The removal characteristics of As and Se ions from aqueous solution by hexadecyl trimethyl ammonium bromide (HTMAB) modified anthracite (HTMAB-AT) were investigated under various conditions of contact time, pH and temperature. When the pH is 6, the zeta potential value of anthracite (AT) is 24 mV and on the other hand, the zeta potential value of the HTMAB-AT is +44 mV. It can be seen that the overall increase of about 60 mV. Increasing the (+) potential value indicates that the surface of the adsorbent had a stronger positive charge, so adsorption for the anion metal was increased. The isotherm data was well described by Langmuir and Temkin isotherm model. The maximum adsorption capacity was found to be 7.81 and 6.89 mg/g for As and Se ions from the Langmuir isotherm model at 298 K, respectively. The kinetic data was tested using pseudo first and pseudo second order models. The results indicated that adsorption fitted well with the pseudo second order kinetic model. The mechanism of the adsorption process showed that adsorption was dependent on intra particle diffusion model according to two step diffusion. The thermodynamic parameters(ΔGo, ΔHo, and ΔSo) were also determined using the equilibrium constant value obtained at different temperatures. The thermodynamic parameters indicated that the adsorption process was physisorption, and also an endothermic and spontaneous process.
This study is mainly focused on micellar effect of tetradecyltrimethyl ammonium bromide(TTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). Dephosphorylation of DPNPIN is accelerated by BI⊖ ion in 10-2 M Carbonate buffer(pH 10.7) of 4×10-4 M TTABr solution up to 80 times as compared with the reaction in Carbonate buffer by no benzimidazole(BI) solution of TTABr. The value of pseudo first order rate constant(kψ) of the reaction in TTABr solution reached a maximum rate constant increasing micelle concentration. The reaction mediated by R-BI⊖ in micellar solutions are obviously slower than those by BI⊖, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI⊖ in Stern layer of micellar solution. The surfactant reagent, TTABr, strongly catalyzes the reaction of DPNPIN with R-BI and its anion(R-BI⊖) in Carbonate buffer(pH 10.7). For example, 4×10-4 M TTABr in 1×10-4 M BI solution increase the rate constant(kψ=99.7×10-4 1/sec) of the dephosphorylation by a factor ca. 28, when compared with reaction(kψ=3.5×10-4 1/sec) in BI solution(without TTABr). And no TTABr solution, in BI solution increase the rate constant(kψ=3.5×10-4 1/sec) of the dephosphorylation by a factor ca. 39, when compared with reaction (kψ=1.0×10-5 1/sec) in water solution(without BI).
This study is mainly focused on micellar effect of cetyltrimethyl ammonium bromide(CTABr) solution including alkylbenzimidazole(R-BI) on dephosphorylation of isopropyl-4-nitrophenylphosphinate(IPNPIN) in carbonate buffer(pH 10.7). The reactions of IPNPIN with R-BI⊖ are strongly catalyzed by the micelles of CTABr. Dephosphorylation of IPNPIN is accelerated by BI⊖ ion in 10-2 M carbonate buffer(pH 10.7) of 4×10-3 M CTABr solution up to 89 times as compared with the reaction in carbonate buffer by no benzimidazole(BI) solution of 4×10-3 M CTABr. The value of pseudo first order rate constant(kψ) of the reaction in CTABr solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BI⊖ in micellar solutions are obviously slower than those by BI⊖, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI⊖ in Stern layer of micellar solution. The surfactant reagent, CTABr, strongly catalyzes the reaction of IPNPIN with R-BI and its anion(R-BI⊖) in carbonate buffer(pH 10.7). For example, 4×10-3 M CTABr in 1×10-4 M BI solution increase the rate constant(kψ=98.5×10-3 sec-1) of the dephosphorylation by a factor ca.25, when compared with reaction(kψ=3.9×10-4 sec-1) in 1×10-4 M BI solution(without CTABr). And no CTABr solution, in 1×10-4 M BI solution increase the rate constant(kψ=3.9×10-4 sec-1) of the dephosphorylation by a factor ca.39, when compared with reaction (kψ=1.0×10-5 sec-1) in water solution(without BI). This predicts that the reactivities of R-BI⊖ in the micellar pseudophase are much smaller than that of BI⊖. Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CTABr.
In this study, reaction model and reactions rate accelerated by o-iodosobenzoate ion(IB⊖) on hydrolysis reaction of p-nitrophenyl valate(NPV) using ethyl tri-octyl ammonium mesylate(ETAMs) for quaternary ammonium salts, the phase transfer catalysis(PTC) reagent, were investigated. The effect of IB⊖ on hydrolysis reaction rate constant of NPV was weak without ETAMs solutions. Otherwise, in ETAMs solutions, the hydrolysis reactions exhibit higher first order kinetics with respect to the nucleophile, IB⊖, and ETAMs, suggesting that reactions are occurring in small aggregates of the three species including the substrate(NPV), whereas the reaction of NPV with OH⊖ is not catalyzed by ETAMs. Different concentrations of NPV were tested to measure the change of rate constants to investigate the effect of NPV as substrate and the results showed that the effect was weak. This means the reaction would be the first order kinetics with respect to the nucleophile. This behavior for the drastic rate-enhancement of the hydrolysis is referred as 'Aggregation complex model' for reaction of hydrophobic organic ester with o-iodosobenzoate ion(IB⊖) in hydrophobic quarternary ammonium salt(ETAMs) solutions.
This study is mainly focused on micellar effect of cetylpyridinium chloride(CPyCl) solution including alkylbenzimidazole( R-BI) on dephosphorylation of diphenyl-4-nitrophenylphosphinate(DPNPIN) in carbonate buffer(pH 10.7). The reactions of DPNPIN with R-BI⊖ are strongly catalyzed by the micelles of CPyCl. Dephosphorylation of DPNPIN is accelerated by BI⊖ ion in 10 -2 M carbonate buffer(pH 10.7) of 4×10 -3 M CPyCl solution up to 100 times as compared with the reaction in carbonate buffer by no BI solution of 4×10 -3 M CPyCl. The value of pseudo first order rate constant(k m BI) of the reaction in CPyCl solution reached a maximum rate constant increasing micelle concentration. Such rate maxima are typical of micellar catalyzed bimolecular reactions. The reaction mediated by R-BI⊖ in micellar solutions are obviously slower than those by BI⊖, and the reaction rate were decreased with increase of lengths of alkyl groups. It seems due to steric effect of alkyl groups of R-BI⊖ in Stern layer of micellar solution. The surfactant reagent, cetylpyridinium chloride(CPyCl) , strongly catalyzes the reaction of diphenyl-4-nitrophenylphosphinate(DPNPIN) with alkylbenzimidazole (R-BI) and its anion(R-BI⊖) in carbonate buffer(pH 10.7). For example, 4×10 -3 M CPyCl in 1×10 -4 M BI solution increase the rate constant (kψ=1.0×10 -2 sec -1 ) of the dephosphorylation by a factor ca.14, when compared with reaction (kψ=7.3×10 -4 sec -1 ) in 1×10 -4 M BI solution(without CPyCl). And no CPyCl solution, in 1×10 -4 M BI solution increase the rate constant (kψ=7.3×10 -4 sec -1 ) of the dephosphorylation by a factor ca.36, when compared with reaction (kψ=2.0×10 -5 sec -1 ) in water solution(without BI). This predicts that the reactivities of R-BI⊖ in the micellar pseudophase are much smaller than that of BI⊖ . Due to the hydrophobicity and steric effect of alkyl group substituents, these groups would penetrate into the core of the micelle for stabilization by van der Waals interaction with long alkyl groups of CPyCl.
New functional surfactant, N,N-dimethyl-N-dodecyl-N-(2-methyl benzimidazoyl) ammonium chloride(DDBAC) having benzimidazole(BI) functional group have been synthesized and the critical micellar concentration of DDBAC measured by surface tentiometry and electric conductivity method was 8.9×10-4M. Micellar effects in DDBAC functional surfactant solution on the hydrolysis of p-nitrophenylacetate(p-NPA), p-nitrophenylpropionate(p-NPP) and p-nitrophenylvalerate(p-NPV) were observed with change of various pH (Tris-buffer). The pseudo first rate constants of hydrolysis of p-NPA, p-NPP and p-NPV in optimum concentration of DDBAC solution increase to about 160, 280 and 600 times, respectively, as compared with those of aqueous solution at pH 8.00(Tris-buffer). It is considered that benzimidazole functional moiety accelerates the reaction rates of hydrolysis because they act as nucleophile or general base. In optimum concentration of DDBAC solution, the rate constants of hydrolysis of p-NPP and p-NPV increase to about 1.5 and 3.0 times, respectively, as compared with that of p-NPA. It means that the more the carbon numbers of alkyl group of substrates, the larger the binding constants between DDBAC micelle and substrates are. To know the hydrolysis mechanism of p-NPCE(p-NPA, p-NPP and p-NPV), the deuterium kinetic isotope effects were measured in D2O solutions. Consequently the pseudo first order rate constant ratios in H2O and D2O solution, kH2O/kD2O, were about 2.8~3.0 range. It means that the mechanism of hydrolysis were proceeded by nucleophile and general base attack in approximately same value.
The aim of this study is, firstly, to find out what kinds of inorganic species are produced in the photocatalytic oxidation of ammonium-nitrogen containing water and, secondly, to seek the influence of anion for the photocatalytic oxidation of ammonium contained compounds. The photoenergy above 3 eV(λ<415 nm) was effectively absorbed by TiO2 and TiO2/polymer was used to be oxidized NH4-N in wastewater to NO3-N. Existing the anion as Cl-, the rate of photocatalytic oxidation decreased regardless of other condition. This result showed that the chloride ions reduced the rate of oxidation by scavenging oxidizing radical species as OH- and OCl-. Some of the added ion might have blocked the active sites of the catalyst surface, thus deactivated the catalyst.
The specific ion effects are observed in the alumina-metal EDTA(Ethylene Diamine Tetraacetic Acid) system. These effects seem to be associated with the fluidity of the metal ion in the complex. A consideration of the order of adsorption of the complexes on alumina indicates that a specific ion effect also affects the stability of the system. It is clear that EDTA and its heavy metal complexes have a significant effect on the dewaterability of alumina. These effects are not well represented by zeta potential measurements, especially for EDTA alone. With the nonspeciating complexes, though, the maximum permeability is predicted by the pHzpc from zeta potential measurements. At other pH value, the refiltration rate is better predicted by the state of coagulation as measured by log W.
In the present paper, batch and semi-continuous settling characteristics of a binary calcium carbonatewater system were investigated. Using experimental data of batch settling characteristics, a graphical analysis for a semi-continuous thickening column was developed and compared with experimental results on the basis of Kynch theory, only where the feed velocity line was within the limits of Kynch theorem Ⅲ. The analysis showed good agreement with experiments. Quite erroneous results, however, was observed for the analysis of a sludge region on the underloaded operation, which was considered due to the deviation from the limits of theory.