Analysis of iodine species in aqueous solutions

Iodine is a biologically important trace element. Its behaviour in the environment and in human metabolism is determined by the type of iodine species which takes part in chemical reactions. Knowledge of their concentrations is necessary to understand and describe the iodine reaction paths. A separation procedure is proposed for quick determination of common forms of iodine-iodide, iodate ions, molecular iodine and organoiodine (in the form of CH(3)I). The procedure consists of sequential sorption by passing the sample solution first through a solid-phase extraction cartridge to separate I(2) and CH(3)I from IO(3)(-) and I(-) then through an anion-exchange resin in a cartridge to retain the latter two species. Each loaded cartridge is eluted to separate the sorbed pair of species. Concentration determination of the resulting four solutions can be performed by standard methods, e.g. by spectrophotometry, tracer counting or with ion-selective electrodes.     

Redox-potentiometric determination of polyethylene glycol-20 000 by its reaction with iodine

A simple and rapid procedure for the potentiometric determination of polyethylene glycol with a molecular mass of 20000 (PEG-20000) was proposed. The procedure is based on the empirically found stoichiometry of the reaction of PEG-20000 precipitation with iodine. Titration was performed to a constant potential of the I ₃ ⁻ /3I⁻¹ redox couple measured with a platinum electrode. The relative standard deviation for PEG-20000 concentrations from 6.0 to 19.9 g/L was ≤5%.     

Radiochemical studies of the retention of volatile iodine in aqueous solutions

Volatile molecular iodine and organic iodine species would be generated under radiation in the gas space and sump of nuclear power plant containments during a severe accident involving core melt. Engineered and currently installed safety systems might not effectively retain highly volatile iodine species. Fast and efficient conversion to non-volatile species within the containment would lower the potential risk of a significant release into the environment and therefore, methods must be sought to reduce iodine volatility to a minimum or, ideally, to remove it completely. This paper presents the results of an experimental programme to obtain a fast and efficient reduction of highly volatile organic iodide species in aqueous solution into iodide ions.     

A phosphate catalyzed reaction of iodine with hydrazine in aqueous solutions

Pulse radiolysis was utilized to study the kinetics of the iodine-hydrazine reaction in aqueous solutions containing phosphate buffer in the pH range 5.5 to 7. The reaction rate was found to be proportional to and [I^–]^–1, but did not show simple proportionality to [H⁺]^–1 and was considerably higher than that found earlier when the pH of solutions was adjusted with HClO₄ or H₃BO₃. The results are in a formal agreement with the assumption that in phosphate buffered solutions a complex N₂H₄. HPO ₄ ^2– is formed, reacting with I₂ with a rate constant which is greater than that ascribed earlier to the reaction of N₂H₄ with I₂/Ref. 1/.     

Thermal analysis of aqueous micellar solutions

A micro differential temperature scanning calorimeter was used to characterize the structural changes between different types of micelles in aqueous solutions of ionic surfactants: anionic — sodium dodecylsulfate (SDS) — and cationic — hexadecyltrimethyl ammonium bromide (CTAB). Moreover, this technique allowed to confirm the existence of peculiar types of complexes between surfactants and selected solutes. In SDS solutions containing polyethylene glycols (PEG), the presence of complexes formed by small micelles adsorbed along the chains of the polymers was evidenced in the case of long enough polymer chains. In CTAB-phenol solutions, due to strong interactions between the polar heads of surfactant and phenol, molecular complexes of a composition of 1:1 molar ratio have been characterized. Depending on the ratio [phenol]/[CTAB], the rheological behaviour was found to change from fluid to viscoelastic and gel-like solutions, owing to the growth of elongated rod-like micelles. With entangled worm-like micelles, the important role of kinetics to reach the thermodynamic equilibria was shown.     

Determination of iodine concentration in aqueous solutions by proton activation analysis: preliminary results for digested human thyroids

The aim of our studies is to check the possibilities of using proton activation analysis as a competitive method over other analytical techniques applied for iodine determination. It is well known that long-term irradiation of biological samples leads to their decomposition and formation of gaseous radiolysis products, which increase the pressure inside the sample container. In case of using proton beam another problem with liquid samples appears. It is the production of ⁷Be via spallation reactions ¹⁶O(p, spall)⁷Be. The Compton effect from ⁷Be γ-line increases the detection limits for isotopes with low-energy γ-lines. AIC-144 cyclotron at The Niewodniczański Institute of Nuclear Physics Polish Academy of Science can accelerate protons up to energy of 60 MeV which is sufficient for (p,5n) reaction needed to obtain ¹²³I (T _1/2 = 13.27 h, Eγ = 159 keV, I = 83%) from stable ¹²⁷I, thus the Compton effect from ⁷Be was the main factor perturbing the analysis. Separation and removal of ⁷Be is required to improve the detection limit. The paper presents a method and an example of its application to the determination of iodine concentration in digested fragments of human thyroids obtained during surgical treatment of patients with different types of thyroid tumor.     

Adsorption of iodine from aqueous solutions by samples of tire yarn from regenerated cellulose

The adsorption of iodine by rayon tire yarn samples from aqueous solutions in which the concentration of iodide and triiodide ions is suppressed was studied. Fowler and Guggenheim's model of adsorption on regular localized monolayers appeared to be applicable to the adsorption phenomena considered. It is concluded that adsorption takes place on patches of sites in the cellulose–water gel.     

Catalytic end-point detection in titrimetric analysis

In catalytic end-point detection, the first drop of titrant in excess is not used for a stoichiometric reaction with the indicator (as in conventional titrations) but acts as, or liberates, a catalyst for the indicator reaction. A very small excess of titrant thus suffices to catalyze large amounts of the indicator reaction mixture. Such catalytic end-points are therefore very sensitive. Terminology is discussed briefly. The various types of titration (direct, with a “brake”, reversed, indirect and substitution) and of end-point detection (visual, olfactory, photometric, thermometric and electrometric) are described. Applications of these techniques are summarized.     

NMR analysis of cellulose dissolved in aqueous NaOH solutions

Low molecular weight cellulose (degree of polymerization = ca 15) was dissolved in 4-- 30% NaOD/D2O, and relationships between 1H- and 13C-chemical shifts of the cellulose and NaOD concentrations were studied in terms of the dissociation of three hydroxyl groups of cellulose in aqueous NaOH solutions. All C---H proton resonances were shifted upfield linearly with an increase in the NaOD concentration, indicating that all C---H protons of cellulose undergo the electron-shielding effect by NaOH. On the other hand, the shifting patterns of carbon resonances varied among the six carbons: C1 and C4 carbons undergo the electron-shielding effect, whereas C2, C3, C5, and C6 carbons experience the electron-deshielding effect by NaOH. Changes in 13C-chemical shifts of cellulose carbons in 4--30% NaOD/D2O indicate that C3---OH has the highest resistance to dissociation in aqueous NaOH of the three hydroxyl groups of an anhydroglucose residue. It is plausible, at least from the aspects of 13C-chemical shifts, that cellulose molecules dissolving in 20--30% NaOH behave differently from those swollen in 20--30% NaOH as alkali- cellulose     

Spectral analysis of naringenin deprotonation in aqueous ethanol solutions

The deprotonation of 5,7-dihydroxy-2-(4-hydroxyphenyl)chroman-4-one (naringenin) was studied in aqueous solutions of ethanol and 0.1 mol L^?1 sodium perchlorate at 25°C. The chemical species that contributed to deprotonation were evaluated together with their pure spectral characteristics and concentration profiles by some chemometric methods. The deprotonation constants assigned by pK ₁, pK ₂, and pK ₃ were determined by multivariate curve analysis of spectral data at different pcH values. The pure spectral analysis concordant with the theoretical prediction of deprotonation constants indicates that the acidity of hydroxyl groups in naringenin decreases in the order: 7-OH, 4′-OH, 5-OH. The effects of the solvent on deprotonation were analysed in terms of the linear solvation energy relationships using the model of Kamlet, Abboud, and Taft (KAT). Multiple linear regressions were aimed towards correlating the deprotonation constants with the microscopic parameters containing hydrogen-bond acidity (α), dipolarity/polarisability (π*), and hydrogen-bond basicity (β). The most significant parameter was found to be the hydrogen-bond acidity of binary mixtures.     

Accuracy analysis on concentration determination of molecular iodine in gamma irradiated solutions

Journal of Radioanalytical and Nuclear Chemistry - The gamma irradiated aqueous samples containing I2 and I? were measured by two different analysis methods using an UV–VIS...     

Chlorite as an oxidising agent in titrimetric analysis

The possibilities of using a solution of sodium chlorite as an oxidising agent in titrimetric analysis have been investigated. Such a solution, in the absence of light, is chronometrically stable and convenient for the direct titration of sulphite (in applying the titre to a known solution of sulphite); iron, by its reduction to iron^II with tin^II chloride (the result to be read from the difference between the potential-jump corresponding to iron^II × tin^II and the first jump corresponding to tin^II); arsenite; iodide. The titration is generally carried out in an acidic medium, with the occasional application of catalysts such as potassium iodate.     

Pulse radiolysis of pentacyanonitrosylferrate/II/ ions in aqueous solutions

Pulse radiolysis of aqueous solutions of sodium pentacyanonitrosylferrate/II/ Na₂[Fe/CN/₅NO] /sodium nitroprusside/ was studied in the presence of ethylene glycol as an OH radical scavenger. The rate constants of the one-electron reduction of nitroprusside ion were measured with e _q ^– and with radicals derived from some alcohols /ethylene glycol, ethanol, 2-propanol/ as reducing species. The results show that the transition state for the reduction by alcohol radicals is polar. The only observed product of reduction is the Fe/CN/₅NO^3– ion, which then undergoes a slow dissociation to form Fe/CN/₄NO^2–. Only a small isotope effect k_H/k_D=1.08 was observed in D₂O solutions for the dissociation reaction. This suggests an intramolecular electron transfer as rate-determining step for the dissociation reaction.Dedicated to Professor Schulte-Frohlinde on the occasion of his 60th birthday.     

Polarized Raman spectra of aqueous solutions and band component analysis

Polarized Raman spectra of water in ν (OH) and δ (OH₂) regions has been recorded for various aqueous solutions of electrolytes of types AB and AB₂ (A=Li, Na, K, Ca; B=F, Cl, Br, I, NO₃) over a wide concentration range. The isotropic and anisotropic components of the intensity of ν (OH) band has been analysed as a function of concentration and as function of the nature of the ions by means of the Fourier transform analysis.     

Polyaniline coated micro-capillaries for continuous flow analysis of aqueous solutions

The inner walls of fused silica micro-capillaries were successfully coated with polyaniline nanofibres using the “grafting” approach. The optical response of polyaniline coatings was evaluated during the subsequent redoping–dedoping processes with hydrochloric acid and ammonia solutions, respectively, that were passed inside the micro-capillary in continuous flow. The optical absorbance of the polyaniline coatings was measured and analysed in the wavelength interval of [300–850 nm] to determine its optical sensitivity to different concentrations of ammonia. It was found that the optical properties of polyaniline coatings change in response to ammonia solutions in a wide concentration range from 0.2 ppm to 2000 ppm. The polyaniline coatings employed as a sensing material for the optical detection of aqueous ammonia have a fast response time and a fast regeneration time of less than 5 s at room temperature. The coating was fully characterised by scanning electron microscopy, Raman spectroscopy, absorbance measurements and kinetic studies. The response of the coatings showed very good reproducibility, demonstrating that this platform can be used for the development of micro-capillary integrated sensors based on the inherited sensing properties of polyaniline.