Formation Of Outer-sphere Complexes Research Articles

Displacement of aqua ligands from the hydroxopentaaquarhodium(III) ion by 1-hydroxybenzotriazole (HOBt): A kinetic and mechanistic approach

The kinetics of the reaction of HOBt with [Rh(H2O)5(OH)]2 + has been studied spectrophotometrically in aqueous medium as a function of [Rh(H2O)5OH2 + ], [HOBt], pH and temperature. At pH 4.3, the reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyrings equation. Thermodynamic parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent with an associative mode of activation. The product of the reaction has been characterized by IR and ESI-mass spectroscopic analysis. The kinetics of the reaction of HOBt with [Rh(H2O)5(OH)]2+ has been studied spectrophotometrically in aqueous medium as a function of [Rh(H2O)5OH2+], [HOBt], pH and temperature. At pH 4.3, the reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyrings equation. Thermodynamic parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent with an associative mode of activation.

Solution Speciation Controls Mercury Isotope Fractionation of Hg(II) Sorption to Goethite

The application of Hg isotope signatures as tracers for environmental Hg cycling requires the determination of isotope fractionation factors and mechanisms for individual processes. Here, we investigated Hg isotope fractionation of Hg(II) sorption to goethite in batch systems under different experimental conditions. We observed a mass-dependent enrichment of light Hg isotopes on the goethite surface relative to dissolved Hg (ε(202)Hg of -0.30‰ to -0.44‰) which was independent of the pH, chloride and sulfate concentration, type of surface complex, and equilibration time. Based on previous theoretical equilibrium fractionation factors, we propose that Hg isotope fractionation of Hg(II) sorption to goethite is controlled by an equilibrium isotope effect between Hg(II) solution species, expressed on the mineral surface by the adsorption of the cationic solution species. In contrast, the formation of outer-sphere complexes and subsequent conformation changes to different inner-sphere complexes appeared to have insignificant effects on the observed isotope fractionation. Our findings emphasize the importance of solution speciation in metal isotope sorption studies and suggest that the dissolved Hg(II) pool in soils and sediments, which is the most mobile and bioavailable, should be isotopically heavy, as light Hg isotopes are preferentially sequestered during binding to both mineral phases and natural organic matter.

Kinetic and Mechanistic Study of the Interaction of Diethyldithiocarbamate Anion with Diaquaethylenediamineplatinum(Ii) Ion in Aqueous Medium

The interaction of diethyldithiocarbamate (Et2DTC) with diaquaethylenediamineplatinum(II) has been studied spectrophotometrically in aqueous medium as a function of [substrate complex], [ligand], temperature and pH at constant ionic strength. The reaction proceeds via rapid outer-sphere association complex formation followed by two consecutive steps: the first is ligand dependent and second is assigned to intramolecular ring closure. The low enthalpy and negative entropy of activation indicate an associative mode of activation for both steps.

Enrofloxacin sorption on smectite clays: Effects of pH, cations, and humic acid

Enrofloxacin (ENR) occurs widely in natural waters because of its extensive use as a veterinary chemotherapeutic agent. To improve our understanding of the interaction of this emerging contaminant with soils and sediments, sorption of ENR on homoionic smectites and kaolinite was studied as a function of pH, ionic strength, exchangeable cations, and humic acid concentration. Batch experiments and in situ ATR–FTIR analysis suggested multiple sorption mechanisms. Cation exchange was a major contributor to the sorption of cationic ENR species on smectite. The decreased ENR sorption with increasing ionic strength indicated the formation of outer-sphere complexes. Exchangeable cations significantly influenced the sorption capacity, and the observed order was Cs<Ca<K. The peak shifts of the COO− stretch, coupled CO stretch and OH deformation, and the result of irreversible desorption FTIR spectra indicated that OH of the carboxyl group was involved in the formation of inner-sphere surface complexes. The XRD analysis confirmed that interlayer intercalation is an important contributor to ENR sorption, while humic acid had a negligible contribution to the interlayer intercalation. The results of this study provide new insight into the molecular mechanisms of ENR sorption on clay minerals.

Biologically active thiosemicarbazone Fe chelators and their reactions with ferrioxamine B and ferric EDTA; a kinetic study

The Fe(III) abstraction from Fe(III)/DFO and Fe(III)/EDTA complex systems by thiosemicarbazone ligands derived from 2-acetylpyridine has been studied from a kinetico-mechanistic perspective at relevant pH conditions and at varying temperatures and buffer solutions. The reactions have been found to be extremely dependent on the dominant E/Z isomeric form of the TSC ligands present in the reaction medium. Consequently the isomerisation processes occurring on the free ligands have also been monitored under equivalent conditions. The isomerisation process is found to be acid dependent, despite the absence of protonation under the conditions used, and presumably proceeds via an azo-type tautomer of the ligand. In all cases the existence of outer-sphere interaction processes has been established, both promoting the reactions and producing dead-end complexes. The better oriented forms of the ligands (EZ thiolate) have been found to react faster with the [Fe(HDFO)](+) complex, although for mono-N(4) substituted thiosemicarbazones the process is retarded by the formation of a dead-end outer-sphere complex. A comparison with the abstraction of Fe(III) from [Fe(EDTA)(H(2)O)](-) has also been conducted with significant differences in the kinetic features that implicate keystone outer-sphere interactions which dominate reactivity, even with isomeric forms that are not the best suited for direct complexation.

Electric Relaxation Processes in Chemodynamics of Aqueous Metal Complexes: From Simple Ligands to Soft Nanoparticulate Complexants

The chemodynamics of metal complexes with nanoparticulate complexants can differ significantly from that for simple ligands. The spatial confinement of charged sites and binding sites to the nanoparticulate body impacts on the time scales of various steps in the overall complex formation process. The greater the charge carried by the nanoparticle, the longer it takes to set up the counterion distribution equilibrium with the medium. A z+ metal ion (z > 1) in a 1:1 background electrolyte will accumulate in the counterionic atmosphere around negatively charged simple ions, as well as within/around the body of a soft nanoparticle with negative structural charge. The rate of accumulation is often governed by diffusion and proceeds until Boltzmann partition equilibrium between the charged entity and the ions in the medium is attained. The electrostatic accumulation proceeds simultaneously with outer-sphere and inner-sphere complex formation. The rate of the eventual inner-sphere complex formation is generally controlled by the rate constant of dehydration of the metal ion, k(w). For common transition metal ions with moderate to fast dehydration rates, e.g., Cu(2+), Pb(2+), and Cd(2+), it is shown that the ionic equilibration with the medium may be the slower step and thus rate-limiting in their overall complexation with nanoparticles.

Eu(III) complexes as anion-responsive luminescent sensors and paramagnetic chemical exchange saturation transfer agents.

The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex.

In situ ATR–FTIR and surface complexation modeling studies on the adsorption of dimethylarsinic acid and p-arsanilic acid on iron-(oxyhydr)oxides

Arsenic is an element that exists naturally in many rocks and minerals around the world. It also accumulates in petroleum, shale, oil sands, and coal deposits as a result of biogeochemical processes, and it has been found in fly ash from the combustion of solid biofuels. Arsenic compounds in their organic and inorganic forms pose both a health and an environmental risk, and continue to be a challenge to the energy industry. The environmental fate and removal technologies of arsenic compounds are controlled to a large extent by their surface interactions with inorganic and organic adsorbents. We report thermodynamic binding constants, K binding, from applying the triple-layer surface complexation model to adsorption isotherm and pH envelope data for dimethylarsinic acid (DMA) and p-arsanilic acid (p-AsA) on hematite and goethite. Ligand exchange reactions were constructed based on the interpretation of ATR–FTIR spectra of DMA and p-AsA surface complexes. Surface coverage of adsorbates was quantified in situ from the spectral component at 840 cm −1. The best fit to the DMA adsorption data was obtained using outer-sphere complex formation, whereas for p-AsA, the best fit was obtained using two monodentate inner-sphere surface complexes. The significance of the results is discussed in relation to improving modeling tools used by environmental regulators and the energy sector for optimum control of arsenic content in fuels.

Uptake of methylated arsenic by a polymeric adsorbent: Process performance and adsorption chemistry

Methylated arsenic in groundwater has caused a series of health problems to human beings. A N-methylglucamine modified chitosan polymeric adsorbent was successfully developed for efficient adsorption of methylated arsenic from water solution. Adsorption behaviors of two common methylated arsenic species, monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA), onto the adsorbent were investigated in this paper. The surface modification increased the adsorption capabilities for the arsenic. The uptake of MMA was higher than that of DMA throughout all pH values. The maximum adsorption capacities were 15.4 mg/g for MMA and 7.1 mg/g for DMA, exhibiting competitive advantages with other reported materials. The affinity of these arsenic species for the adsorbent followed a pattern of MMA > DMA. The adsorption equilibrium was achieved within 20 h. The uptake of MMA and DMA was dependent upon the concentration of background electrolytes, indicating the formation of outer-sphere complexes of both organoarsenic species with the adsorbent during the adsorption. The existence of natural organic matter and competitive anions cause decrease in the uptake of both arsenic species. Furthermore, the simultaneous uptake of organic contaminants such as humic acid was observed. The spectroscopic analysis demonstrated the strong attachment of both organic arsenic species onto the amine functional group of the adsorbent.

Sorption of selenium(VI) onto anatase: Macroscopic and microscopic characterization

The sorption of selenium(VI) onto pure anatase, a polymorph of titanium dioxide, was investigated. At the macroscopic level, batch experiments and electrophoretic mobility measurements were performed. Selenium(VI) retention was found to be pH-dependent, i.e. sorption of selenium(VI) decreases with increasing pH (pH range 3.5–11). Selenium(VI) sorption dependence on the ionic strength was also evidenced, i.e. sorption increases while the ionic strength decreases. Electrophoretic mobility measurements showed that selenium(VI) sorption had no effect on the isoelectric point of anatase. At the microscopic level, XPS (X-ray Photoelectron Spectroscopy) measurements evidenced the absence of reduction of selenium(VI) during the sorption process. Furthermore, the nature of the sorbed surface species at the anatase/liquid interface was elucidated using Attenuated Total Reflection Fourier-Transform Infrared (ATR FT-IR) spectroscopy. The spectroscopic results strongly suggested the formation of outer-sphere complexes on the whole pH range, in agreement with batch sorption experiments and electrophoretic mobility findings.

Crystallographic controls on uranyl binding at the quartz/water interface

Molecular dynamics methods were used to simulate UO(2)(OH)(2)(0) binding to pairs of oxo sites (O(S)) on three low-index planes of α-SiO(2) in contact with water. Differences in binding site distributions on the (001), (010) and (101) planes produced distinct sets of stable U inner-sphere species. Steric constraints prevented bidentate coordination to the (001) surface, resulting in a mononuclear monodentate complex, [UO(2)(OH)(2)(H(2)O)(n)O(S)] (90% for n=1 and 10% for n=2 over 5 ns production runs). Binuclear bidentate coordination, [UO(2)(OH)(2)(H(2)O)(n)(O(S))(2)], was however favored on the (010) (99% for n=0 and 1% for n=1) and the (101) (72% for n=0 and 28% for n=1) planes. These results underscore a predominant four-coordinated equatorial shell for U when complexed to the quartz/water interface. Potential of mean force calculations uncovered a diversity of metastable outer- and inner-sphere complexes at local energy minima up to ∼0.4 nm from the surface. These calculations point to important differences in both energetic requirements and mechanisms for the approach of UO(2)(OH)(2)(0) to different quartz surfaces. Binding strengths are affected by binding site distribution, steric freedom, U hydration and OH orientation, and increase in the order (001) (3.7 kJ mol(-1)) < (101) (5.6 kJ mol(-1)) < (010) (6.5 kJ mol(-1)). A general binding mechanism involves (1) formation of monodentate outer-sphere complexes, (2) removal of oxo-bound waters, (3) formation of one (monodentate), then two (bidentate) direct U-O(S) bonds (inner-sphere), and (4) expulsion of excessive waters from the equatorial shell of U.

Adsorption of Zn2+ and Cu2+ onto sulphate and phosphate-modified bentonite

The modification of bentonite with sulphate and phosphate increased the cation exchange capacity (CEC) and adsorption of Cu2+ and Zn2+ but decreased the specific surface area (SSA). Phosphate modified bentonite had the highest adsorption capacity for both metal ions. The Fourier transformed infrared spectra indicated the bonding of sulphate and phosphate bentonite with sulphate and phosphate by the hypochromic and hyperchromic shifts are typical of physisorption and chemisorption mechanisms. Phosphate and sulphate were adsorbed through inner-sphere and outer-sphere complex formation. The isotherms were better fitted by the Langmuir model than the Freundlich model.

ChemInform Abstract: 2H and 7Li Solid‐State MAS NMR Study of Local Environments and Lithium Adsorption on the Iron(III) Oxyhydroxide, Akaganeite (β‐FeOOH).

2H and 7Li MAS NMR spectroscopy have been applied to characterize the surface and bulk hydroxyl groups and Li+ sorption on the iron oxyhydroxide akaganeite (β-FeOOH), a common soil mineral with a large surface area and uptake capacity for toxic cations and anions. The formation of both inner and outer-sphere complexes on the surface of akaganeite was confirmed, the former giving rise to 7Li NMR signals with large 7Li hyperfine shifts. The concentrations of these complexes was determined as a function of pH and possible Li+ binding modes and sites are proposed based on their 7Li hyperfine shifts. The binding is compared with those of the other FeOOH polymorphs, goethite and lepidocrocite. The modes of binding are similar to those of goethite, except that sites at the entrances to the tunnels become available for binding, particularly for nanosized akaganeite particles.

2H and 7Li Solid-State MAS NMR Study of Local Environments and Lithium Adsorption on the Iron(III) Oxyhydroxide, Akaganeite (β-FeOOH)

2H and 7Li MAS NMR spectroscopy have been applied to characterize the surface and bulk hydroxyl groups and Li+ sorption on the iron oxyhydroxide akaganeite (β-FeOOH), a common soil mineral with a large surface area and uptake capacity for toxic cations and anions. The formation of both inner and outer-sphere complexes on the surface of akaganeite was confirmed, the former giving rise to 7Li NMR signals with large 7Li hyperfine shifts. The concentrations of these complexes was determined as a function of pH and possible Li+ binding modes and sites are proposed based on their 7Li hyperfine shifts. The binding is compared with those of the other FeOOH polymorphs, goethite and lepidocrocite. The modes of binding are similar to those of goethite, except that sites at the entrances to the tunnels become available for binding, particularly for nanosized akaganeite particles.

Kinetics and mechanism of the interaction of DL-penicillamine with cis-diaqua(cis-1,2-diaminocyclohexane)platinum(II) perchlorate in aqueous medium

The kinetics of the interaction of DL-penicillamine with cis-[Pt(cis-dach)(OH2)2]2+ has been studied spectrophotometrically as a function of [cis-[Pt(cis-dach)(OH2)2]2+], [DL-penicillamine], and temperature at a particular pH (4.0), where the complex exists predominantly as the diaqua species and DL-penicillamine as a zwitterion. The substitution reaction proceeds via rapid outer sphere association, followed by two slow consecutive steps. The first is the conversion of title complex into an inner sphere complex and the second is the slower chelation step whereby another aqua ligand is replaced. The association equilibrium constant (K E) for the outer sphere complex formation has been evaluated together with rate constant for two subsequent steps. The activation parameters for both steps have been evaluated using the Eyring equation: ( = 36 ± 4 kJ mol−1, = −175 ± 12 JK−1 mol−1 and = 44 ± 1 kJ mol−1, = −189 ± 3 JK−1 mol−1). The low enthalpy of activation and large negative value of entropy of activation are consistent with an associative mode of activation for both consecutive steps. The kinetic study has been substantiated by conductivity measurement, product isolation, IR and ESI-MS spectroscopic analysis.

Kinetics and mechanism of the reaction of hydroxopentaaquarhodium(III) ion with l-Arginine in aqueous solution

The kinetics of the aqua ligand substitution from hydroxopentaaquarhodium(III) ion, [Rh(H2O)5(OH)]2+, by l-Arginine has been studied spectrophotometrically as a function of Arginine concentration, and temperature, at pH 4.3. The reaction proceeds via a rapid outer sphere association complex formation step followed by two consecutive steps. The first of these involves ligand-assisted anation, while the second involves chelation as the second aqua ligand is displaced. The association equilibrium constant for the outer sphere complex formation has been evaluated together with the rate constants for the two subsequent steps. The activation parameters for both steps have been evaluated using Eyring’s equation. Thermodynamic parameters calculated from the temperature dependence of the outer sphere association equilibrium constants are also consistent with an associative mode of activation. The product of the reaction has been characterized by conductivity measurement and IR spectroscopic analysis.

Sorption characteristics and mechanisms of oxyanions and oxyhalides having different molecular properties on Mg/Al layered double hydroxide nanoparticles

The sorption ability of fast-coprecipitated and hydrothermally-treated Mg/Al layered double hydroxide nanoparticles (FCHT-LDH) for various oxyhalides and oxyanions was evaluated. Interactions of oxyhalide such as monovalent bromate or oxyanions such as divalent chromate and divalent vanadate with FCHT-LDH were investigated using a combination of macroscopic (batch sorption/desorption studies and electrophoretic mobility (EM) measurements) and microscopic techniques (CHNS/O, XRD, FTIR, XPS, and EXAFS analyses). The sorption studies on various oxyanions and oxyhalides suggested that their sorption characteristics on FCHT-LDH were largely governed by their ionic potentials and molecular structures. Oxyanions which have ionic potentials higher than 7 nm −1 were found to be more readily sorbed by FCHT-LDH than oxyhalides with ionic potentials lower than 5 nm −1. The results obtained also demonstrated that trigonal pyramid oxyhalides showed a lower degree of specificity for FCHT-LDH than the tetrahedral coordinated oxyanions. From the macroscopic and microscopic studies, monovalent oxyhalide sorption on FCHT-LDH was postulated to occur mainly via anion exchange mechanism with subsequent formation of outer-sphere surface complexes. For polyvalent oxyanion sorption on FCHT-LDH, the mechanisms were possibly associated with both anion exchange and ligand exchange reactions, resulting in the coexistence of outer-sphere and inner-sphere surface complexes.

Adsorption mechanisms of metal cations from water on an oxidized carbon surface

Adsorption of Cr(III), Mn(II), Cu(II) and Zn(II) on an oxidized activated carbon cloth was studied. Its surface chemistry was characterized by potentiometric titration. This technique revealed the amount of surface oxygen functionalities and their acidity constant distribution. The acidity constant range involved in the metal cation adsorption was obtained from this distribution. Metal cation adsorption increased with higher adsorption temperature due to the increase in the negative surface charge of the oxidized activated carbon. Adsorption was by proton exchange and the number, amount and strength of the surface acid groups involved could be obtained. The proton exchange was by an inner-sphere or outer-sphere surface metal complex formation mechanism. In the case of divalent cation adsorption, the increase in temperature changed the adsorption mechanism from outer-sphere to inner-sphere. However, the adsorption mechanism of Cr(III) was outer-sphere and independent of temperature. Adsorption capacity augmented with the increase in the charge-to-size ratio of the hexa-aquo cations. In addition, the adsorption capacity of divalent cations increased with the rise in stability of the surface metal complex formed.

Adsorption of MCPA on goethite and humic acid-coated goethite

Anionic pesticides are adsorbed on the mineral oxide fraction of the soil surface but considerably less on the organic fraction, so that the presence of organic matter causes a decrease in the amount of pesticide adsorbed, and may affect the mechanism of adsorption. In the present study we investigated the adsorption of the weak acid pesticide MCPA on the surface of goethite and of humic acid-coated goethite, selected as models of the mineral oxide fraction and organic components present in soil systems. Adsorption of the anionic form of the pesticide on goethite fitted an S-type isotherm and the amount adsorbed increased as the ionic strength decreased and the pH of the medium decreased. Application of the charge distribution multi site complexation model (CD-MUSIC model) enabled interpretation of the results, which suggested the formation of inner and outer sphere complexes between the pesticide and the singly-coordinated surface sites of goethite. Less pesticide was adsorbed on the humic acid-coated goethite than on the bare goethite and the pattern fitted an L-type isotherm, which indicates a change in the mechanism of adsorption. Simplified calculations with the CD-MUSIC model enabled interpretation of the results, which suggested that the pesticide molecules form the same type of surface complexes as in the previous case.

Ab initio molecular dynamics study of the hydration of Li+, Na+ and K+ in a montmorillonite model. Influence of isomorphic substitution

The present work reports ab initio molecular dynamics simulations, based on density functional theory using the PBE functional, of Li(+)- Na(+)- and K(+)-montmorillonites, considering three types of isomorphic substitutions in the montmorillonite layer: tetrahedral (T(sub)), octahedral (O(sub)) and both (OT(sub)). These simulations allow us to evaluate the effect of each type of substitution on the inner- outer-sphere complex formation of the alkali cations. It is observed that, for the three kinds of substituted montmorillonites, K(+) remains bound to the surface confirming its role as swelling inhibitor. In contrast, Li(+) tends to hydrate and coordinate to 4 water molecules in all cases, except for OT(sub), for which one of the two Li(+) cations remains bound to the oxygens close to the substituted tetrahedral site. Finally, Na(+) presents an intermediate behaviour, binding to the surface in T(sub) montmorillonite but being hydrated in O(sub). These simulations show that the hydration/adsorption behaviour of alkali cations in the swelling process of montmorillonite depends on the affinity of the cation for water and the surface, as well as on the type of substitution that controls the negative charge on surface oxygen atoms.