Determination of molybdenum in steels by flow-injection spectrophometry

A flow-injection procedure is proposed for the determination of molybdenum in steels based on the thiocyanate method. Effects of iron(III), acidity, reagent concentration and interfering species were investigated by using flow-injection systems with the merging zones approach which reduced drastically the number of standard solutions to be prepared. Full details of system design are given. The procedure can be applied to several types of steel samples of industrial relevance. After dissolution of the steels in aqua regia, molybdenum can be determined in the range 0.10–4.00% (w/w) at a rate of up to 270 samples per hour with relative standard deviations less than 2%. The results agree with those obtained by atomic absorption spectrometry with the standard addition method and by plasma atomic emission spectrometry, and with certified values of standard reference samples.     

On-line electrolytic dissolution of alloys in flow injection analysis : Part 2: Spectrophotometric determination of molybdenum in steels

Electrolytic dissolution of steels is used for the determination of molybdenum by the flow injection spectrophotometric thiocyanate method. A direct current (200 mA) is applied for 8 s to the solid sample placed on a simple electrolytic chamber; the dissolved material serves as the injected sample zone. The best electrolyte for use as carrier stream is 1.0 M KCl/0.1 M HCl. No measurable baseline drift was observed during continous operation for 4 h. The sample throughput is 40 h^?1. Calibration is done with reference steel standards and is linear in the range o.7–2.7% (w/w) molybdenum; for a content of 2.21%, the relative standard deviation is 2.3% (n=10).     

The spectrophotometric determination of cobalt after extraction of tetramethylene-bis(triphenyl-phosphonium) tetrathiocyanatocobaltate(II) with microcrystalline benzophenone

Cobalt (0–130 μg) is determined spectrophotometrically at 625 nm after its adsorptive extraction as tetramethylene-bis(triphenylphosphonium) tetrathiocyanatocobalt(II) on microcrystalline benzophenone at pH 6.5 after dissolution of the solid phase in acetylacetone. The system is applied to the determination of cobalt (0.2–10%) in high-speed tool steels without prior separation of iron.     

Spectrophotometric determination of cobalt after extraction of tetrathiocyanatocobaltate(II) with brilliant green into microcrystalline naphthalene

Cobalt (0–20 μg) is determined spectrophotometrically at 635 nm after its adsorptive extraction as tetrathiocyanatocobaltate(II) with Brilliant Green on microcrystalline naphthalene at pH 6.5 and dissolution of the solid phase in toluene. The effects of pH, diverse ions and making studies are reported. The system is applied to the determination of cobalt (0.2–10%) in high-speed tool steels without prior separation of iron.     

Rapid determination of lead in steel by flameless atomic absorption spectrometry

A method for the determination of 1–100 p.p.m. of lead in high- and low-alloy steels by flameless atomic absorption is described. The sample was dissolved in aqua regia. and 2 μl of the diluted solution were pipetted into a Massmann-type furnace. Ashing of the sample at 625°C eliminated influences from hydrochloric acid. Fe, Cr and Ni gave similar negative interferences, which were compensated for by using low-alloy steel with standard additions. An interlaboratory comparison showed that this method gave the same result as extraction with TOPO in MIBK. The procedure could also be applied to commercial instruments. The time for a complete analysis including dissolution was 15 min.     

A simple procedure for hydrodynamic injection in flow injection analysis applied to the atomic absorption spectrometry of chromium in steels

The proposed technique for hydrodynamic injection is based on commutation in a simple flow-injection system with only one peristaltic pump. Precise results (usually r.s.d. < 1%) are attained even when injected volumes are small (1–10 μl). Dead-volume effects are associated with the mechanical flexibility of the system and with diffusion; differences between effective sample size and the dimensions of the injection duct are emphasized, particularly for small volumes. The proposed technique is checked for a spectrophotometric model system and confirmed by the atomic absorption spectrometry of chromium in steels. With a sampling rate of 120 h^?1, the precision is better than 99% for chromium contents in the 0.0–30.0% (w/w) range. The results agree well with those obtained by i.c.p./a/e/s. and conventional a.a.s.     

New solvents for cellulose: Hydrazine/thiocyanate salt system

The hydrazine/thiocyanate system was found to be an excellent solvent for cellulose. The solubility and solution properties were investigated. Even at room temperature, the combinations of hydrazine and lithium, sodium, and potassium thiocyanate had high dissolution power for cellulose, up to an 18% (w/w) maximum, unrelated to the polymorph, whereas a combination with ammonium thiocyanate exhibited a solubility difference among celluloses I, II, and III. The effect of the temperature cycling of the system for the rapid dissolution of cellulose was investigated thermodynamically. In these systems, a high concentration of salts was necessary to effect the cellulose dissolution; this suggested that an undissociated salt–solvent complex played an important role in the cellulose dissolution as implied by electroconductivity measurements of the hydrazine/salt system. Gel and liquid‐crystal formation was observed in all systems above 4 and 6% (w/w) cellulose concentrations, respectively. The values of both critical concentrations were quite similar to those observed in the ammonia/ammonium thiocyanate system studied earlier in our laboratories. The gelation temperature was between approximately 10 and 50 °C, depending on the salt and cellulose concentration. The dependence of the cellulose solubility on the degree of polymerization was also examined. It is suggested that these solvent systems have great potential for the fiber and film formation of cellulose. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 601–611, 2002; DOI 10.1002/pola.10135     

Determination of trace levels of calcium in steels by carbon-furnace atomic-absorption and atomic-emission spectrometry

Methods are described for the determination of trace levels of calcium in steels by atomic-absorption and atomic-emission spectrometry with a carbon furnace for atomization and excitation. In both cases, a commercial electrothermal atomic-absorption instrument was used. Samples were analysed after dissolution in a mixture of nitric, hydrochloric, and hydrofluoric acids.     

The effect of acetohydroxamic acid on stainless steel corrosion in nitric acid

We present the first study of the effect of acetohydroxamic acid (AHA) on the corrosion behaviour of stainless steels. Particularly, studies have been performed using steels and physico-chemical conditions equivalent to those proposed for use in advanced nuclear reprocessing platforms. In these, AHA has been shown to have little effect on either steel passivation or reductive dissolution of both SS304L and SS316L. However, under transpassive dissolution conditions, AHA while in part electrochemically oxidised to acetic acid and nitroxyl/hydroxylamine, also complexes with Fe^3 +, inhibiting secondary passivation and driving transpassive dissolution of both steels.     

Determination of Mo and Bi in steels by electrothermal atomic absorption spectrometry after complexation and sorption on activated carbon

A simple method for the preconcentration of Mo and Bi in steels is proposed. The analytes are complexed with the ammonium salt of dithiophosphoric acid O,O-diethyl ester and sorbed onto activated carbon. After desorption into a small volume of nitric acid at low pH, Mo and Bi are determined by electrothermal atomic absorption spectrometry. Iron(III) is reduced to Fe(II), which is not complexed and not significantly retained on the carbon. Enrichment factor of 23 and 26 were obtained for Mo and Bi, respectively. The method was applied to the analysis of four certified reference steels, after acid dissolution in a microwave system and good agreement was obtained with the certified or recommended values.     

Spectrophotometric determination of perchlorate after extraction of its brilliant green ion-pair with microcrystalline benzophenone

Perchlorate (0–30 μg) can be determined spectrophotometrically at 639 nm after its adsorptive extraction with Brilliant Green on microcrystalline benzophenone at pH 6.5 after dissolution of the solid phase in benzene. The effects of pH and diverse ions are reported. The system is applied to the determination of ? 0.003% (w/w) perchlorate in samples of potassium chlorate after prior destruction of chlorate.     

A study of the tungsten-hydroquinone color: Spectrophotometric determination of tungsten in tungsten steels

The red color produced by tungsten and hydroquinone in a concentrated sulfuric acid medium was studied. Various factors affecting the color were examined including the effects of phosphoric acid, water, hydrochloric acid, tin(II) chloride, and wavelength of measurement. The interferences from iron, molybdenum, vanadium, and titanium were studied. A method is described for the determination of tungsten in tungsten steels that involves precipitation of the tungsten with cinchonine. ignition to tungstic oxide, dissolution of the tungstic oxide in sodium hydroxide, and development of the tungsten hydroquinone color on an aliquot of the solution.     

Thermal, spectroscopic, and dissolution studies of the simvastatin–acetylsalicylic acid mixtures

The objective of the present investigation was to study the effect of eutectic formation on in vitro dissolution of simvastatin (SIM) released from mixtures with acetylsalicylic acid (ASA) prepared by a grinding method. SIM–ASA mixtures were characterized by means of differential scanning calorimetry (DSC), infrared spectroscopy (IR), X-ray powder diffractometry (XRPD), and in vitro dissolution tests. IR spectroscopy and XRPD studies indicated no interaction between SIM and ASA in the solid state. The DSC investigation has revealed that SIM and ASA form a simple eutectic system containing 66.6 % w/w of SIM at the eutectic point. In vitro dissolution studies of SIM and its mixtures with ASA were carried out. The eutectic mixture shows an appreciable increase in the dissolution rate in comparison with other ratios and SIM in 0.5 % w/v sodium lauryl sulfate. The dissolution enhancement of SIM was related to the effective wetting of the drug particles with a significantly reduced size released from eutectic composition. In conclusion, dissolution of SIM can be enhanced through eutectic formation with ASA by means of simple mechanical activation (a grinding method).     

Thermal,spectroscopic, and dissolution studies of ketoconazole–Pluronic F127 system

One strategy for improving the dissolution of poorly water soluble drugs is to prepare solid dispersions such as binary mixtures with hydrophilic carriers. These mixtures are generally characterized by better solubility than those of the individual components from which they are formed. In the present study, solid dispersions of ketoconazole (KET) with Pluronic F127 (PLU) were prepared by the grinding method. Solid–liquid equilibria in the system being studied were investigated by differential scanning calorimetry. A phase diagram for the whole range of compositions was constructed. The investigation revealed that ketoconazole and Pluronic F127 form a simple eutectic system containing 4.4 % w/w of ketoconazole at the eutectic point. The results of Fourier transform infrared spectroscopy and X-ray powder diffractometry studies of obtained mixtures suggest that there is no drug-carrier interaction and both components are crystalline in the solid dispersion with the whole range of composition. The prepared mixtures show an appreciable improvement of the dissolution rate of KET in 0.5 % w/v sodium lauryl sulfate. The improvement of the dissolution rate of drug is additionally increased by effective solubilization.     

Accurate and precise reference method for the determination of chromium in high-alloy steel

Methods for determining chromium in high-alloy steels based on potentiometric titration after oxidation of chromium(III) to chromium(VI) with peroxodisulphate were studied using different dissolution procedures, viz., dissolution in HClHNO₃ and fuming with H₂SO₄H₃PO₄, dissolution in HClHNO₃ and fuming with HClO₄, dissolution in HClHNO₃HF in a microwave oven, fusion in sodium peroxide in a zirconium crucible and dissolution in dilute H₂SO₄ and oxidation with H₂O₂. A back-titration was used with dichromate after addition of solid ammonium iron (II) sulphate.The dissolution procedures were tested on 24 certified reference materials (0.01–3.3% C, 10–325% Cr). All procedures except the second gave good results for samples with ? 0.8% C. For samples with ? 0.8% C, the third and fourth procedures gave significantly higher values and better precisions, and gave the best results for all samples. The relative standard deviations were, with few exceptions, below 0.2%.     

Experimentally determined temperature–concentration phase diagrams of monodisperse alkanes with chains containing between 100 and 200 carbons

The temperature–concentration phase (T–c) diagrams of the uniform n-alkanes C₁₀₂H₂₀₆, C₁₂₂H₂₄₆, C₁₆₂H₃₂₆, and C₁₉₈H₃₉₈ in toluene have been determined for solution concentrations in the range 0.1 to 6% (w/w). The shorter alkanes display a “classical” behavior with the expected, strong dependence of dissolution temperature on solution concentration. The longest alkane displays a very different, “polymeric” type behavior with a concentration independent dissolution temperature (for both extended and folded chain crystals). It is argued that no current theory of polymer dissolution is able to explain this behavior. It is suggested that a locally higher concentration occurs when molecules are partially attached to a crystal either during crystallization or dissolution, and that this increased local concentration accounts for the independence of dissolution temperature on the global concentration. There are some small variations in the dissolution temperature of crystals of the same thickness grown at the same concentration, but at different temperatures. These are ascribed to differences in the stacking of the separate layers. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 3188–3200, 1999     

Flow-injection spectrophotometric determination of cobalt by extraction as tetrathiocyanatocobaltate(II) with the ethylenebis(triphenylphosphoniu) cation

Cobalt (0–10 μg) may be determined spectrophotometrically at 625 nm after flow-injection extraction into chloroform of the ion associate ethylenebis(triphenylphosphonium) tetrathiocyanatocobaltate(II). The carrier stream contained 10% (w/v) ammonium fluoride and the reagent stream contained 0.5% (w/v) ethylenebis (triphenylphosphonium) bromide and 5% (w/v) ammonium thiocyanate. The injection rate was 20 h^?1. The calibration graph is linear up to 20 μg ml^?1 and detection limit is 0.23 μg ml^?1 cobalt, based on injection volumes of 500 μl. The system has been applied to the determination of cobalt in a range of tool steels.     

Characterization of Precipitates in Ti-Stabilized Steels with Low-Energy Electron-Induced X-Ray Spectrometry and Scanning Electron Microscopy

 Various kinds of precipitates can influence the mechanical properties of Ti-stabilized steels. The qualitative composition of the Ti inclusions can be characterized microscopically, whereas for quantitative information to be obtained time-consuming selective dissolution must be used. The present study aims at chemical speciation of the isolated precipitates as a solid phase with the help of soft-X-ray spectrometry. Whether the method is capable of giving both qualitative and quantitative information on the composition of Ti-mixtures is discussed. The precipitates in Ti-stabilized steels are investigated after chemical dissolution of the steel matrix with a bromine/methanol mixture (1:10). By combination of soft-X-ray spectrometry with X-ray fluorescence (XRF) and scanning electron microscopy (SEM) both qualitative and quantitative characterization of the precipitates can be performed. They were found to consist mainly of TiC and TiN. Received July 1, 1998. Revision December 29, 1998.     

Thermal study of the polyethyleneglycol 6000-triamterene system

This paper examines binary polyethyleneglycol (molecular weight 6000)-Triamterene (PEG 6000-T) solid dispersions (5–40 w/w% of T) prepared by the fusion carrier method, and physical mixtures (5–90 w/w% of T) are studied using DSC and Hot Stage Microscopy (HSM). The use of these combined techniques allows to explain the thermal behaviour on the basis of dissolution of T in the liquid carrier according to the progressive disappearance of the original crystals over a wide range of temperatures (ca. 100°C). The above fact, and possibly the sublimation of T, also could explain that at low T content (<- 30 w/w%), DSC curves exhibited only a single endothermic peak and/or weak endothermic peaks. On the basis of DSC data, a tentative phase diagram of this system is proposed.     

Automated determination of tin and nickel in brass by on-line anodic electrodissolution and electrothermal atomic absorption spectrometry

The application of an on-line metallic alloy dissolution system using anodic electrodissolution in a flow injection system for the determination of tin and nickel in copper alloys is described. After the electrolyzed material was collected in the autosampler cup, determination was carried out using electrothermal atomic absorption spectrometry (ETAAS). Using specific software developed in Turbo Pascal 7.0, it is possible to control electrolysis time, intensity of the applied current, and triggering of the three-way solenoid valves that push the fluids. Through manipulation of these variables, it is possible to adjust the analytical signal to within the working range of the spectrometer. Calibration of the spectrometer was accomplished by processing reference material. For tin, relative standard deviations for a series of measurements (n=5) performed on the same point and on different points of the sample was smaller than 2 and 4%, respectively; for nickel, 2 and 5%, respectively. The results for tin and nickel were in good agreement with those obtained through application of the classical methodology, as well as with data obtained by optical emission spectrometry. The detection limit for tin was 0.001% (w/w), whereas for nickel it was 0.003% (w/w). The analytical throughput is 30 samples h⁻¹.