Removal of Ammonium from Wastewater by Pure Form Low-Silica Zeolite Y Synthesized from Halloysite Mineral

Pure form, single phase, and highly crystalline low-silica zeolite Y was synthesized from natural nanotubular halloysite mineral by the hydrothermal method. In the synthesis process, the halloysite consisted of SiO₂ and Al₂O₃ was used as starting material with adding supplementary silica and alumina sources. Ammonium adsorption properties of the as-synthesized zeolite Y were studied using batch experiments and the results revealed that its adsorption properties were strongly dependent on contact time, adsorbent dosage, pH, ionic strength, temperature, and initial concentration. The equilibrium data fit well with the Langmuir isotherm compared with the Freundlich isotherm. Kinetic studies showed that the adsorption followed the pseudo-second-order model. Thermodynamic parameters such as change in free energy (ΔG ⁰), enthalpy (ΔH ⁰), and entropy (ΔS ⁰) were also determined, which indicated that the adsorption of ammonium on zeolite Y was a spontaneous and exothermic process at ambient conditions. Due to its low cost, high adsorption capacity and fast adsorption rate, the zeolite Y synthesized from halloysite has the potential to be utilized for the cost-effective removal of ammonium from wastewater.     

The investigation of adsorption thermodynamics and mechanism of a cationic surfactant,CTAB, onto powdered active carbon

In this study, the adsorption mechanism of cethyltrimethylammonium bromide (CTAB), a cationic surfactant, onto powdered active carbon (PAC) from aqueous solution was investigated and also some thermodynamic quantities such as isosteric adsorption enthalpy and entropy for this system were determined. In addition, the mechanistic and thermodynamic results of the experiments were supported with the surface zeta potential measurements. It was found that 5 min is sufficient in order to reach adsorption equilibrium. The adsorption of CTAB onto active carbon/water interface mainly takes place through ion exchange, the ion pairing and hydrophobic bonding. The predominant mechanisms in the lower CTAB concentrations are probably ion exchange and ion pairing. The hydrophobic bonding mechanism predominates with the increasing CTAB concentration. It was determined that the signs of isosteric adsorption enthalpy (ΔH_ζ) and isosteric adsorption entropy (ΔS_ζ) for adsorption of CTAB onto PAC are negative and positive, respectively. As temperature increases, the amount of CTAB adsorbed is decreased indicating the exothermic nature of adsorption process. This decreasing verifies the negative sign expected of (ΔH_ads)_ζ. As a result of the adsorption, since the number of the water molecules surrounding the hydrocarbon tails of CTAB molecules decreases and thus the degree of freedom of the water molecules increases, the positive sign of (ΔS_ads)_ζ points out the hydrophobic bonding mechanisms.     

Modification of highly brittle polystyrene sulfonic acid-co-maleic acid crosslinked sodium alginate membrane into flexible membranes by the incorporation of dibutyl phthalate as a plasticizer for pervaporation separation

To convert highly brittle into flexible membrane, the polystyrene sulfonic acid-co-maleic acid crosslinked sodium alginate (PSSAMA/NaAlg) membrane was modified by incorporating the different weight% of dibutyl phthalate (DBP) as a plasticizer. The effect of DBP content on the physico-chemical properties of the membranes was thoroughly examined. The membranes exhibited lower glass transition temperatures with increasing the plasticizer content in the matrix of PSSAMA/NaAlg. The separation performance of the membranes for water/isopropanol and water/1,4-dioxane was studied at different temperatures. Among the modified membranes, the membrane containing 6 wt% of DBP exhibited the highest separation factors of 24,129 with a flux of 13.57 × 10⁻² kg/m² hr and 23,353 with a flux of 12.99 × 10⁻² kg/m² hr for water/isopropanol and water/1,4-dioxane at 30°C, respectively. From the temperature-dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The estimated activation energy values for permeation of water (E_pw) and isopropanol (E_pIPA) were, respectively, ranged between 12.09 and 8.79, and 42.52 and 32.79 kJ/mol. A negative heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Langmuir's mode of sorption was predominant. Based on the results, it is concluded that the modified membranes demonstrated excellent pervaporation performance for the separation of water/isopropanol and water/1,4-dioxane.     

Influence of a monomeric plasticizer on the water-sorption behaviour of food-grade plastics packaging materials

The interaction of water with poly(vinylchloride) and poly(vinylidene chloride-vinylchloride) (p(VdC-VC)) plasticized with different amounts of a monomeric plasticizer (dioctylphthalate) has been studied using inverse gas chromatography. The present work was focused on the effect of temperature and plasticizer content on the water sorption behaviour of these plastics packaging materials. Values for thermodynamic parameters such as Gibb's free energy (ΔG_s), enthalpy (ΔH_s), entropy (ΔS_s) and activity coefficient (γ) corresponding to sorption of water by the polymers have been calculated using chromatographic retention data. It was found that the sorption of water vapours increases with increasing the amount of plasticizer and decreases with increasing temperature. The Van Deemter equation was found to be applicable to these systems and was used to determine diffusion coefficients and activation energies for diffusion. Diffusion coefficient values increase with increasing amounts of plasticizer and they also increase with increasing temperature; this latter increase is accompanied by a decrease in the activation energy for diffusion. Present results were also compared to our own previous data, using a polymeric plasticizer.     

The determination of enthalpies of sublimation by means of thermal conductivity manometers

This paper describes an investigation into the suitability – for the determination of enthalpies of sublimation of low volatility substances – of thermal conductivity manometers which are operated according to the method described by Engelsman. By making use of the known vapour pressure-temperature relation of liquid mercury the characteristics of the manometers are obtained. They show deviations from linearity at higher pressures; in spite of this the most suitable manometers still have linear ranges of three to four decades. One of the thermal conductivity manometers (TCM) was used for the determination of the enthalpies of sublimation of benzophenone (Δ_sH = 22.60 ± 0.10 kcal mole⁻¹), benzoic acid (Δ_sH = 21.05 ± 0.05 kcal mole⁻¹), ferrocene (Δ_sH = 17.7 ± 0.4 kcal mole⁻¹) and trans-stilbene (Δ_sH = 24.40 ± 0.15 kcal mole⁻¹). As the measurements on ferrocene fell outside the linear range of the manometer, it was necessary to introduce a correction coefficient derived from the measurements on benzophenone and benzoic acid in order to obtain satisfactory results.     

Modification of tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane using chitosan and its application to the pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate crosslinked poly(vinyl alcohol) membrane was modified by varying the amounts of chitosan. The resulting membranes were characterized by Fourier transform infrared spectroscopy and differential scanning calorimetry. The effects of chitosan content and feed composition on the pervaporation performance of the membranes were analyzed. The modified membranes exhibit simultaneous increase of both flux and selectivity. The membrane containing 15 mass % of chitosan shows the highest separation selectivity of 2991, with a flux of 2.39 × 10^?2 kg/(m² h) at 30°C for 10 mass % of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that the membranes could be used effectively to break the azeotropic point of water–isopropanol mixture, so as to remove water from the isopropanol. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are significantly lower than those of isopropanol permeation (E_pIPA), suggesting that the membranes developed here have higher separation ability for water–isopropanol system. In addition, difference was negligibly small between the activation energy values of total permeation (E_p) and water permeation (E_pw), indicating that coupled transport is minimal because of a higher selective nature of membranes. The E_p and E_D values ranged between 40.92 and 52.60, and 39.58 and 52.47 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values observed in all the membranes suggests that Henry's mode of sorption is predominant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1380–1389, 2006     

Fluidization Characteristics in Micro‐Fluidized Beds of Various Inner Diameters

The fluidization characteristics of quartz sand and fluid catalytic crack (FCC) catalyst particles in six micro‐fluidized beds with inner diameters of 4.3, 5.5, 10.5, 15.5, 20.5, and 25.5 mm were investigated. The effects of bed diameter (D_t), static bed height (H_s), particles and gas properties on the pressure drop and minimum fluidization velocity (u_mf) were examined. The results show that the theoretical pressure drops of micro‐fluidized beds deviated from the experimental values under different particles and gas properties. The possible reason is due to an increase in bed voidage under smaller bed diameters. The equations for conventional fluidized beds did not fit for micro‐fluidized beds. u_mf increased with decreasing D_t. When the ratio of H_s to D_t ranged from 1:1 to 3:1, u_mf was characterized by a linear equation with H_s, while the slope of the equation u_mf versus H_s decreased with increasing D_t. In this paper, D_t/d_p and H_s/d_p were defined as dimensionless variables and a new equation was developed to predict u_mf in micro‐fluidized beds under the present experimental conditions.     

Study of the Dehydration of Isopropanol by a Pervaporation‐Based Hybrid Process

The permeation characteristics of the commercial polymeric membrane PERVAP^® 2201 were studied to carry out the dehydration of binary water/isopropanol mixtures. The influence of the composition (2–75 wt % H₂O) and temperature of the feed (311.15–348.15 K) on the membrane performance was studied. The selected membrane showed a high selectivity towards water in the entire concentration range. It was found that the permeation rate increased with the water content and the operating temperature. The influence of the temperature on the flux can be described by an Arrhenius‐type expression. The commercial software Aspen Plus was used to simulate the dehydration of isopropanol by means of a hybrid process combining distillation and pervaporation.     

Structural and Preliminary Explosive Property Characterizations of New 3,4,5‐Triamino‐1,2,4‐triazolium (Guanazinium) Salts

Two new highly stable energetic salts were synthesized in reasonable yield by using the high nitrogen‐content heterocycle 3,4,5‐triamino‐1,2,4‐triazole and resulting in its picrate and azotetrazolate salts. 3,4,5‐Triamino‐1,2,4‐triazolium picrate (1) and bis(3,4,5‐triamino‐1,2,4‐triazolium) 5,5′‐azotetrazolate (2) were characterized analytically and spectroscopically. X‐ray diffraction studies revealed that protonation takes place on the nitrogen N1 (crystallographically labelled as N2). The sensitivity of the compounds to shock and friction was also determined by standard BAM tests revealing a low sensitivity for both. B3LYP/6–31G(d, p) density functional (DFT) calculations were carried out to determine the enthalpy of combustion (Δ_cH (1) =−3737.8 kJ mol⁻¹, Δ_cH (2) =−4577.8 kJ mol⁻¹) and the standard enthalpy of formation (Δ_fH° (1) =−498.3 kJ mol⁻¹, (Δ_fH° (2) =+524.2 kJ mol⁻¹). The detonation pressures (P (1) =189×10⁸ Pa, P (2) =199×10⁸ Pa) and detonation velocities (D (1) =7015 m s⁻¹, D (2) =7683 m s⁻¹) were calculated using the program EXPLO5.     

Electrochemical removal of boron from water: Adsorption and thermodynamic studies

The present work provides an electrochemical removal of boron from water and its kinetics, thermodynamics, isotherm using mild steel and stainless steel as anode and cathode respectively. The various operating parameters on the removal efficiency of boron were investigated, such as initial boron ion concentration, initial pH, current density and temperature. The results showed that the optimum removal efficiency of 93.2% was achieved at a current density of 0.2 A dm^?2 at pH of 7.0. First‐, second‐order rate equations, Elovich and Intraparticle models were applied to study adsorption kinetics. Adsorption isotherms of boron on Fe(OH)₃ were determined and correlated with isotherm equations such as Langmuir, Freundlich and D‐R models. Thermodynamic parameters, such as standard Gibb's free energy (ΔG°), standard enthalpy (ΔH°) and standard entropy (ΔS°), were also evaluated by Van't Hoff equation. The adsorption process follows second‐order kinetics. The adsorption of boron preferably fits with Langmuir adsorption isotherm suggesting monolayer coverage of adsorbed molecules. The adsorption of boron onto Fe(OH)₃ was found to be spontaneous and endothermic. © 2011 Canadian Society for Chemical Engineering     

Mass transfer behaviour of gas-evolving particulate-bed electrode

Rates of mass transfer for the cathodic reduction of potassium ferricyanide at a particulate bed of graphite supported on a horizontal nickel disc were studied under H₂-evolving conditions. Variables studied were: H₂ discharge rate, particle size and bed height. The rate of mass transfer was found to increase to a maximum in the presence of the bed which was about 4.5 times compared to that of the supporting disc. The rate of mass transfer was found to increase with H₂ discharge rate, particle size and bed height. Polarization was measured for beds of different particle size and it was found that the presence of the bed increased polarization especially at relatively high current densities, the increase in polarization was independent of particle size of the bed. Comparison with an O₂-evolving particulate electrode was made and possible practical applications were pointed out.Symbols K mass transfer coefficient (cm s^–1) - V H₂ discharge rate (cm³cm^–2s^–1) - I current consumed in reducing potassium ferricyanide (A) - A supporting disc area (cm²) - F Faradays constant (96 500 C mol^–1) - C Potassium ferricyanide concentration (mol cm^–3) - Z number of electrons involved in the reaction     

Use of a selective extractant-impregnated resin for removal of Pb(II) ion from waters and wastewaters: Kinetics,equilibrium and thermodynamic study

Adsorption of Pb(II) ion by a novel extractant-impregnated resin, EIR, was studied as a function of various experimental parameters using batch adsorption experiments. The new EIR was prepared by impregnating gallocyanine (GCN) onto Amberlite XAD-16 resin beads. The EIR was characterized by nitrogen analysis and SEM micrographs. The new EIR showed excellent selectivity factor values (α) for Pb(II) adsorption respect to other metal ions. The effects of some chemical and physical variables were evaluated and the optimum conditions were found for Pb(II) removal from aqueous solutions. The equilibrium adsorption isotherm was fitted with the Langmuir adsorption model. The maximum adsorption capacity (q_max) of EIR for Pb(II) ions was found to be 367.92 mg g⁻¹. The kinetic studies showed that the intra-particle diffusion is the rate-controlling step. Also, the intra-particle diffusion coefficients, D_ip values, were of the order of 10⁻¹² m² s⁻¹. The values of enthalpy (ΔH°) were positive, which confirms the endothermic nature of adsorption process. Also, the positive entropy changes (ΔS°) were showed that the randomness increased along with the adsorption process. In addition, the obtained negative values of Gibbs free energy (ΔG°) indicated feasible and spontaneous nature of the adsorption process at different temperatures. The new adsorbent was very stable so that it can be successfully used for many consecutive cycles without significant loss in its adsorption capacity.     

Synthesis of crosslinked oxidized starch and its adsorption behavior for calcium ion

Cornstarch, after crosslinking with epichlorohydrin (4%, v/w, dry basis of the starch), was oxidized with hydrogen peroxide over the catalyst Cu(II). The newly synthesized products were applied to examine the calcium ion removal activity from water, under various conditions. Removal efficiency of calcium ion from aqueous solution increased proportionally with carboxyl content and the dose of crosslinked oxidized starch in the solution. Ionization of carboxyl groups in starch was necessary for the effective calcium removal. When the pH of the solution was adjusted below 4.0, the starch was no longer an effective calcium‐sequestering agent. Adsorption isotherm models were developed, wherein the best fit was obtained in the Langmuir model. Thermodynamic study indicated that the adsorption process was exothermic, and the enthalpy change (ΔH^θ), the entropy change (ΔS^θ), and free energy change (ΔG^θ) of the adsorption process were calculated with adsorption isotherm data and basic thermodynamic relations. It was assessed that adsorption occurred by strong electrostatic interactions with the negative adsorption enthalpy (ΔH^θ). The regeneration and reusability of oxidized starch were also assessed and were found to retain the adsorption capacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1539–1546, 2006     

Complexes of Hydrogen Peroxide with Dioxoactinide(VI) Species in Aqueous Carbonate and Bicarbonate Media. Formation of An(VI)–H2O2 Complexes

The spectra for 1:1 complexes formed between triscarbonatouranium(VI) + H₂O₂ and triscarbanatoneptunium(VI) + H₂O₂ are presented. The respective rates of formation (25°C, 0.05 M NA₂CO₃) are 565 ± 41 M⁻¹ s⁻¹ and (2.19 ± .01) X 10³ M⁻¹ s⁻¹. The corresponding activation parameters are ΔH* = 67.8 ± 3.2 kJ/m, 43.6 ± 2.0 kJ/m, ΔS* = 30 ± 11 J/m °K and −36 ± 7 J/m °K, respectively. The U(VI) complex appears to be stable over a period of months while the Np(VI) complex is formed as a transient species that disappears via a complex process.     

Kinetics of removal of impurities from gases by high pressure adsorption

Among other processes, adsorption is used for the removal of hydrogen sulphide from natural gases. Hereby, competitive adsorption of the different gas components plays an important role, e.g., that of carbon dioxide. Data of equilibrium loading and adsorption kinetics are required for the design of adsorbers, filled with molecular sieve. In order to obtain these data under the prevailing operating conditions, hydrogen sulphide was removed from gas mixtures H₂S/CH₄ and H₂S/CO₂/CH₄, in a pilot plant, by adsorption on molecular sieve 5A. The equilibrium loading, the height of transfer zone, and the length of unused bed were determined from the measured breakthrough curves of H₂S. With these data, the breakthrough time and the optimum process conditions were calculated for a practical example.     

Determination of the Initiating Capability of Detonators Containing TKX‐50, MAD‐X1, PETNC,DAAF, RDX,HMX or PETN as a Base Charge,by Underwater Explosion Test

A comprehensive investigation to determine the initiation power of detonators containing as a base charge the novel explosives: dihydroxylammonium 5,5′‐bis(tetrazolate‐1N‐oxide) – TKX‐50, dihydroxylammonium 5,5′‐bis(3‐nitro‐1,2,4‐triazolate‐1N‐oxide) – MAD‐X1, pentaerythritol tetranitrocarbamate – PETNC and 3,3′‐diamino‐4,4′‐azoxyfurazan – DAAF in comparison with RDX, HMX and PETN was undertaken. In order to estimate the initiation power of the detonators, the underwater initiating capability test was used. The total energy as a sum of the primary shock wave energy and the bubble gas energy was determined for each of these explosives, by measuring the overpressure of the shock waves generated in water. Moreover, the complete synthesis for novel explosives is presented. The thermal behavior of the explosives was investigated using DSC (differential scanning calorimetry). The gas phase absolute molar enthalpies at 298 K and 10⁵ Pa were calculated theoretically using the modified complete basis set method (CBS‐4M; M referring to the use of minimal population localization) with the Gaussian 09 software. Gas phase standard molar enthalpies of formation (ΔH_f°_(g)) at 298 K were computed using the atomization energy method. Standard molar enthalpies of formation (▵H_(s)°) were calculated using ΔH_f°_(g) and the standard molar enthalpies of sublimation by applying Trouton’s rule. The Chapman‐Jouguet (CJ) characteristics based on calculated ▵H_(s)° values were computed using the EXPLO5 V6.01 thermochemical computer code. For the calculations the theoretical maximum densities and densities obtained during the experiments presented in this work were used.     

STUDIES ON THE ADSORPTION OF FURFURAL FROM AQUEOUS SOLUTION ONTO LOW-COST BAGASSE FLY ASH

The present study deals with the sorptive removal of furfural from aqueous solution by carbon-rich bagasse fly ash (BFA). Batch studies were performed to evaluate the influence of various experimental parameters, namely, initial pH (p H ₀), adsorbent dose, contact time, initial concentration, and temperature on the removal of furfural. Optimum conditions for furfural removal were found to be p H ₀ ≈ 5.5, adsorbent dose ≈4 g/L of solution, and equilibrium time ≈4 h. The adsorption followed pseudo-second-order kinetics. The effective diffusion coefficient of furfural is of the order of 10^?13 m²/s. Equilibrium adsorption data on BFA was analyzed by Freundlich, Langmuir, Dubnin-Radushkevich, Redlich-Peterson, and Temkin isotherm equations using regression and error analysis. The Redlich-Peterson isotherm was found to best represent the data for furfural adsorption onto BFA. Adsorption of furfural on BFA is favorably influenced by a decrease in the temperature of the operation. Values of the change in entropy (ΔS ⁰) and heat of adsorption (ΔH ⁰) for furfural adsorption on BFA were negative. The high negative value of change in Gibbs free energy (ΔG ⁰) indicates the feasible and spontaneous adsorption of furfural on BFA.     

Polymeric surfactants for enhanced oil recovery. IV—Thermodynamic properties of ethoxylated alkylphenol formaldehyde polymeric surfactants

The thermodynamic properties of some low molecular weight ethoxylated alkylphenol formaldehyde polymeric surfactants have been investigated. Surface tension as a function of concentration of the surfactants in aqueous solutions was measured at 28, 38, 48 and 58°C, using the spinning drop technique. From these measurements, the minimum area per molecule at the aqueous solution/air interface (A_min) was determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) for these polymeric nonionics were calculated. Micellization is more sensitive to ethylene oxide chain length while adsorption is more dependent on the length of the alkyl chain.     

Thermodynamic parameters of amitriptyline hydrochloride–additives at cloud point: effects of the ethanol–water mixed media

Abstract

Addition of organic solvents is known to change the properties of amphiphiles through modification of bulk phase. Amitriptyline hydrochloride (AMT) is a tricyclic amphiphilic drug which is usually used as an antidepressant. In drug delivery, the cloud point (CP) of the drug is an important parameter. This article discusses the effects of ethanol–water (EtOH–WR) compositions on the energetic parameters, such as changes in Gibbs energy of clouding (Δ_sG⁰), enthalpy of clouding (Δ_sH⁰), and entropy of clouding (TΔ_sS⁰) of AMT-additive systems. Monovalent alkali halide salts, cationic conventional surfactants, and gemini surfactants were used as additives in the EtOH–WR mixed media whose compositions were varied between 0 and 15% (w/w). The Δ_sG⁰ values are positive for all the additives and the values decrease with the rise in mole fractions of the additives. The Δ_sH⁰ and TΔ_sS⁰ were noted to be positive except for KF in 15% EtOH–WR mixed media.     

Adsorption-hydration hybrid process for CO2 capture in a fixed bed of activated carbons

This work reports an investigation of using a fixed bed of activated carbons (ACs) to capture CO₂ at hydrate formation conditions. The experiments were conducted at 277.15 K and 3.5 MPa. The water saturation (WS) of the fixed bed of ACs varies from 0% to 100%. The results indicate that an adsorption-hydration hybrid process occurred in the fixed bed of wet ACs while a single adsorption process occurred in the fixed bed of dry ACs. The adsorption-hydration hybrid process performs better than the single adsorption process for CO₂ capture. Gas consumption at 100% WS is 3.18 times greater than that obtained using dry ACs (single adsorption process). It is found that 40% WS is an optimal value, and the gas consumption obtained at this WS is larger than that obtained at 0%, 70%, and 100% WS. This gas consumption is also greater than that obtained using stirred reactors at the same temperature and pressure conditions, so the adsorption-hydration hybrid process achieved in the fixed bed of wet ACs has a greater potential to capture CO₂ in comparison with the single adsorption or hydrate formation process.