Derivative spectrophotometry in the determination of metal ions with 4-(pyridyl-2-azo)resorcinol (PAR)

Derivative spectrophotometry has been applied for the elimination of the mutual spectral interferences and the analysis of binary, ternary and quaternary mixtures of complexes of microgram amounts of divalent ions of cobalt, copper, lead, manganese, nickel, zinc and iron with 4-(pyridyl-2-azo)resorcinol (PAR) in the range of 0.05–1 g/ml (0.2–4 g/ml for lead). The first derivative spectra can be used for the determination of both components in the majority of binary mixtures except of Cu(II) and Co(II) and systems containing Fe(II). The second and the third derivative spectra allow to determine one constituent in some ternary and quaternary mixtures.     

Simultaneous spectrophotometric determination of metal ions with 4-(pyridyl-2-azo)resorcinol (PAR)

Summary A new method for the simultaneous determination of the divalent ions of cadmium, cobalt, copper, lead, manganese, nickel and zinc in binary, ternary and quaternary mixtures based on the application of a multiple linear regression programme to the spectra of the complexes of these ions with 4-(pyridyl-2-azo)resorcinol (PAR) was developed. The detection limits afforded by the proposed method range from 0.02 g/ml for Co(II), Mn(II), Ni(II) and Zn(II) to 0.10 g/ml for Pb(II). The method is rapid and quite simple as it entails no prior separation, and was successfully applied to the analysis for the above-mentioned ions in synthetic samples and real alloys.     

Chemometric methods for the simultaneous determination of some water-soluble vitamins

Two spectrophotometric methods, derivative and multivariate methods, were applied for the determination of binary, ternary, and quaternary mixtures of the water-soluble vitamins thiamine HCI (I), pyridoxine HCI (II), riboflavin (III), and cyanocobalamin (IV). The first method is divided into first derivative and first derivative of ratio spectra methods, and the second into classical least squares and principal components regression methods. Both methods are based on spectrophotometric measurements of the studied vitamins in 0.1 M HCl solution in the range of 200-500 nm for all components. The linear calibration curves were obtained from 2.5-90 microg/mL, and the correlation coefficients ranged from 0.9991 to 0.9999. These methods were applied for the analysis of the following mixtures: (I) and (II); (I), (II), and (III); (I), (II), and (IV); and (I), (II), (III), and (IV). The described methods were successfully applied for the determination of vitamin combinations in synthetic mixtures and dosage forms from different manufacturers. The recovery ranged from 96.1 +/- 1.2 to 101.2 +/- 1.0% for derivative methods and 97.0 +/- 0.5 to 101.9 +/- 1.3% for multivariate methods. The results of the developed methods were compared with those of reported methods, and gave good accuracy and precision.     

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.     

Simultaneous determination of chlorzoxazone and ketoprofen in binary mixtures and in ternary mixtures containing the chlorzoxazone degradation product by reversed-phase liquid chromatography

New, simple, rapid, and precise reversed-phase high-performance liquid chromatographic (LC) methods were developed for the simultaneous determination of chlorzoxazone (CH) and ketoprofen (KT) in binary mixtures and in ternary mixtures containing the CH degradation product, 2-amino-4-chlorophenol (CD). The analytes were separated by LC on a Lichrosphere 60 C18 column (250 x 4 mm, 5 microm). The mobile phases, methanol-water (40:60, v/v) at 1 mL/min and methanol-0.05% phosphoric acid (60:40, v/v, pH 2.81) at 1.5 mL/min, satisfactorily resolved the binary and ternary mixtures, respectively. The UV detector was operated at 280 nm for the determination of CH and at 254 nm for the determination of KT and CD. Linearity, accuracy, and precision were found to be acceptable over the concentration ranges of 20-240 and 5-60 microg/mL for CH and KT, respectively, in the binary mixtures and 50-300, 10-60, and 20-160 microg/mL for CH, KT, and CD, respectively, in the ternary mixtures. The optimized methods proved to be specific, robust, and accurate for the quality control of CH and KT in pharmaceutical preparations.     

Mixed Ligand Complexes of Ni(II) with Arylidene- Anthranilic Acids and Some Lewis Bases

Some binary and ternary complexes of Ni(II) with arylideneanthranilic acids and Lewis bases have been prepared and characterized by elemental analyses, IR spectra and X-ray powder diffraction. On the basis of the IR spectra it was found that the Schiff bases used act as monobasic bidentate ligands except for the ortho-hydroxy derivative which acts as a dibasic tridentate ligand. From X-ray analysis it is concluded that the binary Ni(II) chelates are isostructural, and the ternary Ni(II) complexes are also isostructural.     

Effect of molecular structure on the phase behaviour of some liquid crystalline compounds and their mixtures VIII. Quaternary mixtures of enantiotropes

Transition temperatures of quaternary mixtures prepared from the cyano and nitro derivatives of the two series, 4-hexadecyloxyphenyl 4-substituted benzoates (Ia,b) and 4-substituted phenyl 4-hexadecyloxy benzoates (IIa,b) have been determined by DSC and the transitions identified with polarized light microscopy. The cyano and nitro derivatives, in both series, were used because their molecules are enantiotropic. The method described before for the ternary system was extended to elucidate the eutectic composition of the quaternary system from the knowledge of either the eutectic compositions of the four possible ternary mixtures or of those of the six individual binary systems. A general equation was deduced to calculate the eutectic composition of any multi-component system from values determined for their individual binary systems. T_c values of binary, ternary, or quaternary mixtures were related to the polarizability anisotropy, Deltaalpha_X, of the individual C_Ar-X bonds. The mixture law was successfully applied.     

Liquid-liquid equilibria of (cyclohexane + acetonitrile + methylcyclohexane + toluene) and of {(acetonitrile + methylcyclohexane) + benzene or + toluene or + cyclohexane or + chlorobenzene} at 298.15 K

Tie-line results at 298.15 K and atmospheric pressure are reported for (cyclohexane + acetonitrile + methylcyclohexane + toluene) and for {(acetonitrile + methylcyclohexane) + benzene or + toluene or + cyclohexane or + chlorobenzene). The extended UNIQUAC and UNIQUAC equations are used to correlate binary vapour-liquid equilibria and mutual solubilities for 10 mixtures constituting the ternary mixtures and to predict the ternary and quaternary liquid-liquid equilibria by use of only binary parameters.     

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.     

Reassessment of the binary, ternary, and quaternary interactions in mixed electrolytes from thermodynamic quantities: The systems with uncommon ions containing hydrophobic character

Accurate estimates of the binary, ternary, and quaternary interactions in aqueous ionic mixtures with uncommon ions with hydrophobic character are presented. For this purpose, the values of the excess Gibbs free energy of mixing, Delta m G(E), obtained from our earlier isopiestic osmotic coefficients (Kumar, A. J. Phys. Chem. B2003, 107, 2808) for the mixtures of NaCl with four guanidinium (Gn+) salts-CH3COOGn, GnNO3, GnClO4, and Gn2SO4-are analyzed with the help of the method developed by Leifer and Wigent. The methodology of Leifer and Wigent is based on the equations of Scatchard-Rush-Johnson and Friedman's cluster integral expansion theory. The Scatchard-Rush-Johnson theory explicitly considers the quaternary and higher-order ionic interactions in the mixtures as compared to the specific ion interaction theory of Pitzer, which accounts for binary and ternary interactions only. The contributions due to binary, ternary, and quaternary interaction terms to total Delta m G(E) are estimated and discussed critically. Also, the interaction between the same two cations, for example, Gn+ - Gn+, is estimated and found significant, which otherwise cannot be obtained by the use of Pitzer's theory. The information obtained from the analysis of Delta(m)G(E) is also supported by the newly measured excess volumes of mixing, Delta m V(E), at 298.15 K. The individual contributions of the binary, ternary, and quaternary interaction terms to total Delta m V(E) are described. The binary, ternary, and quaternary interaction terms for both Delta m G(E) and Delta m V(E) are analyzed in terms of Friedman's cluster integral expansion theory.     

Parafac decomposition of three-way kinetic-spectrophotometric spectral matrices corresponding to mixtures of heavy metal ions

Binary and ternary mixtures of some of the following heavy metal ions Zn(II), Ni(II), Pb(II), Co(II) and Cd(II) were analyzed by a ligand substitution kinetic method. Three-way data matrices were generated by acquisition of UV-Vis spectra (332-580 nm) as a function of the time of a substitution reaction observed between the complex of the heavy metal ions with the non selective metallochromic indicator 4-(2-pyridylazo) resorcinol (PAR) and EDTA, and of different relative concentration of the metal ions (1-6 mM). The PARAFAC trilinear model, without restrictions, was used in the data analysis. A full decomposition of the data matrices was obtained (spectra, concentration and time profiles). It was shown that ligand substitution kinetic methods coupled to three-way chemometric analytical methods can be used for the development of robust sensors for the analysis of binary [Zn(II)+Ni(II), Pb(II)+Cd(II), Zn(II)+Pb(II)] or ternary [Zn(II)+Pb(II)+Co(II)] mixtures of metal ions in the micromolar concentration range.     

Spectrophotometric and spectrodensitometric determination of paracetamol and drotaverine HCl in combination

Thin-layer chromatography, first derivative, ratio spectra derivative spectrophotometry and Vierordt's method have been developed for the simultaneous determination of paracetamol and drotaverine HCl. TLC densitometric method depends on the difference in Rf values using ethyl acetate:methanol:ammonia (100:1:5 v/v/v) as a mobile phase. The spots of the two drugs were scanned at 249 and 308 nm over concentration ranges of 60-1200 microg/ml and 20-400 microg/ml with mean percentage recovery 100.11%+/-1.91 and 100.15%+/-1.87, respectively. The first derivative spectrophotometric method deals with the measurements at zero-crossing points 259 and 325 nm with mean percentage recovery 99.25%+/-1.08 and 99.45%+/-1.14, respectively. The ratio spectra first derivative technique was used at 246 and 305 nm with mean percentage recovery 99.75%+/-1.93 and 99.08%+/-1.22, respectively. Beer's law for first derivative and ratio spectra derivative methods was obeyed in the concentration range 0.8-12.8 and 0.4-6.4 microg/ml of paracetamol and drotaverine HCl, respectively. Vierordt's method was applied to over come the overlapping of paracetamol and drotaverine HCl in zero-order spectra in concentration range 2-26 and 2-40 microg/ml respectively. The suggested methods were successfully applied for the analysis of the two drugs in laboratory prepared mixtures and their pharmaceutical formulation. The validity of the methods was assessed by applying the standard addition technique. The obtained results were statistically agreed with those obtained by the reported method.     

Simultaneous spectrophotometric determination of levodopa and carbidopa in pharmaceutical formulations and water samples by using mean centering of ratio spectra and H-point standard addition methods

Two spectrophotometric methods are described for the simultaneous determination of binary mixtures of carbidopa and levodopa in pharmaceutical formulations, without prior separation steps, using the mean centering of ratio spectra and H-point standard addition methods (HPSAM). The methods are based on the difference in the absorption spectra for the products of the reaction of carbidopa and levodopa with 4-aminobenzoic acid in the presence of periodate ion at pH 4.0. The methods allow rapid and accurate determination of carbidopa and levodopa. The results showed that the methods were capable to simultaneous determination of 0.30-10.00 microg ml(-1) and 0.50-10.00 microg ml(-1) each of carbidopa and levodopa. The proposed methods were successfully applied to the simultaneous determination of carbidopa and levodopa in pharmaceutical samples.     

Effect of molecular structure on the phase behaviour of some liquid crystalline compounds and their mixtures VIII. Quaternary mixtures of enantiotropes

Transition temperatures of quaternary mixtures prepared from the cyano and nitro derivatives of the two series, 4-hexadecyloxyphenyl 4-substituted benzoates (Ia,b) and 4-substituted phenyl 4-hexadecyloxy benzoates (IIa,b) have been determined by DSC and the transitions identified with polarized light microscopy. The cyano and nitro derivatives, in both series, were used because their molecules are enantiotropic. The method described before for the ternary system was extended to elucidate the eutectic composition of the quaternary system from the knowledge of either the eutectic compositions of the four possible ternary mixtures or of those of the six individual binary systems. A general equation was deduced to calculate the eutectic composition of any multi-component system from values determined for their individual binary systems. T_c values of binary, ternary, or quaternary mixtures were related to the polarizability anisotropy, Deltaalpha_X, of the individual C_Ar-X bonds. The mixture law was successfully applied.     

Binary,ternary and quaternary complexes invloved in the systems pyridoxamine-glycine-imidazole with some bivalent metal ions

Equilibrium-based computer models using MINIQUAD-75 program were utilized to determine the stoichiometry and formation constants involved in the systems pyridoxamine(Pm)-glycine (Gly)-imidazole (lmd) with CO(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions. The data were obtained from potentiometric pH titration of the various binary and ternary quaternary systems under physiological-like conditions (0.15 M NaNO₃-37°C). Various composition ratios of metal and ligands were used. The ligand concentrations did not exceed 4 times the concentration of metal ion in the binary systems and 4 times of the metal ions in ternary systems. In case of the quaternary systems only imidazole concentrations were two or four times the concentrations of metal ions keeping those of other ligands equal to that of metal ions. The stability constants of the quaternary species are discussed in terms of binary and ternary constants as are the effect of ring size on the stability of mixed ligand species. In addition, electrostatic as well as statistical effects also are mentioned and the biological implications of these model equilibria are described.     

Applications involving the iodide ion: VII. Determination of small amounts of cerium(IV) and analysis of its mixtures with some metal ions

A simple, rapid, and reliable method for cerium(IV) alone; in presence of a variety of cations involving rare earths and iron (III); or in binary, ternary, and quaternary mixtures is given. By its aid 10^?3 down to 1.5 × 10^?5 mole of cerium(IV) were determined with requisite accuracy and precision. The potential breaks detecting the end points ranged from a maximum of 410 to a minimum of 100 mV/0.1 ml of 0.05 or 10^?4M titrant, respectively. Analysis of 15 mixtures using the present method together with other recommended procedures was always much less tedious or time-consuming than reported methods.     

The analysis of the zero-order and the second derivative spectra of retinol acetate, tocopherol acetate and coenzyme Q10 and estimation of their analytical usefulness for their simultaneous determination in synthetic mixtures and pharmaceuticals

The aim of the present work was to develop a simple and rapid method of retinol acetate, tocopherol acetate and coenzyme Q(10) determination in pharmaceuticals without involving any preparation operations like separation or masking. The values of second derivative amplitude at 212 nm for tocopherol, 351 nm for retinol and 222 nm for coenzyme were used for construction of calibration graphs. Beer's law is obeyed in the concentration range 0.5-20, 0.5-7.5 and 0.5-30 microg ml(-1) for retinol acetate, tocopherol acetate and coenzyme, respectively. The elaborated procedures were successfully applied to the simultaneous determination of studied compounds in their binary synthetic mixtures and in commercial preparations with high reliability and repeatability. Spectral properties of retinol acetate allows to determine its contents in ternary mixture which includes Vitamin E and coenzyme Q(10).     

H-point standard addition method for simultaneous spectrophotometric determination of Co(II) and Ni(II) by 1-(2-pyridylazo)2-naphthol in micellar media

A very simple and selective spectrophotometric method for simultaneous determination of Co(II) and Ni(II) by 1-(2-pyridylazo) 2-naphthol (PAN), in micellar media, using H-point standard addition method (HPSAM) is described. The ligand and its metal complexes (Co(II)-PAN and Ni(II)-PAN) were made water-soluble by the neutral surfactant Triton X-100, and therefore, no extraction with organic solvents was required. Formation of both the complexes was complete within 10 min at pH 9 (adjusted by ammonia buffer). The linear range was 0.10-2.00 microg ml(-1) for Co(II) and 0.05-1.50 microg ml(-1) for Ni(II). The relative standard deviation (R.S.D.) for the simultaneous determination of 0.50 microg ml(-1) each of Co(II) and Ni(II) was 2.32 and 3.13%, respectively. Interference effects of common anions and cations were studied and the method was applied to simultaneous determination of Co(II) and Ni(II) in alloy samples. The method was compared with derivative spectrophotometric method.     

An improved colorimetric determination of lead(II) in the presence of nonionic surfactant.

Phenanthraquinone monophenyl thiosemicarbazone (PPT), an excellent color-forming chelating agent, combines to Pb(II) to form a slightly soluble complex in aqueous solution. To determine this metal ion, a tedious and time-consuming separation technique, such as liquid-liquid extraction, has to be performed. However, the Pb(II)-PPT complex could be determined conveniently by ultraviolet-visible (UV-Vis) spectrophotometry at 520 nm in a Tween 80 micellar medium that has polyoxyethylene groups. After conditions, such as the pH, the concentration of PPT and the stability, were adjusted to their optimum values, the sensitivities of the Pb(II) ions in the Tween 80 micellar medium and in chloroform were compared. It was shown that the sensitivity of Pb(II) in the Tween 80 micellar medium was higher than in chloroform. The interference from different cations and anions was studied. Beer's law was obeyed over a concentration range of 0-40 microg ml(-1). The detection limit of Pb(II) was 0.036 microg ml(-1). The recovery yields of the lead(II) in the synthetic mixtures and water samples ranged from 98 to 99.8%, and their relative standard deviations (RSD) were below 4%. The proposed method was successfully applied to the determination of lead in certified reference samples, biological samples and in environmental water samples.     

A new method of Fourier-transform smoothing with ratio spectra derivative spectrophotometry

A new method which combines Fourier-transform smoothing with ratio spectra derivative spectrophotometry has been developed for analysis of binary and ternary mixtures. The method proposed has been applied to the simultaneous determination of a binary mixture of 0.974-2.026 x 10(-2) g L(-1) nitrate and nitrite and to a ternary mixture of 1.840-3.888 x 10(-3) g L(-1) histidine, phenylalanine, and tryptophan. The relative standard derivations are between 0.07 and 5.3% for the former system, and between 0.5 and 7.3% for the latter. The results show that the method proposed is more accurate than multiple linear regression.