Inorganic particulates in removal of toxic heavy metal ions

Adsorption behavior of zinc ions on hydrous zirconium oxide (HZO) in aqueous solution has been studied as a function of concentration (10^–2–10^–8M), temperature (303–333 K) and pH 3–8 of adsorptive solution applying radiotracer technique. The kinetics of adsorption follows first order rate law and agrees well with the classical Freundlich isotherm in the entire range of adsorptive concentration. The removal was found to be increasing with pH of the adsorptive solution while it was suppressed in the presence of acid concentrations. The overall process is found to be endothermic and irreversible in nature.     

Adsorption of low level51Cr(VI) from aqueous solution by bismuth trioxide: Kinetic and IR study

Radiotracer technique has been used for the investigation of adsorption of chromium (VI) traces on bismuth trioxide from aqueous solution. The effect of pH (2–10), concentration of chromate solution (10^–6–10^–2M) and temperature (303–323 K) has been thoroughly investigated. The influence of certain foreign ions has also been studied. The calculated kinetic and thermodynamic parameters indicate the first order rate law, spontaneity and exothermic nature of the adsorption process. Further, IR studies have established the chemical interaction between the sorbate and sorbent and a possible mechanism of the sorption process based on ligand exchange has been proposed.     

Kinetics of adsorption and desorption of sodium alkyl sulfates to and from nylon particles

The desorption rate of surfactant ions from nylon particles was investigated at the concentrations below the critical micelle concentration by applying the stopped-flow method. A mixing cell of stopped-flow spectrophotometer was modified with platinum electrodes for electric conductivity detection. The change in electric conductivity with time in the desorption process was monitored by a memory-recorder system. The surfactants used were sodium decyl, sodium dodecyl, sodium tetradecyl, and sodium hexadecyl sulfates. The desorption rate was independent of the surfactant concentration and the rate constants were obtained by applying the first-order reaction scheme. The adsorption rate constants were estimated from the experimental desorption rate constants and equilibrium constants assuming the second-order kinetics. The desorption rate constants were determined to be 1–6 sec^–1 and the adsorption rate constants to be 2–8×10⁴ mol^–1 dm³ sec^–1; the former decreased and the latter increased with increasing number of carbon atoms in alkyl chain of the surfactants.     

Adsorption studies of cesium on a new inorganic exchanger ammonium molybdophosphate-alumina (AMP-Al2O3)

The applicability of ammonium molybdophosphate-alumina (AMP-Al₂O₃) for the efficient removal of Cs from aqueous solution by adsorption has been investigated. The kinetics of adsorption of cesium ions has been studied by using radioanalytical procedure over a concentration range of 10⁻⁴−10⁻² mol.dm⁻³ and in the temperature range of 303–318 K. The results showed that the uptake follows the first order rate law with respect to cesium concentration and obeys Langmuir and modified Freundlich adsorption isotherm in the concentration range studied. Equilibrium adsorption values at different temperatures have been utilised to evaluate change in standard thermodynamic parameters (ΔH ⁰, ΔG ⁰ and ΔS ⁰). From the thermodynamic parameters it is found that the process is exothermic in nature.     

Kinetic Study of Erbium Ion Adsorption on Activated Charcoal from Aqueous Solutions

The kinetics of the adsorption of erbium ions on activated charcoal from aqueous solutions has been studied in the temperature range of 10 to 40∘C. It was observed that the diffusion of erbium ions in to the pores of activated charcoal controls the kinetics of the adsorption process, and the values of intra-particle diffusion rate constant, k_d (g/g ⋅ min^1/2) were evaluated as 0.7 × 10⁻³ to 1.6 × 10⁻³ in the temperature range studied. Various thermodynamic parameters Δ H, Δ G and Δ S were also computed from values of the equilibrium constant K_C. The results showed that the adsorption of erbium ions on activated charcoal is an endothermic process.     

Feasibility study of aqueous adsorption of Cr(VI) on titanium dioxide

Sorption of chromium radionuclide has been studied in the pH range of 1–10 on titanium dioxide from aqueous solutions. The adsorption isotherm obtained is of the Freundlich type. The kinetic study of adsorption and desorption of tagged chromate ions at different temperatures show that the adsorption process is exothermic innnature. Further, the feasibility of adsorption process is confirmed by calculating the thermodynamic parameters.     

Piezoelectric Sensor in Situ Monitoring Adsorption of Fibrinogen and Surfactant onto a Self-Assembled Monolayer of Alkanethiols

This report describes the use of a piezoelectric quartz crystal (PQC) sensor to investigate the nonspecific adsorption of fibrinogen (FN) and sodium dodecyl sulfate (SDS) onto a self-assembled monolayer (SAM) of alkanethiols on gold. The change in adsorption mass was monitored in situ by the PQC sensor. A kinetics model was proposed to describe the adsorption of the FN and SDS on the hydrophobic SAM surface. The adsorption kinetics parameters were determined from the responses of the PQC. The adsorption and desorption rate constants of the FN on the SAM surface were estimated to be (6.18 ± 0.53) × 10³ M⁻¹ s⁻¹ and (6.74 ± 0.72) × 10⁻³ s⁻¹, respectively. The rate constants for the adsorption and desorption of SDS on the SAM are (24.3 ± 1.4 M⁻¹ s⁻¹) and (1.52 ± 0.11) × 10⁻² s⁻¹, respectively. The adsorption of SDS on the SAM was reversible. The fractional coverage of the FN on the SAM surface was estimated from kinetics analyses to be 42–86% for the FN concentration range 25–400 μg/ml. Over 80% of the FN is irreversibly adsorbed on the SAM surface with respect to dilution of the bulk phase. The fraction of FN reversibly adsorbed increases with the bulk concentration of FN.     

Static and Kinetic Studies on the Adsorption Behavior of Sulfadiazene

To investigate the nature of interactive forces between sulfadiazene molecules and alumina surface the experiments were performed for the adsorption of sulfadiazene (SD) from its aqueous sulution onto the alumina surfaces at 25 ± 0.2°C and the influence of factors such as increasing concentration of SD (4.0–20.0 × 10^–3 mol cm^–3), the time required for adsorption equilibrium, pH (2.0–12.0) and temperature (5–45°C) of the adsorption medium, the presence of ions like Cl^–, SO^2– ₄ and PO^3– ₄ (0.01–0.30 M) and organic solvents (5% v/v) were observed on the course of adsorption of SD. Various adsorption and kinetic parameters such as adsorption coefficient, the rate constants for adsorption and desorption were also evaluated. The results of the above cited studies facilitated to formulate the mechanisms of interaction between SD and alumina surfaces. From application view point the present work may be a potential tool for an effective chromatographic separation of sulfa drugs from industrial effluents.     

Phosphate desorption kinetics from goethite as induced by arsenate

The kinetics of the arsenate-induced desorption of phosphate from goethite has been studied with a batch reactor system and ATR-FTIR spectroscopy. The effects of arsenate concentration, adsorbed phosphate, pH and temperature between 10 and 45 °C were investigated. Arsenate is able to promote phosphate desorption because both oxoanions compete for the same surface sites of goethite. The desorption occurs in two steps: a fast step that takes place in less than 5 min and a slow step that lasts several hours. In the slow step, arsenate ions exchange adsorbed phosphate ions in a 1:1 stoichiometry. The reaction is first order with respect to arsenate concentration and is independent of adsorbed phosphate under the experimental conditions of this work. The rate law is then r = k_r[As], where r is the desorption rate, k_r is the rate constant and [As] is the arsenate concentration in solution. The values of k_r at pH 7 are 1.87 × 10⁻⁵ L m⁻² min⁻¹ at 25 °C and 7.95 × 10⁻⁵ L m⁻² min⁻¹ at 45 °C. The apparent activation energy of the desorption process is 51 kJ mol⁻¹. Data suggest that the rate-controlling process is intraparticle diffusion of As species, probably As diffusion in pores. ATR-FTIR spectroscopy suggests that adsorbed phosphate species at pH 7 are mainly bidentate inner-sphere surface complexes. The identity of these complexes does not change during desorption, and there is no evidence for the formation of intermediate species during the reaction.     

Inorganic particulates in removal of toxic heavy metal ions

Adsorption behavior of zinc, cadmium and mercury ions on hydrous titanium oxide in aqueous solution has been studied as a function of concentration of the metal ion (10⁻²−10⁻⁷M), temperature (303–333 K) and pH 3–10 by applying radiotracer technique. The kinetics of adsorption follows the first order rate law and agrees well with the classical Freundlich isotherm. The removal was found to increase with increasing pH but was suppressed in the presence of EDTA. The overall process is endothermic and irreversible in nature. Part VII. Efficient removal of cadmium ions from aqueous solutions by hydrous manganese oxideS. P. Mishra, D. Tiwary, Radiochim. Acta, 80 (1998) 213.     

Factors affecting interaction of radiostrontium with river sediments

Uptake of radiostrontium by sediments from two small streams was studied as a function of pH and composition of aqueous phase, of the concentration of strontium, of contact time, temperature and liquid-to-solid ratio (V/m), using laboratory model experiments. Between pH 5 and 12 the uptake increased with pH and shifted to higher pH values with increasing V/m ratio. Addition of cations suppressed the uptake in the order Na⁺<K⁺<Ca²⁺. Increase in strontium concentration had negligible effect up to 10^–5–10^–4 mol·dm^–3 concentration due to high concentrations of dissolved and exchangeable strontium present in the systems. The V/m ratio had no influence on K_d in the range of V/m=20–446 cm³ · g^–1 but K_d value for V/m=0.79 cm³ · g^–1 was significantly lower. Two-step kinetics of the uptake was observed in most cases with a rapid first step (<100 min) followed by a slow increase. No difference was found between the uptake at 10°C and 22°C. Adsorbed radiostrontium could be easily desorbed with river water. The easiness of desorption decreased with repeated desorption. Drying of sediment did not affect the first desorption, repeated desorptions slightly decreased. Conclusions were drawn on the mechanism of radiostrontium uptake and on the importance of the factors studied for modelling of radiostrontium migration in rivers.     

Kinetics and mechanism of ligand substitution of mono(polyamine)-nickel(II) complexes with 4-(2-pyridylazo)resorcinol

Summary The kinetics and mechanism of ligand substitution reactions of tetraethylenepentamine nickel(II), Ni (Teren), and triethylenetetraamine nickel(II), Ni(Trien), with 4-(2-pyridylazo)resorcinol (parH₂) have been studied spectrophotometrically at I=0.1 M (NaClO₄) at 25°C. In both systems two distinct reaction steps are observed. The rapid first step follows the rate law d[Ni(Polyamine)(ParH₂)]/dt=k₁ [Ni(Polyamine)] [ParH₂]. The formation of ternary complexes of Ni (Polyamine) with ParH₂ has been investigated under second order equal concentration conditions. The values of second order rate constants for the Trien and Teren reactions are (2.1±0.2)×10⁴ M^–1s^–1 and (7.8±0.6)×10³ M^–1s^–1 respectively at pH=9.0, I=0.1 M and 25°C.The rate law for the second step may be written as d[Ni(Par)₂]/dt=k₂[Ni(Polyamine)(ParH₂)]. Values of k₂ for the Trien and Teren systems are (2.5±0.1)×10^–4 s^–1 and (4.76±0.3)×10^–5 s^–1 respectively.     

Investigation of adsorption behaviour of mercury in microamounts on manganese dioxide from aqueous solutions

Adsorption of mercury onto manganese dioxide was studied in relation to the concentrations of electrolyte, adsorbent and adsorbate and foreign ions. Adsorption of other metal ions under similar conditions was also measured. Adsorption decreases with increasing electrolyte concentration. Thiosulfate, thiocyanate, iodide and all cations tested suppress the adsorption; the greater the ionic potential of cation, the weaker the adsorption of mercury. Adsorption follows the Freundlich-type isotherm over a wide range of mercury concentration (10^–7–10^–8 g·ml^–1). 98% of the adsorbed mercury can be eluted from the oxide column with 60 ml of 3M nitric acid solution.     

The effect of resin particle size on the rate of ion release: interactions in mixed bed systems

The aim of the present study is to evaluate the influence of resin particle sizes on the rate of ions release from a mixture of ion-exchange resins (named NMTD) which supplies calcium, fluoride, and phosphate ions as the main mineral content, and to elucidate the different phenomena taking place through the related ion-exchange process. The final goal of the study, related to dental application (enamel restoration), is to limit the particle size range, since the rate of ion release is a key parameter in the successful achievement of such objective. Weak-type ion-exchange resins, loaded with the appropriate ions, were ground and sieved into granulometric fractions of bead diameters of 0.1–0.075, 0.075–0.063, and 0.063–0.05 mm. Particle size was controlled by a laser diffraction particle distribution analyzer. The experiments on the kinetics of ions release were carried out under batch conditions in artificial saliva desorption solution thermostatized at 37 °C. The release of Ca²⁺ and F^– was determined by corresponding ion-selective electrodes automatically controlled, whereas H₂PO₄^– was measured spectrophotometrically by the inductively coupled plasma–optical emission technique (ICP-OES). The results of this study show that the process of ion-exchange for the different particle size fractions of resins is critical for the study of the kinetics release of the ions immobilized in the corresponding mixed bed polymeric matrices. In fact, despite the apparent narrow range of particle sizes of the mixed bed systems studied, appreciable differences in the rate of ions release are obtained. Since the ion release rate is depending on the contact surface, an increase of factor of 2 in particle size represents an increase of an order of magnitude of the resin contact surface due to the resin porosity. In this concern, it has been observed that the rate of ions release increases when particle size decreases. The interactions occurring during the ion release from the mixed bed resins (containing calcium-, fluoride-, and phosphate-loaded resins) can be interpreted by the following phenomena: H₂PO₄^–, which hardly modifies its rate of release in the presence of Ca²⁺ and F^– in the mixture, promotes a considerable increase in the rate of Ca²⁺ release due to the formation of a calcium dihydrogen phosphate soluble complex. F^– also produces an acceleration in the rate of Ca²⁺ release due to the formation of solid CaF₂ on the surface of cationic resin particles, which in contrast leads to a decrease in the rate of F^– release.     

Novel Coated-Wire Membrane Sensor Based on Bis(Acetylacetonato) Cadmium(II) for the Determination of Chromate Ions

A new electrode based on a complex of chromate ions with bis(acetylacetonato) cadmium(II) as a carrier was developed for detection of chromate in aqueous solution. The electrode exhibited linear response with Nernstian slopes of –28.8±0.5mVper decade for chromate within the concentration range of 2.5×10^–6–0.1M. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plots was almost 1.0×10^–6M. The electrodes exhibited good selectivities for chromate. The response time of the electrode was <25s over the entire concentration range. The electrode can be used in the pH range 8.0–12.0 for chromate. It was used as an indicator electrode in titration with Pb(NO₃)₂ and for the determination of chromate ion in wastewater samples.     

Kinetics and mechanism of pentacyanohydroxoferrate(III) formation from mono(aminocarboxylato)iron(III) complexes

Summary The kinetics and mechanism of the system: [FeL(OH)]^2–n + 5 CN^– [Fe(CN)₅(OH)]^3– + L^n–, where L=DTPA or HEDTA, have been investigated at pH= 10.5±0.2, I=0.25 M and t=25±0.1 C.As in the reaction of [FeEDTA(OH)]^2–, the formation of [Fe(CN)₅(OH)]^3– through the formation of mixed ligand complex intermediates of the type [FeL(OH)(CN)_x]^2–n–x, is proposed. The reactions were found to consist of three observable stages. The first involves the formation of [Fe(CN)₅(OH)]^3–, the second is the conversion of [Fe(CN)₅(OH)]^3– into [Fe(CN)₆]^3– and the third is the reduction of [Fe(CN)₆]^3– to [Fe(CN)₆]^4– by oxidation of L^n– The first reaction exhibits a variable order dependence on the concentration of cyanide, ranging from one at high cyanide concentration to three at low concentration. The transition between [FeL(OH)]^2–n and [Fe(CN)₅(OH)]^3– is kinetically controlled by the presence of four cyanide ions around the central iron atom in the rate determining step. The second reaction shows first order dependence on the concentration of [Fe(CN)₅(OH)]^3– as well as on cyanide, while the third reaction follows overall second order kinetics; first order each in [Fe(CN)₆]^3– and L^n–, released in the reaction. The reaction rate is highly dependent on hydroxide ion concentration.The reverse reaction between [Fe(CN)₅(OH)]^3– and L^n– showed an inverse first order dependence on cyanide concentration along with first order dependence each on [Fe(CN)_5– (OH)]^3– and L^n–. A five step mechanism is proposed for the first stage of the above two systems.     

Ruthenium(III) catalysed oxidation of glycerol by acidified KBrO3: a kinetic study

Kinetic investigations on the Ru^III-catalysed oxidation of glycerol by an acidified solution of KBrO₃ in the presence of Hg(OAc)₂ as a scavenger have been carried out in the 30–50 °C range. First order kinetics in the lower KBrO₃ concentration range tended to zero order at higher concentrations. The reaction follows zero order kinetics in glycerol and [H⁺]; the order is one with respect to [Ru^III]. An increase in [Cl^–] showed a positive effect, while addition of NaClO₄ has a negligible effect on the reaction rate. Hg(OAc)₂ and D₂O have an insignificant effect on the reaction rate. A suitable mechanism in conformity with the kinetic observations has been proposed and thermodynamic parameters computed.     

Kinetics and Mechanism of the Autocatalytic Oxidation of L-Asparagine in a Moderately Concentrated Sulfuric Acid Medium

The reaction kinetics of the Autocatalytic Oxidation of L-asparagine by permanganate ions has been investigated in moderately strong acid medium using the spectrophotometric technique. In all cases studied, an autocatalytic effect due to Mn²⁺ ions formed as a reaction product was observed. Both catalytic and noncatalytic processes were determined to be first order with respect to the permanganate ions while a first and a fractional order with respect to the amino acid for noncatalytic and catalytic reactions were obtained, respectively. The overall rate equation for this process may be written asd[MO₄ ^–]/dt= k´₁[MnO₄ ^–]+k´₂[MnO₄ ^–][Mn⁺²],where k´₁ and k´₂ are rate pseudoconstants for noncatalytic and catalytic reactions, respectively. The influence of some factors such as temperature and reactant concentration on the rate constants has been studied, and the activation parameters have been calculated. Reaction mechanisms satisfying observations for both catalytic and noncatalytic routes have been presented.     

Anodic Dissolution of Gold in Cyanide Solutions Containing Lead Ions: Effect of the Solution pH

The effect of the electrode potential on the gold dissolution rate in alkali–cyanide solutions with and without 10^–5 M of hydroxy compounds of lead is studied. With the compounds, the process rate passes through a maximum, whose potential E _m shifts in the negative direction and whose height drops with increasing pH. The pH dependence of E _m is linear, with the slope dE _m/dpH = –71 ± 5 mV, and correlates with that of the potential at which lead adatoms start to undergo desorption from the gold surface in alkali solutions. Without the compounds, the gold dissolution rate in alkali–cyanide solutions is independent of the solution pH at E < 0. Thus, the effect of the solution pH in this potential range is connected not with a direct participation of hydroxide ions in the anodic process but is of a secondary nature caused by the dependence of the region of adsorption of catalytically active lead adatoms on the hydroxide ion content in solution.     

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.