Chromatography of inorganic ions o sulfoethyl cellulose layer in hydrochloric acid and in hydrochloric acid-ammonium thiocyanate media

Summary Chromatographic behavior of 51 inorganic ions has been systematically studied on layers of sulfoethyl (SE) cellulose, a strongly acidic exchanger, in hydrochloric acid and in acid-ammonium thiocyanate media. The sorption of most of the ions on he SE-cellulose decreases with increasing concentration of the acid and the thiocyanate. The characteristic retention of some metal ions of SE-cellulose layer can be recognized over a low concentration of the acid or the salt. Feasibilities for separations of analytical interest are also presented in both systems.     

Thin-layer chromatography of inorganic lons phosphate on cellulose in acetic acid and in acetic acid-ammonium acetate media

Summary Systematic study for the chromatographic behaviour of 49 inorganic ions has been carried out on cellulose phosphate layer in acetic acid and acetic acid — ammonium acetate media. Feasibilities for the effective separations of analytical interest are demonstrated on the 0.25 mm layer in both media.     

Chromatography of inorganic ions on cellulose phosphate layer in hydrochlorid acid and in acid ammonium thiocyanate media

Summary Thin-layers of an intermediately acidic cation exchanger, cellulose phosphate (P-cellulose), have systematically been used to study the chromatographic behavior of 58 inorganic ions in both hydrochloric acid and acid ammonium thiocyanate media (0.01–2.0 mol dm⁻³). In both solvent systems, the R _f values of many bivalent cations increase with increasing concentration of the acid and thiocyanate. Polyvalent metal ions including beryllium (II) and the others are strongly retained on the P-cellulose in the acid and thiocyanate systems tested. Palladium(II), mercury(II), ruthenium(III), rhenium(VII), arsenic(III), selenium(IV) and tellurium(IV) are not adsorbed on P-cellulose to any great extent. For silver(I), indium(III), gold(III), and platinum(IV), there are marked differences in the chromatographic behavior between hydrochloric acid and acid ammonium thiocyanate systems. Multicomponent separations conducted on P-cellulose plates with these eluents are presented.     

Thin-layer chromatography of inorganic ions on polyethyleneimine cellulose in sulfuric acid and acid-ammonium sulfate media

Summary The thin-layer chromatographic behavior of 49 inorganic ions on polyethyleneimine (PEI) cellulose, a weakly basic anion-exchanger, has been systematically studied in sulfuric acid and ammonium sulfate media (both 0.01–1.0 moldm⁻³). The sorption on the cellulose decreases with increasing concentration of the acid or sulfate for most of the ions and to a lesser extent for Hg(II), Bi(III), Th(IV), Nb(V), and U(VI). The R_f values of Pd(II), Ru(III), Au(III), Pt(IV), and Ta(V) are extremely low in both systems. Ba(II), Pb(II), Sb(III), Mo(VI), and W(VI) are also strongly retained on the layer. Oxy-anions such as As(III) and Se(VI) are not adsorbed on the cellulose to any great extent, but Re(VII) distributes on the plate with a R_f value of about 0.5. The characteristic retention on PEI-cellulose layer of several polyvalent ions, which form anionic sulfato complexes, can be observed in ammonium sulfate media. Possibilities for separations of analytical interest are also demonstrated in both systems.     

Titrimetric and spectrophotometric assay of pantoprazole in pharmaceuticals using cerium(IV) sulphate as oxidimetric agent

Titrimetric and spectrophotometric assay of pantoprazole sodium sesquihydrate (PSS) using cerium(IV) sulphate as the oxidimetric reagent is described. The methods are based on the oxidation of PSS with a measured excess of Ce(IV) sulphate followed by the determination of unreacted oxidant using different reaction schemes. In titrimetry, the unreacted oxidant was determined by back titration with ferrous ammonium sulphate (FAS) in sulphuric acid medium. Spectrophotometry involves the reduction of unreacted Ce(IV) sulphate with a fixed quantity of Fe(II). The resulting Fe(III) is complexed with thiocyanate and the absorbance is measured at 470 nm. In both the methods, the amount of Ce(lV) sulphate reacted corresponds to PSS concentration. Titrimetry is applicable over 1–10 mg range whereas in spectrophotometry, the calibration graph is linear in the range of 0.5–7.0 μg/mL and the calculated molar absorptivity value is 1.58 × 10⁵ L/mol cm. The validity of the proposed methods was tested by analyzing pure and dosage forms containing PSS. Statistical treatment of the results reflects that the proposed procedures are precise, accurate and easily applicable to the determination of PSS in pure form and in pharmaceutical formulations.     

Enhanced capacity of chitosan for transition-metal ions in sulphate-sulphuric acid solutions

Batch measurements have shown that the collection yields of chitosan for chromium(III), iron(III), nickel, copper(II), zinc and mercury(II) from sulphuric acid solutions are higher when the solutions contain ammonium sulphate, or when chitosan conditioned in ammonium sulphate is used, particularly at pH 3.0 and 5.0. The contrary is verified for the oxy-anions vanadate, chromate and molybdate. Manganese is never collected. At pH 1.0 no collection occurs. A procedure for recycling chromatographic columns includes fixation of Cu or Ni from a sulphate solution at pH 3-5 on sulphate-conditioned chitosan, and elution with 0.1M sulphuric acid/0.1M ammonium sulphate at pH 1.0; the presence of sulphate in the eluent obviates the detrimental effect of sulphuric acid on the next cycle. Sulphate is the favoured counter-ion of the chelated cations and its action produces shorter chromatographic bands. The interaction of sulphate with chitosan is discussed in terms of crystallinity and steric distribution of the protonated amino-groups in the polymer. Data on the new diethylaminohydroxypropylcellulose are included.     

Kinetics of iridium(III) catalyzed oxidation of benzaldehyde and <Emphasis Type="Italic">p</Emphasis>-nitrobenzaldehyde by cerium(IV) in aqueous acidic medium

Oxidation of benzaldehyde and p-nitro-benzaldehyde by cerium(IV) sulphate in aqueous sulphuric acid is strongly catalyzed by iridium(III) chloride. The complex formed between cerium(IV) and the organic substrate in the first equilibrium step gives another complex in the presence of iridium(III), which ultimately gives the corresponding aromatic acids as the product of oxidation. The order of the reaction follows first-order kinetics at low concentrations to zero order at higher concentrations of both the oxidant and organic substrate. The rate is directly proportional to the concentration of catalyst, but decreases sharply with increasing H⁺ ions and cerium(III) concentrations, while change in ionic strength of the medium or the concentration of acetic acid and Cl⁻ ions has no effect on the rate.     

Extraction of sulphuric acid from technological solution of hydroxylamine sulphate

The extraction of sulphuric acid from solutions containing hydroxylamine sulphate and ammonium sulphate with Cyanex 923 and the acid stripping from loaded Cyanex 923 are studied at 20 and 50°C. The effect of the numbers of extraction and stripping stages and the volume phase ratios in extraction and stripping upon sulphuric acid recovery is discussed. The process can be design to obtain a high or low recovery of sulphuric acid but with its low or high concentration, respectively.     

Etude du comportement des metaux alcalins sur le pentoxyde d'antimoine hydrate

The behaviour of Na⁺, K⁺, Rb⁺ and Cs⁺ ions on hydrated antimony pentoxide (HAP) has been studied, in various acid media and in ammonium hydroxide. The retention capacity of HAP for the alkali metal ions, as well as their retention rate, has been determined in all the media studied. Curves showing the variation of distribution coefficient values with acid or base concentration are presented.     

Flame Atomic Absorption Spectrometric Determination of Arsenic After Volatilization of As(III) with Chloride Ions

 The generation of volatile species of As(III) as a means to introduce arsenic into a flame atomic absorption spectrometer has been studied. The method is based on the reaction between As(III) and chloride ions in sulphuric acid medium. The reaction is performed in a discontinuous or batch mode. With this method 130 μl of a solution containing 17.5% (w/v) sodium chloride and As(III) are injected by a 500 ml.min⁻¹ N₂ carrier gas flow into 1 ml of concentrated sulphuric acid. The gaseous compounds generated are introduced into the spectrometer through the nebulizer and As is determined. Received October 3, 1998. Revision January 6, 1999.     

Spectrophotometric determination of dissolved tri n-butyl phosphate in aqueous streams of Purex process

A spectrophotometric method is developed for the determination of dissolved tri-n butyl phosphate (TBP) in aqueous streams of Purex process used in nuclear fuel reprocessing. The method is based on the formation of phosphomolybdate with added ammonium molybdate followed by reduction with hydrazine sulphate in acid medium. Orthophosphate and molybdate ions combine in acidic solution to give molybdophosphoric (phosphomolybdic) acid, which upon selective reduction (with hydrazinium sulphate) produces a blue colour, due to molybdenum blue. The intensity of blue colour is proportional to the amount of phosphate. If the acidity at the time of reduction is 0.5?M in sulphuric acid and hydrazinium sulphate is the reductant, the resulting blue complex exhibits maximum absorption at 810?C840?nm. The system obeys Lambert?CBeer??s law at 830?nm in the concentration range of 0.1?C1.0???g/ml of phosphate. Molar Absorptivity was determined to be 3.1?×?10^4?L?mol^?1?cm^?1 at 830?nm. The results obtained are reproducible with standard deviation of 1?% and relative error less than 2?% and are in good agreement with those obtained by ion chromatographic technique.     

Chromatography of inorganic ions on sulfoethyl cellulose layer in mixed sulfuric acid-organic solvent media

Summary The thin-layer chromatographic behavior of 49 inorganic ions has been systematically studied on layers of sulfoethyl (SE) cellulose, a strongly acidic cation-exchanger, with binary solvent mixtures consisting of sulfuric acid and an organic solvent such as methanol or acetone. The characteristic retention on the cellulose layer can be recognized for some ions forming sulfato complexes in the acid-organic solvent medium, and some aspects of the behavior are discussed. Chromatographic separations of analytical interest are also demonstrated on the SE-cellulose layer with acid-methanol and acid-acetone solutions used as mobile phases.     

Dry state preparation of radioiodine labeled meta-iodobenzylguanidine

Radioiodination of meta-iodobenzylguanidine (MIBG) by the isotopic exchange technique in the dry state has been performed. Benzoic acid, pivalic acid and acetamide have been used as molten protic media to promote isotopic exchange reactions. Ammonium sulphate, diammonium hydrogen ortho-phosphate and ammonium chloride were used as catalysts which provide acidic media to facilitate exchange reactions. Maximum radiochemical yields of 97.1±1.3% and 84.3±1.6% [¹³¹I] MIBG were obtained when ammonium sulphate and benzoic acid were used. High radiochemical yields of 88.3±1.1% and 74.4±1.5% [¹³¹I] MIBG were also obtained in case of diammonium hydrogen orthophosphate and pivalic acid which suggests their successful use as reaction media in the radioiodination of MIBG. The activation energy for the exchange reaction in ammonium sulphate was calculated to be 10.8 kcal/mole.     

Adsorption behaviour of some actinides on zirconium phosphate stability constant determinations

The adsorption behaviour of thorium, protactinium, uranium, neptonium and plutonium on zirconium phosphate from nitric acid and ammonium nitrate solutions was investigated. Partition data from the mentioned media together with that from chloride solutions were used to calculate formation constants for the concerned elements in the range of Cl⁻ and NO ₃ ⁻ activities <1M. Obtained β values were compared with those reported in the literature and indicated reasonable agreement.     

Thermal behaviour of nickel(II) sulphate,nitrate and halide complexes containing ammine and ethylenediamine as ligands

Thermal behaviour of nickel amine complexes containing SO₄ ²⁻, NO₃ ⁻, Cl⁻ and Br⁻ as counter ions and ammonia and ethylenediamine as ligands have been investigated using simultaneous TG/DTA coupled with mass spectroscopy (TG/DTA–MS). Evolved gas analyses detected various transient intermediates during thermal decomposition. The nickel ammonium sulphate complex produces NH, N, S, O and N₂ species. The nickel ammonium nitrate complex generated fragments like N, N₂, NO, O₂, N₂O, NH₂ and NH. The halide complexes produce NH₂, NH, N₂ and H₂ species during decomposition. The ligand ethylenediamine is fragmented as N₂/C₂H₄, NH₃ and H₂. The residue hexaamminenickel(II) sulphate produces NiO with crystallite size 50 nm. Hexaammine and tris(ethylenediamine)nickel(II) nitrate produce NiO in the range 25.5 nm and 23 nm, respectively. The halide complexes produce nano sized metallic nickel (20 nm) as the residue. Among the complexes studied, the nitrate containing complexes undergo simultaneous oxidation and reduction.     

Hydrolysis of titanium sulphate compounds

The influence of TiOSO₄ and free sulphuric acid concentrations in the starting solution on the degree of titanyl sulphate conversion to hydrated titanium dioxide and post-hydrolytic sulphuric acid was studied. Titanyl sulphate solution, an intermediate product in the commercial preparation of titanium dioxide pigments by sulphate route, was used. It was found that the degree of hydrolysis markedly depends on the studied parameters. The lower was the content of TiOSO₄ in the starting solution, the higher conversion was achieved. The degree of hydrolysis at the final stage varied between 81 % (420 g TiOSO₄ dm⁻³, 216 g H₂SO₄ dm⁻³) and 92 % (300 g TiOSO₄ dm⁻³, 216 g H₂SO₄ dm⁻³). The same relation was obtained when changing the concentration of free H₂SO₄ in the starting solution. The degree of hydrolysis at the final stage varied between 49 % (261 g H₂SO₄ dm⁻³, 340 g TiOSO₄ dm⁻³) and 96 % (136 g H₂SO₄ dm⁻³, 340 g TiOSO₄ dm⁻³). The particle size of the obtained hydrated titanium dioxide (HTD) also depends on the initial solution composition. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Synergistic and antagonistic effects between halide ions and carboxymethyl cellulose for the corrosion inhibition of mild steel in sulphuric acid solution

The corrosion and corrosion inhibition effect of carboxymethyl cellulose (CMC) for mild steel in sulphuric acid medium was investigated using chemical (weight loss and hydrogen evolution) techniques at 30–60 °C. The effect of addition of halide ions (Cl⁻, Br⁻, and I⁻) was also studied. It was found that CMC functions as an inhibitor for acid induced corrosion for mild steel. Inhibition efficiency increases with increase in immersion time but decreases with increase in temperature. Addition of halide ions reveals that chloride ions (Cl⁻) antagonize the inhibition process whereas iodide ions (I⁻) exert synergistic effect on the corrosion inhibition by CMC. Corrosion inhibitive effect was afforded by adsorption of CMC molecules onto the mild steel surface both in the absence and presence of halide ions which was found to follow Langmuir adsorption isotherm model. The phenomenon of physical adsorption is proposed from decrease in inhibition efficiency with increase in temperature. The inhibition mechanism was further corroborated by the values of thermodynamic and kinetic parameters obtained from the experimental data.     

Chromatography of inorganic ions on polyethyleneimine cellulose layer in hydrochloric acid — Ammonium thiocyanate media

Summary Thin-layer chromatographic behavior of 58 inorganic ions on polyethyleneimine (PEI) cellulose has been systematically surveyed in hydrochloric acid — ammonium thiocyanate media. In this media most of the ions distribute chromatographically on the layer. Ag(I), Hg(II), Pd(II), Au(III), Bi(III), Ru(III), Pt(IV), Nb(V), Ta(V), Mo(VI), and W(VI) are strongly retained, while alkali earths(II), Mg(II), As(III), Ti(IV), and Te(VI) are not absorbed to any great extent in this system. An interesting correlation was found between the R_f values on PEI-cellulose in the thiocyanate media and the paramagnetic moment of the rare earths(III). An oddeven fluctuation against the atomic number is also found for the heavy rare earths(III). Chromatographic separation of many inorganic ions of analytical interest is demonstrated in this system.     

2-Nitrodiphenylamine as a versatile high-potential reversible oxidation-reduction indicator

The use of 2-nitrodiphenylamine as a reversible indicator has been investigated in the titration of iron(II) with cerium(IV) sulphate, potassium dichromate and sodium vanadate in sulphuric acid media. Accurate results can be obtained with cerium(IV) sulphate in 0.5–5.0 M acid, with potassium dichromate in 5.0–7.0 M acid, and with sodium vanadate in 5.0–7.5 M acid. With cerium(IV) sulphate the titrations are preferably conducted in 2.0 M sulphuric acid or in a 1.0 M. sulphuric acid-1.0 M pechloric acid medium. Tungstic acid, acetic acid, arsenic(III) and manganese(II) do not interfere. In titrations of iron(II) with dichromate and vanadate, the colour changes at the end-point are much more vivid with 2-nitrodiphenylamine than with ferroin.     

Anion-exchange separation of uranium (VI) from thorium,zirconium, titanium,lanthanides and other elements in malonic and ascorbic acid media

Summary The anion-exchange behaviour of uranium (VI) has been studied extensively in various mineral acid media [1], but similar studies with organic acid solutions are lacking. Although the negatively charged complex of uranium in acetic acid was studied [2, 3], very small amounts of uranium could be separated and phosphate interfered. Such studies were further extended to non-aqueous media [4]. The anionic ascorbate complex of uranium and thorium were separated by selective elution with 1 mol dm^–3 hydrochloric acid and 3 mol dm^–3 sulphuric acid [5–7] respectively. Some attempts were also made to study complexes of uranium in formic and propionic acid [1] and it was separated from copper and thorium in oxalate media [4]. However systematic studies in malonate and to some extent in ascorbate media are lacking. This paper presents such studies.