Quantitative determination of hexavalent chromium in aqueous solutions by UV-Vis spectrophotometer

In the last decade, different methods have been developed for the determination of chromium(VI) concentration in water. These methods use high cost equipment or they require a long preparation time. Because of their drawbacks, this paper describes an on-line, rapid and sensitive procedure for the determination of Cr(VI) concentrations in aqueous solutions via pH and absorption measurements. Only four Cr(VI) species are considered. The effects of pH and of total amount of chromium on the Cr(VI) speciation are investigated. The molar absorptivities of four chromium species at 371 nm are determined by minimising an objective function. The knowledge of these molar absorptivities and the measurements of pH and absorption at 371 nm lead to a rapid determination of total Cr(VI) concentration. The reliability and applicability of the method were confirmed using synthetic water samples.      

Infrared spectroscopy of aqueous ionic salt solutions at low concentrations

The analysis by infrared spectroscopy of aqueous solutions of the binary inorganic salts NaI and NaCl and the ternary salts CaCl2 and BaCl2 at concentrations from 1000 to 2 mM was carried out to complement a previous study done at higher concentrations on nine binary salts (alkali halides) and one ternary salt (MgCl2) [J.-J. Max and C. Chapados, J. Chem. Phys. 115, 2664 (2001)]. These salts are completely ionized in aqueous solutions, forming monoatomic species that do not absorb IR but that perturb the surrounding water, modifying its spectrum. The factor analysis of the spectra revealed that all these salt solutions were composed of two water types: pure water and salt solvated water. The authors obtained pure salt solvated water spectra for all the salts using an extrapolation technique. The water types obtained are constant for the binary and ternary salts down to 2 mM. For the binary salts, we determine that 5.0 and 4.0 water molecules are solvated to the Na+-Cl- and Na+-I- ion pairs, respectively. These numbers are the same as that obtained at higher concentrations. For the new ternary salts, we find that 6.0 and 8.0 water molecules are solvated to Ca++-(Cl-)2 and Ba++-(Cl-)2 ion pairs, respectively. These numbers are higher than the four water molecules solvated to Mg++-(Cl-)2 ion pairs determined previously, but show a progression that follows their atomic numbers. These results constitute new experimental results on "simple" systems whose molecular organization is still a matter of debate. The IR method that probes the system at the molecular level is a method different than the macroscopic ones that give the activity coefficients. The IR gives direct observation at the molecular level of the strong ion-water interactions that are often neglected and its water structure not considered in macroscopic methods. The present results and their analysis together with those obtained by other methods will facilitate the determination of the organization of these aqueous systems.     

A simple spectrophotometric determination of hydrogen peroxide at low concentrations in aqueous solution

The procedure described for the determination of hydrogen peroxide in aqueous solution, at concentrations in the rnage 1?120×10^?6 mol l^?1, is based on reduction of copper (II) ions by hydrogen peroxide in the presence of excess of 2,9-dimethyl-1,10-phenanthroline (DMP) to form the copper (I)-DMP complex. The copper (I)-DMP complex is determined directly by spectrophotometric measurement at 454 nm.     

Modeling of gamma-ray radiolysis data at moderate and low solute concentrations in aqueous solutions

A radiation chemical model developed for use in pulse radiolysis studies employing high energy electrons has been applied to the calculation of yields in aqueous chemical systems irradiated with ⁶⁰Co γ-rays. The fit between model calculations and experimental data is almost within experimental error in most instances. Trends are accurately predicted where quantitative agreement is not found. Predictions of molecular yields of H₂ and H₂O₂ in the presence of scavengers of precursors of these molecules are in good agreement if an initial molecular yield is assumed for both molecules. Agreement between model predictions and experimental data is reasonable at low solute concentrations where back reactions of spur intermediates are important. The model appears to be useful in modeling steady state γ radiolysis as well as pulse radiolysis data. Implications of the model in predicting possible errors in rate constant determinations are discussed.     

Electroinjection determination of aluminum in aqueous solutions

A procedure is proposed for determining aluminum(III) in water over a concentration range of 0.1–2.0 mg/L in the presence of commensurable amounts of iron(III) using electroinjection analysis. The following parameters were varied in the experiments: the composition and pH of a working buffer solution, the reagent-to-metal concentration ratio, the time of sample injection, the composition of a buffer solution in sample preparation for analysis, the concentration of the reagent (Xylenol Orange), and the reaction time. As a result of this, the sensitivity and selectivity of determining aluminum were improved as compared with the currently available procedures.     

Taylor dispersion measurements at low electrolyte concentrations. I. Tetraalkylammonium perchlorate aqueous solutions

An equipment for the determination of mutual diffusion coefficients using the Taylor's dispersion technique is described. The radius of the capillary was determined with the help of various calibration methods. Diffusion coefficients of aqueous tetraalkylammonium perchlorates, Me₄NClO₄, and Et₄NClO₄, were measured at 25°C in the concentration range 10^–3 to 5×10^–2 mol-dm^–3, and the slightly soluble Pr₄NClO₄ up to 1×10^–2 mol-dm^–3. The slope of linear plots ofD vs. is in agreement with theory, in contrast to the limiting valuesD ₀, which all deviate by about –5% from the Nernst-Hartley values.     

Precision determination of deuterium in aqueous solutions by a pycnometer method

Precision determination of deuterium (deuterium oxide) in aqueous mixtures were made by a pyenometer method over the range of 1 to 99 atom-% deuterium. The average deviation was ± 0.02 atom-%, deuterium.Absolute values of high-deuterium content samples are obtained by reference to a sample of high deuterium oxide content (> 99 atom-% deuterium) which has been measured by a mass spectrometer, instead of to distilled water. Matched-standards are also provided for intermediate-content (25–75 atom-%) deuterium oxide samples.     

Spreading of surfactant solutions over thin aqueous layers at low concentrations: Influence of solubility

A small droplet of aqueous surfactant solution at concentration below CMC was deposited on a thin water layer. A moving circular wave in the centre was formed. The time evolution of the radius of the wave was monitored. Two surfactants of different solubility were used. It was shown that the time evolution of the moving front (i) proceeds in two stages: a fast first stage and slower second stage; (ii) the time evolution of the front motion substantially depends on the surfactant solubility. We suggest a qualitative explanation of the phenomenon, which reasonably agrees with our experimental observations.     

Photoelectrochemical determination of inorganic mercury in aqueous solutions

An analytical method using an optical probe in a photoelectrochemical cell for the sensitive and selective determination of aqueous Hg²⁺ is presented. A previously synthesized Hg²⁺ selective chemosensor, proven to be Hg²⁺ sensitive up to 2 μg L⁻¹, has been immobilized onto indium tin oxide (ITO) electrodes in a composite form with polyaniline. The coated ITO electrode was placed in a photoelectrochemical cell under closed circuit conditions in which the optical recognition of the chemosensor was converted to a measurable signal. A composite of the fluorescent chemosensor, Rhodamine 6G derivative (RS), and polyaniline (PANI) was immobilized on ITO glass plates and subjected to photovoltage measurements in the absence and presence of Hg²⁺. The optical responses of the coated electrode were used to determine the sensitivity and selectivity of the immobilized sensor to Hg²⁺ in the presence of background ions. The optical response of the PANI-dye coated electrode increased linearly with increasing Hg²⁺ concentration in the range 10-150 μg L⁻¹, with a detection limit of 6 μg L⁻¹.     

Photometric cyclic-injection determination of arsenic in aqueous solutions

A procedure for the photometric on-line determination of trace arsenic in aqueous solutions was developed. The procedure is based on the reaction gas extraction of arsenic as arsine followed by liquid-absorption separation from a gas phase into a solution of a photometric reagent (2-(p-nitrophenyl)-3,5-diphenyltetrazolium chloride). The determination limit was 10 μg/L at a sample volume of 50 mL.     

Calorimetric determination of activated carbons in aqueous solutions

The interactions among five samples of activated carbons, obtained from different lignocellulosic materials with different degrees of activation of approximately 20% and aqueous solutions of phenol and 4-nitro phenol are studied by means of the determination of immersion enthalpies. It is established that the obtained activated carbons are of a basic character and show values for the pH at the point of zero charge, pH_PZC, that range from 7.4 to 9.7 and, in all cases, higher total basicity contents than the values obtained for total acidity. The immersion heat of the activated carbons in CCl₄ and water is determined obtaining values which are higher for CCl₄ immersion and vary from 31.4 to 48.6 J g⁻¹. The hydrophobic factor, hf, it is calculated from the relation between of the immersion heat of the activated carbons in CCl₄ and the immersion heat in water, the obtained values were 2.98 and 6.75, which are greater than 1 due to the greater values obtained in CCl₄ when compared to the values obtained in water. Immersion enthalpies in phenol solution range from 7.6 to 13.9 J g⁻¹ and for the case of 4-nitro phenol such enthalpies range from 12.7 to 20.5 J g⁻¹; all the 5 samples studied showed a higher value for the heat of immersion in aqueous solutions of 4-nitro phenol.     

Americium and samarium determination in aqueous solutions after separation by cation-exchange

The concentration of trivalent americium and samarium in aqueous samples has been determined by means of alpha-radiometry and UV–Vis photometry, respectively, after chemical separation and pre-concentration of the elements by cation-exchange using Chelex-100 resin. Method calibration was performed using americium (²⁴¹Am) and samarium standard solutions and resulted in a high chemical recovery for cation-exchange. Regarding, the effect of physicochemical parameters (e.g. pH, salinity, competitive cations and colloidal species) on the separation recovery of the trivalent elements from aqueous solutions by cation-exchange has also been investigated. The investigation was performed to evaluate the applicability of cation-exchange as separation and pre-concentration method prior to the quantitative analysis of trivalent f-elements in water samples, and has shown that the method could be successfully applied to waters with relatively low dissolved solid content.     

The determination of hydrogen peroxide in aqueous solutions by square wave voltammetry

Hydrogen peroxide in aqueous solutions can be determined directly by square wave voltammetry. The method is applicable to samples with a large range of pH in matrices ranging from distilled de-ionized water to sea-water. Its dynamic range extends from 0.5 to at least 1000 microM and the precision is about +/-6% at 2.5 microM and +/-2% at 215 microM. In comparison to DC and differential pulse polarography, by using square wave voltammetry the scan time is reduced from minutes to a fraction of a second, the sensitivity is increased by several-fold and the dynamic range has been greatly expanded at both the lower and the upper end by at least an order of magnitude. The low detection limit allows this method to be applied to the determination of H(2)O(2) in some samples of rainwater.