• Korean Journal of Soil Science and Fertilizer
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• 제44권6호
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• pp.1063-1070
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• 2011

In this study, total of 5 different chemical amendments were evaluated for determining kinetic parameters and stabilization efficiency of heavy metals in aqueous phase. Standard solution of Cd and Pb ($100mg\;L^{-1}$) was mixed with various ratio of amendments (1, 3, 5, 10%) and heavy metal stabilization efficiency was monitored for 24hrs. All examined amendments showed over 90% of removal efficiency for both Cd and Pb except zerovalent iron (ZVI) for Cd (43-63%). Based on result of heavy metal stabilization efficiency, it was ordered as $CaCO_3$ > Dolomite > Zeolite > Steel slag > ZVI for both Cd and Pb in aqueous phase. For kinetic study, first order kinetic model was adapted to calculate kinetic parameters. In terms of reaction rate constants (k), zeolite showed the fastest reaction rate (k value from 0.4882 for 1% to 2.0105 for 10%) for Cd and ZVI (k value from 0.2304 for 1% to 0.5575 for 10%) for Pb. Considering reaction rate constant and half life for heavy metal stabilization, it was ordered as Zeolite > $CaCO_3$ > Dolomite > Steel slag > ZVI for Cd and $CaCO_3$ > Dolomite > Steel slag > Zeolite > ZVI for Pb. Overall result in this study can be interpreted that lime containing materials are more beneficial to remove heavy metals with high efficiency and less time consuming than absorbent materials.

• Applied Chemistry for Engineering
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• 제28권5호
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• pp.597-600
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• 2017

$(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

• Journal of the Korean Chemical Society
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• 제55권3호
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• pp.346-353
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• 2011

Base hydrolysis of 7-hydroxy-2H-chromen-2-one (HC) and 7-hydroxy-2H-chromen-2-one-4-acetic acid (HCA) in aqueous-methanol and aqueous-acetone mixtures were studied kinetically at temperature range from 283 to 313 K. The activation parameters of the reactions were evaluated and discussed. Moreover, the change in the activation energy barrier of the investigated compounds from water to water-methanol and water-acetone mixtures was estimated from the kinetic data. It is observed that the change in activation barriers is more or less the same for the hydrolysis of HC and HCA. Base hydrolysis of HC and HCA follows a rate law with $k_{obs}=k_2[OH^-]$. The decrease in the rate constants of HC and HCA as the proportion of methanol or acetone increases is due to the destabilization of $OH^-$ ion. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Moreover, these values refer to the rigidity and stability of the intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

• Korean Chemical Engineering Research
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• 제47권6호
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• pp.676-682
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• 2009

Devolatilization of the Refuse Derived Fuel(RDF) which is produced at WonJu in Korea was characterized in air atmosphere with variation of heating rate(10, 20 and $30^{\circ}C/min$) in TGA. The results of TG Analysis have shown that the pyrolysis and char combustion of the RDF occurred in the range of $350{\sim}700^{\circ}C$ depending on the heating rate. Activation energy of the RDF which was determined by using Friedman and Ozawa-Flynn-Wall method was in the range of 14.44~18.40 kcal/mol. Also, reaction order(n) and pre-exponential factors(A) were 1.219 and $3.02{\times}10^5$ by using Friedman method, respectively. In order to find out the devolatilization mechanism of the RDF, twelve solid-state mechanisms defined by Coats Redfern Method were tested. The results of the Coats Redfern Method have shown that chemical reaction is the effective mechanism by comparison with the value of the activation energy which was derived from the Friedman and Flynn-Wall-Ozawa method and correlation coefficient from twelve solid-state mechanisms of Coats Redfern Method. The solid state decomposition mechanism of the RDF was found to be a decelerated $F_1$ type, random nucleation with one nucleus on the individual particle.

• Korean Chemical Engineering Research
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• 제47권2호
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• pp.169-173
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• 2009

Effects of variations sulfur/accelerator ratio on cross-linking and thermal degradation behavior of NR/CR rubber compounds were studied using both dynamic DSC and non-isothermal TGA. DSC thermograms of the given samples were obtained with several different heating rates, and after cross-liked in DSC, TGA thermograms with the same samples also obtained. Kissinger analysis was applied to assess the activation energies for the cross-linking and thermal decomposition processes. Results showed that the formation and thermal decomposition reaction of the samples occurred in the overall temperature range of $120{\sim}180^{\circ}C$ and $350{\sim}450^{\circ}C$, respectively, exhibiting that data could be well-fittable by Kissinger method. Furthermore, formation activation energy by DSC was estimated as $83.0{\pm}5.0kJ/mol$, which was much smaller than that of degradation by TGA, $147.0{\pm}2.0kJ/mol$. From these results, it was considered that, although variations of sulfur/accelerator ratio in the present experiments affected little on the formation mechanism and/or thermal degradation, they could play roles as the catalysts which lower the activation energy of formation. Because of stabilization after formation reaction, however, they have no more effects on the lowering the activation energy, showing higher values when decomposition, caused by main-chain scissions.

• Journal of the Korean Chemical Society
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• 제55권2호
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• pp.177-182
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• 2011

A diketo-type ligand was synthesized by the Knoevenagel condensation reaction of thiophene-2-aldehyde with acetylacetone, subsequently its transition metal complexes with Cu(II), Ni(II), and Co(II) chlorides were also prepared. All the complexes were characterized by various physico-chemical methods. The molar conductivity data reveals ionic nature for the complexes. The electronic spectrum and the EPR values suggest square planar geometry for the Cu(II) ion. Interaction of the Cu(II) complex with CTDNA (calf thymus DNA) was studied by absorption spectral method and cyclic voltammetry. The $k_{obs}$ values versus [DNA] gave a linear plot suggesting psuedo-first order reaction kinetics. The cyclic voltammogram of the Cu(II) complex reveals a quasi-reversible wave attributed to Cu(II)/Cu(I) redox couple for one electron transfer with $E_{1/2}$ values -0.240 V and -0.194 V. respectively. On addition of CTDNA, there is a shift in the $E_{1/2}$ values 168 mV and 18 mV respectively and decrease in Ep values. The shift in $E_{1/2}$ values in the presence of CTDNA suggests strong binding of Cu(II) complex to the CTDNA.

• Korean Chemical Engineering Research
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• 제59권4호
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• pp.565-573
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• 2021

Isotherms, kinetics and thermodynamic properties for adsorption of Brilliant Green(BG), Quinoline Yellow(QY) dyes by activated carbon were carried out using variables such as dose of adsorbent, pH, initial concentration, contact time, temperature and competitive. BG showed the highest adsorption rate of 92.4% at pH 11, and QY was adsorbed at 90.9% at pH 3. BG was in good agreement with the Freundlich isothermal model, and QY was well matched with Langmuir model. The separation coefficients of isotherm model indicated that these dyes could be effectively treated by activated carbon. Estimated adsorption energy by Temkin isotherm model indicated that the adsorption of BG and QY by activated carbon is a physical adsorption. The kinetic experimental results showed that the pseudo second order model had a better fit than the pseudo first order model with a smaller in the equilibrium adsorption amount. It was confirmed that surface diffusion was a rate controlling step by the intraparticle diffusion model. The activation energy and enthalpy change of the adsorption process indicated that the adsorption process was a relatively easy endothermic reaction. The entropy change indicated that the disorder of the adsorption system increased as the adsorption of BG and QY dyes to activated carbon proceeded. Gibbs free energy was found that the adsorption reaction became more spontaneous with increasing temperature. As a result of competitive adsorption of the mixed solution, it was found that QY was disturbed by BG and the adsorption reduced.

• Journal of the Korean Chemical Society
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• 제31권4호
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• pp.344-351
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• 1987

Kinetic studies on the complexing of $[Mo_2O_4(H_2O)_6]^{2+}$ with thiocyanate have been carried out using the spectrophotometric method. The observed rate constant is given by, $k_{obsd}=\{\\k_0+k_H[H^+]\}\;[SCN^-]^2+k_r$. At $25^{\circ}C$ and ionic strength of 2.84 the values of $k_f\;and\;k_r\;are\;5.96{\pm}0.35\;M^{-2}s^{-1}\;and\;(5.45{\pm}4.77){\times}10^{-4}s^{-1}$, respectively. Activation parameters from data at $20^{\circ}$∼$35^{\circ}C\;are\;{\Delta}H^*=38.04{\pm}5.31kJmol^{-1}\;and\;{\Delta}S^*=-172.69JK^{-1}mol^{-1}$. The mechanisms are discussed.

• Journal of the Korean Chemical Society
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• 제20권1호
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• pp.73-86
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• 1976

Four unreported derivatives of N-arylsulfonylbenzamide and six derivatives of N-arylsulfonylbenzimidothiophenyl ester were prepared. These were; p-methyl-N-(arylsulfonyl)benzamide, m-methyl-N-(arylsulfonyl)benzamide, m-nitro-N-(arylsulfonyl)benzamide, p-methoxy-N-(arylsulfonyl)benzamide, p-methyl-N-(arylsulfonyl)benzimidothiophenyl esters, p-chloro-N-(arylsulfonyl)benzimidothiophenyl ester, m-methyl-N-(arylsulfonyl)benzimidothiophenyl ester, p-nitro-N-(arylsulfonyl)benzimidothiophenyl ester, m-nitro-(arylsulfonyl)benzimidothiophenyl ester and p-methoxy-N-(arylsulfonyl)benzimidothiophenyl ester. The rate constants of the hydrolysis of N-arylsulfonylbenzimidothiophenyl esters were determined by ultraviolet spectrophotometry at various pH and rate equations which can be applied over a wide pH range were obtained. From the rate equation and substituent effects, one can conclude that above pH 11, the hydrolysis of N-arylsulfonylbenzimidothiophenyl esters are initiated by the attack of hydroxide ion, however, below pH 9, started by the addition of a water molecule on the azomethine group. At pH 9∼11, the competitive reaction between a water molecule and hydroxide ion is anticipated to occur.

• Journal of the Korean Chemical Society
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• 제56권1호
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• pp.92-101
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• 2012

The degradation of one of the commercially important hydrogel based on acrylic acid and acryl amide, (acrylic acid-co-acryl amide) hydrogels, by means of ultrasound irradiation and its combination with heterogeneous ($TiO_2$) was investigated. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. The extent of sonolytic degradation increased with increasing ultrasound power (in the range 30-80 W). $TiO_2$ sonophotocatalysis led to complete (acrylic acid-co-acryl amide) hydrogels degradation with increasing catalyst loading, while, the presence of $TiO_2$ in the dark generally had little effect on degradation. Therefore, emphasis was totally on the sonolytic and sonophotocatalytic degradation of hydrogels and a synergy effect was calculated for combined degradation procedures (Ultrasound and Ultraviolet) in the presence of $TiO_2$ nanoparticles. $TiO_2$ sonophotocatalysis was always faster than the respective individual processes due to the enhanced formation of reactive radicals as well as the possible ultrasound-induced increase of the active surface area of the catalyst. A kinetics model based on viscosity data was used for estimation of degradation rate constants at different conditions and a negative order for the dependence of the reaction rate on total molar concentration of (acrylic acid-co-acryl amide) hydrogels solution within the degradation process was suggested.