0000000000117616
AUTHOR
G.ramis Ramos
Continuous-flow tristimulus colorimetry: a new approach for gradient scanning techniques
Abstract A flow-injection gradient scanning technique for colour evaluation by means of tristimulus colorimetry is described. Equipment and data acquisition requirements are discussed. The program CHROMA.FIA data the treatment and comparative chromatic analysis is presented. The chemical and flow conditions were optimized. Comparative studies using metallochromic indicators with both the flow-injection and the conventional batch procedures were made. The continuous-flow procedure provides good results and is more than fifteen times faster than the manual titrimetric procedure.
Acid—base properties of azo dyes in the presence of surfactants
Abstract The changes in the acid—base properties of an azo dye produced by the presence of surfactants, at surfactant concentrations below and above the CMC, are quantitatively described using a simple model and spectrophotometric and potentiometric measurements. The azo dye formed by aniline and N -(1-naphthyl)-ethylenediamine, and the surfactants sodium dodecyl sulphate, Triton X-100 and N -cetylpyridinium chloride (NCPC) are used. The protonation constants of the free and surfactant-bound dye species, the binding constant of the protonated and unprotonated forms of the dye, and the average aggregation number of the dye—NCPC aggregates are evaluated.
Determination of tyrosine and phenylalanine by derivatization with nitric acid and differential pulse polarography
Abstract The determination of tyrosine and phenylalanine by differential pulse polarography, after separation by thin-layer chromatography and derivatization with nitric acid to form the nitro compounds, is proposed. Experimental conditions for the derivatization treatment are established and the polarographic determination is optimized.
The catalytic-thermometric determination of molybdenum in steels based on the hydrogen peroxide-iodide indicator reaction
Abstract The Mo VI -catalysed hydrogen peroxide-iodide reaction has been optimised for thermometry in an HCl medium using the initial slope method. The substitution of sodium perborate by H 2 O 2 and the conversion of the reaction to a process showing a Landolt effect are considered and discussed. The linear range extended from 0.2 μg Mo VI ml −1 to 1.2 μg Mo VI ml −1 with a detection limit of 0.06 μg Mo VI ml −1 . Interferences were also studied. The optimised procedure was applied to the evaluation of molybdenum in steels after extraction with α-benzoinoxime in chloroform.
Reduction of Convective Low-Frequency Noise in Thermal Lens Spectrometry
The construction and optimization of a thermal lens spectrometer with coaxial pump/probe configuration is reported. The low-frequency noise of convective origin is studied in detail, and it is demonstrated that a horizontal slit, instead of a pinhole, can be used as a simple way of reducing the noise to a negligible level without losing sensitivity.
Detection of banned drugs in sport by micellar liquid chromatography
Abstract A rapid method for the determination of banned drugs in sport (including stimulants, anabolic steroids and diuretics) based on micellar liquid chromatography is proposed. The mobile phase is an aqueous solution of a surfactant (sodium dodecyl sulphate in this instance) and the stationary phase is octadecylsilica. The retention parameters of the drugs were established and the effect of a mobile phase organic modifier on the chromatographic behaviour of the compounds was studied. Improvements in efficiency were achieved by control of the temperature of the mobile phase. This method allows the direct injection of urine samples for the determination of drugs excreted free in urine: ami…
Spectrophotometric determination of mercury(II) and silver(I) with copper(II) and diethyldithiocarbamate in the presence of triton X-100
Abstract Procedures for the determination of mercury and silver by displacement of diethyldithiocarbamate (DDTC) from its copper complex in the presence of 1% Triton X-100, and measurement of the decrease in the Cu(DDTC) 2 absorbance, are described. The use of the surfactant avoids the need for an extraction step. Reproducibility within 1% and detection limits of 0.25 ppm Hg(II) and 0.45 ppm Ag(I) have been obtained, and linear calibration ranges up to 13 ppm Hg(II) and 15 ppm Ag(I). In the presence of 0.1 M EDTA very good selectivity is achieved.
Examination of the least-squares method applied to the evaluation of physicochemical parameters with linearized equations
Physicochemical parameters are frequently evaluated by the least-squares method after linearization of the equation which relates the experimental variables to the parameters of interest. When a given set of data is treated to evaluate (n+1) parameters. (n+2) nominally identical linearized equations are possible; each of these leads to different sets of values of the parameters which are also affected by different variances. These differences are also observed when statistical weights are used. Two methods for establishing which one of the (n+2) equations is best for fitting the data, i.e., simulation of experiments and propagation of errors, are discussed, compared and applied to a potenti…
Thermal lens spectrometric determination of cerium with oxine
Abstract The spectrophotometric and photothermal (TLS) procedures for cerium determination using 8-hydroxyquinoline (oxine), after extraction into chloroform, are compared. Photothermal measurements are made using a coaxial pump/probe thermal lens spectrometer. The use of high-purity reagents at low concentrations permits a decrease in the TLS blank signal and noise, leading to a limit of detection of 9 × 10−9 M (cerium extract concentration), 40-fold lower than the spectrophotometric value. The dynamic range extended up to 6 × 10−7 M and the relative standard deviation for 5 × 10−7 M cerium was 3.9%.
Flow-injection spectrophotometric determination of arylamines and sulphonamides by diazotization and coupling in a micellar medium
Abstract In a sodium dodecyl sulphate (SDS) micellar solution, the rate of coupling of a diazonium ion with N-(1- naphthyl)ethylenediamine (NED) increases greatly, the protonation of the resulting azo dyes takes place at higher pH values and the dyes are more soluble. These favourable features were applied to the development of a simple flow-injection spectrophotometric procedure for the determination of diazotizable substances of pharmaceutical interest. Limits of detection in the range 0.2–0.5 μg ml−1 (signal-to-noise ratio=3), with relative standard deviation of 0.7–3% (n=3) for 5 μg ml−1 standards, were obtained.
Inhibition of the precipitation of barium salts in sodium dodecyl sulfate/0.1 M HCl/n-pentanol microemulsions and liquid crystals
Abstract The phase ternary diagram of the sodium dodecyl sulfate (SDS)/0.1 M HCl/n-pentanol system is studied. Three monophase regions were observed: water rich and n-pentanol rich microemulsions, and a liquid crystal. These media have a strong ability to control the rate of crystal growth of barium sulfate and barium dodecyl sulfate, the precipitation being totally inhibited in the liquid crystal region.
Colorimetric determination of arylamines and sulphonamides by diazotization and coupling in a micellar solution
Abstract The use of a micellar solution as a means for improving the colorimetric determination of arylamines by diazotization and coupling is studied. Sodium dodecylsulphate (SDS), Triton X-100 (TX-100) and N -cetylpyridinium chloride (NCPC), together with the diazotizable substances aniline and sulphanilic acid and the coupling agents 1-naphthylamine and N -(1-naphthyl)ethylenediamine are used as model compounds. The protonation constants of the dyes follow the order SDS>H 2 O>TX-100>NCPC. In an SDS micellar solution the coupling rate increases greatly, allowing the rapid formation of the protonated dyes in an acetate buffer. Other advantages are the possibility of analysing very non-pola…
Some observations on the determination of sulfite by reduction to sulfide with sodium borohydride
Abstract Sodium borohydride is studied as an agent for reducing sulfite to sulfide. Rapid reductions are attained with greater than 97% recovery in the range 700–1200 μg of S/50 ml. Sulfate is not reduced.
Determination of aniline in vegetable oils by diazotization and coupling in a microemulsion medium
Abstract A microemulsion containing sodium dodecyl sulphate and n -pentanol in a mass ratio of 1 : 4, water and a vegetable oil was investigated using pseudo-tenary phase diagrams. The medium can co-solve important amounts of vegetable oils and aqueous solutions over a wide range of ionic strengths. A procedure for the determination of 1.4–140 μg ml −1 of aniline in vegetable oils using ionic diazotization and coupling reactions was developed. The absorbance was measured in an optically clear microemulsion containing 4% or 20% of oil. The procedure is much simpler and rapid than the official chromatographic methods and gives almost the same limits of detection (ca. 05 μg ml −1 ) using no mo…
Comparative study of several programs used in the potentiometric evaluation of equilibrium constants including an error sensitivity analysis
Abstract The programs MINIQUAD, MINIPOT, SUPERQUAD and PHCONST are applied to the evaluation of the protonation constants of several hypothetical polyprotic substances using simulated titrations, and the precision and accuracy of the results are discussed and compared. When statistical weights are used the results are very similar, the accuracy being better with PHCONST. Error sensitivity analysis was used as a means of establishing the influence of a systematic error of an experimental variable on the accuracy of the determination. An algorithm for the accurate calculation of error sensitivities is proposed and checked. Error sensitivities can be used to make a choice between the various m…
OPKINE, a multipurpose program for kinetics
The program OPKINE is presented for the study of reaction mechanisms and multicomponent analysis in dynamic conditions. This program is written in FORTRAN-77 for IBM 30/90 and VAX 8300 computers, and permits the simultaneous evaluation of both rate constants and initial reagent concentrations or, alternatively, rate constants and sensitivities. Up to 20 kinetic curves, with up to 400 points each, can be treated to evaluate up to 40 parameters. Integration of the system of differential equations is performed by means of the Runge–Kutta–Fehlberg method. OPKINE is provided with the Simplex, and modified versions of the Davidon–Fletcher–Powell and Gauss–Newton–Marquardt optimization methods. A …
Formation rates and protonation constants of azo dyes in a sodium dodecylsulphate micellar solution.
The effects of a sodium dodecylsulphate micellar solution on the coupling rates of several diazotizated arylamines with N-(1-naphthyl)-ethylenediamine and the shifts in the protonation constants of the corresponding azo dyes are quantitatively studied. Aniline, o-, m- and p-aminobenzoic acids, ethyl p-aminobenzoate and several sulphadrugs are used, and the relationships among the intensity of the effects and the molecular structure of the diazonium ions and the dyes are discussed. A single simplified procedure for the determination of all the substances at pH = 1.3 +/- 0.3, where coupling is quickly completed to directly produce the protonated form of the dyes, is established and applied to…
Graphical representation of polynuclear acid-base and complex equilibria.
Abstract A calculation procedure for diagrams of log CM = ƒ(pL) at various values of the ratio of analytical concentrations, CL/CM, in polynuclear binary systems is described. The diagrams are useful in the resolution of analytical problems of practical interest involving acid-base equilibria (such as the preparation of buffer solutions) and complex equilibria. The presence of a solid phase is also considered.
Information content of data and variables and types of weighting in least-squares regression methods
Abstract Algorithms are given for evaluating the relative amount of useful information related to a particular parameter which is carried by individual data points and intervals of the variables. The algorithms provide an efficient means of using the information contained in a set of data. Applications to the optimization of weighting in regression methods are described. Several informational and combined informational-statistical types of weighting are studied as a means of improving the accuracy and precision of the parameters obtained by non-linear regression.
A kinetic-catalytic method for iodide based on the simultaneous addition of inhibitor and substrate
Abstract A kinetic-catalytic method of analysis, based on the addition of a mixture of inhibitor and substrate, at a constant rate, over the catalyst in the presence of the other component of the indicator reaction is studied. The method is applied to the determination of iodide using the Ce(IV)As(III) catalytic reaction and Hg(II) as inhibitor. Under suitable experimental conditions the absorbance of the unconsumed Ce(IV) is inversely proportional to the initial iodide concentration.
Stiffness-Adaptive Taylor method for the integration of non-stiff and stiff kinetic models
A systematic derivation procedure that greatly facilitates the application of the Taylor method to the integration of kinetic models is developed. In addition, an algorithm that gives the integration step as a function of the required level of accuracy is proposed. Using the Taylor method, application of this algorithm is immediate and largely reduces the integration time. In addition, a new method of integration of kinetic models, whose most important feature is the self-adaptability to the stiffness of the system along the integration process, is developed. This “stiffness-adaptive” Taylor method (SAT method) makes use of several algorithms, combining them to meet the particular requireme…
Thermal Lens Spectrometric Detection of Catecholamines after Oxidation to Aminochromes
Abstract Experimental conditions for the spectrophotometric and thermal lens spectrometry (TLS) detection of catecholamines after oxidation to aminochromes with hexacyanoferrate (III) are optimized. At the low concentrations used in TLS, and in a 0.07 M citrate buffer, catecholamine oxidation can be performed at pH 7 and is immediate, whereas a lower pH value is required in spectrophotometry to avoid aminochrome polymerisation, the oxidation reactions being much slower. Similar TLS sensitivities are obtained for all catecholamines which facilitates HPLC evaluation. Sensitivity can be enhanced using a 50% ethanol-water medium. The linear dynamic range extends over two orders of magnitude, th…
Gravimetric determination of palladium with biguanide sulfate
Abstract Biguanides are interesting reagents for the determination of palladium owing to their solubility, chemical resistance, and selectivity in moderately acidic solutions. A procedure for the gravimetric determination of palladium(II) in the form of Pd(HL)2SO4, where HL = biguanide, is proposed and the conditions of precipitation, treatment of the precipitate, precision, accuracy, and selectivity of the procedure are discussed.
High-performance liquid chromatographic determination of diuretics in urine by micellar liquid chromatography.
The use of micellar liquid chromatography for the determination of diuretics in urine by direct injection of the sample into the chromatographic system is discussed. The retention of the urine matrix at the beginning of the chromatograms was observed for different sodium dodecyl sulphate (SDS) mobile phases. The eluent strengths of a hybrid SDS-methanol micellar mobile phase for several diuretics were compared and related to the stationary phase/water partition coefficient with a purely micellar mobile phase. The urine band was appreciably narrower with a mobile phase of 0.05 M SDS-5% methanol (v/v) at 50 degrees C (pH 6.9). With this mobile phase the determination of bendroflumethiazide an…
On the preparation of simple and universal buffers including polynuclear species
A simple generalized procedure for the calculation of electrolyte concentrations in pH-buffers is proposed. Mixtures of acid-base systems and formation of polynuclear species at high ionic strengths are considered, and a diagram useful for the study and preparation of the buffers is shown.