• Journal of Environmental Science International
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• v.25 no.12
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• pp.1717-1726
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• 2016

In this study, the reductive decolorization of three acid and basic dyes using modified zero-valent iron (i.e., acid-washed iron (Aw/Fe) and palladium coated iron (Pd/Fe)) at various pH conditions (pH 3~5) was experimentally investigated and the decolorization characteristics were evaluated by analyzing the absorbance spectra and reaction kinetics. In the case of acid dyes such as methyl orange and eriochrome black T, color removal efficiencies increased as initial pH of the dye solution decreased. However, the color removal of methylene blue, a basic dye, was not affected much by the initial pH and more than 70% of color was removed within 10 min. During the decolorization reaction, the absorbance of methyl orange (${\lambda}_{max}=464nm$) and eriochrome black T (${\lambda}_{max}=528nm$) decreased in the visible range but increased in the UV range. The absorbance of methylene blue (${\lambda}_{max}=664nm$) also decreased gradually in the visible range. Pseudo-zero order, pseudo-first order, and pseudo-second order kinetic models were used to analyze the reaction kinetics. The pseudo-second order kinetic model was found to be the best with good correlation. The decolorization reaction rate constants ($k_2$) of methylene blue were relatively higher than those of methyl orange and eriochrome black T. The reaction rate constants of methyl orange and eriochrome black T increased with a decrease in the initial pH.

• Bulletin of the Korean Chemical Society
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• v.23 no.2
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• pp.291-294
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• 2002

The reactions of triplet oxygen atom with halomethanes as a potential fire extinguisher were studied by a discharge flow-chemiluminescence imaging method. The experiments were carried out under second order conditions. The bimolecular atom-molecule reaction rate constants were determined in terms of the initial rate method. The initial concentration of oxygen atom was also determined under second order rate law instead of the pseudo-first order conditions with $[O(^3P)]_0{\ll}[sample]_0$. The second order conditions were more reliable than pseudo-first order conditions for the determinations of rate constants. The rate constants of the reactions $CF_3I\;+\;O(^3P)$, $CH_3PI\;+\'O(^3P)$, and $CHBrCl_2\;+\;O(^3P)$ were determined to be $5.0\;{\times}\;10^{-12}$ , $1.1\;×\;0^{-11}$ , and $1.9\;{\times}\;10^{-14}cm^3molecule^{-1}s^{-1}$, respectively.

• Bulletin of the Korean Chemical Society
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• v.17 no.3
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• pp.269-273
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• 1996

Alkyl halides were reduced to the corresponding alkanes by the homonuclear bridging hydride, (μ-H)[(η5-MeCp)Mn(CO)2]2-PPN+ in THF at the elevated temperatures (40-60 ℃) under the pseudo first order reaction conditions where excess of alkyl halide was employed under nitrogen atmosphere. The reaction is of overall second order; first order with respect to [bridging hydride] and first order with respect to [alkyl halide] with the activation parameters, ΔH≠=28.93 kcal/mol and ΔS≠=17.95 e.u. The kinetic data, the ESR evidence and the reaction with cyclopropyl canbinyl bromide ensure that two possible reaction pathways are operable in this reaction: (1) concerted mechanism, and (2) single electron transfer pathway are in competition leading to the same product, the corresponding alkane.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.11
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• pp.804-811
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• 2011

The aim of this study is to evaluate the applicability of adsorption models for understanding adsorption properties of adsorbents. For this study, the adsorption charateristics of $NO_3^-$ by commercial anion exchange resin, PA-308, were investigated in bach process. The adsorption kinetic data for $NO_3^-$ by anion exchange resin showed two stage process comprising a fast initial adsorption process and a slower second adsorption process. Both the pseudo-first-order kinetic model and the pseudo-second-order kinetic model could not be used to predict the adsorption kinetics of $NO_3^-$ onto anion exchange resin for the entire sorption period. Only the fast initial portion ($t{\leq}20min$) of adsorption kinetics was found to follow pseudo-first-order kinetic model and controlled mainly by external diffusion that is very fast and high, whereas, the slower second portion (t > 20 min) of adsorption kinetics seems to be controlled by a second-order chemical reaction and by intraparticle diffusion.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• Environmental Engineering Research
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• v.25 no.2
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• pp.178-185
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• 2020

The aim of this study is to investigate the degradation of ciprofloxacin (CIP) from its aqueous solutions via different advanced oxidation processes (AOP). The effects of persulfate (PS) concentration, pH, zinc oxide nanoparticles (ZnO-NPs) dose, initial CIP concentration, and reaction time on the degradation of CIP were studied. It was found that the sonochemical (US) degradation is a less efficient process (with removal efficiency of 36%) compared to the sono-nano-chemical (US/ZnO) process which resulted in removal efficiency of 70%. Maximum removal of 99% was obtained using the sono-nano-chemical/PS (US/ZnO/PS) process at a frequency of 60 kHz, time of 10 min, pH of 7, initial CIP concentration of 25 mg/L, and PS concentration of 476.06 mg/L. The addition of PS and ZnO-NPs to the process enhanced the rate of US degradation of CIP. In addition, the kinetic parameters for the US/ZnO/PS process were obtained by fitting the kinetic data into the pseudo-first-order and pseudo-second-order kinetic models. The kinetic data was found to fit into the pseudo-first-order kinetic model than the pseudo-second-order model. The results showed that the AOP using US/ZnO/PS is a promising technique for the treatment of ciprofloxacin containing solutions.

• Journal of the Korean Chemical Society
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• v.21 no.4
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• pp.227-234
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• 1977

The reaction of phenylhydrazine with bromine in sulfuric acid solution has been studied kinetically. The pseudo-second-order rate constant is approximately inversely proportional to hydrogen-ion concentration when the concentration of sulfuric acid is lower than 1M. arom the study of the effect of potassium bromide concentration on the rate constant, it is concluded that both neutral bromine and tribromide ion participate in the reaction, the rate constants in 0.01M $H_2SO_4$ being $5{\times}10^5M^{-1},sec^{-1}\;and\;0. 7{\times}10^5M^{-1},sec^{-1}$, respectively at $20^{\circ}C$. The pseudo-second-order rate constant of 2.4-dinitrophenylhydrazine-bromine reaction is independent of hydrogen ion concentration. From the KBr addition experiment, the rate constants for $Br_2\;and\;Br_3^-$ were obtained as $1.2{\times}10^5M^{-1},sec^{-1}\;and\;2.0{\times}10^4M^{-1},sec^{-1}$, respectively.

• Journal of the Korean GEO-environmental Society
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• v.11 no.1
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• pp.45-51
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• 2010

Cadmium (Cd) adsorption by the activated carbon containing hydroxyapatite (HAP) was investigated. Cd adsorption with different HAP mass ranged from 10% to 30%. With more HAP, more Cd was adsorbed. These results suggest that the higher HAP dose causes an increase of the ion exchange potential in HAP sorbent. Kinetics and equilibrium studies were investigated in series of batch adsorption experiments. Langmuir and Freundlich isotherm models were fit to the equilibrium data and Cd adsorption on HAP sorbent were found to follow the Freundlich isotherm model well in the initial adsorbate concentration range. The simple kinetic model, the pseudo first order kinetic model and the pseudo second order kinetic model, were used to investigate the adsorption. The adsorption reaction of Cd followed the pseudo second order kinetic model, and the adsorption pseudo second order kinetic constants ($k_2$) increased with increasing initial HAP amounts onto activated carbon. Also, intraparticle diffusion model was used to investigate the adsorption mechanism between adsorbate and adsorbent in the aqueous phase. Surface adsorption reaction and intraparticle diffusion occur simultaneously Cd adsorption mechanism from aqueous phase in this study.

• Korean Chemical Engineering Research
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• v.61 no.2
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• pp.273-277
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• 2023

The biosorption of methylene blue (MB) from aqueous solution was investigated using dried Rhodotorula glutinis as the biosorbent. The effects of pH, initial dye concentration, biosorbent dosage, and kinetic studies were determined to obtain valuable information for biosorption. Results indicated that most of the adsorbed MB bound within 30 minutes of contact and the MB adsorption capacity increased from 21.1 to 101.8 mg/g with the initial MB concentration increased from 50 to 300 mg/L. Additionally, the MB adsorption capacity gradually increased from pH 4.0 to 9.0, reaching its peak at an initial pH of 9.0. As the biomass load was increased from 0.25 to 4.0 g/L, the MB removal efficiency increased from 14.1 to 84.5%. The Langmuir model provided the best fit throughout the concentration range, and the maximum adsorption capacity (q_max) and Langmuir constant (b) were determined to be 135.14 mg/g and 0.026 l/mg, respectively. Furthermore, the biosorbent process of R. glutinis was found to follow pseudo-second-order kinetics and the calculated q_eq,cal value showed good agreement with the experimental q_eq value. Overall, the biosorption of MB by R. glutinis can be characterized as a monolayer, single site type phenomenon, and the rate-limiting step was determined to be the chemical reaction between the adsorbent and the adsorbate.

• Journal of Korean Society of Water and Wastewater
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• v.29 no.3
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• pp.407-414
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• 2015

The effect of activated carbon particle diameter (i.e. US sieve No. $8{\times}10$ ($d_p{\approx}2.19mm$), $18{\times}20$ ($d_p{\approx}0.92mm$), $50{\times}60$ ($d_p{\approx}0.27mm$) and $170{\times}200$ ($d_p{\approx}0.081mm$) on caffeine adsorption is investigated. BET surface area was increased with decreasing particle diameter ($d_p$), and caffeine adsorption rates increased with decreasing $d_p$. Moreover, pseudo-second order model is predicted the experimental data more accurately than pseudo-first order model, and the fastest rate constant ($k_2$) was $1.7g\;mg^{-1}min^{-1}$ when $d_p$ was 0.081 mm. Surface diffusion coefficient (Ds) was decreased with decreasing $d_p$ based on the minimum sum of square error (SSE). Practically, certain ranges of Ds are acceptable with high reliability ($R^2$) and it is determined that the effect of $d_p$ on Ds is unclear. The effect of pH on caffeine adsorption indicated the dependency of m/L ratio (mass liquid ratio) and $pH_{pzc}$. The $pH_{pzc}$ (i.e. $7.9{\pm}0.2$) was not affected by $d_p$. The higher caffeine adsorption at pH 4 and pH 7 than at pH 10 is due to $pH_{pzc}$, not $pk_a$ of caffeine.