• Title/Summary/Keyword: nonlinear chemical process

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Breakthrough Curves and Miscible Displacement of Cadmium Through Double-Layered Reclaimed Soils Amended with Macroporous Granule

  • Kim, Hye-Jin;Ryu, Jin-Hee;Kim, Si-Ju;Park, Mi-Suk;Chung, Doug-Young
    • Korean Journal of Soil Science and Fertilizer
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    • v.44 no.1
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    • pp.15-21
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    • 2011
  • Transport of heavy metals such as Cd is affected by several rate-limiting processes including adsorption and desorption by exchange reactions in soils. In this study, column transport and batch kinetic experiments were performed to assess Cd mobility in a double-layered soil with a reclaimed saline and sodic soil (SSS) as top soil and macroporous granule (MPG) as a bottom layer. For individual soil layer having different physical and chemical properties, Cd was considered to be nonlinear reactivity with the soil matrix in layered soils. The dispersive equation for reactive solutes was solved with three types of boundary conditions for the interface between soil layers. The adsorption of Cd with respect to the saline-sodic sandy loam and the MPG indicated that the nature of the sites or the mechanisms involved in the sorption process of Cd was different and the amounts of Cd for both of samples increases with increasing amounts of equilibrium concentration whereas the amount of Cd adsorbed in saline-sodic sandy loam soil was higher than that in MPG. The results of breakthrough curve indicating relative Cd retardation accompanied by layer material and sequence during leaching showed that the number of pore volumes to reach the maximum relative concentration of 1 increased in the order of MPG, SSS, and double layer of SSS-MPG. Breakthrough curves (BTCs) from column experiments were well predicted with our double-layered model where independently derived solute physical and retention parameters were implemented.

Non-linear optical properties of PECVD nanocrystal-Si nanosecond excitation (PECVD로 제조된 나노결정실리콘 비선형 광학적특성)

  • Yang, Hyeon-Hun;Kim, Han-Wool;Kim, Joo Hoe;Kim, Chul Joong;Lee, Chang Gwon
    • 한국신재생에너지학회:학술대회논문집
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    • 2011.11a
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    • pp.60.2-60.2
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    • 2011
  • A study of the non-linear optical properties of nanocrystal-Si embedded in SiO2 has been performed by using the z-scan method in the nanosecond and femtosecond ranges. Substoichiometric SiOx films were grown by plasma-enhanced chemical-vapor deposition(PECVD) on silica substrates for Si excesses up to 24 at/%. An annealing at $1250^{\circ}C$ for 1 hour was performed in order to precipitate nanocrystal-Si, as shown by EFTEM images. Z-scan results have shown that, by using 5-ns pulses, the non-linear process is ruled by thermal effects and only a negative contribution can be observed in the non-linear refractive index, with typical values around $-10-10cm^2/W$. On the other hand, femtosecond excitation has revealed a pure electronic contribution to the nonlinear refractive index, obtaining values in the order of 10-12 cm2/W. Simulations of heat propagation have shown that the onset of the temperature rise is delayed more than half pulse-width respect to the starting edge of the excitation. A maximum temperature increase of ${\Delta}T=123.1^{\circ}C$ has been found after 3.5ns of the laser pulse maximum. In order to minimize the thermal contribution to the z-scan transmittance and extract the electronic part, the sample response has been analyzed during the first few nanoseconds. By this method we found a reduction of 20% in the thermal effects. So that, shorter pulses have to be used obtain just pure electronic nonlinearities.

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Kinetic Study on Nucleophilic Displacement Reactions of Y-Substituted-Phenyl 2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Effects of Modification of 2-MeO in Benzoyl Moiety by 2-Me on Reactivity and Reaction Mechanism

  • Lee, Ji-Youn;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3795-3799
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    • 2013
  • The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

Effect of Lugol's Iodine Preservation on Cyanobacterial Biovolume and Estimate of Live Cell Biovolume Using Shrinkage Ratio (Lugol's Iodine Solution 첨가 후 보존 기간별 남조류 세포부피 변화 및 수축비를 이용한 생세포 부피 산정)

  • Park, Hae-Kyung;Lee, Hyeon-Je;Lee, Hae-Jin;Shin, Ra-Young
    • Journal of Korean Society on Water Environment
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    • v.34 no.4
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    • pp.375-381
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    • 2018
  • The monitoring of phytoplankton biomass and community structure is essential as a first step to control the harmful cyanobacterial blooms in freshwater systems, such as seen in rivers and lakes, due to the process of eutrophication and climate change. In order to quantify the biomass of phytoplankton with a wide range in size and shape, the measurement of cell biovolume along with cell density is required for a comprehensive review on this issue. However, most routine monitoring programs preserve the gathered phytoplankton samples before analysis using chemical additives, because of the constraint of time and the number of samples. The purpose of this study was to investigate the cell biovolume change characteristics of six cyanobacterial species, which are common bloom-causing cyanobacteria in the Nakdong River, after the preservation with Lugol's iodine solution. All species showed a statistically significant difference after the addition of Lugol's iodine solution compared to the live cell biovolume, and the cell biovolume decreased to the level of 34.0 ~ 56.3 % at maximum in each species after the preservation. The nonlinear regression models for determining the shrinkage ratio by a preservation period were derived by using the cell biovolume measured until 180 days preservation of each target species, and the equation to convert the cell biovolume measured after preservation for a certain period to the cell biovolume of viable cell was derived using that formula. The conversion equation derived from this study can be used to estimate the actual cell biovolume in the natural environment at the time of sampling, by using the measured biovolume after the preservation in the phytoplankton monitoring. Moreover this is expected to contribute to the final interpretation of the water quality and aquatic ecosystem impacts due to the cyanobacterial blooms.