Determination of trace amounts of thiocyanate by a new kinetic procedure based on an induction period

A new, simple and sensitive kinetic spectrophotometric method with no need for removing of interfering substances is proposed for the determination of thiocyanate ion in biological and water samples. The procedure is based on the inhibiting effect of thiocyanate on the sodium periodate-potassium bromide-meta cresol purple (MCP) system in acidic media. The induction period of the reaction is proportional to the SCN- concentration. The decolorization of meta cresol purple by the reaction products was used to monitor the reaction spectrophotometrically at 525 nm. Under optimum conditions, thiocyanate can be determined in the range of 0.02-0.8 microg ml(-1) with a 3sigma detection limit of 5 ng ml(-1). The relative standard deviations for 10 replicate determinations of 0.060, 0.10 and 0.50 microg ml(-1) thiocyanate are 3.7, 2.4 and 1.0%, respectively. This method has been successfully used to the determination of thiocyanate content in smokers and non-smokers saliva and spiked water sample.     

Rapid determination of chromium(VI) in electroplating waste water by use of a spectrophotometric flow injection system

A new rapid and sensitive FI method is reported for spectrophotometric determination of trace chromium(VI) in electroplating waste water. The method is based on the reaction of Cr(VI) with sodium diphenylamine sulfonate (DPH) in acidic medium to form a purple complex (lambda(max) = 550 nm). Under the optimized conditions, the calibration curve is linear in the range 0.04-3.8 microg ml(-1) at a sampling rate of 30 h(-1). The detection limit of the method is 0.0217 microg ml(-1), and the relative standard deviation is 1.1% for eight determinations of 2 microg ml(-1) Cr(VI). The proposed method was applied to the determination of chromium in electroplating waste water with satisfactory results.     

Determination of formaldehyde in foodstuffs by flow injection spectrophotometry using phloroglucinol as chromogenic agent

A spectrophotometric method for the determination of formaldehyde in foodstuffs was described by using phloroglucinol as the chromogenic agent. The reaction between formaldehyde and phloroglucinol could occur rapidly at room temperature under mild conditions. The spectrophotometric measurements were conducted at 474nm of an unstable intermediate orange product of the reaction, which greatly increased the sample throughput. Flow injection technique was used to control the merging and reaction timing of the reagents and sample. A detection limit (3sigma) of 0.023microg ml(-1) was achieved. The relative standard deviation was 0.29% for the determination of 7microg ml(-1) formaldehyde (n=11). The proposed method was applied to the analyses of formaldehyde in several preserved foodstuffs and the results were in good agreement with those obtained by a standard method.     

Kinetic spectrophotometric method for the determination of oxalic acid by its catalytic effect on the oxidation of safranine by dichromate

A new catalytic kinetic spectrophotometric method for the determination of oxalic acid has been described based on its catalytic effect on the redox reaction between safranine and dichromate in dilute sulfuric acid media. The reaction is monitored photometrically by measuring the decrease in absorbance of safranine at the maximum wavelength of 530 nm. Under the optimum conditions, a calibration graph from 0.10 to 10.00 microg ml(-1) of oxalic acid with a detection limit of 0.08 microg ml(-1) was obtained. The relative standard deviation (R.S.D.) for ten replicate measurements of 1.0 and 5.0 microg ml(-1) oxalic acid was 2.7 and 2.5%, respectively. The purposed method is simple, sensitive, selective and inexpensive. The applicability of the proposed method was determined by the determination of oxalic acid in spinach and wastewater samples with satisfactory results.     

Flow-injection spectrophotometric determination of sulfadiazine and sulfamethoxazole in pharmaceuticals and urine.

A rapid and sensitive flow-injection spectrophotometric method is proposed for the determination of sulfadiazine and sulfamethoxazole. This method is based on the diazotization of sulfonamide with sodium nitrite, and a coupling reaction of the diazo-compound with alpha-naphthylamine. The optimum experimental conditions are obtained by using the controlled and weighted centroid simplex method. The linear ranges for the determination of sulfadiazine and sulfamethoxazole are 0.2-20 microg ml(-1) and 0.1-20 microg ml(-1), and their detection limits are 0.06 microg ml(-1) and 0.05 microg ml(-1), respectively, and the sampling frequency is 130 samples per hour. The method has been used to determine sulfadiazine and sulfamethoxazole in pharmaceuticals and urine without separation. The results are in agreement with those obtained by a high-performance liquid chromatograph technique at the 95% confidence level.     

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.     

Spectrophotometric determination of urea in dermatologic formulations and cosmetics

A rapid, relatively sensitive, and low-cost method for the determination of water-soluble urea content in dermatological therapy products and cosmetics is proposed using a new spectrophotometric assay with water as the only extraction solvent. Spectrophotometric methods involve addition of a known excess of bromate to urea in an acid medium, followed by the determination of residual bromine and chlorine reacting with methyl orange and measurement of absorbance at 505 nm. The absorbance increases linearly with urea concentration (r = 0.9998). The systems obey Beer's law for 6 - 90 microg ml(-1). The calculated apparent molar absorbance values are found to be 4.537 x 10(3) dm(3) mol(-1) cm(-1) and the Sandell's sensitivity is 0.013 microg cm(-2). The variables affecting the rate of the reaction were investigated. The relative standard deviation for five-replication determination of 60 microg ml(-1) urea was 2.1% and the detection limit of the method is 0.34 ng ml(-1).     

Spectrophotometric determination of platinum in glass after extraction with polyurethane foam

A spectrophotometric method has been developed for determination of trace amounts of platinum in glass. The method is based on the extraction of platinum(II) from 1M hydrochloric acid containing 0.2M stannous chloride and 4 x 10(-4)M dithizone onto polyurethane foam, elution with acetone (containing 3% v/v concentrated hydrochloric acid) and measurement of the absorbance of the eluate at 530 nm. Beer's law is obeyed up to 10.0 microg/ml Pt. The minimum platinum level in the eluate that can be determined by this method is 0.1 microg/ml.     

A simple flow injection spectrophotometric determination of nitrite based on its reaction with thiourea.

A simple flow injection spectrophotometric method for the determination of nitrite is described. Nitrite injected into the flow system reacts with thiourea in acidic medium and the generated thiocyanate ion reacts with Fe(III) in the reagent solution to produce a highly colored product. The influences of chemical and physical parameters including reagent concentrations, sample volume injected, flow rates of the carrier and reagent solutions, reaction coil length and reaction temperature, were studied and optimum values of these parameters were established. Under the optimum conditions, the calibration curve for nitrite was linear over the concentration range 0.36 - 90 microg ml(-1) without preconcentration and over the range 3.8 - 500 ng ml(-1) with a simple online preconcentration step using an anion exchange column. The corresponding detection limits were 0.36 micro ml(-1) and 3.8 ng ml(-1), respectively. Up to 25 samples can be analyzed per hour, with an average relative standard deviation of < or = 1.2%. Interferences by various foreign ions were studied and the method was applied to the determination of nitrite in water and spiked water samples.     

Simultaneous determination of manganese and zinc in mixtures using first- and second-derivative spectrophotometry

A new direct spectrophotometric determination of manganese with 5,8-dihydroxy-1,4-naphthoquinone (naphthazarin,NAZA) is reported. Absorption maximum, molar absorptivity and Sandell's sensitivity of 1:2 (M:L) complex are 695 nm, 1.88x10(4) l mol(-1) cm(-1) and 2.92 ng cm(-2), respectively. A linear calibration graph is obtained up to a concentration of 7.2 mug ml(-1) of manganese. The optimum range for determination (Ringbom) is between 0.20 and 6.8 mug ml(-1). A rapid method for simultaneous determination of manganese and zinc in their mixture using derivative spectra is described. The range 0.28-5.6 mug ml(-1) manganese could be determined in the presence of 0.33-6.8 mug ml(-1) zinc and vice versa. The developed method was applied to the simultaneous spectrophotometric determination of manganese and zinc in some synthetic mixtures and was found to give satisfactory results.     

Analysis of cement and cement raw meal by atomic absorption spectrophotometry using a new fusion agent

A new fusion agent is proposed for the analysis of cement and cement raw meal using AAS. In the described method, 0.8 g of the fusion agent, consisting of equal portions of oxalic acid, lithium carbonate and lithium tetraborate, was mixed with 0.2 g of the sample, and the mixture was fused for 10 min at 925 degrees C in a platinum crucilbe. The fusion cake was dissolved with dilute hydrochloric acid (1 + 10) and diluted to 500 ml for the determination of Si, Al, Fe, Ti, Na and K expressed as SiO(2), Al(2)O(3), Fe(2)O(3), TiO(2), Na(2)O, and K(2)O respectively. For the determination of Ca and Mg (expressed as CaO and MgO respectively), 10 ml of the previous sample solution were mixed with 4 ml of 6% (m/v) lanthanum nitrate solution and the solution was diluted to 100 ml. The method was found to have good accuracy and precision. The time required to determine the eight elements was around 80 min for each sample.     

Spectrofluorimetric and spectrophotometric stability-indicating methods for determination of some oxicams using 7-chloro-4-nitrobenz-2-oxa-1,3-diazole (NBD-Cl)

Two sensitive and selective spectrofluorimetric and spectrophotometric stability-indicating methods have been developed for the determination of some non-steroidal anti-inflammatory oxicam derivatives namely lornoxicam (Lx), tenoxicam (Tx) and meloxicam (Mx) after their complete alkaline hydrolysis. The methods are based on derivatization of alkaline hydrolytic products with 7-chloro-4-nitrobenz-2-oxa-1,3-diazole (NBD-Cl). The products showed an absorption maximum at 460 nm for the three studied drugs and fluorescence emission peak at 535 nm in methanol. The color was stable for at least 48 h. The optimum conditions of the reaction were investigated and it was found that the reaction proceeds quantitatively at pH 8, after heating in a boiling water bath for 30 min. The methods were found to be linear in the ranges of 1-10 microg ml(-1) for Lx and Tx and 0.5-4.0 microg ml(-1) for Mx for spectrophotometric method, while 0.05-1.0 microg ml(-1) for Lx and Tx and 0.025-0.4 microg ml(-1) for Mx for the spectrofluorimetric method. The validity of the methods was assessed according to USP guidelines. Statistical analysis of the results revealed high accuracy and good precision. The suggested procedures could be used for the determination of the above mentioned drugs in pure and dosage forms as well as in the presence of their degradation products.     

An insight into the solution equilibria of magnesium(II) with purpurin and spectrophotometric determination of magnesium

The complexation equilibria of magnesium(II) with purpurin (PURP) are studied spectrophotometrically as a function of pH in 50% (v/v) ethanol-water medium at 20 degrees C. The uncharged complex formed at pH 9.5 allows precise and accurate determination of magnesium over the concentration range 0.8-4.3 mug ml(-1). The molar absorptivity of the Mg-PURP complex at 540 nm and detection limit for Mg are 9.2x10(3) l mol(-1) cm(-1) and 75 ng ml(-1), respectively. The proposed method is rapid and possesses reasonable selectivity. Under the optimum conditions, the use of first-derivative spectrophotometry has the advantage of high sensitivity than normal spectrophotometry and allows the determination of 0.2 mug ml(-1) of magnesium. The validity of the method is examined by analysing several SRM Portland cement samples and a variety of cement materials of variable magnesia content.     

Flow injection determination of formaldehyde by its catalytic effect on the oxidation of sulfonazo III by bromate with spectrophotometric detection.

A simple and sensitive flow injection method with spectrophotometric detection was developed for the determination of formaldehyde. The method is based on the catalytic effect of formaldehyde on the oxidation of sulfonazo III with bromate in acidic media. The decrease in absorbance of the reaction mixture was measured at 566 nm. The calibration graph was linear in the range of 0.005 to 2.80 microg ml(-1) formaldehyde at a rate of 38 +/- 4 samples h(-1). The limit of detection was 4 ng ml(-1). The relative standard deviations for ten replicate measurements of 0.20, 0.50 and 1.00 microg ml(-1) formaldehyde were 1.3, 0.8 and 0.7%, respectively. The method was applied to the determination of formaldehyde in river water, shampoo and melamine-formaldehyde resin.     

Development and validation of spectrophotometric, TLC and HPLC methods for the determination of lamotrigine in presence of its impurity

Three reliable, rapid and selective methods have been developed and validated for the determination of lamotrigine in the presence of its impurity, 2,3-dichlorobenzoic acid. The first method is spectrophotometric method using p-chloranilic acid forming a colored product with lambda(max) 519+/-2 nm. All variables affecting the reaction have been investigated and the conditions were optimized. Beer's law was obeyed over a concentration range of 10-200 microg ml(-1) with mean accuracy 100.13+/-0.44%. The molar ratio of the formed ion-association complex is found to be 1 : 1 as deduced by Job's method. The conditional stability constant (K(f)), standard free energy (DeltaG), molar absorptivity(epsilon), and sensitivity index were evaluated. The second method is based on TLC separation of the cited drug (Rf=0.75+/-0.01) from its impurity (Rf=0.23+/-0.01) followed by densitometric measurement of the intact drug spots at 275 nm. The separation was carried on silica gel plates using ethyl acetate : methanol : ammonia 35% (17 : 2 : 1 v/v/v) as a mobile phase. The linearity range was 0.5-10 microg/spot with mean accuracy 99.99+/-1.33%. The third method is accurate and sensitive stability-indicating HPLC method based on separation of lamotrigine from its impurity on a reversed phase C(18) column, using a mobile phase of acetonitrile : methanol : 0.01 M potassium orthophosphate (pH 6.7+/-0.1) (30 : 20 : 50 v/v/v) at ambient temperature 25+/-5 degrees C and UV detection at 275 nm in an overall analysis time of about 6 min., based on peak area. The injection repeatability, intraday and interday repeatability were calculated. The procedure provided a linear response over the concentration range 1-12 microg ml(-1) with mean accuracy of 99.50+/-1.30%. The proposed methods were successfully applied for the determination of lamotrigine in bulk powder, in dosage form and in presence of its impurity. The results obtained were analyzed by ANOVA to assess that no significant difference between each of the three methods and the reported one. The validation was performed according to USP guidelines.     

Simultaneous determination of aluminium and iron in glasses,phosphate rocks and cement using first- and second-derivative spectrophotometry

First- and second-derivative spectrophoto-metric methods for the simultaneous determination of aluminium and iron in their mixtures are described. The methods are based on the colored complexes formed by aluminium and iron with hematoxylin in the presence of cetyltrimethylammonium bromide as a surfactant. The zero-crossing method has been utilized to measure the first- and second-derivative value of the derivative spectrum. Aluminium (0.05-1 microg ml(-1)) could be determined in the presence of iron (0.09-1.6 microg ml(-1)) and vice versa. The detection limits of aluminium and iron are 0.01 and 0.09 microg ml(-1), respectively in the first-derivative mode and 0.014 and 0.1 microg ml(-1) in the second-derivative mode. The proposed method has been applied to the simultaneous determination of aluminium and iron in glasses, phosphate rocks, cement and magnesite alloy.     

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.     

Highly sensitive and selective spectrophotometric and spectrofluorimetric methods for the determination of ropinirole hydrochloride in tablets

Three sensitive, selective, accurate spectrophotometric and spectrofluorimetric methods have been developed for the determination of ropinirole hydrochloride in tablets. The first method was based on measuring the absorbance of drug solution in methanol at 250 nm. The Beer's law was obeyed in the concentration range 2.5-24 microg ml(-1). The second method was based on the charge transfer reaction of drug, as n-electron donor with 7,7,8,8-tetracyanoquinodimethane (TCNQ), as pi-acceptor in acetonitrile to give radical anions that are measured at 842 nm. The Beer's law was obeyed in the concentration range 0.6-8 microg ml(-1). The third method was based on derivatization reaction with 4-chloro-7-nitrobenzofurazan (NBD-Cl) in borate buffer of pH 8.5 followed by measuring the fluorescence intensity at 525 nm with excitation at 464 nm in chloroform. Beer's law was obeyed in the concentration range 0.01-1.3 microg ml(-1). The derivatization reaction product of drug with NBD-Cl was characterized by IR, 1H NMR and mass spectroscopy. The developed methods were validated. The following analytical parameters were investigated: the molar absorptivity (epsilon), limit of detection (LOD, microg ml(-1)) and limit of quantitation (LOQ, microg ml(-1)), precision, accuracy, recovery, and Sandell's sensitivity. Selectivity was validated by subjecting stock solution of ropinirole to acidic, basic, oxidative, and thermal degradation. No interference was observed from common excipients present in formulations. The proposed methods were successfully applied for determination of drug in tablets. The results of these proposed methods were compared with each other statistically.     

Sequential injection spectrophotometric determination of oxybenzone in lipsticks

A sequential injection (SI) procedure for the spectrophotometric determination of oxybenzone in lipsticks is reported. The colorimetric reaction between nickel and oxybenzone was used. SI parameters such as sample solution volume, reagent solution volume, propulsion flow rate and reaction coil length were studied. The limit of detection was 3 microg ml(-1). The sensitivity was 0.0108+/-0.0002 ml microg(-1). The relative standard deviations of the results were between 6 and 12%. The real concentrations of samples and the values obtained by HPLC were comparable. Microwave sample pre-treatment allowed the extraction of oxybenzone with ethanol, thus avoiding the use of toxic organic solvents. Ethanol was also used as carrier in the SI system. Seventy-two injections per hour can be performed, which means a sample frequency of 24 h(-1) if three replicates are measured for each sample.     

Determination of strontium and simultaneous determination of strontium oxide, magnesium oxide and calcium oxide content of Portland cement by derivative ratio spectrophotometry

A derivative spectrophotometric method has been developed for the determination of strontium in Portland cement. The method is applied successfully for the simultaneous determination of SrO, MgO and CaO. It is based on the use of Alizarin Complexone (AC) as a complexing agent and measurement of the derivative ratio spectra of the analytes. Interferences of manganese(II) and zinc(II) were eliminated by precipitation. The validity of the method was examined by analyzing several Standard Reference Material (SRM) Portland cement samples. The strontium complex formed at pH 9.5 allows precise and accurate determination of strontium over the concentration range of 1.5-18 mg L⁻¹ of strontium. The MDL (at 95% confidence level) was found to be 25 ng mL⁻¹ for strontium in National Institute of Standards and Technology (NIST) cement samples using the proposed method.