Coordination of extraframework Li+ cation in the MCM-22 and MCM-36 zeolite: FTIR study of CO adsorbed

Nature and population of Li⁺ cationic sites in MCM-22 zeolite and its pillared form (MCM-36) were investigated by means of adsorption of CO as a probe molecule. CO stretching frequency and adsorption heat were measured by FTIR spectroscopy and adsorption microcalorimetry. Intrazeolitic carbonyl complexes on Li⁺ cations in MCM-22 and MCM-36 are characterized by two main vibrational bands at 2,195 and 2,188 cm^?1. Band at higher wavenumbers is ascribed to carbonyls on Li⁺ ions coordinated only to two oxygen atoms at the intersection of 10-ring channels and interacting with CO molecule by energy around 45 kJ mol^?1. Band at 2,188 cm^?1 was assigned to the carbonyls on Li⁺ cations located on top of 5 or 6-rings on the channel walls and coordinated to three or four oxygen atoms, interacting with CO molecule by energy 33–36 kJ mol^?1. Effect of pillaring and layered form of zeolite on nature and population of Li⁺ cationic sites is also discussed, as well as the formation of dicarbonyl complexes.     

Polyvinyl alcohol fibers with functional phosphonic acid group: synthesis and adsorption of uranyl (VI) ions in aqueous solutions

PVA functionalized with vinylphosphonic acid was prepared as a new adsorbent for uranyl (VI) adsorption from aqueous solutions. The vinylphosphonic acid was cografted onto PVA fibers by preirradiation grafting technique. The adsorbent were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The adsorbent was observed to possess a fibrous structure and was bonded with phosphonic acid groups successfully. The adsorbent was used for the adsorption of low levels uranyl (VI) ions from aqueous solutions. The influence of analytical parameters including pH, adsorption time, amount of adsorbent, metal ion concentration, and temperature were investigated on the recovery of uranyl (VI) ion in aqueous solution. The maximum adsorption capacity (32.1 mg g^?1) and fast equilibrium time (30 min) were achieved at pH of 4.5 at room temperature. Thermodynamic parameters (ΔH° = 2.695 kJ mol^?1; ΔS° = 31.15 J mol^?1 K^?1; ΔG° = ?6.748 kJ mol^?1) show the adsorption of an exothermic process and spontaneous nature, respectively. The possible coordination mechanism was illustrated. Adsorption and desorption coexist in aqueous solutions and then the system becomes equilibrium.     

Kinetic and thermodynamic parameters of volatilization of biodiesel from babassu, palm oil and mineral diesel by thermogravimetric analysis (TG)

The boiling point and volatility are important properties for fuels, as it is for quality control of the industry of petroleum diesel and biofuels. In addition, through the volatility is possible to predict properties, such as vapor pressure, density, latent heat, heat of vaporization, viscosity, and surface tension of biodiesel. From thermogravimetry analysis it is possible to find the kinetic parameters (activation energy, pre-exponential factor, and reaction order), of thermally simulated processes, like volatilization. With the kinetic parameters, it is possible to obtain the thermodynamic parameters by mathematical formula. For the kinetic parameters, the minor values of activation energy were found for mineral diesel (E = 49.38 kJ mol^?1), followed by babassu biodiesel (E = 76.37 kJ mol^?1), and palm biodiesel (E = 87.00 kJ mol^?1). Between the two biofuels studied, the babassu biodiesel has the higher minor value of activation energy. The thermodynamics parameters of babassu biodiesel are, ΔS = ?129.12 J mol^?1 K^?1, ΔH = +80.38 kJ mol^?1 and ΔG = +142.74 kJ mol^?1. For palm biodiesel ΔS = ?119.26 J mol^?1 K^?1, ΔH = + 90.53 kJ mol^?1 and ΔG = +141.21 kJ mol^?1, and for diesel ΔS = ?131.3 J mol^?1 K^?1, ΔH = +53.29 kJ mol^?1 and ΔG = +115.13 kJ mol^?1. The kinetic thermal analysis shows that all E, ΔH, and ΔG values are positive and ΔS values are negative, consequently, all thermodynamic parameters indicate non-spontaneous processes of volatilization for all the fuels studied.     

Removal of thorium from aqueous solution by adsorption using PAMAM dendron-functionalized styrene divinyl benzene

Third generation poly(amido)amine (PAMAM) dendron was grown on the surface of styrene divinylbenzene (SDB) by divergent polymerization method. This new chelating resin (PAMAMG3-SDB) has been investigated in liquid–solid extraction of thorium. The effects of analytical parameters such as pH, contact time, concentration of thorium, resin dose and temperature on adsorption were investigated. Kinetic and isotherm studies of the adsorption were also carried out to understand the nature of adsorption of thorium on the chelating resin. Kinetic data followed a pseudo-second-order model and equilibrium data were best fitted with Langmuir model. The maximum adsorption capacity of thorium ions was determined to be 36.2 mg g^?1 at 298 K. Thermodynamic parameters such as standard enthalpy, entropy, and free energy of adsorption of thorium on PAMAMG₃-SDB were calculated as ?10.498 kJ mol^?1, 0.0493 kJ mol^?1 K^?1 and ?25.208 kJ mol^?1 respectively at 298 K from temperature dependent equilibrium data.     

Study of adsorption sites heterogeneity in zeolites by means of coupled microcalorimetry with volumetry

Adsorption of CO₂ as probe molecule on alkali-metal zeolites of MFI structure was investigated by joint volumetry–calorimetry. Consideration was given to the interpretation of the heat evolved when a probe molecule is adsorbed on the surface. In particular, the number and the strength of adsorption sites are discussed as functions of zeolite structure, concentration, and nature of extra-framework cation. The adsorption heats (q _iso) of CO₂ interaction with alkali-metal cations decrease for MFI zeolite with high Si/Al in the sequence Li⁺ > Na⁺ > K⁺ from 54 kJ/mol to 49 and 43 kJ/mol, respectively. In addition, the adsorption heats are influenced by concentration of Al in the framework. This phenomenon is attributed to formation of bridged CO₂ adsorption complexes formed between two cations. On the base of quantitative analysis of adsorption processes, presence of geminal adsorption complexes was suggested for adsorption at higher equilibrium pressures.     

Carbon dioxide and nitrogen adsorption on porous copolymers of divinylbenzene and acrylic acid

Porous copolymers of divinylbenzene (DVB) and acrylic acid (AA) having DVB:AA ratios of 6:4, 8:2 and 9:1 were prepared following a distillation-precipitation method, using toluene as the porogenic agent. The materials thus obtained, which showed specific surface area in the range of 380–600 m² g^?1 and pore volume in the range of 0.14–0.18 cm³ g^?1, were investigated as possible adsorbents for CO₂ capture from the flue gas of coal-fired power stations. For that purpose, the isosteric heat of adsorption (and CO₂ adsorption capacity) was analysed from N₂ and CO₂ adsorption equilibrium isotherms obtained over a temperature range. For CO₂, q _st resulted to be in the range of 27–31 kJ mol^?1 (the highest value corresponding to the 6:4 sample), while for N₂ a value of q _st ≈ 12 kJ mol^?1 was obtained. Equilibrium adsorption capacity for CO₂ (at ambient temperature and pressure) showed the value of about 1.35 mmol g^?1. These results are discussed in the broader context of corresponding literature data for CO₂ capture using protonic zeolites.     

Immobilisation of lead(II) ions from aqueous solutions on natural coal

The immobilisation of lead(II) ions from aqueous solutions on natural coal was investigated to compare calculated and measured adsorption enthalpies. For this purpose, adsorption isotherms were measured at temperatures of 303, 333 and 353 K. Adsorption enthalpy ΔH was evaluated from temperature dependence of the equilibrium constant of adsorption using the van‘t Hoff equation. Thus, the value of ΔH = 27 kJ mol^?1 was obtained manifesting endothermic effect of lead(II) immobilisation on the coal. However, based on the flow and immersion calorimetric measurements, the exothermic character of lead(II) adsorption on the studied coal was proven with a value of about ?7 kJ mol^?1.     

Adsorptive removal of thorium from aqueous solution using diglycolamide functionalized multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with diglycolamide (DGA) through chemical covalent route. The adsorption behavior of the DGA-functionalized-MWCNTs (DGA-MWCNTs) towards thorium from aqueous solution was studied under varying operating conditions of pH, concentration of thorium, DGA-MWCNTs dosages, contact time, and temperature. The effective range of pH for the removal of Th(IV) is 3.0–4.0. Kinetic data followed a pseudo-second-order model. The equilibrium data were correlated with the Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models. The equilibrium data are best fitted with Langmuir model. The equilibrium Th(IV) sorption capacity was estimated to be 10.58 mg g^?1 at 298 K. The standard enthalpy, entropy, and free energy of adsorption of the thorium with DGA-MWCNTs were calculated to be 8.952 kJ mol^?1, 0.093 kJ mol^?1 K^?1 and -18.521 kJ mol^?1 respectively at 298 K. The determined value of sticking probability (0.072) and observed kinetic and isotherm models reveal the chemical adsorption of thorium on DGA-MWCNTs.     

Sorption of trifluoromethane in activated carbon

Sorption isotherms for trifluoromethane (R-23) in activated carbon have been measured at ca. 298 and 323 K using a gravimetric microbalance. High-resolution TEM images of the activated carbon show a very uniform microstructure with no evidence of any contaminants. The adsorption in the activated carbon reaches about 22.8 mol kg^?1 at 2.0 MPa and 298 K or 17.6 mol kg^?1 at 2.0 MPa and 323 K. Three different adsorption models (Langmuir, multi-site Langmuir, and BET equations) have been used to analyze the activated carbon sorption data, with a particular interest in the heat of adsorption (?ΔH). The heat of adsorption for R-23 in the activated carbon was about 29.78 ± 0.04 kJ mol^?1 based on the multi-site Langmuir model and is within the range of typical physical adsorption. According to the IUPAC classification, the activated carbon exhibits Type I adsorption behavior and was completely reversible. Compared with our previous work for the sorption of R-23 in zeolites (5A (Ca,Na-A), 13X (Na-X), Na,K-LSX, Na-Y, K,H-Y, Rb,Na-Y) and ionic liquids ([omim][TFES] and [emim][Tf₂N]) the activated carbon had the highest adsorption capacity. The adsorption process in the activated carbon also took less time than in the zeolites or the ionic liquids to reach thermodynamic equilibrium.     

Thermodynamics and kinetics of NAD+ adsorption on a glassy carbon electrode

Thermodynamics and kinetics of nicotinamide adenine dinucleotide (NAD⁺) adsorption on a glassy carbon (GC) electrode surface was investigated at various electrode potentials and NAD⁺ concentrations using differential capacitance (DC) and attenuated total reflection Fourier transform infrared (ATR-FTIR) techniques. Equilibrium adsorption measurements confirmed that NAD⁺ spontaneously and strongly adsorbs on the GC electrode surface. The affinity of NAD⁺ towards adsorption on the GC electrode surface was found to increase with an increase in electrode potential (charge) to more positive values; the corresponding apparent Gibbs free energy of adsorption was ?32.80?±?0.25, ?35.61?±?0.86, and ?38.02?±?0.40 kJ mol^?1 on negatively, neutral, and positively charged electrode surfaces, respectively. The kinetics of NAD⁺ adsorption is also found to be highly dependent on the electrode surface potential (charge), and it increases with an increase in electrode potential (charge) to positive values. The adsorption process was modeled using a two-step kinetic model, in which the adsorption process involves the formation of two forms of NAD⁺ on the surface: the thermodynamically unstable (NAD⁺ _ads,rev) and stable (NAD⁺ _ads,stable) forms. ATR-FTIR further confirmed that NAD⁺, indeed, adsorbed on the GC electrode surface.     

Removal of thorium from aqueous solution by ordered mesoporous carbon CMK-3

The ability of ordered mesoporous carbon CMK-3 has been explored for the removal and recovery of thorium from aqueous solutions. The textural properties of CMK-3 were characterized using small-angle X-ray diffraction and N₂ adsorption–desorption, and the BET specific surface area, pore volume and the pore size were 1143.7 m²/g, 1.10 cm³/g and 3.4 nm. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CMK-3 showed the highest thorium sorption capacity at initial pH of 3.0 and contact time of 175 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be -0.74 kJ·mol^?1, 9.17 kJ·mol^?1 and 33.24 J·mol^?1·K^?1, respectively, which demonstrated the sorption process of CMK-3 towards Th(IV) was feasible, spontaneous and endothermic in nature. The adsorbed CMK-3 could be effectively regenerated by 0.02 mol/L HCl solution for the removal and recovery of Th(IV).     

Sorption study of uranium on carbon spheres hydrothermal synthesized with glucose from aqueous solution

The ability of oxygen-rich carbon spheres (CSs) produced by hydrothermal carbonization with the glucose has been explored for the removal and recovery of uranium from aqueous solutions. The micro-morphology and structure of CSs were characterized by FT-IR and SEM. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The CSs showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 25 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be ?16.88, 12.09 kJ mol^?1 and 197.87 J mol^?1 K^?1, respectively, which demonstrated the sorption process of CSs towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed CSs could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 3.0 g CSs.     

Adsorption of uranium from aqueous solution using biochar produced by hydrothermal carbonization

The ability of biochar produced by hydrothermal carbonization (HTC) has been explored for the removal and recovery of uranium from aqueous solutions. The micro-morphology and structure of HTC were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The influences of different experimental parameters such as solution pH, initial concentration, contact time, ionic strength and temperature on adsorption were investigated. The HTC showed the highest uranium sorption capacity at initial pH of 6.0 and contact time of 50 min. Adsorption kinetics was better described by the pseudo-second-order model and adsorption process could be well defined by the Langmuir isotherm. The thermodynamic parameters, △G°(298 K), △H° and △S° were determined to be ?14.4, 36.1 kJ mol^?1 and 169.7 J mol^?1 K^?1, respectively, which demonstrated the sorption process of HTC towards U(VI) was feasible, spontaneous and endothermic in nature. The adsorbed HTC could be effectively regenerated by 0.05 mol/L HCl solution for the removal and recovery of U(VI). Complete removal (99.9 %) of U(VI) from 1.0 L industry wastewater containing 15.0 mg U(VI) ions was possible with 2.0 g HTC.     

Removal of Lead (II) Ions by Poly(2‐octadecyl butanedioic acid): Isothermal and Kinetic Studies

Poly(2‐octadecyl‐butanedioic acid), prepared from polyanhydride PA‐18, possesses novel heavy metal adsorption characteristics. The adsorption capacity of this water insoluble polymer for lead (II) was substantially higher than other heterogeneous adsorbants and is equivalent to those obtained with homogeneous sorbants. The polymer exhibited pseudo‐second‐order kinetics and nearly complete adsorption of lead occurred in 15 min with initial lead (II) concentrations greater than 100 mg · L^?1. Adsorptive behavior was accurately predicted by the Dubinin‐Radushkevich isotherm model. The mean free energy of adsorption of lead (II) onto poly(2‐octadecyl‐butanedioic acid) was determined to be 31.6 kJ · mol^?1, suggesting an ion exchange component to the adsorption mechanism. Gibb's free energy values for this process indicate that it is spontaneous. Adsorption was relatively independent of pH in the range of 3–5, due to the utilization of the sodium carboxylate form of the chelating groups, and was not influenced by high Na⁺ concentration and moderate concentrations (up to 200 mg · L^?1) of Ca⁺². Lead (II) solutions containing 2000 mg · L^?1 Ca⁺² did reduce the adsorption of 2000 mg · L^?1 lead (II) by 28%.     

Study of the gadolinium sorption on the C100 ion-exchange resin for the development of the antineutrino detector targets

Adsorption of the gadolinium from H₂O and HCl solutions on the ion-exchange resin C100 is investigated. The experiments were carried out by varying the acidity of the liquid phase, the amount of sorbent, and the temperature. The maximal sorption of the ions Gd³⁺ is observed from the solution 0–0.2 M HCl under optimal conditions, the sorption reaches more than 99.5%. Sorption of Gd³⁺ on C100 from H₂O solution occurs most intensively during the first 3 min then for 30 min the system smoothly comes to equilibrium. The maximal sorption capacity of the resin C100 amounted to 1.2 ± 0.1 mmol g^?1. The thermodynamic parameters of sorption: ΔG = ? 24.20 kJ mol^?1, ΔS = ? 90.27 J mol^?1 K^?1, ?H = ? 50.93 kJ mol^?1 were evaluated. It is shown that the sorption of gadolinium on the ion-exchange resin C100 is described by models of kinetically pseudo-first and pseudo-second order. It is established that the Gd³⁺ sorption on the C100 resin is reversible second order chemical reaction.     

Kinetics and mechanism of the oxidation of tris(2,2′-bipyridine)iron(II) and tris(1,10-phenanthroline)iron(II) complexes by nitropentacyanocobaltate(III) in acidic aqueous medium

The kinetics of the oxidation of tris(2,2′-bipyridyl)iron(II) and tris(1,10-phenanthroline)iron(II) complexes ([Fe(LL)₃]²⁺, LL = bipy, phen) by nitropentacyanocobaltate(III) complex [Co(CN)₅NO₂]^3? was investigated in acidic aqueous solutions at ionic strength of I = 0.1 mol dm^?3 (HCl/NaCl). The reactions were carried out at fixed acid concentration ([H⁺] = 0.01 mol dm^?3) and the temperature maintained at 35.0 ± 0.1 °C. Spectroscopic evidence is presented for the protonated oxidant. Protonation constants of 360.43 and 563.82 dm³ mol^?1 were obtained for the monoprotonated and diprotonated Co(III) complexes respectively. Electron transfer rates were generally faster for [Fe(bipy)₃]²⁺ than [Fe(phen)₃]²⁺. The redox complexes formed ion-pairs with the oxidant with increasing concentration of the oxidant over that of the reductant. Ion-pair constants for these reaction were 160.31 and 131.9 dm³ mol^?1 for [Fe(bipy)₃]²⁺ and [Fe(phen)₃]^2+, respectively. The activation parameters measured for these systems have values as follows: ?H ^≠ (kJ K^?1 mol^?1) = +113.4 ± 0.4 and +119 ± 0.3; ?S ^≠ (J K^?1) = +107.6 ± 1.3 and 125.0 ± 1.6; ?G ^≠ (kJ K^?1) = +81 ± 0.4 and +82.4 ± 0.4; and E _a (kJ mol^?1) = 115.9 ± 0.5 and 122.3 ± 0.6 for LL = bipy and phen, respectively. Effect of added anions (Cl^?, $ {\text{SO}}_{4}^{2 - } $ and $ {\text{ClO}}_{4}^{ - } $ ) on the systems showed decrease in the electron transfer rate constant. An outer-sphere mechanism is proposed for the reaction.     

Biosorption of strontium from aqueous solutions onto spent coffee grounds

A set of experiments was carried out to evaluate the strontium uptake potential of spent coffee grounds (SCG) by batch tests in aqueous medium. Adsorption of Sr²⁺ as a function of contact time and adsorbent dose, pH, particles size, agitation speed, temperature and co-ions presence was investigated. Obtained results revealed that the maximum adsorption took place at pH range of 5–8 and temperature values between 283 and 333 K. Particles size effect was not very significant and agitation speed influenced on the equilibrium time. Competitive adsorption experiments allowed us to classify the negative effect on the Sr²⁺ uptake according to this order Al³⁺ ? Co²⁺ > Mg²⁺ > Ca²⁺ ? Na⁺ > K⁺ > Cs⁺. Kinetic study indicated that the Sr²⁺ uptake was fast and it was well fitted by the pseudo second order reaction model. Adsorption isotherm was well interpreted by Langmuir model. The maximum adsorption capacity was found to be 69.01 mg g^?1 at pH 7, 293 K, particles sizes = 200–400 μm and agitation speed 250 rpm. The thermodynamic study revealed that the process was spontaneous (ΔG ⁰ < 0), exothermic (ΔH ⁰ < 0) with a raised affinity for Sr²⁺ (ΔG ⁰ < 0, ΔS ⁰ > 0) and occurred by physical adsorption (E _a = 8.37 kJ mol^?1). FTIR analysis showed carboxylic acid and amino group presence on SCG surface playing a vital role in Sr²⁺ biosorption.     

Removal of uranium(VI) from aqueous solutions using nanoporous ZnO prepared with microwave-assisted combustion synthesis

The adsorption of the uranyl ions from aqueous solutions on the nanoporous ZnO powders has been investigated under different experimental conditions. The adsorption of uranyl on nanoporous ZnO powders were examined as a function of the contact times, pH of the solution, concentration of uranium(VI) and temperature. The ability of this material to remove U(VI) from aqueous solution was followed by a series of Langmuir and Freunlinch adsorption isotherms. The adsorption percent and distribution coefficient for nanoporous ZnO powders were 98.65 % ± 1.05 and 7,304 mL g^?1, respectively. The optimum conditions were found as at pH 5.0, contact time 1 h, at 1/5 Zn²⁺/urea ratio, 50 ppm U(VI) concentration and 303 K. The monomolecular adsorption capacity of nanoporous ZnO powders for U(VI) was found to be 1,111 mg g^?1 at 303 K. Using the thermodynamic equilibrium constants obtained at different temperatures, various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, have been calculated. Thermodynamic parameters (ΔH° = 28.1 kJ mol ^?1, ΔS° = 160.30 J mol^?1 K^?1, ΔG° = ?48.54 kJ mol^?1) showed the endothermic and spontaneous of the process. The results suggested that nanoporous ZnO powders was suitable as sorbent material for recovery and adsorption of U(VI) ions from aqueous solutions.     

A density functional theory study of the Cu+·(CO)n (n = 1–3) complexes

Density functional theory calculations, with an effective core potential for the copper ion, and large polarized basis set functions have been used to construct the potential energy surface of the Cu⁺·(CO)_n (n = 1–3) complexes. A linear configuration is obtained for the global minimum of the Cu⁺·CO and Cu⁺·(CO)₂ complexes with a bond dissociation energy (BDE) of 35.9 and 40.0 kcal mol^-1, respectively. For the Cu⁺·(CO)₃ complex, a trigonal planar geometry is obtained for the global minimum with a BDE of 16.5 kcal mol^?1. C-coordinated copper ion complexes exhibit stronger binding energy than O-coordinated complexes as a result of C_lp → 4s σ-donation. The computed sequential BDEs of Cu⁺·(CO)_n (n = 1–4) complexes agree well with experimental findings, in which the electrostatic energy and σ-donation play an important role in the observed trend.