Bioadsorption and ion exchange of Cr3+ and Pb2+ solutions with algae

Heavy metals can be removed from effluents and recovered using physico-chemical mechanisms as biosorption processes. In this work “Arribada” seaweed biomass was employed to assess its biosorptive capacity for the chromium (Cr³⁺) and lead (Pb²⁺) cations that usually are present in waste waters of plating industries. Equilibrium and kinetic experiments were conducted in a mixed reactor on a batch basis. Biosorption equilibrium and fluid-solid mass transfer constants data were analyzed through the concept of ion exchange sorption isotherm. The respective equilibrium exchange constants (K _eqCr=173.42, K _eqPb=58.86) and volumetric mass transfer coefficients ((k _mCr a)′=1.13×10⁻³ s⁻¹, (k _mPb a)′=0.89×10⁻³ s⁻¹) were employed for the dynamic analysis of Cr and Pb sorption in a fixed-bed flow-through sorption column. The breakthrough curves obtained for both metals were compared with the predicted values by the heterogeneous model (K _eqCr=171.29, K _eqPb=60.14; k _mCr a=7.81×10⁻² s⁻¹, k _mPb a=2.43×10⁻² s⁻¹), taking into account the mass transfer process. The results suggest that these algae may be employed in a metal removal/recovery process at low cost. An erratum to this article can be found at     

Does Thermochemical Mimicry Extend to Gibbs Energies? The Differences of K+ and NH4 +, and of Na+ and H3O+

Structural Chemistry -     

Mixed Ligand Complexes of Am3+, Cm3+ and Eu3+ with HEDTA and HEDTA + NTA—Complexation Thermodynamics and Structural Aspects

The stability constants and the associated thermodynamic parameters of formation for the 1:1 binary complexes of Am³⁺, Cm³⁺ and Eu³⁺ with N-(2-hydroxyethyl) ethylenediaminetriacetate (HEDTA) and their 1:1:1 ternary complexes with HEDTA + NTA (nitrilotriacate) were determined by distribution ratio measurements using solvent extraction in aqueous solutions of I=0.10?mol?L^?1 (NaClO₄) at temperatures of 0?C45?°C. Formation of these complexes is favored by both the enthalpy (exothermic) and the entropy (endothermic) terms. Luminescence lifetime measurements with Cm and Eu were used to study the coordination environment of these complexes over a range of concentrations and pH values. In the binary complexes M(HEDTA), HEDTA is a hexadentate ligand with three waters of hydration, while in the ternary complexes M(HEDTA)(NTA)^3? we propose that the HEDTA retaines hexadentate coordination with NTA binding via three sites, depending on the pH of the solution, with the observation that the complex may contain a single water of hydration.     

Liquid–liquid equilibria of two binary systems: water+1-pentanol and water+2-methyl-2-butanol and two ternary systems: water+1-pentanol+2-butyloxyethanol and water+2-methyl-2-butanol+2-butyloxyethanol

Liquid–liquid equilibrium phase diagrams for two binary systems: water+1-pentanol and water+2-methyl-2-butanol and two ternary systems: water+1-pentanol+2-butyloxyethanol and water+2-methyl-2-butanol+2-butyloxyethanol at 20°C and 30°C are presented in this paper. The experimental results were correlated with the UNIQUAC model by fitting the effective UNIQUAC binary interaction parameters as a function of temperature. Agreement between the calculated and experimental data was very good.     

Dynamics and mode-selected reaction of NCO+H_2→HNCO+H

The reaction path of the reaction NCO+H2→HNCO + H has been traced by Fukui's theory and the ab initio method. On this basis, the dynamical properties along the reaction path, canonical variational theory (CVT) rate constants and vibrational-mode-selected rate constants have been computed. The results show that the effect of the electron correlation energy on the activation barrier is large, and tiros the correction by MP4 method is effective; the results also show that the recrossing and tunneling effects exist, and thus the corrections by the variational transition state theory (VTST) and the small curvature (SC) approximation method are also effective. In the reaction, the coupling and energy transfer between mode 8(7) and reaction path are strong, so the rate is effectively enhanced while these modes, especially H2 stretching, are vibrationally excited.     

Reactions of Au+ and Au− with benzene and fluorine-substituted benzenes

Reactions of gold anions and cations generated by laser desorption/ionization were studied in the FTICR spectrometer. Au⁻ associated with C₆F₆ to give the novel Au⁻(C₆F₆) complex, whose binding energy was estimated to be 24 ± 4 kcal mol⁻¹ from analysis of the radiative association (RA) kinetics. Au⁺ associated with C₆F₅H to give Au⁺(C₆F₅H), with binding energy estimated to be 31 kcal mol⁻¹. Au⁺ reacted with C₆H₆ to form the well known Au⁺(C₆H₆) and Au⁺(C₆H₆)₂ complexes. The observation of rapid charge transfer from Au⁺(C₆H₆) to C₆H₆ was interpreted as showing that benzene binds more strongly to neutral Au than to Au⁺. The neutral Au–C₆H₆ bond is accordingly concluded to be stronger than about 70 kcal mol⁻¹.     

Photoacoustic Spectrometry Investigation and Determination of Rare Earth Ions Ho3+ and Nd3+ in a Solution

A home-made high sensitive photoacoustic transducer was used to determine the photoacoustic signal in a solution. The photoacoustic spectra of Ho in different solvents were measured and comparedwith its absorption spectrum. The affection factors of photoacousticsensitivity are discussed. The trivalent rare earth ions Ho3+ and Nd3+in an aqueous acetonitrile solution were determined. The detection limit is 5×10-8 mol/L for Ho3+ and 1.0 ×10-7 mol/L for Nd3+, and corresponds to the absorbance of 1.5×10 and 6.3×10-7.respectively.     

Relativistic calculations of AuSi+ and AuSi−

Theoretical calculations of the electronic structure of the ground state and a series of excited states of the AuSi⁺ and AuSi⁻ molecules are presented. The calculations were carried out with the spin-free relativistic infinite-order two-component (IOTC) method and high-level complete active space self-consistent field/complete active space perturbation theory correlated methods. The spin-orbit (SO) coupling was introduced via the restricted active space state interaction method with the use of the atomic mean-field SO integrals. The work presents the spectroscopic parameters of calculated states and full potential energy curves of the ionic AuSi⁺ and AuSi⁻ structures for the first time. Electrostatic potential maps projected on the electron density surface illustrate the significant relativistic effects on going from nonrelativistic to scalar relativistic treatments.     

Transport of 125I−, 137Cs+ and 85Sr2+ in granitoidic rock and soil columns

Transport of ¹²⁵I^?, ¹³⁷Cs⁺ and ⁸⁵Sr²⁺ radionuclides in crushed granitoidic rocks and homogenized soils was studied. Two simple methods for calculation of breakthrough curves in flow column experiments with groundwater as transport medium have been described. The first method, so called non-linear approach, is derived on the assumption of a reversible non-linear sorption isotherm described with Freundlich equation, i.e., with non-constant distribution and retardation coefficients. The second method, so-called linear approach, is applied for reference only, and is based on the assumption of a reversible sorption characterized with linear sorption isotherm, i.e., with constant distribution and retardation coefficients. Both methods model the experimental breakthrough curves with the integrated form of the simple 1-D advection–dispersion equation (ADE) expressed analytically for pulse application of radiotracer to the liquid phase before entering the columns. The integrated form of the ADE equation was modified by the so-called peak position and peak height correction coefficients the advantage of which consists among others in the elimination of the influence of starting concentration. The comparison of both approaches has shown that fitting by means of non-linear approach has given rather reliable values of the transport parameters and calculated dependences, especially in a case of ¹³⁷Cs system characterized evidently with non-linear type of sorption isotherms. As for ¹²⁵I^?, the sorption capacity of all solid samples studied is nearly on the zero level and ¹²⁵I^? is practically not retarded, and from this point of view it behaves as non-interacting component. In addition, it was found that the modified ADE gives rather better results than the classical one.     

Batch and continuous fixed-bed column adsorption of Cs+ and Sr2+ onto montmorillonite–iron oxide composite: Comparative and competitive study

A montmorillonite–iron oxide composite (MIOC) was prepared to assess its effectiveness in the removal of Cs⁺ and Sr²⁺ from aqueous solution. A comparative and competitive adsorption study was conducted in single and binary systems. Used materials have been characterized by X-ray diffraction (XRD) and Infrared spectroscopy. Adsorption of Cs⁺ and Sr²⁺ as a function of contact time and pH was investigated, adsorption data of single metal solutions were well fitted to the Freundlich–Langmuir isotherm models. Equilibrium isotherms for the binary removal of Cs⁺ and Sr²⁺ by MIOC have been analyzed by using non modified and extended Langmuir models with a satisfactory R ² values. Neutral solution pH was found to be favorable for both single and binary systems. The adsorption model analysis revealed that MIOC was more selective for Sr than Cs. The maximum adsorption capacities for individual Cs⁺ and Sr²⁺ solutions were 52.6 and 55.5 mg g^?1, respectively. While the maximum uptakes in the binary system were 41.6 and 47.6 mg g^?1 for Cs⁺ and Sr²⁺, respectively. Column adsorption experiments were carried out at room temperature under the effect of various operating parameters such as bed depth, initial cation concentration and flow rate, Breakthrough curves were well fitted to the Thomas model. Desorption experiments were also conducted to assess the possibility for the reuse of adsorbent and the recovery of cations.     

Synthesis and phosphorescence properties of Dy3+ and (Pr3+–Dy3+) in MgTiO3

Using tetra-n-butyl titanate and magnesium nitrate as raw materials, Dy³⁺ and Pr³⁺ ions in the matrix of magnesium titanate (MgTiO₃) was successfully synthesized by a modified solid-state reaction. The mixtures to achieve a solid-state reaction were heated in porcelain crucibles at 600?°C for 2?h, 900?°C for 6?h, and 1000.0?°C for 2?h. The reaction products obtained in an air atmosphere were characterized by X-ray powder diffractions. The optimization of reaction conditions were carried out by thermal gravimetry and differential thermal analysis methods. Surface and elemental analyses were performed by using on SEM instrument. The excitation and emission spectra were recorded by photoluminescence spectrophotometer.     

High-pressure densities and P–T–x–y diagrams for carbon dioxide+linalool and carbon dioxide+limonene

Liquid and vapor densities for carbon dioxide+linalool, and carbon dioxide+limonene were measured by using a system consisting of two vibrating tube densimeters. The P–T–x–y diagrams and saturated liquid and vapor densities for these two binary mixtures were determined at 313, 323 and 333 K, respectively, as well as at pressures up to 11 MPa. The density of the saturated CO₂ phase increased with increasing pressure. At higher pressure, the density of the liquid phase decreased with increasing pressure, corresponding to an increasing amount of carbon dioxide.     

Mössbauer study and magnetic properties of M-type barium hexaferrite doped with Co + Ti and Bi + Ti ions

Using X-ray powder diffractions, M?ssbauer spectroscopy, and magnetic measurements, the effect of complex dopants (Co2+ + Ti4+) and (Bi3+ + Ti4+) on the fine structure and magnetic properties of M-type barium hexaferrite prepared by hydroxide and carbonate precipitations has been studied. The distribution of cations over five nonequivalent positions of barium hexaferrite with magnetoplumbite structure is discussed. It has been shown that doped barium hexaferrite can be used for high-coercitivity data storage media.     

Determination of the Rate Constants of the Reactions Cr + O2 + M → CrO2 + M and Cr + O2 → CrO + O

Kinetics and Catalysis - The rate constants of the interactions of chromium atoms with molecular oxygen through recombination Cr + O2 + M → CrO2 + M (I) and exchange Cr + O2 → CrO + O...     

Adsorption and diffusion of propane and propylene in Ag+-impregnated MCM-41

Equilibrium data and diffusion characteristics of propane and propylene were determined on mesoporous adsorbents modified with an organic molecule (APTES) and/or impregnated with AgNO₃, in order to obtain a separation by adsorption via π-complexation. Adsorption capacities were determined by a gravimetric technique, while diffusion characteristics were evaluated by the ZLC technique. The equilibrium isotherms data showed that the modification with an organic molecule will weaken the π-interaction between Ag⁺ and double C=C bond. On the other hand slightly higher adsorption capacities for propylene (about 1.5 mol/kg) were obtained for the sample prepared by a direct impregnation with larger amounts of AgNO₃ (M4 sample). Diffusion runs confirmed that the propane desorption rate on M4 sample was much higher compared to propylene. This evidence leads to a potential application of that adsorbent material for a kinetic separation.     

Rotational analysis and deperturbation of the A2Π → X2Σ+ and B'2Σ+ → X2Σ+ emission spectra of MgH

Deperturbation analysis of the A(2)Π → X(2)Σ(+) and B(')(2)Σ(+) → X(2)Σ(+) emission spectra of (24)MgH is reported. Spectroscopic data for the v = 0 to 3 levels of the A (2)Π state and the v = 0 to 4 levels of the B'(2)Σ(+) state were fitted together using a single Hamiltonian matrix that includes (2)Π and (2)Σ(+) matrix elements, as well as off-diagonal elements coupling several vibrational levels of the two states. A Dunham-type fit was performed and the resulting Y(l,0) and Y(l,1) coefficients were used to generate Rydberg-Klein-Rees (RKR) potential curves for the A (2)Π and the B'(2)Σ(+) states. Vibrational overlap integrals were computed from the RKR potentials, and the off-diagonal matrix elements coupling the electronic wavefunctions (a(+) and b) were determined. Zero point dissociation energies (D(0)) of the A(2)Π and B'(2)Σ(+) states of (24)MgH were determined to be 12,957.5 ± 0.5 and 10,133.6 ± 0.5 cm(-1), respectively. Using the Y(0,1) coefficients, the equilibrium internuclear distances (r(e)) of the A(2)Π and B'(2)Σ(+) states were determined to be 1.67827(1) ? and 2.59404(4) A?, respectively.     

Preparation of stable AsBr4+ and I2As-PI3+ salts. Why didn't we succeed to prepare AsI4+ and As2X5+? A combined experimental and theoretical study

In analogy to our successful "PX2+" insertion reactions, an "AsX2+" insertion route was explored to obtain new arsenic halogen cations. Two new salts were prepared: AsBr4+[Al(OR)4]-, starting from AsBr3, Br2 and Ag[Al(OR)4], and I2As-PI3+[Al(OR)]4 from AsI3, PI3 and Ag[Al(OR)4](R=C(CF3)3). The first cation is formally a product of an "AsBr2+" insertion into the Br2 molecule and the latter clearly a "PI2+" insertion into the As-I bond of the AsI3 molecule. Both compounds were characterized by IR and NMR spectroscopy, the first also by its X-ray structure. Reactions of Ag[Al(OR)4] with AsI3 do not lead to ionization and AgI formation but rather lead to a marginally stable Ag(AsI3)2+[Al(OR)]4 salt. Despite many attempts we failed to prepare other PX-cation analogues such as AsI4+, As2X5+ and P4AsX2+(X=Br, I). To explain these negative results the thermodynamics of the formation of EX2+, EX4+ and E2X5+(E = As, P; X = Br, I) was carefully analyzed with MP2/TZVPP calculations and inclusion of entropy and solvation effects. We show that As2Br5+ is in very rapid equilibrium with AsBr2+ and AsBr3(DeltaGo((CH2Cl2))=+30 kJ mol(-1)). The extremely reactive AsBr2+ cation available in the equilibrium accounts for the observed decomposition of the [Al(OR)4]- anion. By contrast, the stability of AsI3 against Ag[Al(OR)4] appears to be kinetic and, if prepared by a suitable route, As2I5+ would be expected to have a stability intermediate between the known P2I5+ and P2Br5+.     

Capture and dissociation in the complex-forming CH(v = 0,1) + D2 → CHD + D, CD2 + H, CD + HD reactions and comparison with CH(v = 0,1) + H2

Rate coefficients for the CH(v = 0,1) + D(2) reaction have been determined for all possible channels (T: 200-1200 K), using the quasiclassical trajectory method and a suitable treatment of the zero point energy. Calculations have also been performed on the CH(v = 1) + H(2) reaction and the CH(v = 1) + D(2) → CH(v = 0) + D(2) process. Most of the results can be understood considering the key role played by the deep minimum of the potential energy surface (PES), the barrierless character of the PES, the energy of the reaction channels, and the kinematics. The good agreement found between theory and experiment for the rate coefficients of the capture process of CH(v = 0) + D(2), the total reactivity of CH(v = 1) + D(2), H(2), as well as the good agreement observed for the related CH(v = 0) + H(2) system (capture and abstraction), gives confidence on the theoretical rate coefficients obtained for the capture processes of CH(v = 1) + D(2), H(2), the individual reactive processes of CH(v = 1) + D(2), H(2), the abstraction and abstraction-exchange reactions for CH(v = 0) + D(2), and the inelastic process mentioned above, for which there are no experimental data available, and that can be useful in combustion chemistry and astrochemistry.     

Capture and dissociation in the complex-forming CH + H2 → CH2 + H, CH + H2 reactions

The rate coefficients for the capture process CH + H(2)→ CH(3) and the reactions CH + H(2)→ CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems.     

Cation-π effects in the complexation of Na+ and K+ with Phe, Tyr, and Trp in the gas phase

Na⁺ and K⁺ gas-phase affinities of the three aromatic amino acids Phe, Tyr, and Trp were measured by the kinetic method. Na⁺ binds these amino acids much more strongly than K⁺, and for both metal ions the binding strength was found to follow the order Phe ≤ Tyr < Trp. Quantum chemical calculations by density functional theory (DFT) gave the same qualitative ordering, but suggested a somewhat larger Phe/Trp increment. These results are in acceptable agreement with predictions based on the binding of Na⁺ and K⁺ to the side chain model molecules benzene, phenol, and indole, and are also in reasonable agreement with the predictions from purely electrostatic calculations of the side-chain binding effects. The binding energies were compared with those to the aliphatic amino acids glycine and alanine. Binding to the aromatic amino acids was found to be stronger both experimentally and computationally, but the DFT calculations indicate substantially larger increments relative to alanine than shown by the experiments. Possible reasons for this difference are discussed. The metal ion binding energies show the same trends as the proton affinities.