Anion—surface interactions: Part I. Perchlorate decomposition and sulphate adsorption hysteresis studied by voltammetry

Cyclic voltammetry has been used to investigate the behaviour of sulphate and perchlorate anions adsorbed on Ir{111} and polycrystalline rhodium. In 0.1 M HClO₄, perchlorate anions decompose on polycrystalline rhodium to give a surface intermediate which inhibits hydrogen adsorption. This is in agreement with a previous study by Wieckowski and coworkers, who showed that the surface intermediate was, in fact, adsorbed chloride. The voltammetry of the same electrode in sulphate containing electrolytes depends critically on the concentration of sulphate and the potential sweep rate. We conclude that hydrogen adsorption can only occur after significant desorption of sulphate. Hysteresis in the adsorption and desorption of sulphate results in an asymmetric hydrogen adsorption region with respect to the potential axis. Ir{111} is shown also to cause decomposition of perchlorate anions, although, contrary to the case of rhodium, the process is very much a chemical one in which electric currents, arising from perchlorate decomposition, were not detected. In sulphuric acid, a strong interaction between anions and the Ir{111} surface is observed, which precludes oxide formation at potentials less than 1 V (Pd---H), behaviour characteristic of a Pt{111} surface in the same electrolyte.     

Thiocyanate-selective electrode based on cobalt(II) complexes of pyrazolone heterocyclic Schiff bases

A new solvent polymeric membrane electrode based on pyrazolone heterocyclic Schiff base complexes of Co(II) is described. It shows a preferential response towards thiocyanate over a range of 2.0 × 10^–6 to 1.0 × 10^–1 mol L^–1 with a slope of –60.2 ± 0.6 mV/dec. The selectivity sequence observed is thiocyanate > hydroxide > nitrite > iodide > perchlorate > citrate > bromide > fluoride > chloride > nitrate > acetate > borate > sulfate > phosphate. The selectivity behavior is discussed in view of axial coordination by uv/vis spectroscopy and the transfer process of thiocyanate across the membrane interface is investigated by the ac impedance technique. The electrode was successfully applied to the determination of thiocyanate in human urine as an indicator for distinguishing between smokers and non-smokers.     

Study on the fluoride adsorption of various apatite materials in aqueous solution

The aim of this study was to evaluate the defluoridation efficiencies of various sorbents in aqueous solution. These sorbents include synthetic nano-hydroxyapatite (n-HAp), biogenic apatite (bone meal), treated biogenic apatite (bone meal prepared by H₂O₂ oxidation) and geogenic apatite (rock phosphate), which were characterized by XRD, FTIR, TEM and SEM. It has been observed that the defluoridation capacities follow the order: n-HAp > BH₂O₂ > B > rock phosphate. The controlling factors, sorbent dose, initial fluoride concentration, pH, contact time and temperature were investigated. The defluoridation capacities increased with the increase in the initial fluoride concentration and contact time, decreased with the increase in the sorbent dose. The optimum pH range for removal of fluoride on various apatite sorbents was considered to be 5.0-6.0. The fluoride adsorption can be explained by Langmuir, Freundlich isotherms, and the adsorption kinetic data follow the pseudo-second-order model. Thermodynamic parameters such as ΔH⁰, ΔS⁰ and ΔG⁰ indicated that the adsorption on various apatite sorbents was spontaneous and endothermic. These results showed that bone meal is a promising material for fluoride adsorption.     

Specific adsorption of anions preceding the dissolution of CuO in acidic solution

The specific adsorption of sulfate and chloride ions on powdered CuO was studied by radiotracer techniques in acidified of 0.5 mol dm^–3 NaClO₄ supporting electrolyte. It was found that the pH and concentration dependence of the adsorption of labelled sulfates could be determined over a wide pH range (2.0≤pH≤7.0), despite the gradual dissolution of the copper oxide. No specific adsorption was found at pH≥7.0. It was postulated that the specific adsorption was preceded by the protonation of the CuO surface. No reliable relationships were found for labelled chlorides, owing to the relatively high desorption rate of the surface complexes formed in the sorption process. The apparent adsorbability of sulfate ions was significantly higher than that of the chloride ions, as shown by the results of competitive adsorption of the two species. This observation was in agreement with the postulated lower desorption rate of the surface complex formed with sulfates than that of species formed with chlorides. Electronic Publication     

Thiocyanate-selective electrode based on cobalt(II) complexes of pyrazolone heterocyclic Schiff bases

A new solvent polymeric membrane electrode based on pyrazolone heterocyclic Schiff base complexes of Co(II) is described. It shows a preferential response towards thiocyanate over a range of 2.0 × 10^–6 to 1.0 × 10^–1 mol L^–1 with a slope of –60.2 ± 0.6 mV/dec. The selectivity sequence observed is thiocyanate > hydroxide > nitrite > iodide > perchlorate > citrate > bromide > fluoride > chloride > nitrate > acetate > borate > sulfate > phosphate. The selectivity behavior is discussed in view of axial coordination by uv/vis spectroscopy and the transfer process of thiocyanate across the membrane interface is investigated by the ac impedance technique. The electrode was successfully applied to the determination of thiocyanate in human urine as an indicator for distinguishing between smokers and non-smokers. Received: 30 September 1997 / Revised: 9 December 1997 / Accepted: 13 December 1997     

Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon

Phosphate removal from aqueous solution was investigated using ZnCl₂-activated carbon developed from coir pith, an agricultural solid waste. Studies were conducted to delineate the effect of contact time, adsorbent dose, phosphate concentration, pH, and temperature. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 5.1 mg/g. Adsorption followed second-order kinetics. The removal was maximum in the pH range 3–10. pH effect and desorption studies showed that adsorption occurred by both ion exchange and chemisorption mechanisms. Adsorption was found to be spontaneous and endothermic. Effect of foreign ions on adsorption shows that perchlorate, sulfate, and selenite decreased the percent removal of phosphate.     

Phosphate uptake behavior and mechanism analysis of facilely synthesized nanocrystalline Zn‐Fe layered double hydroxide with chloride intercalation

Zn‐Fe layered double hydroxide with chloride intercalation (ZFCL) was synthesized by a coprecipitation method at room temperature. ZFCL was characterized by N₂ adsorption‐desorption isotherms, X‐ray diffraction, scanning electron microscope, Zeta‐sizer analyzer, X‐ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The results showed that ZFCL had large surface area and layered structure. The maximum adsorption capacity of ZFCL was 150.6 mg/g at 25°C. That was higher than most other adsorbent which were reported. The kinetic data were described better by the pseudo‐second‐order adsorption kinetic rate model. The adsorption isotherm on the adsorbent was described by Langmuir, Freundlich, and Sips models at pH 6 and followed the fitting order: Sips >Freundlich>Langmuir. Thermodynamic analyses indicated that the phosphate adsorption on ZFCL was endothermic and spontaneous in nature. The sequence of coexisting cations and anions competing with phosphate was Ca²⁺ > Mg²⁺ > Na⁺ and SO₄²⁻ > NO₃⁻ > Cl⁻. ZFCL can be regenerated by the sequential use of NaOH and ZnCl₂. The adsorption capacity remained high as 108.6 mg/g after regeneration of 3 times. The results of zeta potential, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy analyses indicated that the phosphate adsorption mechanisms involved ion exchange, Zn₃(PO₄)₂ precipitation, and the formation of inner‐sphere complex via replacement of surface hydroxyl groups by phosphate.     

Study of Cadmium Extraction with Aliquat 336 from Highly Saline Solutions

A large number of model solutions with high ionic strength were synthesised to mimic industrial conditions and were used as a first approach to study Cd extraction in the presence of chloride at high salinity, as experienced in real industrial solutions. The extractant used throughout in this work was Aliquat 336, a quaternary ammonium salt well known to the hydrometallurgical industry. The effects of some selected anions in addition to chloride (i.e., perchlorate, nitrate, and sulfate) were studied. The distribution of cadmium was measured using ¹⁰⁹Cd as a tracer. Liquid-scintillation spectroscopy quantified the concentration of ¹⁰⁹Cd in both phases. Raman and NMR spectroscopy were employed to gain further insight into the extraction chemistry. A careful analysis of all Cd extraction data showed that within specific windows of the reactant concentrations the chemical reactions could be represented by simplified equations, as discussed thoroughly in the text. Equilibrium constants for the extraction of \({\text{CdCl}}_{3}^{ - }\) from chloride and chloride/sulfate media were determined to be log₁₀K_ext?=?4.9?±?0.8 and log₁₀K_ext?=?5.7?±?0.5, respectively. For the nitrate environment, an exchange reaction involving a LiNO₃ ion pair is proposed and agrees with the experimental data, but was not proven. ¹⁴N-NMR and Raman spectroscopy confirmed that the relative affinity of Aliquat 336 for the relevant anions followed the order: perchlorate?>?nitrate?>?chloride?>?sulfate. Finally, ¹⁴N-NMR enabled the equilibrium constant of the exchange reaction between nitrate and chloride for Aliquat 336 to be determined.     

Determining the second-harmonic signal in electrochemical systems

Processes of adsorption and desorption of the butanol-1, butanol-2, hexanol, pentanol, and isoamyl alcohol molecules on a mercury electrode are studied with use made of the method of a second-harmonic signal in the region of radiowave frequencies. Two potentials are simultaneously applied to the metal/solution interface, specifically, a constant potential and a weak variable potential. The magnitude of the constant potential is close to the corresponding potential of adsorption and the variable potential has an amplitude in the limits of 2 to 20 mV and a frequency varying from a few tens of hertzs to a few tens of kilohertzs. Despite the absence of charge transport during the adsorption between the alcohol molecules and the electrode, the quadratic dependence between a signal of electromagnetic radiation of the radiowave frequencies U and the amplitude of the variable potential E _v1 applied to the metal/solution interface is discovered for all peaks in the curves of the second-harmonic signal for various concentrations of alcohols, various frequencies, and various values of the amplitude of the variable potential. Investigations for systems containing chlorides of sodium, potassium, and cesium in addition to ethylene glycol are conducted. According to an analysis of obtained experimental data, the number of peaks increases with decreasing concentration of chlorides, whereas the size of the sodium, potassium, and cesium cations makes no impact on the magnitude of the emitted signal. At the same time, diminishing the concentration of the chlorides leads to a certain amplification of the signal.     

Comparison of the specific adsorption of sulfate (HSO<Subscript>4</Subscript><Superscript>−</Superscript>) ions on Cr and Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>

The specific adsorption of sulfate ions on powdered Cr was studied by a radiotracer technique using ³⁵S-labeled sulfuric acid in low concentration (c<10^–3 mol dm^–3) in the presence of a large excess of perchlorate supporting electrolyte. The pH and concentration dependence were determined. On the basis of a comparison of the results obtained for Cr₂O₃ and Cr, it can be assumed that, similar to other metals, the overall sorption behavior of Cr is determined by the protective oxide film present on the surface.     

Adsorption and desorption of small molecules for the characterization of solid acids

The relative acid strength and acid amount of solid acids has been determined from the adsorption and desorption of small molecules, such as argon. The order of activation energy for desorption of Ar from a solid acid, determined using temperature-programmed desorption (TPD), is sulfated zirconia > Cs_2.5H_0.5PW₁₂O₄₀ > proton-type zeolites > silica–alumina. The adsorption isotherms were analyzed using Langmuir and Henry equations. The Henry-type adsorption isotherms were also analyzed using the theory of Cremer and Flügge. The heat of Ar adsorption was 22 kJ mol⁻¹ for sulfated zirconia and ca. 17 kJ mol⁻¹ for mordenite, ZSM-5, and beta-zeolite. Molybdenum oxides reduced at 623 and 773 K exhibited a large heat of adsorption (19.3 and 19.7 kJ mol⁻¹, respectively), and these materials are classified as superacids. W-Nb mixed-oxides and tungstated tin oxide (calcined at 1373 K), which are newly developed solid acids, had a heat of adsorption of 18.1 and 16.9 kJ mol⁻¹, respectively. The type of acid site could be distinguished by comparing the heat of adsorption of Ar and N₂. Our data indicate that Ar is useful for the characterization of solid acids.     

Layer-by-layer adsorption of polyelectrolyte and surfactant and adsorption of their complexes on solid surface

The capillary electrokinetics method (measurement of streaming potential and current in a capillary with a radius of 5–7 μm made of fused quartz) is employed to study the structure formation at interfaces between quartz and solutions containing a cationic polyelectrolyte (poly(diallyldimethylammonium chloride) with molecular mass M = 100000−200000) and an anionic surfactant (sodium dodecyl sulfate). The kinetics of surface layer formation is studied upon the layer-by-layer adsorption of the components and the adsorption of their complexes at the same component ratios. It is established that the formation time and the electrokinetic potentials of the surface layers are almost independent of the procedure of their formation. In the case of the layer-by-layer adsorption, the first layers of the polyelectrolyte appear to be virtually undeformed, thus indicating that molecules with a planar conformation prevail in the adsorption layer. Surfactant adsorption enhances the deformation (layer loosening), which decreases with time (layer aging). Layers formed from the complexes have a denser (less deformable) structure. Variations in the electrokinetic potentials of the layers during the long-term pumping of a background electrolyte solution through a capillary witnesses the prevailing desorption of the anionic surfactant, with the desorption being noticeably more pronounced for the layers resultant from the adsorption of the complexes.     

Effect of the nature of the salt precursor of an oxide-hydroxide sorbent on the sorption of oxalate ions

Generalizations are made on the effect of the nature of a precursor (the original salt of a metal) on the sorption activity of hydrogels of oxidehydroxides (OHes) towards oxalate ions using the example of an OH obtained by the alkaline hydrolysis of chloride, perchlorate, and sulfate of Fe(III); chloride, sulfate, and nitrate of Al; and nitrate of Zr(IV). It is established that the sorption of C₂O ₄ ^2? on the studied OHes is described by the Langmuir equation. We find that the sorption activity depends on the nature of the precursor: Al₂(SO₄)₃ > Al(NO₃)₃ > AlCl₃ > ZrO(NO₃)₂ > Fe₂(SO₄)₃ > FeCl₃ > Fe(ClO₄)₃.     

New understanding of the nature of OH adsorption on Pt(1 1 1) electrodes

The adsorption of hydroxyl on Pt(1 1 1) single crystal electrodes from aqueous acidic solutions is carefully reinvestigated. The effect of small additions (10⁻⁸–10⁻⁵ M) of chloride and bisulphate anions on the OH adsorption region in perchloric acid solution has been studied. Two regions can be differentiated in the voltammetric profile, that behave differently after the addition of the foreign anion. The initial broad adsorption process is unaffected until the highest concentration is attained. However, the sharper peak at higher potentials is affected even at the lower anion concentration. Since mass transport limitations allow to discard the anion adsorption as the main process giving this peak, we propose that the two processes are due to the dissociative adsorption of two different kinds of water, that are affected by the anion in a different way. From this idea, a new model, based on the Frumkin adsorption isotherm, is proposed, which gives an excellent fit of the experimental results.     

The effect of surface ion-induced defects on CO adsorption on polycrystalline Ni

CO adsorption on polycrystalline nickel was investigated by dynamic secondary ion mass-spectroscopy at 10⁻⁵–10⁻³ Pa and 300–500 K. An increase of secondary ion currents NiCO⁺/Ni⁺ ratio was found in the range from 300 to 350 K, while at T>350 K it decreased sharply. These data were explained by a kinetic model, in which adsorption and desorption of tightly bound CO goes through weakly bound CO formed due to ion-induced defects.     

Radiotracer study of the adsorption of sulfate ions at a Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> powder/electrolyte solution interface

The pH and concentration dependence of the adsorption of sulfate ions on powdered Bi₂O₃ was studied by a radiotracer technique in the presence of a large excess of perchlorate supporting electrolyte. It was found that, similar to other oxides such as Al₂O₃, Cr₂O₃ and Fe₂O₃, the extent of adsorption is determined by the protonation of the Bi₂O₃ surface. The redox transformations of Bi adatom layers are discussed in the light of the results obtained. It is established that for the interpretation of the redox processes occurring at the Bi/electrolyte interface the role of protonation of the oxide formed and the anion adsorption induced by the oxide layer should be taken into consideration. Electronic Publication     

Determining Sodium Kryptate Adsorption Parameters on a Mercury Electrode in 1 M Na2SO4

The adsorption of a complex of sodium cations with a macrocyclic ligand (Kryptofix^R 222, composition C₁₈H₃₆N₂O₆) as a function of its concentration in 1 M Na₂SO₄ is studied by measuring the differential capacitance on a stationary Hg drop. Adsorption parameters of sodium kryptate are found using a regression analysis method and various versions of a model of two parallel capacitors complemented with the Frumkin adsorption isotherm. The differential capacitance curves, calculated on the basis of these, are compared with experimental data. The difference in model versions that most adequately describe the adsorption data, established for systems in 0.1 and 1 M Na₂SO₄, is explained by the influence of the supporting electrolyte on the adsorption layer structure. Conclusions are made on the absence in the system under study of the salting-out from the bulk solution and on a change in the properties of an adsorption layer of sodium kryptate in the region of potentials of the anodic adsorption–desorption peak following expansion of the adsorption region.     

Thermodynamics of Copper Adsorption-Desorption by Ca-Kaolinite

The temperature effect on Cu adsorption and desorption on kaolinite has been investigated at four temperatures (8°C, 25°C, 30°C and 40°C). The clay sample was saturated with Ca. Copper was sorbed from solutions containing eleven Cu concentrations between 0.0010 and 0.0211 M, equilibrated for 2 days. Cu adsorption decreased, but desorption increased with increasing temperature, indicating that adsorption is an exothermic process while desorption is endothermic. These conclusions are confirmed by the values of H ⁰ estimated for adsorption and desorption.The initial copper concentration is a significant factor influencing mainly the adsorption process, which is spontaneous (G ⁰ < 0) only for low initial Cu concentrations. The desorption process is spontaneous for all Cu concentrations. S ⁰ values have also been calculated. Experimental adsorption data were successfully fitted to the Freundlich isotherm and to the Gouy-Chapman model in order to express the process quantitatively.     

Theoretical studies on the intramolecular cyclization of alkyl halide anions

The intramolecular cyclization reactions of alkyl fluoride and chloride anions¹ were investigated theoretically using the AM1 method. Formation of five-membered ring was the most reactive and that of three-membered ring was the least reactive process in both series. For the fluoride series the reactivity order of n = 5 > 6 > 7 > 4 > 3 was dictated by the enthalpy (ΔH≠) effect while for the chloride series the entropy (ΔS≠) effect was found to play somewhat greater role due to the much better leaving ability of the chloride anion leading to the reactivity order of n = 5 > 6 > 4 > 7 > 3. For both series, BEP principle held and the degree of bond formation was greater with the fluoride series owing to the poor electron acceptor ability of the cleaving bond.     

Miscibility of calcium chloride and sodium dodecyl sulfate in the adsorbed film and aggregates

The adsorption, micelle formation, and coagel-particle formation of sodium dodecyl sulfate in the presence of calcium chloride were studied from the viewpoint of mixed adsorption and aggregate formation of inorganic salt and surfactant. Judging from the phase diagrams of adsorption and aggregate formation, negative azeotropy takes place in the mixed adsorption and aggregate formation of calcium chloride and sodium dodecyl sulfate due to electrostatic attraction between calcium and dodecyl sulfate ions. The miscibility of calcium chloride and sodium dodecyl sulfate in the oriented states increases in the order, particle > adsorbed film > micelle. The difference in the miscibility was ascribed to the difference in geometry between the adsorbed film and micelle and to the interaction between bilayer surfaces in the particle. The particle-micelle equilibrium was thermodynamically considered by using the equilibrium composition of aggregates.