The reaction between oxalatotetraammine-cobalt(III) ion and hydroxide ion in aqueous solution

The rate of the reaction between sodium hydroxide and oxalatotetraamminecobalt(III) ion was measured for a variety of hydroxide ion concentrations and at four temperatures. The rate law below 333 K is given by k_obs = k₀ + k₂[OH⁻]² and above 333 K is shown to be k_obs = k₀ + k₁[OH⁻]. The reaction proceeds with a single rate controlling step, which is interpreted as oxalate ring opening. This is followed by a rapid oxalate loss step.     

Adsorptive removal of uranium from aqueous solution using chitosan-coated attapulgite

Chitosan-coated attapulgite beads were prepared by coating chitosan on naturally and abundantly available attapulgite, and made into spherical beads to adsorb uranium from aqueous solutions. The beads were characterized by SEM, EDS and FT-IR. The characteristics of beads of adsorbing uranium(VI) from aqueous solutions were studied at different conditions of pH, initial uranium concentration, contact time, biomass dosage and temperature. The pseudo-second order rate equation was used to describe the kinetic data, and isotherm data were fitted to Langmuir and Freundlich adsorption models. Thermodynamic parameters (ΔG°, ΔH°, and ΔS°) of the biosorption were also calculated. Thermodynamic parameters of the CAAB, viz., ΔG°(308 K), ΔH°, and ΔS° were determined to be −21.59, 6.29l and 90.51 J/mol K, respectively. The experimental results demonstrate that the beads of chitosan coated onto attapulgite exhibit considerable potential for application in both adsorption and removal of uranium from aqueous solutions.     

Preparation of magnesium hydroxide from nitrate aqueous solution

Nucleation of Mg(OH)₂ was investigated by measuring the electrical conductivity and pH of the Mg(NO₃)₂ reaction solution to which ammonia containing different amounts of NH₄NO₃ was added. NH₄NO₃ increases solubility and slows down precipitation of Mg(OH)₂ in the system. Data are presented on the influence of NH₄NO₃ on the solubility of Mg(OH)₂ at 25°C. The phenomena observed can be explained by the solvation effect of nitrate ions brought to the system with the addition of ammonium nitrate, which was proved by NMR spectroscopy. When the mass fraction of NH₄NO₃ exceeds 15 %, homogeneous nucleation does not proceed. It was found that seeding of the system with Mg(OH)₂ crystals only influenced the rate of Mg(OH)₂ crystallisation, not the size and shape of the crystals. Primary crystals are smaller than 0.1 μm. The large difference in the surface energy of individual crystal planes leads to oriented agglomeration. This process is accelerated in a pressure reactor at 130°C. The resulting polycrystals are hexagonal plates 0.2 μm thin with a diameter of 1–2 μm. Under variable reaction conditions, agglomerates as big as 30 μm can be prepared.     

Phenol removal from aqueous solution by adsorption and ion exchange mechanisms onto polymeric resins

The removal of phenol from aqueous solution was evaluated by using a nonfunctionalized hyper-cross-linked polymer Macronet MN200 and two ion exchange resins, Dowex XZ (strong anion exchange resin) and AuRIX 100 (weak anion exchange). Equilibrium experimental data were fitted to the Langmuir and Freundlich isotherms at different pHs. The Langmuir model describes successfully the phenol removal onto the three resins. The extent of the phenol adsorption was affected by the pH of the solution; thus, the nonfunctionalized resin reported the maximum loading adsorption under acidic conditions, where the molecular phenol form predominates. In contrast both ion exchange resins reported the maximum removal under alkaline conditions where the phenolate may be removed by a combined effect of both adsorption and ion exchange mechanisms. A theoretical model proposed in the literature was used to fit the experimental data and a double contribution was observed from the parameters obtained by the model. Kinetic experiments under different initial phenol concentrations and under the best pH conditions observed in the equilibrium experiments were performed. Two different models were used to define the controlling mechanism of the overall adsorption process: the homogeneous particle diffusion model and the shell progressive model fit the kinetic experimental data and determined the resin phase mechanism as the rate-limiting diffusion for the phenol removal. Resins charged after the kinetic experiments were further eluted by different methods. Desorption of nonfunctionalized resin was achieved by using the solution (50% v/v) of methanol/water with a recovery close to 90%. In the case of the ion exchange resins the desorption process was performed at different pHs and considering the effect of the competitive ion Cl⁻. The desorption processes were controlled by the ion exchange mechanism for Dowex XZ and AuRIX 100 resins; thus, no significant effect for the addition of Cl⁻ under acidic conditions was observed, while under alkaline conditions the total recovery increased, specially for Dowex XZ resin.     

Kinetic study of spiramycin removal from aqueous solution using heterogeneous photocatalysis

Spiramycin macrolide antibiotic (SPM) can be photocatalytically degraded on TiO₂ (anatase variety). The experiments are done in a batch reactor and the effect of some key parameters is investigated under low energy of artificial UV light. The reaction rate is affected by varying TiO₂ dose, pH and SPM concentration. Under optimized conditions, a photodegradation efficiency of 98% is achieved and the SPM photodegradation follows pseudo-first order kinetics. The Langmuir–Hinshelwood (L–H) model is successfully used to fit the experimental data, indicating the dependence of the reaction rate on the chemical reaction step. The L–H model led to the determination of both reaction kinetic and adsorption/desorption equilibrium constants. In order to give an overall estimate of the by-products, chemical oxygen demand, total organic carbon, and calculated average oxidation state monitor the photodegradation process.     

Effective removal of cation dyes from aqueous solution using robust cellulose sponge

Cellulose sponge was proposed to an attractive bio-absorbent owing to its highly efficient, low-cost, biodegradable, and renewable sourcing. In this work, the wasted cotton linter as raw materials, the highly porous and lightweight cellulose sponges were synthesized via a facile chemical crosslinking and freeze-drying process. The resultant cellulose sponge (CA) exhibited an interconnected three-dimensional porous structure through crosslinked with N,N′-methylene bisacrylamide (MBA), which was beneficial to remove organic dyestuffs. The effects of various factors including solution pH, contact time, initial dye concentration, and ionic strength on the adsorption behavior were investigated in detail. Herein, Langmuir isotherm models were selected to determine the adsorption capacity, and the maximum theoretical adsorption capacity for Methylene blue (MB) and Crystal violet (CV) was 123.46 and 76.63 mg/g, respectively. Particularly, the results of kinetic and thermodynamic tests showed that the adsorption performance was a spontaneous endothermic reaction and the adsorption process followed the pseudo-second-order kinetic. Furthermore, cellulose sponges could maintain maximum adsorption capacity even after twelve cycles. Therefore, the eco-friendly cellulose sponge would be a promising adsorbent for effective wastewater treatment.     

Copper removal from aqueous solution using biochar: Effect of chemical activation

The main aim of this study was to test the efficiency of biochar for Cu removal from synthetic and soil solutions, respectively.The biochar was produced from brewers draff via pyrolysis. Additionally, the prepared biochar was also activated using 2 M KOH to enhance its sorption efficiency to remove Cu from both solutions. Two different aqueous solutions were prepared for these experiments: (i) a synthetic using Cu-nitrate salt with 0.01 M NaNO₃ and (ii) soil solution obtained from a Cu-contaminated soil using 0.01 M CaCl₂ leaching procedure. Batch sorption and column experiments were used to evaluate the efficiency of both biochar (BC) and activated biochar (BC_act) to remove Cu from the solutions.Results showed that both biochar samples are pure amorphous carbon and the Cu sorption is thus mainly a result of physical sorption on the biochar surface. Next, chemical activation, using 2 M KOH, significantly increased the total volume of all pores in biochar (from 0.01 ± 0.002 to 8.74 ± 0.18 mL g⁻¹). On the other hand, the BET surface area was similar for both sorbents (BC = 9.80 ± 0.62 m² g⁻¹ and BC_act = 11.6 ± 0.4 m² g⁻¹). Results also demonstrate enhanced sorption efficiency of the BC_act (10.3 mg g⁻¹) in comparison with the BC (8.77 mg g⁻¹). Additionally, enhanced Cu removal during column retention test was observed for the BC_act in both synthetic and soil solutions, respectively.In summary, the results showed that biochar prepared from brewers draff was able to remove Cu from both aqueous solutions.     

Phenol removal from aqueous solution by carbon xerogel

Carbon xerogel (CX) was used for phenol adsorption from aqueous solution. CX was synthesized by sol?Cgel polycondensation of resorcinol with formaldehyde using sodium carbonate (Na₂CO₃) as catalyst. Then, it was dried by convective drying technique and pyrolyzed under inert atmosphere. Phenol adsorption kinetics was very fast, what was attributed to the presence of open pore structure. The kinetic studies showed that the adsorption process could be fitted to a pseudo-second-order model and the particle diffusion process is the rate-limiting step of the adsorption. The phenol removal was maximum and unaffected by pH changes when the initial pH of the phenol solution was in the range of 3?C8. The optimum adsorbent dose obtained for phenol adsorption onto CX was 0.075?g/50?cm³ solution. The Langmuir model described the adsorption process better than the Freundlich isotherm model and the monolayer adsorption capacity is 32?mg?g^?1. Among the desorbing solutions used in this study, the most efficient desorbent was EtOH (100?%) which released about 87?% of phenol bound with the CX.     

Pertechnetate removal from aqueous solution using activated carbon modified with oxidizing and reducing agents

Journal of Radioanalytical and Nuclear Chemistry - The adsorption mechanism of pertechnetate on activated carbon (AC) has been studied. For this work, the surface of commercial AC was modified...     

Adsorptive removal of PPCPs from aqueous solution using carbon-based composites: A review

Far-ranging and improper uses of pharmaceuticals and personal care products (PPCPs) over the last few decades have led to severe water contamination that imposes serious effects on human beings and the ecological system. Therefore, there is an increasing demand for a highly-efficient and environmentally friendly technology for the removal of PPCPs from aqueous solutions. Adsorption technology is an appropriate technology to solve this issue. Carbon-based composites, ranging from modified activated carbon to functionalized biochar, show great potential for this purpose. This review hence elaborates on the environmental occurrences and risks of PPCPs and summarizes the recent progress in removing PPCPs from water using carbon-based adsorbents. The pore structure, relatively large specific surface area (SSA), abundant surface functional groups, highly aromatic structures and the extra excellent characteristics of the cooperative materials contribute to their outstanding adsorption performance. Furthermore, the biochar-clay material is cost effective and more efficient compared to traditional activated carbon regarding the adsorption of PPCPs. Among the emerging adsorbents, graphene and carbon nanotubes composites show superior adsorption ability. Their adsorption mechanisms, such as electrostatic interactions, hydrogen bonding, and pore filling, are discussed in details.     

Efficient adsorptive removal of tetracycline from aqueous solution using phytosynthesized nano-zero valent iron

Recently, nano-zero valent iron (nZVI) has been identified as one of the most promising materials for the removal of a wide range of pharmaceuticals in water. However, nZVI effectiveness in aqueous media is dramatically reduced due to its aggregation and instability. To overcome these problems, castor oil (Ricinus communis Linn.) leaves aqueous extract has been used in this study as a reducing and stabilizing agent to increase the stability of nZVI. The fabricated RCL-nZVI was well characterized using several spectroscopic techniques, e.g., steady-state absorption and fluorescence, SEM, TEM, FTIR, EDS, XRD, XPS, and zeta potential. The green phytosynthesized RCL-nZVI was examined in the adsorptive removal of tetracycline (TC). It was interesting to see that the removal efficiency of TC by RCL-nZVI reached 98% at pH 6 and 25 °C. The efficient removal of TC from the aqueous solution was in accordance with the pseudo-second-order kinetic model and well fitted to Langmuir model with a maximum adsorption capacity of 72.64 mg. g⁻¹. In this study, a plausible removal mechanism was discussed, which primarily involves both adsorption and reduction pathways.     

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.     

Macrocyclic pyridone pentamer‐modified polystyrene nanofiber for selective metal ion removal from aqueous solution

Macrocyclic pyridone pentamer‐functionalized nanofiber was fabricated through electrospinning for selective heavy metal cation removal from aqueous solution. Parameters influencing the adsorption process, including contact time, initial metal cation concentration, and solution pH, were evaluated, and the optimized adsorption condition was figured out accordingly. The adsorption study demonstrated that the process followed the pseudosecond‐order kinetic models and Langmuir isothermal model. The selectivity of the nanofiber toward metal cations was studied, and it was found that it showed a high adsorption affinity toward Pb²⁺ over other metal cations such as Cu²⁺, Ca²⁺, Co²⁺, Zn²⁺, and Ni²⁺. The nanofiber could be easily regenerated by deadsorption with ethylenediaminetetraacetic acid solution. The above results indicate the potential application of the nanofiber in the metal cation separation field.     

Physisorption of hydroxide ions from aqueous solution to a hydrophobic surface

We present results from detailed molecular dynamics simulations revealing a counterintuitive spontaneous physical adsorption of hydroxide ions at a water/hydrophobic interface. The driving force for the migration of the hydroxide ions from the aqueous phase is the preferential orientation of the water molecules in the first two water layers away from the hydrophobic surface. This ordering of the water molecules generates an electrical potential gradient that strongly and favorably interacts with the dipole moment of the hydroxide ion. These findings offer a physical mechanism that explains intriguing experimental reports indicating that the interface between water and a nonionic surface is negatively charged.     

Gold ultra-microelectrode arrays: application to the steady-state voltammetry of hydroxide ion in aqueous solution.

Gold ultra-microelectrode arrays are used to explore the electrochemical oxidation of hydroxide ions and are shown to be analytical useful. Two types of ultra-microelectrode arrays are used; the first consist of 256 individual electrodes of 5 microm in radius, 170 of which are electrochemically active in a cubic arrangement which are separated from their nearest neighbour by a distance of 100 microm. The second array compromises 2597 electrodes of 2.5 microm in radius and of which 1550 of which are electrochemically active in a hexagonal arrangement separated by the nearest neighbour by 55 microm. Well defined voltammetric waves are found with peak currents proportional to the concentration of hydroxide ions in the range 50 microM to 1 mM. Detection limits of 20 microM using the 170 ultra-microelectrode and 10 microM with the 1550 ultra-microelectrode array are shown to be possible but with a higher sensitivity of 4 mA M(-1) observed using the 1550 ultra-microelectrode array compared to 1.2 mA M(-1) with the 170 ultra-microelectrode array.     

Geopolymeric adsorbents from fly ash for dye removal from aqueous solution

Adsorbents from coal fly ash treated by a solid-state fusion method using NaOH were prepared. It was found that amorphous aluminosilicate geopolymers would be formed. These fly ash-derived inorganic polymers were assessed as potential adsorbents for removal of some basic dyes, methylene blue and crystal violet, from aqueous solution. It was found that the adsorption capacity of the synthesised adsorbents depends on the preparation conditions such as NaOH:fly-ash ratio and fusion temperature with the optimal conditions being at 1.2:1 weight ratio of Na:fly-ash at 250-350 degrees C. The synthesised materials exhibit much higher adsorption capacity than fly ash itself and natural zeolite. The adsorption isotherm can be fitted by Langmuir and Freundlich models while the two-site Langmuir model producing the best results. It was also found that the fly ash derived geopolymeric adsorbents show higher adsorption capacity for crystal violet than methylene blue and the adsorption temperature influences the adsorption capacity. Kinetic studies show that the adsorption process follows the pseudo second-order kinetics.     

State of the hydroxide ion in water and aqueous solutions

Conclusion Analysis of these experimental facts leads to the conclusion that in water and aqueous solutions of alkali metal hydroxides it is extremely probable that the hydroxide ion exists in the form H₃O₂ ^–. The marked displacement of the extrapolated chemical shift of the proton of the H₃O₂ ^– ion towards weak fields and the displacement of the frequency of the bending vibrations of the OH bond towards higher frequencies for hydroxide solutions indicate strong hydrogen bonding between the OH^– ion and the H₂O molecule. The comparatively low heat of hydration of the OH^– ion (111 cal/mole) compared with the heat of hydration of the H₊ ion (276 cal/mole) cannot, as has been shown, serve as proof that there is no strong electrostatic bond between the OH^– ion and a water molecule. All the heat of hydration is used up in the formation of this bond; this can be regarded as additional confirmation of the hydrophobic nature of the ion produced. The experimental data on the absolute value of the chemical shift of the proton of the H₃O₂ ^– ion indicate the important role played by the excited state of the proton in this complex. This conclusion agrees with the spectroscopic data.M. V. Lomonosov Moscow State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 12, No. 6, pp. 969–974, November–December, 1971.     

Adsorptive removal of Cr(III) from aqueous solution using tripolyphosphate cross-linked chitosan beads

Chitosan tripolyphosphate (CTPP) beads were prepared at two different cross-linking densities and adsorption of Cr(III) onto it were studied as a function of different operational parameters such as solution pH, equilibration time and initial Cr(III) ion concentration. Higher cross-linked beads were found to have more adsorption capacity at all the experimental pH employed (pH = 3–5), whereas adsorption capacity is found to increase with increase in pH. Adsorption data were analyzed using Langmuir and Freundlich isotherm models. Langmuir model is found be more suitable to explain the experimental results with a monolayer adsorption capacity of 469.5 mg/g. Among the kinetic models used, pseudo-second order kinetic model could best describe the adsorption process. Competition experiments done in presence of Na(I), Mg(II), Ca(II), Al(III) and Fe(III) revealed that, except in the case of Al(III), adsorption of Cr(III) is not significantly affected by the presence of foreign cations. NaCl is found to be a suitable leaching agent for the desorption of adsorbed Cr(III) from CTPP beads. FTIR spectroscopic investigations confirmed that phosphate groups are the principal binding site responsible for the sorption of Cr(III) onto CTPP beads.     

Specific features of phase transformations of amorphous aluminum hydroxide produced by ammoniation of potassium alum

A novel method for neutralization of aluminum salts was suggested for the example of treatment of crystalline potassium alum with gaseous ammonia. An assumption was made that the structure of the forming primary particles is specific. The process of formation of a pseudoboehmite structure was studied in relation to the aging conditions of the aluminum hydroxide precipitate.     

The removal of pharmaceutical pollutants from aqueous solution by Agro-waste

Pharmaceuticals are a unique class of emerging contaminants owing to their intrinsic ability to induce physiological effects on man and animals at low concentrations. Pharmaceuticals are released into the environment via diverse routes; human and animal wastes are the major sources. The persistence and mode of action of pharmaceuticals in the environment make them a major concern. Among methods available for wastewater treatment, the adsorption technique is found to be effective and easy to operate. The expensive nature of commercial activated carbons, however, created a limitation to the adsorption technique; hence the exploration for low-cost and sustainable adsorbents for the removal of different categories of water contaminants. Agricultural wastes offer such advantages as low-cost, abundance and eco-friendly materials in adsorbent preparation. Herein presented are the category and classes of pharmaceuticals cum the risks associated with pharmaceuticals released into the environment. The chemistry of activated carbon/agro wastes viz-a-viz suitability and potency in adsorption of different pharmaceutical waste removal were reviewed; the benefits associated with agricultural wastes usage in pharmaceutical removal have also been presented. Various challenges, gaps cum research prospects in the current field of discussion are herein presented. This work will serve as a tool for public education and enlightenment, help environmentalists make plans for envisaged threats and serve as a guide for policy makers.