The surfactant sensitized analytical reaction of cerium(IV) with some triphenylformazan derivatives

Cationic surfactant, cetylpyridinium bromide (CPB), sensitizes the colour reaction of cerium(IV) with 1,3-o-hydroxyphenyl-5-phenylformazan(I), 1-m-hydroxyphenyl-3-o-hydroxyphenyl-5-phenylformazan(II) and 1-m-carboxyphenyl-3-o-hydroxyphenyl-5-phenylformazan(III). The formation of a soluble ternary complex of stoichiometric ratio 1:1:1 (Ce(IV)-R-CPB) is responsible for the observed enhancement in the molar absorptivity and Sandell sensitivity of the formed complex, when a surfactant is present. The ternary complex exhibits absorption maxima at 596, 571 and 607 nm (epsilon=6.05 x 10(4), 6.28 x 10(4) and 8.06 x 10(4)L mol(-1)cm(-1)) using triphenylformazan derivatives I, II and III, respectively. Beer's law is obeyed between 0.15 and 2.5 microg ml(-1), whereas, optimum concentration range applying Ringbom method is in the range 0.30-2.25 microg ml(-1). Conditional formation constants in the presence and absence of CPB for Ce(IV) complexes have been calculated. The proposed method has been successfully applied to the analysis of magnesium-base cerium alloys and synthetic mixtures corresponding to various cerium alloys.     

Validated kinetic spectrophotometric method for the determination of metoprolol tartrate in pharmaceutical formulations

A kinetic spectrophotometric method has been described for the determination of metoprolol tartrate in pharmaceutical formulations. The method is based on reaction of the drug with alkaline potassium permanganate at 25+/-1 degrees C. The reaction is followed spectrophotometrically by measuring the change in absorbance at 610 nm as a function of time. The initial rate and fixed time (at 15.0 min) methods are utilized for constructing the calibration graphs to determine the concentration of the drug. Both the calibration graphs are linear in the concentration range of 1.46 x 10(-6)-8.76 x 10(-6) M (10.0-60.0 microg per 10 ml). The calibration data resulted in the linear regression equations of log (rate)=3.634+0.999 log C and A=6.300 x 10(-4)+6.491 x 10(-2) C for initial-rate and fixed time methods, respectively. The limits of quantitation for initial rate and fixed time methods are 0.04 and 0.10 microg ml(-1), respectively. The activation parameters such as E(a), DeltaH(double dagger), DeltaS(double dagger) and DeltaG(double dagger) are also evaluated for the reaction and found to be 90.73 kJ mol(-1), 88.20 kJ mol(-1), 84.54 J K(-1) mol(-1) and 63.01 kJ mol(-1), respectively. The results are validated statistically and through recovery studies. The method has been successfully applied to the determination of metoprolol tartrate in pharmaceutical formulations. Statistical comparison of the results with the reference method shows excellent agreement and indicates no significant difference in accuracy and precision.     

Gas and liquid chromatography of metal chelates of pentamethylene dithiocarbamate

Capillary GC and HPLC of metal chelates of pentamethylene dithiocarbamate were examined. Copper(II), nickel(II), cobalt(III), iron(III), manganese(II) and chromium(III) chelates formed in slightly acidic media (pH 5) were extracted in methyl isobutyl ketone or chloroform. Capillary GC elution and separation was carried out on methylsilicone DB-1 column (25 m x 0.2 mm I.D.) with film thickness 0.25 microm. Electron-capture detection was used. Elution was carried at initial column temperature 200 degrees C with an increment at a rate of 5 degrees C/min up to 250 degrees C and maximum temperature was maintained for 10 min. Symmetrical peaks with baseline separation were obtained with the metal chelates investigated with linear calibration range between 5 and 25 microg/ml for each metal ion and detection limits in the range of 0.5-6.0 microg/ml corresponding to 27-333 pg of metal ion reaching to the detector. HPLC separation was carried out from LiChrosorb ODS, 5 microm column and complexes eluted with methanol-water-1 mM sodium acetate (70:28:2, v/v) with a flow-rate of 1.2 ml/ml. UV detection was at 260 nm. The detection limits obtained were in the range 2-6 microg/ml. The methods were applied to the determination of metal ions in canal water and coal samples with RSD values within 4.15%. The results when compared with a standard flame atomic absorption spectrophotometric method and revealed no significant difference.     

Spectrofluorimetric determination of drugs containing active methylene group using N1-methyl nicotinamide chloride as a fluorigenic agent

A spectrofluorimetric method was described for the determination of drugs containing active methylene groups adjacent to carbonyl groups. The method was applied successfully to the determination of three life saving cardiovascular drugs, with narrow therapeutic indices: pentoxifylline (I), propafenone hydrochloride (II) and acebutolol hydrochloride (III), in laboratory-prepared mixtures, in commercial tablets and in plasma samples. The method involved the reaction of each of the tested drugs with N1-methyl nicotinamide chloride (NMNCl) in the presence of alkali, followed by addition of formic acid, where highly fluorescent reaction products were produced. The produced fluorescence were measured quantitatively at 472 nm (lambdaex 352 nm), 409 nm (lambdaex 310 nm) and 451 nm (lambdaex 266 nm) for (I), (II), and (III) respectively. The method was linear over concentration ranges of 10-1000 microg/ml , 0.2-12 microg/ml and 0.08-10 microg/ml in standard solutions for (I), (II), and (III) respectively. In spiked human plasma samples, calibration graphs were linear over concentration ranges of 20-1000 microg/ml, 0.2-15 microg/ml and 0.08-10 microg/ml for (I), (II), and (III) respectively. The method showed good accuracy, specificity and precision in both laboratory-prepared mixtures and spiked human plasma samples. The proposed method is simple, with low instrumentation requirements, suitable for quality control application, bioavailability and bioequivalency studies.     

Colour reaction of gold with 5-(4-sodium sulphonatephenylazo)-8-aminoquinoline and its analytical application

The synthesis of 5-(4-sodium sulphonatephenylazo)-8-aminoquinoline (SPAQ) is described, and a simple, rapid, selective and sensitive new spectrophotometric method for determination of gold is developed. SPAQ reacts with gold(III), and in the presence of cetyl trimethyl ammonium bromide cationic surfactant and upon making the solution alkaline, forms a blue-green 1:3 (metal:ligand) with an absorption maximum at 605 nm. Beer's law is obeyed over the concentration range 0-2 microg/ml gold. The molar absorptivity and Sandell's sensitivity of the method are 1.48 x 10(5) 1.mole(-1).cm(-1) and 0.0013 microg/cm(2), respectively. The interference of various ions has been studied and the method has been used for the determination of microamounts of gold in ores and anode slimes.     

Catalytic spectrophotometric determination of trace aluminium with indigo carmine

A new catalytic spectrophotometric method is described for the determination of trace amounts of Al(III). The methods based on catalytic action of Al(III) on the oxidation of indigo carmine (IC) by ammonium persulfate in hexamethylene tetramine-hydrochloric acid ((CH2)6N4-HCl) buffer medium (pH 5.4) and in the presence of surfactant-TritonX-100. The effects of some factors on the reaction speed were investigated. Aluminium concentration is linear for 0-1.2x10(-7) g/ml in this method. The detection limit of the proposed method is 1.96x10(-8) g/ml. Most of the foreign ions except for Cu(II), Fe(III) do not interfere with the determination, and the interference of Cu(II) and Fe(III) in this method can be removed by extraction with sodium diethyldithiocarbamate-carbon tetrachloride (DDTC-CCl4). This system is a quasi-zero-order reaction for Al(III), but it is a quasi-first-order reaction for IC. The apparent rate constant is 2.62x10(-5) s-1 and the apparent activation energy is 6.60 kJ/mol in the system. The proposed method was applied to the determination of trace aluminium(III) in real samples with satisfactory results.     

Potentiometric determination of bromate using an Fe(III)-Fe(II) potential buffer by circulatory flow-injection analysis.

A method for the potentiometric determination of bromate by circulatory flow injection analysis (CFIA) is described. The procedure involves the use of an Fe(III)-Fe(II) potential buffer solution, which is recycled via a reservoir. The analytical method is based on a linear relationship between the concentration of bromate and a very transient potential change in the electrode potential due to the generation of intermediate bromine during the reaction of bromate with the Fe(III)-Fe(II) potential buffer solution, which also contains NaBr, (NH4)6Mo7O24 and H2SO4. An aliquot (5 microl) of a bromate sample solution was injected into the stream of the potential buffer solution, 100 ml of which was circulated at a flow rate of 1 ml/min; the potential buffer solution stream was then returned to the reservoir after passing through a flow-through redox electrode detector. A potential change due to the reaction of the injected sample with the potential buffer in a reaction coil was measured with the detector in the form of a peak signal. The effects of the bromide, sulfuric acid and Fe(III)-Fe(II) concentrations in the potential buffer, and length of the reaction coil on the peak heights were examined in order to optimize the proposed CFIA method. The analytical sensitivities to bromate were 5.6 mV/microM for 1 x 10(-2) M and 30.9 mV/microM for 1 x 10(-3) M in the concentration of Fe(III)-Fe(II) in a potential buffer solution containing 0.35 M NaBr, 0.2% (NH4)6Mo7O24 and 1 M H2SO4. The detection limit of bromate obtained by a 1 x 10(-3) M Fe(III)-Fe(II) potential buffer solution was 0.02 microM (2.5 ppb). The numbers of repetitive determinations in which the relative sensitivities within 5% were regarded as being tolerated were ca. 4000 and 2000 for the use of only 100 ml of 1 x 10(-2) M and 1 x 10(-3) M Fe(III)-Fe(II) potential buffer solution, respectively.     

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.     

Spectrophotometric studies on the simultaneous determination of cadmium and mercury with 4-(2-pyridylazo)-resorcinol

A new method for direct spectrophotometric determination of cadmium with 4-(2-pyridylazo)-resorcinol is reported. Absorption maximum, molar absorptivity and Sandell's sensitivity of the 1:1 (M:L) complex are 510 nm, 2.5 x 10(5) l mol(-1) cm(-1) and 3.55 ng cm(-2), respectively. A linear calibration graph is obtained up to 4.49 microg ml(-1). The zero-crossing measurement technique is found suitable for the direct measurement of the first-derivative value at the specified wavelengths. Cadmium(II) (0.42-9.2 microg ml(-1)) and mercury(II) (0.35-7.4 microg ml(-1)) in different ratios have been determined simultaneously. A critical evaluation of the proposed method is performed by statistical analysis of the experimental data. The developed method was applied to the simultaneous spectrophotometric determination of Cd and Hg in some synthetic mixtures and was found to give satisfactory results.     

Speciation of dissolved iron(II) and iron(III) in environmental water samples by gallic acid-modified nanometer-sized alumina micro-column separation and ICP-MS determination

A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%.     

Extraction-spectrophotometric determination of germanium(IV) with mandelic acid and malachite green

A method has been developed for determination of germanium, based on complexation with mandelic acid and extraction of the ion-associate formed with Malachite Green (MG) into chlorobenzene. A weakly acidic aqueous solution (pH 2.5-3.5) at room temperature is used and indirect determination is achieved by measuring the absorbance of MG in the extract, at 628 mn. The calibration graph is linear over the range (0.17-8.63) x 10(-6) (0.05-2.50 mug of germanium); the apparent molar absorptivity is 1.33 x 10(5) 1.mole(-1).cm(-1). The interferences from Fe, Ti, Sn(IV), Mo, and SB(III) can be eliminated by addition of trans-1,2-diaminocyclohexanetetra-acetic acid and sodium diethyldithiocarbamate.     

Interaction of nickel with 4-(2'-benzothiazolylazo) salicylic acid (BTAS) and simultaneous first-derivative spectrophotometric determination of nickel(II) and iron(III)

The solution properties of nickel complex with 4-(2'-benzo-thiazolylazo) salicylic acid (BTAS) have been studied by zero-order absorption spectrophotometry in 40% (v/v) ethanol at 20 degrees C and an ionic strength of 0.1 mol dm(-3) (KNO(3)). The equilibria that exist in solution were established and the basic characteristics of complexes formed were determined. A new direct spectrophotometric method for the determination of trace amounts of the nickel is proposed based on the formation of the Ni (BTAS) complex at pH 7.0. The absorption maximum, molar absorbtivity, and Sandell's sensitivity of 1:1 (M:L) complex are 525 nm, 0.6 x 10(4) l mol(-1) cm(-1) and 2.824 x 10(-9) microg cm(-2), respectively. The use of first-derivative spectrophotometry eliminates the interference of iron and enables the simultaneous determination of nickel and iron using BTAS. Quantitative determination of Ni(II) and Fe(III) is possible in the range (0.59-7.08) and (2.1-8.4) microg ml(-1), respectively with a relative standard deviation of 0.5%. The proposed method has been successfully applied to the simultaneous spectrophotometric determination of nickel and iron in steel alloys and aluminum alloys.     

Potentiometric flow injection determination of amylase activity by using hexacyanoferrate(III)-hexacyanoferrate(II) potential buffer

A highly sensitive potentiometric flow injection determination of amylase activity was carried out, utilizing a redox reaction of hexacyanoferrate(III) in alkaline media with reducing sugar as product of the enzymatic hydrolysis reaction of starch with amylase. The analytical method is based on the potential change detection of a flow-through type redox electrode detector due to the composition change of a [Fe(CN)(6)](3-)-[Fe(CN)(6)](4-) potential buffer solution, which is caused by the redox reaction with the product of the enzymatic reaction. A linear relationship exists between the potential change (peak height) and the activity of amylase. Amylase of a wide activity range from 2.5x10(-2) to 1.2x10(-4) U ml(-1) can be determined by the changing the concentrations of the [Fe(CN)(6)](3-)-[Fe(CN)(6)](4-) potential buffer from 10(-3) to 10(-5) M. The lower detection limit of amylase activity is 6.0x10(-5) U ml(-1). The sampling rate and relative standard deviation are 15 h(-1) and 0.9% (n=5) for 3.8x10(-3) U ml(-1) of amylase. The present method was successfully applied to determine amylase activity in real samples (commercial digestive medicines) with an accuracy of 4% compared with analytical results obtained using the present method with those achieved using the conventional titration method.     

Rapid spectrophotometric determination of chromium(III)

A spectrophotometric procedure is suggested for the determination of Cr(III). The reaction between Cr(III) and 2-(5-bromo-2-pyridylazo)-5-dimethylaminophenol is accelerated by sodium dodecyl sulphate(SDS), sodium benzoate causes a further increase in the absorbance of the chelate. The optimum pH range for the reaction is 5-5.8(benzoate buffer). The chelate exhibits maximum absorbance at 590 nm, obeys Beer's law over the concentration range 0.02-0.56 microg/ml of Cr(III), has molar absorptivity of 7.8 x 10(4) 1. mol(-1) cm(-1) and a Sandell sensitivity of 0.66 ng/cm. The metal to ligand ratio is 1:2 in the absence of SDS and 1:1 in its presence. A procedure for the determination of Cr(III) and Cr(VI), when present together, is described. The method has been applied to the analysis of Cr(III) in tap water.     

Determination of hydrogen peroxide by iron(III) complex of thiacalix[4]arenetetrasulfonate on a modified ion-exchanger with peroxidase-like catalytic activity.

An iron(III) complex of thiacalix[4]arenetetrasulfonate on a modified anion-exchanger (Fe3+-TCAS(A-500)) has shown high peroxidase-like activity at pH 5 - 6 for the reaction of quinoid-dye formation between 3-methyl-2-benzothiazolinone hydrazone and N-(3-sulfopropyl)aniline in the presence of hydrogen peroxide. Utilizing the peroxidase-like activity of Fe3+-TCAS(A-500) for this reaction, a method using Fe3+-TCAS(A-500) was applied for the spectrophotometric determination of hydrogen peroxide. The calibration curve by the method using Fe3+-TCAS(A-500) was linear over the range from 1 to 10 microg of hydrogen peroxide in a 1 ml sample solution. The apparent molar absorptivity for hydrogen peroxide was 2.4 x 10(4) l mol(-1) cm(-1). which was about 80% of that by peroxidase under the same conditions. This determination method of hydrogen peroxide using Fe3+-TCAS(A-500) was applied for the determination of glucose in diluted normal and abnormal control serum I and II.     

Spectrophotometric determination of rifampicin through chelate formation and charge transfer complexation in pharmaceutical preparation and biological fluids

Two simple and accurate spectrophotometric methods for determination of Rifampicin (RIF) are described. The first method is based on charge transfer (CT) complex formation of the drug with three pi-electron acceptors either 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 7,7,7,8-Tetracyanoquinodimethane (TCNQ) or 2,3,5,6-Tetrachloro-1,4-benzoquinone (p-chloranil) in acetonitrile. The method is followed spectrophotometrically by measuring the maximum absorbance at 584 nm, 761 nm (680 nm) or 560 nm for DDQ, TCNQ and p-chloranil, respectively. Under the optimized experimental conditions, the calibration curves showed a linear relationship over the concentration ranges of 5-140 microg/ml, 2-45 microg/ml (5-120 microg/ml) and 15-200 microg/ml, respectively. The second method is based on the reaction of RIF with iron(III) forming a water insoluble violet complex which is extracted into chloroform. The method determines RIF in concentration range of 10-240 microg/ml at 540 nm. The proposed methods applied to determination of RIF in capsule, human serum and urine samples with good accuracy and precision. The results were compared statistically with the official method and showed no significant different between the methods compared in terms of accuracy and precision.     

Spectrophotometric determination of some drugs for osteoporosis

Three simple, accurate and sensitive spectrophotometric methods are developed for the determination of some new drugs for the treatment of osteoporosis: risedronate sodium (I), alendronate sodium (II) and etidronate disodium (III). The first method is based on the measurement of difference in absorbance (Delta A) of risedronate sodium in 0.01 mol l(-1) hydrochloric and 0.1 mol l(-1) sodium hydroxide at 262 nm. Beer's law is obeyed over a concentration range of 15-150 microg ml(-1) with mean recovery 99.75+/-1.22 and molar absorptivity (epsilon) 1.891 x 10(3). The second method is based on the reaction of the primary amino group of (II) with ninhydrin reagent in methanolic medium in the presence of 0.05 mol l(-1) sodium bicarbonate. The colored product is measured at 568 nm, and the linearity range is found to be 3.75-45 microg ml(-1) with mean recovery 99.77+/-0.73 and epsilon 9.425 x 10(3). The third method is based on oxidation of the three mentioned drugs with ceric (IV) sulphate in 0.5 mol l(-1) sulphuric acid at room temperature and subsequent measurement of the excess unreacted cerium (IV) sulphate at 320 nm. The method obeyed Beer's law over a concentration range of 2-24 microg ml(-1) for the three drugs with mean recovery 99.79+/-1.16, 99.73+/-1.38 and 99.86+/-1.13 and epsilon 14.427 x 10(3), 13.813 x 10(3) and 14.000 x 10(3) for drugs I, II, III respectively. The proposed methods were successfully applied for the determination of the studied drugs in bulk powder and in pharmaceutical formulations. The results were found to agree statistically with those obtained the reported methods. Furthermore, the methods were validated according to USP regulations and also assessed by applying the standard addition technique.     

Spectrophotometric determination of some aromatic amines

A method for spectrophotometric determination of four aromatic amines is described. The method is based on the reaction between the amine and the colorless Fe(III)-ferrozine complex. The amine reduces iron from Fe(III) to Fe(II) which forms a violet colored complex with ferrozine. The method is suitable for to the determination of 1,4-phenylenediamine, 2,4-diaminotoluene, 8-aminoquinoline and 2-amino-3-hydroxypyridine. The effect of different factors such as; pH, stability of the complex, temperature, ferrozine concentration, Fe(III) concentration and methanol concentration have been studied. The composition of the complex as well as the tolerance amount of other amines have been reported. Maximum absorbance is at 562 nm and Beer's law is obeyed over the ranges 0.17-1.6 ppm for 1,4-phenylenediamine, 0.45-3.7 ppm for 2,4-diaminotoluene, 0.51-3.4 ppm for 8-aminoquinoline and 0.53-4.4 ppm for 2-amino-3-hydroxypyridine. The obtained molar absorbtivities were 4.7x10(4), 2.0x10(4), 1.6x10(4), 1.5x10(3) l mol(-1) cm(-1) respectively.     

A simple and rapid spectrophotometric determination of thallium(III) with trifluoperazine hydrochloride.

A simple, sensitive and rapid spectrophotometric method was developed for the determination of thallium(III) using trifluoperazine hydrochloride (TFPH). The method is based on the oxidation of TFPH by thallium(III) in a phosphoric acid medium to form a red-colored radical cation with an absorption maximum at 505 nm. Beer's law is valid over the concentration range of 0.5 - 6.5 microg ml(-1) of thallium(III). The molar absorptivity and Sandell's sensitivity of the color system are 2.14 x 10(4) l mol(-1) cm(-1) and 0.0095 microg cm(-2), respectively. The optimum reaction conditions and other analytical parameters were evaluated. The tolerance limit of the method towards various ions usually associated with thallium has been studied. The proposed method has been successfully applied to the analysis of thallium in alloys, minerals, standard reference material, water, and urine samples.     

Simultaneous determination of gallium and indium with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in cationic micellar medium using derivative spectrophotometry.

A new derivative spectrophotometric method for rapid and selective trace analysis of Ga3+ and In3+ and for their simultaneous determination using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in a cationic micellar medium is reported. Molar absorptivity and Sandell's sensitivity of 1:1 Ga+ and In3+ complexes at their lambda(max) 553 nm and 558 nm are: 7.22 x 10(4) l mol(-1) cm(-1) and 5.85 x 10(4) l mol(-1) cm(-1), and 0.96 ng cm(-2) and 1.96 ng cm(-2), respectively. Linearity is observed in the concentration range 0.023-0.700 microg ml(-1) for gallium and 0.076-1.52 microg ml(-1) for indium; IUPAC detection limit is 0.012 and 0.035 ng ml(-1), respectively. These metal ions interfere with the determination of each other. However, 0.07-0.70 microg ml(-1) Ga3+ and 0.115-1.150 microg ml(-1) In3+ could be determined simultaneously when present together by the derivative method without any prior separation. The proposed procedures have been successfully applied for the individual and simultaneous determination of gallium and indium in synthetic binary mixtures, standard reference materials and environmental samples.