• 한국환경과학회지
• /
• 제25권12호
• /
• pp.1717-1726
• /
• 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
• /
• 제23권2호
• /
• pp.291-294
• /
• 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
• /
• 제17권3호
• /
• pp.269-273
• /
• 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.

• 대한환경공학회지
• /
• 제33권11호
• /
• pp.804-811
• /
• 2011

본 연구는 흡착제의 흡착특성을 이해하는데 이용되는 각종 흡착모델의 적용성을 평가하는데 목적이 있다. 이를 위해 상용의 음이온교환수지(PA-308)를 이용하여 질산성질소에 대한 흡착특성을 회분식 실험을 통해 조사하였다. 음이온교환수지에 의한 질산성질소의 속도실험 결과는 초기의 빠른 흡착과정과 후기의 느린 흡착 과정의 두 가지 단계의 과정으로 이원화되는 경향을 나타내었다. 1차 속도식과 2차 속도식 모두 전체 반응시간에서의 질산성질소에 대한 음이온교환수지의 흡착속도를 수식화 할 수 없었다. 초기의 빠른 흡착반응($t\leq$ 20분)은 1차 속도식에 따르고 외부확산에 의해 거의 지배되는 거동을 보이는 반면, 후기 느린 흡착반응(t > 20분)은 2차 속도 화학반응과 내부확산, 즉 세공 내 확산에 의해서 일어남을 알 수 있었다.

• Bulletin of the Korean Chemical Society
• /
• 제33권7호
• /
• pp.2269-2273
• /
• 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
• /
• 제25권2호
• /
• pp.178-185
• /
• 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.

• 대한화학회지
• /
• 제21권4호
• /
• pp.227-234
• /
• 1977

황산산성에서 페닐히드라진과 브롬의 반응을 속도론적으로 검토하였다. 겉보기 2차 반응속도상수는 1M 이하의 황산농도에서는 수소이온 농도에 대략 역비례한다. KBr 첨가의 영향을 검토하여 $Br_2\;및\;Br_3^-$가 반응화학종이고, 이들의 속도상수는 $20^{\circ}C$의 0.01M $H_2SO_4$용액에서 각각 $5{\times}10^5M^{-1},sec^{-1}\;및\;0. 7{\times}10^5M^{-1},sec^{-1}$임을 밝혔다. 2,4-디니트로 페닐히드라진의 브롬과의 반응속도상수는 수소이온 농도에 거의 무관계하며 $Br_2\;및\;Br_3^-$에 대하여 각각 $1.2{\times}10^5M^{-1},sec^{-1}\;및\;2.0{\times}10^4M^{-1},sec^{-1}$이다.

• 한국지반환경공학회 논문집
• /
• 제11권1호
• /
• pp.45-51
• /
• 2010

본 연구는 hydroxyapatite(HAP) 첨가 활성탄(HAP sorbent)의 카드뮴에 대한 흡착특성을 조사하였다. HAP 첨가량의 변화에 따른 카드뮴의 제거특성은 HAP 첨가량이 증가 할수록 카드뮴의 제거량은 흡착에 의한 영향으로 증가하는 것으로 나타났다. 이러한 결과는 HAP에 의한 이온교환능력의 증가에 의한 것으로 사료된다. 동역학적 흡착과 흡착평형에 관한 연구는 연속적인 회분식 실험을 통하여 조사하였다. 조사된 흡착평형 데이터는 Langmuir와 Freundlich isotherm mode을 사용하여 살펴보았으며, 초기 흡착질의 농도 변화에 따른 HAP 첨가 활성탄의 카드뮴의 흡착은 Freundlich isotherm model에 적합한 것으로 나타났다. Cd의 흡착반응의 동역학적 연구를 위하여 유사 1차 반응속도와 유사 2차 반응속도 모델을 사용하 Cd 흡착반응의 흡착 메커니즘을 조사하였다. 유사 2차 반응속도를 따르며, 유사 2차 반응속도 상수는 활성탄에 HAP의 첨가량이 증가할수록 증가하는 것을 확인할 수 있었다. 또한, intraparticle diffusion model을 사용하여 수용액상의 흡착질과 흡착매질과의 흡착 메커니즘을 조사하였다. 수용액상 카드뮴의 흡착 메커니즘은 흡착질과 흡착매질에서 표면흡착반응과 입자내 확산이 동시에 일어나는 것으로 확인되었다.

• Korean Chemical Engineering Research
• /
• 제61권2호
• /
• pp.273-277
• /
• 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.

• 상하수도학회지
• /
• 제29권3호
• /
• pp.407-414
• /
• 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.