Equilibrium and dynamic surface properties of long-chain quaternary ammonium hydroxides with different chain length and number

The equilibrium and dynamic surface tensions of five long-chain alkyl ammonium hydroxides (AAH) at the air/aqueous solution interface were investigated, and the effects of the length and number of alkyl chain on surface tensions had been discussed. With the increase of the length, the equilibrium surface tension (EST) increased from 28.65 to 40.52?mN/m. While, for the double chains at the critical micelle concentration (CMC), the EST decreased from 32.71 to 26.61?mN/m with the length increasing. In addition, the adsorption behaviors of the AAH were analyzed and the effective diffusion coefficients (D_eff) were calculated on basis of the Ward–Tordai equation. Moreover, the time required to attain the EST decreases with the increase of surfactant concentration. The longer the C–H chain is, the lower surface tension at initial concentration is. What’s more, the diffusion processing of the AAH to air/water interface mainly depends on the surfactant concentration, and the adsorption is controlled by diffusion mechanism in a dilute concentration, while under a high concentration the adsorption is controlled by mixed diffusion–kinetic mechanism.     

Adsorption equilibrium and kinetics of cesium onto insoluble Prussian blue synthesized by an immediate precipitation reaction between Fe3+ and [Fe(CN)6]4−

The adsorption equilibrium and kinetics of cesium ion (Cs⁺) onto insoluble Prussian blue (PB) prepared by an immediate precipitation reaction between Fe³⁺ and [Fe(CN)₆]^4? was investigated under initial Cs⁺ concentration of under 0.15 mmol/L. Synthesis conditions in this method were almost insensitive to the adsorption ability of insoluble PB, and this method provided one of the smallest PB crystallites among synthesis methods. Even when molar concentration of H₃O⁺ was more than 200 times higher or molar concentration of K⁺ was more than 50,000 times higher than that of Cs⁺ in the aqueous solution, the equilibrium adsorption amount was reduced by only approximately one-half to two-third of that in the pure system; that is, the insoluble PB synthesized possessed a considerably high adsorption selectivity for Cs⁺. In contrast to the excellent adsorption ability under adsorption equilibrium, adsorption rate was quite slow. It took at least 2 weeks at 25 °C to completely attain the adsorption equilibrium, even though the primary particle size (crystallite size) and secondary particle size (aggregate size of the crystallites) were sufficiently small at approximately 14 nm and 53–106 μm, respectively. This slow adsorption is primarily due to the large resistance of intracrystalline diffusion; the intracrystalline diffusion coefficient was extremely small at less than 3.3 × 10^?22 m²/s. We also found that increase in temperature could significantly decrease this diffusion resistance, resulting in much quicker elimination of Cs⁺ from the aqueous solution.     

Study on Dynamic Interfacial Tension of 3‐Dodecyloxy‐2‐hydroxypropyl Trimethyl Ammonium Chloride at n‐Decane/Water Interface

Dynamic interfacial tension (DIT) and interface adsorption kinetics at the n‐decane/water interface of 3‐dodecyloxy‐2‐hydroxypropyl trimethyl ammonium chloride (R₁₂TAC) were measured using spinning drop method. The effects of R_nTAC concentration and temperature on DIT have been investigated, the reason of the change of DIT with time has been discussed. The effective diffusion coefficient, D _a, and the adsorption barrier, ?_a, have been obtained with extended Word‐Tordai equation. The results show that the higher the concentration of surfactants is, and the smaller will be the DIT and the lower will be the curve of the DIT, and the R₁₂TAC solutions follow a mixed diffusion‐activation adsorption mechanism in this investigation. With increase of concentration in bulk solution of R₁₂TAC from 8×10^?4 mol · dm^?3 to 4×10^?3 mol · dm^?3, D _a decreases from 2.02×10^?10 m^?2 · s^?1 to 1.4×10^?11 m^?2 · s^?1 and ? _a increases from 2.60 kJ · mol^?1 to 9.32 kJ · mol^?1, while with increase of temperature from 30°C to 50°C, D _a increases from 2.02×10^?10 m^?2 · s^?1 to 5.86×10^?10 m^?2 · s^?1 and ε_a decreases from 2.60 kJ · mol^?1 to 0.73 kJ · mol^?1. This indicates that the diffusion tendency becomes weak with increase strength of the interaction between surfactant molecules and that the thermo‐motion of molecules favors interface adsorption.     

Concentration effects associated with the kinetics of ruthenium ions adsorption on activated charcoal

The batch kinetics of ruthenium ions adsorption on activated charcoal has been investigated over a wide range of ruthenium ions concentration (0.05–0.40 g/L) at room temperature of 23 ± 1 °C in 3 M HNO₃ solution. The adsorption process of ruthenium ions proceeds via two stages: the first stage is rather fast, followed by slower one, indicative of boundary layer and intra-particle diffusion effects respectively. The mechanism of the adsorption is predominantly diffusion and the intra-particle diffusion played a significant role in rate determining, but it was not the only main rate determining step throughout the adsorption process. Both intra-particle and boundary layer diffusion seem significant in the rate controlling step. It was also observed that the adsorption of ruthenium ions adsorption process is best accounted for using pseudo second order kinetic model and the overall rate of adsorption process appears to be controlled by more than one step, namely the external mass transfer and intra-particle diffusion mechanism. Moreover, the adsorption of ruthenium ions obeys the Freundlich and the Langmuir isotherms in the concentration range studied.     

Adsorption of Li by a lithium ion-sieve using a buffer system and application for the recovery of Li from a spent lithium-ion battery

A lithium ion-sieve manganese oxide (MO) derived from Li-enriched MO was prepared by the glycolic acid complexation method. The Li adsorption performance in a LiCl–NH₃·H₂O–NH₄Cl buffer solution, simulated a spent lithium-ion battery (LIB) processing solution, and actual spent LIB processing solution were studied. An adsorption capacity of 27.4 mg/g was observed in the LiCl–NH₃·H₂O–NH₄Cl buffer solution (Li concentration of 0.2 mol/L, pH?=?9), and the adsorption behavior conformed to the Langmuir adsorption isotherm equation with a linear correlation coefficient (R²) of 0.9996. An adsorption capacity of 19 mg/g was observed in the simulated buffer spent battery solution (Li concentration of 0.15 mol/L, pH?=?7), and an adsorption capacity of 17.8 mg/g was observed in the actual spent battery solution (Li concentration of 0.15 mol/L, pH?=?7). X-ray diffraction, scanning electron microscope, and infrared spectrum results revealed that the structure and morphology of MO are stable before and after adsorption, and the adsorption of MO in all of the abovementioned buffer systems conforms to the Li⁺–H⁺ ion-exchange reaction mechanism. The lithium ion-sieve MO demonstrates promise for the recovery of lithium from spent LIBs.     

Lipophilic counterion effect on aggregation and adsorption behavior of quaternary ammonium surfactants

The obvious different aggregation and adsorption behavior of six newly quaternary ammonium surfactants with different lipophilic counterions has been discoverd by measurements of equilibrium and dynamic surface tension, fluorescence and conductivity. Interestingly, the critical micelle concentration (CMC) and its surface tension γ_CMC decrease with the increasing counterion chain length. However, three methods have confirmed that an exception of CMC increases slightly from C₁₆NC₁ to C₁₆NC₂. According to experimental results, a balanced mechanism between hydrophobicity and electrostatic of counterion is proposed. Besides, the dynamic surface tension results show the diffusion coefficient increases with the increasing counterion length both at a short time (D_t?→?0) and long time (D_t?→?∞), which indicates a faster adsorption process. Unlike the inorganic counterion, the diffusion coefficient decreases with the increase of hydrophobic chain length. This is attributed to the strong electrostatic interactions between counterions and cationic headgroups.     

Investigation on Adsorption Dynamics of Protein/Tween‐20 Mixture at the Surface of Solution by Surface Pressure Measurement

The dynamic surface tension (γ_t) and apparent diffusion coefficient (D) of nonionic surfactant Tween‐20 in the presence and absence of bovine serum albumin (BSA) have been investigated via the measurements of surface pressure (π) at different time (t). The curves of γ_t～t are obtained from π～t isotherms. Results show that the γ_t～t relationships of Tween‐20 solution with or without BSA accord with the Ward‐Tordai equation in the region of initial adsorption. D value obtained from the γ_t～t^1/2 curves shows that the diffusion of Tween‐20 slows down with the increase of the concentration of Tween‐20 (c _Tween‐20). And D value of Tween‐20 in the presence of BSA is almost the same as that of the system without BSA when c _Tween‐20 is constant, suggesting that the interaction between Tween‐20 and BSA is weak.     

Removal of cationic dyes: basic magenta and methylene blue from aqueous solution by adsorption on modified loofah

Modified loofah was prepared by a simple chemical graft method to improve its adsorption for cationic dyes. Experimental results showed that the maximum amounts of basic magenta and methylene blue loaded on the modified loofah were 83.5 and 85.5 mg g^?1, and that on the unmodified loofah were 22.2 and 33.7 mg g^?1, respectively. The adsorption for both dyes could reach equilibrium after 300 min. A pseudo-second-order model is suitable for describing the adsorption and desorption kinetics of both dyes on the modified sorbent. According to the intra-particle diffusion model, sorption and desorption processes for the two dyes both presented two distinct phases and were mainly controlled by intra-particle diffusion. The dye-loaded modified loofah could be regenerated by using the mixture solution of HCl and ethanol (V_HCl:V_ethanol = 3:2) as eluent. Adsorption in the binary system showed that adsorption of the dyes was depressed by the presence of the other dye, and the two dyes could be removed efficiently when the initial concentrations were lower than 5.0 × 10^?5 mol L^?1. The Langmuir competitive model was suitable to predict the sorption isotherm in the binary system.     

Optimization using response surface methodology for fast removal of hazardous azo dye by γ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>@CuO nanohybrid synthesized by sol–gel combustion

An efficient adsorption system was developed for removal of hazardous Direct Blue 71 as a sample azo dye. The γ-Fe₂O₃@CuO adsorption system was synthesized based on a sol–gel combustion route and characterized by energy-dispersive X-ray (EDX) analysis, X-ray diffraction (XRD) analysis, vibrating-sample magnetometry (VSM), and field-emission scanning electron microscopy (FESEM) techniques. The response surface methodology with Box–Behnken design was used to evaluate the effects of pH, shaking time, and adsorbent dose on dye adsorption. The results showed that solution pH was the parameter with greatest effect on dye adsorption. Adsorption equilibrium was reached quickly, within 8 min. Study of isotherms revealed adsorption capacity of 45.7 mg g^?1 according to the Freundlich model. Sorbent regeneration could be performed using methanol–NaOH (0.1 mol L^?1) solution.     

Adsorption kinetics and equilibrium modeling of cesium on copper ferrocyanide

The copper ferrocyanide (CuFC) prepared in this study was characterized using X-ray diffraction and scanning election microscopy. The distribution of particle sizes of the CuFC suspension was determined. The adsorption kinetics data were evaluated for an intraparticle diffusion model, a pseudo-first order model and a pseudo-second order model at temperatures of 288, 298 and 308 K, respectively. It was found that the adsorption process of Cs⁺ on CuFC was best described by a pseudo-second order kinetic model, with a correlation coefficient (R ²) equal to 1.000, and the adsorption rate constant increased with increasing temperature. This result indicated that chemisorptions took place during the adsorption process. The adsorption equilibrium data fit well to the Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. The mean adsorption energy (E) between 11 and 13 kJ/mol at different temperatures indicated that ion exchange was the main mechanism during the adsorption process. Thermodynamic parameters were also evaluated during the adsorption. The values of the standard Gibbs free energy change (ΔG ^o) and standard enthalpy change (ΔH ^o) suggested that the adsorption was a spontaneous and endothermic process. The distribution coefficient (K _d) was more than 2.94 × 10⁶ mL/g when the pH of solution was between 2.6 and 10.9, and the initial Cs⁺ concentration was 100 μg/L. The existence of K⁺ and Na⁺ did not affect the adsorption of Cs⁺ on CuFC when the concentration of K⁺ and Na⁺ in the solution was below 20 and 1,000 mg/L, respectively.     

Removal of Th4+ ions from aqueous solutions by graphene oxide

The removal of Th⁴⁺ ions from aqueous solutions was investigated using single-layer graphene oxide (GO) as a sorbent which was prepared by the modified Hummers’ method through batch adsorption experiments at room temperature. Structural characterizations of the sorbent were also investigated. The influences of the pH value of solution, contact time, sorbent dose, ionic strength, the initial metal ion concentration and temperature on the adsorption of Th⁴⁺ were also investigated. These results indicated that the adsorption of Th⁴⁺ was dependent on the pH and independent on the ionic strength. The sorbent provided significant Th⁴⁺ removal (>98.7 %) at pH 3.0 and the adsorption equilibrium was achieved after only 10 min. The Langmuir adsorption isotherm fit the absorption profile very closely, and indicated that a maximum adsorption capacity of 1.77 mmol g^?1 of GO (411 mg g^?1) after 2 h. The thermodynamic parameters showed that this adsorption process was endothermic and spontaneous. Moreover, the desorption level of Th⁴⁺ from GO, by using 0.1 mol L^?1 H₂SO₄ as a stripping agent, was 84.2 ± 1.2 %, and that of 0.5 mol L^?1 HNO₃ as a stripping agent, was 79.8 ± 3.0 %.     

Studies on Dynamic Surface Tension of an Outstanding Microemulsifier in Supercritical CO2 and Its Wetting Performance

Dodecyl polyoxyethylene(4) polyoxypropylene(5) ether (LS45) is an outstanding microemulsifier in supercritical CO₂. The dynamic surface tension (DST) of this nonionic surfactant was investigated by using the maximum bubble pressure instrument. The effects of concentration and temperature on DST parameters (n, t_i, t*, t_m, and R_1/2) and its adsorption mechanism were discussed by Rosen's empirical equation and the asymptotic Ward and Tordai equation for the LS45 solution system. Finally, the parameters at 1 s related to Draves's wetting performance, pC_20(1s), C_1s (i)*, and C_1s*, analyzed. The results showed that were with increase of bulk concentration and temperature, dynamic surface activity increased. Parameters at 1 s indicated that LS45 is of high surface activity and a very good wetting agent. One‐second related parameters, C_1s (i)* and C_1s*, are valuable in the treatment of practical applications of surfactants. Optimum wetting can be expected at the concentration of 4.8×10^?4 mol/dm³ for LS45 solution.     

A study of the factors affecting the adsorption of cobalt ions onto Pakistani coal powder from solutions

Large deposits of coal are abundantly available in Pakistan. An attempt has been made to check its efficacy for the cobalt ions from aqueous solutions in order to exploit the locally available naturally occurring cheaper material for the decontamination/removal of metal ions from nuclear and industrial effluents. The adsorption behavior of cobalt ions on coal powder has been studied as a function of various physicochemical parameters i.e., stirring speed, shaking time, pH, concentration of cobalt ions, temperature, etc. Conditions for the uptake of cobalt ions were established. Adsorption dynamics models such as intra-particle diffusion model, pseudo-first order kinetic model (Lagergren’s equation) and pseudo-second order kinetic model were applied to the adsorption data to elucidate the adsorption process and its mechanism. Results reveal that the adsorption mechanism is predominantly diffusion and both intra-particle and boundary layer diffusion seem significant in the rate controlling step. The adsorption process is best accounted for using pseudo second order kinetic model and the overall rate of adsorption process appears to be controlled by more than one step, namely the external mass transfer and intra-particle diffusion mechanism. The existence of two slopes in the Freundlich plot also confirms the surface diffusion and intra-particle diffusion modes of adsorption. The Langmuir isotherm equation was obeyed well in the whole range of cobalt ions concentration with high value of correlation coefficient (r ²  = 0.999). The adsorption energy (E _a) calculated from D–R isotherm was 6.756 kJ/mol indicating physical nature of adsorption. The adsorption of cobalt ions increased with the increase of temperature and thermodynamic parameters such as ΔH, ΔS and ΔG were calculated. Results suggested that the cobalt ions adsorption on coal powder is endothermic (ΔH 33.90 kJ/mol) and spontaneous (negative ΔG values) process. The adsorption of other metal ions on coal powder was studied at optimized condition for cobalt ions to check its selectivity. Consequently, cobalt ions can be removed from Zr, Ru Eu, Er, Sm, Gd, Dy, Ce, U, and Th ions, where as Cs, Cr and Sr ions reduces the adsorption of cobalt ions by co-adsorption and their reducing affect is in the order of Sr > Cr > Cs.     

Interfacial Properties of Aqueous Nonionic Fluorocarbon Surfactant Solutions

The equilibrium, dynamic surface tensions, and surface dilatational elasticity of aqueous solutions of nonionic fluorocarbon surfactant are reported. The critical micellar concentration, CMC (0.023 mM) and equilibrium surface tension (24.6 m N . m^?1) at CMC were measured by Wilhelmy plate method for aqueous solution of C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=20), abbreviated as EF122A. The surface tension decay is slower for C₈F₁₇SO₂N(C₃H₇)(C₂H₄O)_nH (n=10) system, abbreviated as EF122B compared to the EF122A system over short time region, which indicates the slow transport of the surfactant molecules to the surface. The relaxation time for surface tension decay is estimated by fitting a series of exponentials to the dynamic surface tension data and it decreases with temperature for EF122A. Slow exchange of monomers between bulk and interface is reflected in the high elasticity value of the air‐liquid interface for EF122B compared with EF122A within measured frequency window (0.125–1.25 Hz).     

十八烷基二甲基氯化铵水溶液动态表面张力及吸附动力学研究

使用最大气泡法测定了十八烷基二甲基氯化铵（C_(18)DAC）水溶液的动态表 面张力,考察了浓度、温度等对其DST的影响,详细表征了DST随时间的变化过程, 计算了动态表面张力的各种参数（n,t_i,t~*,t_m,R_(1/2)）。结合Word- Tordai方程计算了表观扩散系数（D_a）和吸附势垒（E_a）,对其吸附动力学模式 进行了研究,探讨了DST参数的物理意义。结果表明,t~*值越小,吸附势垒E_a越 大,宏观扩散系数D_a越小,表面活性剂分子越不易吸附在溶液表面;C_(18)DAC低 浓度时吸附属于扩散控制模式,高浓度时属于混合控制模式;高浓度时,在吸附初 期（t → 0）为扩散控制模式,吸附后期（t → ∞）为混合控制模式。     

Interaction of elemental mercury with selenium surfaces: model experiments for investigations of superheavy elements copernicium and flerovium

The adsorption behavior of ¹⁹⁷Hg and ^183–185Hg on red amorphous selenium (red a-Se) and trigonal selenium (t-Se) was investigated experimentally by off-line and on-line gas chromatographic methods, in preparation of a sensitive chemical separation and characterization of the transactinides copernicium (Cn, Z = 112) and flerovium (Fl, Z = 114). Monte-Carlo simulations of a diffusion controlled deposition were in good agreement with the experimental results, assuming as interaction limits ?ΔH _ads ^red a-Se (Hg) > 85 kJ/mol, and ?ΔH _ads ^t-Se (Hg) < 60 kJ/mol. Both Se allotropes can be used as stationary surfaces in comparative gas-chromatographic chemical investigations of Cn and Fl.     

烷基聚葡糖苷溶液的表面吸附平衡与动力学

用吊片法和气泡最大压力法分别测定了烷基聚葡糖苷(APG)C₉.₆G_1.3水溶液的平衡和动态表面张力,研究了APG水溶液表面的吸附平衡、动力学及其影响因素.测得其cmc(临界胶束浓度)为0.032g/L.吸附过程由初始的扩散控制转变到势垒控制,吸附势垒为4～7kJ/mol.温度升高,平衡和动态表面张力均减小,吸附量增加;加入无机盐,平衡和动态表面张力增大,吸附量亦增加;醇类的吸附使动态表面张力下降速率加快,表明APG与醇分子间有协同吸附作用.     

A Nonpolar,Nonamphiphilic Molecule Can Accelerate Adsorption of Phospholipids and Lower Their Surface Tension at the Air/Water Interface

The adsorption dynamics of a series of phospholipids (PLs) at the interface between an aqueous solution or dispersion of the PL and a gas phase containing the nonpolar, nonamphiphilic linear perfluorocarbon perfluorohexane (PFH) was studied by bubble profile analysis tensiometry. The PLs investigated were dioctanoylphosphatidylcholine (DiC₈‐PC), dilaurylphosphatidylcholine, dimyristoylphosphatidylcholine, and dipalmitoylphosphatidylcholine. The gas phase consisted of air or air saturated with PFH. The perfluorocarbon gas was found to have an unexpected, strong effect on both the adsorption rate and the equilibrium interfacial tension (γ_eq) of the PLs. First, for all of the PLs, and at all concentrations investigated, the γ_eq values were significantly lower (by up to 10 mN m^?1) when PFH was present in the gas phase. The efficacy of PFH in decreasing γ_eq depends on the ability of PLs to form micelles or vesicles in water. For vesicles, it also depends on the gel or fluid state of the membranes. Second, the adsorption rates of all the PLs at the interface (as assessed by the time required for the initial interfacial tension to be reduced by 30 %) are significantly accelerated (by up to fivefold) by the presence of PFH for the lower PL concentrations. Both the surface‐tension reducing effect and the adsorption rate increasing effect establish that PFH has a strong interaction with the PL monolayer and acts as a cosurfactant at the interface, despite the absence of any amphiphilic character. Fitting the adsorption profiles of DiC₈‐PC at the PFH‐saturated air/aqueous solution interface with the modified Frumkin model indicated that the PFH molecule lay horizontally at the interface.     

Adsorption and diffusion of nitrogen, methane and carbon dioxide in aluminophosphate molecular sieve AlPO4-11

The knowledge about the adsorption and diffusion properties (specially about diffusion) of aluminophosphate molecular sieves is very scarce in the literature. These materials offer interesting properties as adsorbents as they have a polar framework and do not contain charge-balancing cations. In this work, the adsorption isotherms of nitrogen, methane and carbon dioxide over an AlPO₄-11 sample synthesized in our laboratories have been measured with a volumetric method at 25, 35, 50 and 65 °C over a pressure range up to 110 kPa. The adsorption capacities of each gas are determined by the strength of interaction with the pore surface (carbon dioxide > methane > nitrogen). The equilibrium selectivity to carbon dioxide is quite high with respect to other adsorbents without cations due to the polarity of the aluminophosphate framework. The adsorption Henry’s law constants and diffusion time constants of nitrogen, methane and carbon dioxide in the synthesized AlPO₄-11 material have been measured from pulse experiments. A pressure swing adsorption (PSA) process for recovering methane from a carbon dioxide/methane mixture (resembling biogas) has been designed using a dynamic model where the measured adsorption equilibrium and kinetic information has been incorporated. The simulation results show that the proposed process could be simpler than other PSA processes for biogas upgrading based on cation-containing molecular sieves such as 13X zeolite, as it can treat the biogas at atmospheric pressure, and it requires a lower pressure ratio, to produce high purity methane with high recovery.     

Effect of alkaline and alkaline–earth cations on the supercapacitor performance of MnO2 with various crystallographic structures

The electrochemical performances of the α-, γ-, and δ-MnO₂ with different crystallographic structures were systematically investigated in 0.5 mol/L Li₂SO₄, 0.5 mol/L Na₂SO₄, 1 mol/L Ca(NO₃)₂, and 1 mol/L?Mg(NO₃)₂ electrolytes. The results showed that the electrochemical performances of the manganese dioxides depended strongly on the crystallographic structures of MnO₂ as well as the cation in the electrolytes. Because the δ-MnO₂ consists with layers of structure and the interlayer separation is 7 Å, which is suitable for insertion/extraction of some alkaline and alkaline–earth cations, the δ-MnO₂ electrode showed the higher specific capacitance than that of α-MnO₂ and γ-MnO₂. We also found that the α-, γ-, and δ-MnO₂ electrodes in the Mg(NO₃)₂ electrolyte showed a higher specific capacitance, while all the α-, γ-, and δ-MnO₂ electrodes in the Li₂SO₄ electrolyte exhibited a better cycle life. The reason for the different behavior of Li⁺ and Mg²⁺ during the charge/discharge process can be ascribed to the charge effect of the cations in the electrolytes. The ex situ X-ray diffraction (XRD) and long-time cyclic voltammogram measurements were used to systematically study the energy storage mechanism of MnO₂-based electrodes. A progressive crystallinity loss of the materials is also observed upon potential cycling at the oxidized states. A reasonable charge/discharge mechanism is proposed in this work.