An ion-exchange scheme for the determination of the major cations in sea water

A cation-exchange scheme is described for the determination of the principal cations in sea water. The cations are adsorbed onto a column of Amberlite CG 120. Sodium and potassium are eluted together using 0.15 M ammonium chloride and determined gravimetrically as sulphates; potassium is then determined gravimetrically as potassium tetraphenylboron and sodium is determined by difference. Magnesium and calcium are eluted by means of 0.35 M ammonium chloride and 1 M ammonium acetylacetonate (pH 9.6) respectively, and titrated with EDTA. Finally, strontium is eluted with 2 M nitric acid and determined by flame photometry. Tests made using an artificial sea water showed that the method had coefficients of variation of 0.02, o.22, 0.04, 0.08 and 0.8% for sodium, potassium, magnesium, calcium and strontium respectively.     

The influence of chemical activation of the M45K20 sorbent on the heat effects of sorption of ammonium ions

Calorimetric measurements were performed and the heat effects of sorption of ammonium ions from aqueous solutions by the M₄₅K₂₀ natural sorbent and its acid- and alkali-activated forms were calculated.     

A study of the sorption properties of natural calcium clinoptilolite by using radioactive indicators

The sorption of monovalent ions (cesium, silver, thallium, mercury), bivalent ions (strontium, barium, lead, copper, cobalt, zinc) and polyvalent ions (cerium) on calcium clinoptilolite under dynamic conditions has been studied. Both the dynamic exchange capacities in the different break-through of the ions and the degree of the exchanging ions in sorption of different metal cations have been determined. The good selectivity of calcium clinoptilolite in relation to cesium and strontium is displayed in the presence of sodium. The influence of various factors on the sorption the thermal and radiation treatment of the sorbent, the pH and concentration of solutions, equilibration time, presence of alkali and alkali earth ions deactivating agents—EDTA, citric acid tartaric acid, and boric acid in solution has been studied. The optimum conditions of sorption have been determined. Experiments for the desorption of cesium and strontium have been carried out. The possibility to use calcium clinoptilolite for the purpose of deactivation of radioactive wastes is shown. The better sorption properties of that sorbent, compared to calcium clinoptilolite, can be explained by the higher aluminium content, as well as by a prevalence of calcium and magnesium in its ion exchange complex.     

Ammonium sorption from aqueous solutions by the natural zeolite Transcarpathian clinoptilolite studied under dynamic conditions

The scope of this study is ammonium-ion uptake from synthetic aqueous solutions onto raw and pretreated forms of the natural zeolite Transcarpathian clinoptilolite under dynamic conditions. Hydrogen ions displaced exchangeable cations on the clinoptilolite in distilled water (sodium ions) and hydrochloric acid (sodium, potassium, and calcium ions) and destroyed the zeolite framework structure in the last case. Ammonium uptake onto the zeolite occurs by exchange with Na(+), Ca(2+), and K(+) ions. Although Na(+) ions were observed to be more easily exchanged for both hydrogen and ammonium ions, the role of Ca(2+) ions increased with zeolite saturation by NH(+)(4) ions. The maximum sorption capacity of the clinoptilolite toward NH(+)(4) ions, estimated under dynamic conditions, is significantly higher than that measured under static conditions; proximity of the values of a distribution coefficient and a retardation factor for different conditions (215-265 dm(3)/kg and 979-1107, respectively) allows us to use these parameters to model ammonium uptake onto the clinoptilolite. Slowing down or interruption in filtration resulted in the improvement of ammonium sorption properties of the zeolite. The ammonium removal improves with use of the finer fractions of the clinoptilolite up to 0.35 mm. A recycling study results confirmed the importance of external diffusion for ammonium sorption by the clinoptilolite. Preliminary treatment of the sorbent confirmed the predominant importance of the ion-exchange mechanism. The advantage of prior NaCl treatment of the clinoptilolite in improvement of ammonium removal over the other techniques was shown.     

Thermometric titration of some molybdates,molybdic acid,and molybdenum trioxide

A thermometric titrator equipped with differential thermistor is used for the titration of molybdenum in sodium molybdate, potassium molybdate, magnesium molybdate, tetramethylammonium molybdate, and tetraethylammonium molybdate, based on their reactions with hydrochloric acid, and in ammonium paramolybdate, molybdic acid, and molybdenum trioxide, based on their reactions with sodium hydroxide. Orthomolybdates and ammonium paramolybdate were determined in the 0.5–0.005 M range; sufficient solid molybdic acid or molybdenum trioxide was taken to give a final 0.01–0.5 M solution in 20 ml of water. The method is simple and very quick. The standard deviation varies from 0.5 to 1.5% depending on the amount of sample taken.     

Preconcentration and determination of calcium and magnesium in brine with flow-injection systems

On-line preconcentration on a chelating resin (Dowex A-1) and elution with 0.1 M hydorchloric acid is followed by spectrophotometry based on the metal complexes formed with 1- (2-hydroxy-4-diethylamino-1-phenylazo)-2-hydroxynaphthalene-3,6-disulfonic acid. The total concentration of calcium and magnesium is determined; in a second sample, calcium is masked with a ligand buffer containing excess of barium(II) and EGTA, and magnesium is determined. The calcium concentration is measured by difference. Magnesium (1–30 μg l^?1 and calcium (8– 10 μg l^?1) in 2.5 M sodium chloride can be determined. Calcium and magnesium in analytical reagent-grade sodium chloride and potassium chloride and primary standard sodium chloride are aslo determined. The method based on the exchange between calcium ions and Mg(EDTA) is proposed to enchance the sensitivity for calcium.     

Calcium ion selective membrane electrode

The calcium salts of the mono- and diesters of [4-(1,1,3,3-tetramethylbutyl)phenyl phosphoric acid] have been prepared, and the individual esters as well as mixtures of the esters have been used with several varieties of polyvinyl chloride to construct macro membrane electrodes selective to calcium ions. These electrodes have been calibrated by using solutions of CaCl₂ and Ca ion buffers. The mixed ester electrodes showed Nernstian response in the concentration range 10^-1 to 10^-7M; the diester electrodes showed Nernstian response down to 7.9 x 10^-8M. The detection limit of the mixed ester electrode was 10^-8M, whereas that of the diester electrode was 7.9 x 10^-9M. Contrary to these results, the monoester electrodes showed unsatisfactory behavior. The responses of both the mixed ester and diester electrodes to calcium ions were not affected by the presence of sodium, potassium, or other divalent ions. Only ferric and lanthanum ions showed interferences with the electrode response to calcium ions. p]The electrode response was independent of pH in the approximate range 5–8 at a CaCl₂ concentration of 10^-4M. As the Ca ion concentration was increased, the range of pH independence widened to approximately 4–8. The dynamic response time constant of the mixed ester electrode was in the range 0.7–1.5 sec, whereas that of the diester electrode was in the range 0.5–0.75 sec.     

Activity coefficients of components of the sorbent phase in the nonexchange sorption of chloride-containing electrolytes on AN-31 low-basicity anion exchanger in the Cl form

Activity coefficients of components of the sorbent phase in the nonexchange sorption of chloride-containing electrolytes (hydrochloric acid and potassium, sodium, and magnesium chlorides) on AN-31 low-basicity anion exchanger in the Cl form are calculated and analyzed. Peculiarities of the sorption of the investigated electrolytes on the anion exchanger are discussed.     

Comparative characteristics of the ion-exchange properties of natural clinoptilolites from Bulgaria and the USSR for the purpose of purification of liquid wastes from nuclear power plants. Part I: Study of the equilibrium sorption of cesium and strontium ions from solutions of different composition

The ion-exchange equilibrium of cesium and strontium ions on clinoptilolites from different deposits — Dzegvi and Tedzami /Georgian SSR/, Beli Plast and Beli Bair /Bulgaria/ in different cationic forms of the sorbents /natural, sodium, calcium and ammonium/ is studied. The static ion-exchange capacities are determined. The sorption isotherms are plotted and the corresponding distribution coefficients are calculated. Mechanical characteristics which are important for the assessment of the technological use of the sorbents in dynamic conditions are determined. The clinoptilolite from Beli Plast deposit has the highest capacity in comparison with the other studied zeolites. The selectivity of the clinoptilolites from Bulgarian deposits is independent of the cationic form of the sorbent while the selectivity of the Georgian clinoptilolites strongly depends on the cationic form; the selectivity of the ammonium form of Tedzami sorbent is the highest.     

Sorption of Cd<Superscript>2+</Superscript> with the product formed by alkali treatment of boron production wastes

Experiments on sorption of Cd²⁺ ions from aqueous CdCl₂ solutions with calcium hydrosilicate prepared from borogypsum (boron production waste) showed that this cheap sorbent can be used for effi cient sorption of Cd²⁺ ions in a wide range of solid: liquid ratios.     

Preconcentration of lead, cadmium and zinc on silica gel loaded with diethyldithiocarbamate prior to their determination by flame-atomic absorption spectrometry

A silica gel sorbent loaded with sodium diethyldithiocarbamate has been developed for the preconcentration of lead, cadmium and zinc prior to their determination by flameatomic absorption spectrometry (FAAS). The sorption and desorption of the metal ions was studied under both static and dynamic conditions. The metal ions were quantitatively retained on the silica gel sorbent based on an equilibrium time of less than 1 min. In case of the batch method, the effects of pH, shaking time, amount of sorbent, and desorption time were investigated. Among the desorption agents studied, only EDTA in ammonium chloride/ammonia buffer yielded quantitative recoveries. Freundlich's sorption isotherms determined for each metal show that sufficient sorption ability is obtained. The column method allows the preconcentration of metal ions from large sample volumes (e.g. 200 mL) using a flow rate of 5 mL min^–1. The influence of foreign ions present in natural waters and saline solutions was examined. The reproducibility of the total analytical method, expressed as relative standard deviation (RSD) is 1.8, 0.5 and 0.6%, for lead, cadmium and zinc, respectively.     

Natural radioactivity in building materials utilized in the State of Kuwait

A simple radiochemical procedure is described for the determination of⁹⁰Sr in brines, which are very highly concentrated in sodium, calcium, potassium, magnesium, chloride and sulfate ions. The method is based on the different solubility of yttrium as compared to that of strontium, calcium and magnesium in ammonium chloride solutions, and utilizes Eichroms resin TRU·Spec for the purification of the yttrium fraction. The overall time required for the⁹⁰Sr analysis (excluding the counting time) is less than one day. Because the procedure involves only rather simple steps, it is well suited for routine analyses of large sample numbers.     

Retention of Some Metal Ions and Their Separation on Silica Gel Modified with Acid Red 88

 Acid Red 88 is strongly extracted by chloroform solutions of Aliquat 336 by an ion exchange mechanism and for its reextraction from the ion pair formed, relatively high concentrations of mineral acids are required. By impregnation of silica with the ion pairs between the cation of Aliquat 336 and the anion of the dye a chelating sorbent for metal ions can be obtained. The sorbent prepared may be successfully used for separation of mixtures of various metal ions by the column extraction chromatography technique, additional purification of sodium and potassium salts from ions of heavy metals and for concentration of trace amounts of ions of various metals from aqueous solutions followed by their quantitative determination. The sorbent can be used repeatedly in the process of sorption and desorption of metal ions (especially those forming less stable complexes with the reagent) after regeneration with solutions of perchloric acid. Received January 28, 1998. Revision March 1, 1999.     

Effect of sorbed molecules on the resistivity of alkali metal-graphite intercalation compounds

Alkali metal-graphite intercalation compounds with the composition of MC₂₄ (M=K, Rb, Cs) were prepared by heating a mixture of MC₈ (saturated compound) and graphite sheet (Grafoil) at 350-450 °C. The resistivity perpendicular to the layer planes (ρ_c) of the resulting compounds was determined by the two-terminal method. The anisotropy factor of the resistivity, (ρ_c/ρ_a), of KC₂₄ prepared from Grafoil was ∼130, being about 1/6-1/10 in magnitude compared with that of KC₂₄ prepared from highly oriented pyrolytic graphite. The resistivity change during sorption of hydrogen (at 90 K), ethylene (at 194 K) and acetylene (at 194 K) was determined. The resistivity of MC₂₄ increased with increase of the sorbed amount of H₂. The magnitude of the increase was in the order KC₂₄>RbC₂₄>CsC₂₄. This resistivity increase was considered to be due to the expansion along c-direction which reduces the charge-transfer interaction between the carbon layers and potassium ions, resulting in the decrease of the density of the conduction electron. The resistivity of MC₂₄ increased extensively during sorption of C₂H₄ and C₂H₂. It was discussed in connection with the in-plane structural transition and chemical interaction between alkali metal ions and sorbed molecules.     

Adsorption of alkali and alkaline earth radionuclides on zeolite from water solutions

The adsorption of cesium and strontium ions from water solutions on zeolite has been investigated in presence of sodium, potassium, magnesium and calcium ions. Distribution ratios of cesium and strontium on the zeolite were determined in solutions of various compositions and solution volume to sorbent weight ratios (batch factor). Breakthrough curves for zeolite layers are reported.     

Response of polyacrylamide—acyclic poly(oxyethylene)-coated ion-selective electrodes to alkali and alkaline earth metal ions in propylene carbonate and its thermodynamic application

The response of ion-selective electrodes with a membrane of polyacrylamide (PAA) coupled to acyclic poly(oxyethylene) neutral carriers to lithium, sodium, potassium, magnesium and barium ions in propylene carbonate (PC) was investigated. Tetraethylene glycol monododecyl ether (POE4) and hexaethylene glycol monododecyl ether (POE6) were used as the acyclic poly(oxyethylene). Both the PAA-POE4 and the PAA-POE6 electrodes showed a more rapid dynamic response in PC than that in acetonitrile. Nernstian responses to lithium, magnesium and barium ions were obtained with the PAA-POE4 electrode. The selectivity coefficients, logk_Ba²⁺,M^x+, for lithium, sodium, potassium and magnesium ions vs. barium ion obtained in PC with the PAA-POE4 electrode were 3.6, 0.23, 0.02 and 1.1, respectively. The PAA-POE4 electrode was applied to obtain the successive formation constants of the barium ion in PC with N, N-dimethylacetamide (DMA). From the successive formation constants obtained in PC-rich solutions, the Gibbs free energies of transfer of the barium ion from PC to DMA and to PC-DMA mixtures were calculated. The electrode was also used to obtain directly the Gibbs free energies of transfer of the barium ion from PC to PC-DMA mixtures. The calculated values of the free energies were in good agreement with the values obtained experimentally, suggesting that the electrode responded to variations in solvation energy for the barium ion.     

Chelating tendencies in the rows of polymeric sorbents and their copper(II) and lead(II) complexes

The physicochemical properties of chelating polymer sorbents (CPSs), derivatives of poly(styrene-2-hydroxy-〈1-azo-1′〉-2′-hydroxybenzene), are studied with respect to copper and lead ions. The following sorption parameters are determined: the optimum acidity, temperature, and duration; the sorption capacity of the sorbent (SCS); and stability constants of polychelates. Quantitative correlations are found between the dissociation constants (pK′ _a) of the analytical functional group (AFG) of the sorbent, and the pH₅₀ of chelation of the tested metals; between p K′ _a and the stability of the complexes (logβ); and between pK′_a and the charge of the oxygen atom of the complexing group (z); these correlations are intended for use in elucidating the effect of the structural features and acid-base properties of the AFG on the chemisorption parameters of copper(II) and lead(II). These correlations predict the physical-chemical properties of sorbents and the sorption parameters of trace elements for preconcentrating and separating them from biological, natural, and technical objects     

Sorption of radioactive strontium on a silica-titania mixed hydrous oxide gel

A silica-titania (Si–Ti) mixed hydroxide gel with Ti to Si mole ratio of 11 was prepared. Studies on the sorption of radiostrontium from alkaline solutions having various concentrations of sodium were carried out with Si–Ti. The distribution coefficient (K _d) of strontium decreased with increasing concentrations of sodium from 0.1 to 4.0 mol·dm^–3. The plot of logK _d versus log [Na⁺] gave a slope of –0.55 as against the theoretical value of –2.0. This suggests that some other paths in addition to the simple stoichiometric ion exchange is also existing for sorption. From pH titrations the pH_pzc of Si–Ti was found to be 4.22 coinciding nearly with the pH sorption edge. An attempt was made to correlate the sorption results with the surface characteristics of the sorbent. It was found that sorption is favored when the surface of the sorbent transforms into an anionic form. Sharp increase in the sorption of strontium was observed when the equilibrium pH was between 7 and 10. This behavior could be attributed to the abrupt increase in net negative charge on the surface of the sorbent.     

The quantitative separation of calcium from magnesium,aluminium and other elements by cation-exchange chromatography in ethanol-hydrochloric acid

Magnesium can be separated from calcium by elution with 3.0 M hydrochloric acid containing 60% ethanol from a column of AG₅₀W-X8 cation-exchange resin. Calcium is retained and can be eluted with 3.0 M hydrochloric acid or 2.0 M nitric acid. The separation factor of (α_Mg^ca=5.6 is considerably higher than that in aqueous hydrochloric acid and comparable to those obtained with organic complexing reagents. Separations are sharp and quantitative; up to 10 mmol of magnesium can be separated from 0.01 mmol of calcium and vice versa on a 60-ml column. Al, Fe(III), Mn, Ni(II), Co(II), Zn, Cd, Cu(II), Pb(II), U(VI), Be, Ga, Ti(IV) in the presence of H₂O₂ and many other elements accompany magnesium and can be separated from calcium quantitatively. Sr, Ba, Zr, Hf, Th, Sc, La and the rare earths are retained together with Ca, but can be separated by other methods.     

A contribution to the use of tetravalent manganese in solutions of sulfuric acid as an oxidimetric reagent

The preparation of solutions of manganese(IV) sulfate in 9 M sulfuric acid as well as the stability of these solutions was studied for 0.00501 M concentration of manganese(IV) ions. Potentiometric titration of solutions of primary standard substances, potassium iodide and sodium hexacyanoferrate, was recommended for determining the titer of 0.005 M reagent solutions. It was verified that manganese(IV) sulfate can be used for determining low concentrations of organic substances by direct titration determination of hydroquinone, p-aminophenol, and metol and by indirect determination of oxalic acid.