied to the determination of molybdenum(VI) in plant foodstuffs.     

Triphenyltetrazolium chloride as a new analytical reagent for molybdenum(VI): Application to plant analysis

Solvent extraction of molybdenum(VI) ion associate with triphenyltetrazolium chloride (TTC) has been studied. TTC was proposed as reagent for the spectrophotometric determination of micro amounts of molybdenum(VI) at λ_max 250 nm. The optimum conditions for extraction of molybdenum(VI) as an ionassociation complex with TTC has been determined. Beer’s law is obeyed in the range of 0.5–10 μg/mL molybdenum(VI). The molar absorptivity of the ion-pair is 1 × 10⁶ L/mol cm. The sensitivity of the method is 9.6 × 10⁻⁵ μg/cm². The characteristic values for the extraction equilibrium and the equilibrium in the aqueous phase are: distribution constant K _D = 32.64, extraction constant K _ex = 2.19 × 10¹⁰ association constant β = 6.71 × 10⁸. The interferences of different cations, anions on molybdenum(VI) determination were also investigated. A sensitive and selective method for the determination of microquantities of molybdenum(VI) has been developed. The determination was carried out without preliminary separation of molybdenum. A novel procedure of molybdenum(VI) extraction and spectrophotometric determination in different plant samples was examined.     

Adsorbing colloid flotation separation and polarographic determination of Mo(VI) in water

A method is described for the flotation and determination of Mo(VI) in water at ng/ml levels. Mo(VI) is preconcentrated and separated by adsorbing colloid flotation employing aluminium(III) hydroxide as collector and sodium lauryl sulphate as surfactant at pH 5.3 ± 0.1. The molybdenum content in the froth is estimated by using the catalytic wave of Mo(VI) in the presence of nitrate by charging current compensated d.c. polarography (CCCDCP) or differential pulse polarography (DPP). The effect of variables such as pH, ionic strength, concentration of collector and surfactant, time of stirring and gas flow-rate on the recovery of Mo by flotation is reported. The effects of various cations and anions on the flotation and determination of Mo are studied. This method is employed for the determination of molybdenum in natural fresh water samples.     

Determination of Molybdenum(VI) At Trace Levels by a Catalytic Polarographic Method

Abstract

ARSTRACT

A d.c. polarography method for molybdenum (VI) determination at trace levels has been developed. The reaction is catalytic between molybdenum, salicylaldoxime (SCAD) and bromate in acetic-acetate medium. The obtained peak is proportional to molybdenum (VI) concentrations in the range 1.08.10^?a to 1.37.10^?6 M. The proposed procedure is selective, the most serious interferents being W(VI), Pb(II) and Fe(II). It is applied to molybdenum determination in steel samples after iron extraction by ethyl ether.     

Application of adsorptive cathodic differential pulse stripping method for simultaneous determination of copper and molybdenum using pyrogallol red

A reliable and sensitive procedure for the simultaneous determination of trace levels of copper and molybdenum is proposed. The complexing of copper(II) and molybdenum(VI) with pyrogallol red (PGR) is analyzed by cathodic stripping differential pulse voltammetry based on the adsorption collection of the complexes onto a hanging mercury drop electrode (HMDE). The effect of chemical and instrumental parameters on the sensitivity and selectivity were studied. Copper and molybdenum peaks potential were observed at about +0.13 and −0.22 V versus Ag/AgCl electrode, respectively. A standard addition method was utilized for the analysis of voltammogram data, under the optimum conditions and with accumulation time of 90 s. The measured peak current at about +0.14 and −0.22 V is proportional to the concentration of Cu(II) and Mo(VI) over the range of 2-70 and 0.8-80 ng ml⁻¹, respectively. The limit of detection are 0.3 and 0.1 ng ml⁻¹ for Cu(II) and Mo(VI), respectively. The capability of the method for the analysis of real samples was evaluated by determination of copper and molybdenum in river water, tap water and alloy. Atomic absorption spectrometry was applied as a reference method for determination of copper and molybdenum in water samples.     

Catalytic spectrophotometric determination of molybdenum (VI) with the hydrazine-metanil yellow system

A new catalytic Spectrophotometric method for the determination of trace amounts of molybdenum (VI) has been proposed. The method is based on the catalytic effect of Mo(VI) on the reduction of metanil yellow by hydrazine dihydrochloride. Under experiment condition, the linear range of determination is 20–160 ng/mL for molybdenum and the detection limit is 11.2ng/mL. The method has been used to determine trace molybdenum in bean samples with the recovery of 96.0–99.0%, with relative standard deviations of 1.50–2.53%.     

Spectrophotometric Determination of Trace Amounts of Molybdenum in Steel and Pure Iron with a New Chromogenic Reagent Dimethoxyhydroxyphenylflurone

ABSTRACT

A simple method for the direct determination of trace molybdenum in low alloy steel and pure iron with selectivity and sensitivity is reported. In the presence of TritonX-100 and sulphuric-phosphoric acid medium, a new chromogenic reagent dimethoxyhydroxyphenyl-flurone (DMHPF) forms a red complex with molybdenum(VI). The molar absorptivity is obeyed from the range of 0? 8 μg/25 ml for molybdenum(VI). Most of metal ions and 35000-fold amounts of iron do not interfere with the determination of molybdenum. The proposed method has been successfully used for the determination of trace amounts of molybdenum in steel and pure iron specimens.     

Sequential Injection Photometric Determination of Molybdenum Using Organic Wetting Film Extraction

Wetting film extraction was combined with colorimetry to determine nanogram amounts of molybdenum(VI). The simple extraction procedure enhanced sensitivity and selectivity while maintaining a high sample throughput. Extraction and back extraction steps were exploited to exclude interference from the 31 metal species and 11 anions tested. In the first step, molybdenum(VI) was extracted into a toluene film as an ion paired complex. Molybdenum(VI) reacted with thiocyanate to form anionic molybdenum(V) and/or molybdenum(VI) thiocyanate complexes. The complexes were extracted into a toluene film containing tetraheptylammonium bromide as ion pairing reagent. The thiocyanate ligands were displaced by 1,5-diphenylcarbazone (DPC) to form a more intensely colored complex (λ_max= 540 nm). DPC was introduced in the back extraction solvent, methanol. The relative standard deviation was 2.5% for 50 ng ml⁻¹of molybdenum(VI) (n= 10) at a rate of 25 samples h⁻¹. The detection limit (3 × baseline noise) was 2.5 × 10⁻⁸M.     

Spectrophotometric determination of molybdenum based on charge transfer complexes sensitized by copper(II)

A new high sensitive spectrophotometric determination of trace molybdenum was investigated. The sensitivity of the determination of molybdenum, which based on the color charge transfer complex of molybdotungstophosphate-3,3′,5,5′-tetramethylbenzidine, was greatly enhanced by copper(II) ions in the presence of polyvinyl alcohol. The improved method maintained the features of simplicity, rapidity and selectivity, especially eliminating the interference from tungsten. Under the optimum conditions, Beer's law was obeyed over the range from 2 to 32 ng ml⁻¹ molybdenum with molar absorptivity being 4.92×10⁵ l mol⁻¹ cm⁻¹ at 660 nm. The relative standard deviation was 1.2% under nine determinations for 16 ng ml⁻¹ Mo(VI). The present method had been applied to the determination of trace molybdenum in tungsten ores with satisfactory results.     

Kinetic-spectrophotometric determination of molybdenum (VI) and tungsten (VI) in mixtures

A simple kinetic-spectrophotometric method is described for the determination of molybdenum(VI) and tungsten(VI) in mixtures, without prior separation. The method is based on the catalytic effect of molybdenum(VI) and tungsten(VI) on the oxidation of 2,4-diaminophenol dihydrochloride (DAP) by hydrogen peroxide in acidic medium. The reaction was followed spectrophotometrically by measuring the rate of change in absorbance with time at 500 nm. A partial inhibition in the catalytic activity of each catalyst, when the other one is present, at all ratios of Mo(VI) W(VI) mixtures studied was observed. On the other hand, the catalytic activity of tungsten(VI) dropped to zero whilst that of molybdenum(VI) decreased slightly, in the presence of citrate ions. Two sets of experiments were carried out, the first in the absence and the other in the presence of citrate, and the resolution of Mo(VI)/W(VI) mixtures was achieved by solving two simultaneous equations. Various molar ratios of Mo(VI) W(VI), at the 10^–6 M level, from 0.2 1 to 5 1 can be determined with satisfactory precision and accuracy. The selectivity of the method was investigated and the method was applied successfully to the determination of molybdenum and tungsten in each other's presence in steel.     

Cathode ray polarography and differential pulse polarography of the catalytic molybdenum(VI) wave

The optimum conditions of electrolyte composition and pH were studied for the cathode ray polarography (c.r.p.) of the catalytic molybdenum(VI) wave; 1–2 M potassium nitrate at pH 1.6–2.2 is optimum, the detection limit is 3 × 10^-9 M (0.3 ppb) molybdenum(VI). Equal molar concentrations of foreign electroactive substances do not interfere at the potential of the molybdenum wave and 500-fold amounts of these can be tolerated if their c.r.p. peaks are separated from the molybdenum wave by 0.1 or 0.2 V. Similar conditions were used for the differential pulse polarography of the catalytic wave. The detection limit is 2 × 10^-8 M (2 ppb). being limited in part by lead impurities which contribute to the background.     

An improved flow-injection system for spectrophotometric determination of molybdenum and tungsten in tool steels

A flow-injection procedure for simultaneous spectrophotometric determination of tungsten and molybdenum in steel alloys is proposed. The method exploits the catalytic effects of Mo(VI) and W(VI) on the rate of iodide oxidation by hydrogen peroxide under acidic conditions. A novel strategy for ion-exchange separation of the potential interfering species is proposed, and an AG50W-X8 cationic resin mini-column is used. The sample is injected twice, originating two sequential plugs, citrate being added to one of them in order to suppress the W(VI) catalytic activity thus providing the kinetic discrimination.The system handles 70 samples per hour and requires 1.6 mg KI per determination. A linear response is verified up to 10 mg l⁻¹ Mo (or W) in the injectate, and signal additivity is 98-103%. Results are precise (R.S.D. < 0.04) and in agreement with ICP-OES. Running a standard reference material (IPT-50) assessed also accuracy.     

Novel Reaction for Rapid,Simple, and Sensitive Determination of Molybdenum in Various Samples

Abstract

A new sensitive, selective, rapid, and reproducible method is presented for the analysis of trace amounts of molybdenum (VI) (Mo(VI)). The method is based on the reaction of molybdenum (VI) with a new analytical reagent, 6‐(5‐Chloro‐2‐hydroxy‐4‐sulfophenylazo)‐5‐hydroxy‐1‐naphthalenesulfonic acid, disodium salt. Under optimum reaction conditions, molybdenum (VI) forms a red complex with a maximum absorption peak at 589 nm. The color reaction is rapidly completed at room temperature. The apparent molar absorption coefficient and Sandell sensitivity were 1.13×10⁴ L · mol^?1 · cm^?1 and 0.0084 µg · cm^?2, respectively. Beer's law was obeyed up to 8.5 µg · mL^?1. Methods for the determination of Mo(VI) by first‐derivative spectrophtometry have also been proposed at 547 and 625 nm. The proposed methods offer the advantages of sensitivity, rapidity, selectivity, and simplicity without any prior separation or extraction. The methods have been applied to the determination of Mo(VI) in various environmental samples and some alloys; satisfactory results have been obtained.     

Speciation, liquid-liquid extraction, sequential separation, preconcentration, transport and ICP-AES determination of Cr(III), Mo(VI) and W(VI) with calix-crown hydroxamic acid in high purity grade materials and environmental samples

A new functionalized calix[6]crown hydroxamic acid is reported for the speciation, liquid-liquid extraction, sequential separation and trace determination of Cr(III), Mo(VI) and W(VI). Chromium(III), molybdenum(VI) and tungsten(VI) are extracted at pH 4.5, 1.5 M HCl and 6.0 M HCl, respectively with calixcrown hydroxamic acid (37,38,39,40,41,42-hexahydroxy7,25,31-calix[6]crown hydroxamic acid) in chloroform in presence of large number of cations and anions. The extraction mechanism is investigated. The various extraction parameters, appropriate pH/M HCl, choice of solvent, effect of the reagent concentration, temperature and distribution constant have been studied. The speciation, preconcentration and kinetic of transport has been investigated. The maximum transport is observed 35, 45 and 30 min for chromium(III), molybdenum(VI) and tungsten(IV), respectively. For trace determination the extracts were directly inserted into the plasma for inductively coupled plasma atomic emission spectrometry, ICP-AES, measurements of chromium, molybdenum and tungsten which increase the sensitivity by 30-fold, with detection limits of 3 ng ml⁻¹. The method is applied for the determination of chromium, molybdenum and tungsten in high purity grade ores, biological and environmental samples. The chromium was recovered from the effluent of electroplating industries.     

Determination of traces molybdenum by catalytic adsorptive stripping voltammetry

A reliable and very sensitive procedure for the determination of ultra trace of molybdenum is proposed. Molybdenum was determined by cathodic stripping differential pulse voltammetry based on the adsorption collection of the Mo(VI)-Tiron complex on a hanging mercury drop electrode (HMDE). The variation of peak current with pH, concentration of Tiron and chlorate, plus several instrumental parameters such as accumulation time, accumulation potential and scan rate, were optimized. Under optimized condition, the relationship between the peak current and molybdenum concentration is linear in the range of 0.010-21.0 ng ml⁻¹. The limit of detection was found to be 0.006 ng ml⁻¹. The relative standard deviation for 10 replicates determination of 0.6 and 10 ng ml⁻¹ Mo(VI) is equal to 1.3 and 0.9%, respectively. The method was applied to the determination of molybdenum in river water, tap water, well water, plant foodstuff samples such as cucumber, tomato, carrot, and certified steel reference materials.     

Catalytic Spectrophotometric Determination of Molybdenum

Summary.  A highly selective, sensitive, and simple catalytic method for the determination of molybdenum in natural and waste waters was developed. It is based on the catalytic effect of Mo(VI) on the oxidation of 2-aminophenol with H₂O₂. The reaction is monitored spectrophotometrically by tracing the oxidation product at 430 nm after 10 min of mixing the reagents. Addition of 800 μg · cm⁻³ EDTA conferred high selectivity; however, interfering effects of Au(III), Cr(III), Cr(VI), and Fe(III) had to be eliminated by a reduction and co-precipitation procedure with SnCl₂ and Al(OH)₃. Mo(VI) shows a linear calibration graph up to 11.0 ng · cm⁻³; the detection limit, based on the 3S _b-criterion, is 0.10 ng · cm⁻³. The unique selectivity and sensitivity of the new method allowed its direct application to the determination of Mo(VI) in natural and waste waters. Received April 11, 2001. Accepted (revised) June 18, 2001     

Use of quercetin in an improved method for molybdenum determination in waste water,silicate rocks and diverse alloys

A simple and highly sensitive spectrophotometric method for molybdenum (VI) determination has been developed. The method is based on solubilizing the binary molybdenum-quercetin complex and sensitizing the color reaction with cetyltrimethylammonium bromide (CTAB). The optimal conditions for the quantitative determination of molybdenum are studied. In KCl-HCl buffered medium of pH 2.3, the molar absorptivity of the 122 (Moquercetin-CTAB) ternary complex is 2.03 × 10⁵ 1 · mol^–1 · cm^–1 at 420 nm. The system obeys Beer's law up to 0.30 g/ml of molybdenum and the sensitivity index is 0.47 ng · cm^–2. The method is free of interference of most of the common metal ions and anions. The developed procedure has been successfully applied to molybdenum determination in waste water, silicate rocks and diverse alloys.     

Synthesis,structure and properties of eight novel molybdenum(VI) complexes of the types: [MoO2LD] and [{MoO2L}2D] (L = thiosemicarbazonato ligand,D = N-donor molecule)

Eight new molybdenum(VI) complexes with 4-(diethylamino)salicylaldehyde and 2-hydroxy-3-methoxybenzaldehyde thiosemicarbazones have been prepared. They were characterized as mononuclear [MoO₂LD] or dinuclear [{MoO₂L}₂D] complexes. In all the compounds the MoO₂²⁺ core is coordinated by a tridentate ONS thiosemicarbazonato ligand and by the N-donor molecule (imidazole, pyridine or γ-picoline). All the complexes were characterized by chemical analysis, IR spectroscopy and thermogravimetry. Three of the mononuclear complexes, dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(pyridine)]molybdenum(VI), dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(γ-picoline)]molybdenum(VI) and dioxo[(2-hydroxy-3-methoxybenzaldehyde thiosemicarbazonato)(imidazole)]molybdenum(VI) were also characterized by single-crystal X-ray structural analysis. A spectrophotometric method for the determination of molybdenum based on extraction of ion-pairs formed by the cationic surfactant and the [MoO(SCN)₄]⁻ anion is described.     

3-Hydroxy-2-(2-thienyl)-4H-chromen-4-one as a new reagent for the extraction and trace determination of molybdenum(VI)

A simple, sensitive and selective method for the extraction and trace determination of molybdenum(VI) has been developed; it is based on its reaction with 3-hydroxy-2-(2-thienyl)-4H-chromen-4-one (HTC) in sulphuric acid medium. The 1:2 Mo (VI)-HTC yellow complex is quantitatively extractable into chloroform (_max 420 nm) and is stable for more than 4 h. The procedure eliminates the interference of a large number of metal ions and complexing agents. Beer's law is obeyed in the range of 0–2.85 g Mo/mL with a molar absorptivity, Sandell's sensitivity and standard deviation of 5.28×10⁴ L mol^–1 cm^–1, 0.0018 g Mo/cm² and ±0.0054, respectively. The method has successfully been used for the spectrophotometric determination of molybdenum in steel samples.     

Kinetic-Spectrophotometric Determination of Molybdenum(VI) Based on Its Catalytic Effect on the Thionine-Hydrazine Reaction

Abstract

A kinetic method for the determination of trace amounts of Mo(VI) (0.05-4 μg ml^?1) based on its catalytic effect on the reduction of thionine by hydrazine monochloride in strongly acidic media is reported. The reaction is monitored spectrophotometrically by measuring the decrease in absorbance of thionine at 605 nm after a fixed time (5 min.). The detection limit of the method is 23 ng ml^?1 and the relative standard deviation (RSD) for 0.05 μg ml^?1 of Mo(VI) is 1.2% (n=7). The method is almost free from interferences, especially from large amounts of tungsten. The procedure was successfully applied to the determination of trace amounts of molybdenum in steel.