• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.366-373
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• 1984

Methanolysis rates of benzylbenzenesulfonates, substituted both on the substrate (Y) and on the leaving group (Z), were determined in MeOH-MeCN mixtures. The results showed that the reaction proceeds via the dissociative $S_N2$ mechanism, in which bond breaking proceeds in greater degree compared to bond formation at the transition state(TS). Multiple Hammett correlation analysis showed that the cross term, ${\rho}_{YZ}$, is very small and hence the cross interaction of two substituents, Y and Z, at the TS is not important, supporting the dissociative $S_N2 $ type mechanism. While transition state variations predicted by the quantum mechanical model is shown to agree in general with the experimental results, those predicted by the potential energy surface model failed to account for the leaving group effect properly.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.527-533
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• 1987

Kinetic studies on the complexing of aquamolybdenum(Ⅳ) trimer with thiocyanate have been carried out using the spectrophotometric method. The observed rate constant, $k_{obsd}$ is given by $k_{obsd}\;=\;{k_O + k_H[H^+]^2}(SCN^-) + k_r$. At 25$^{\circ}$C and ionic strength of 2.30 the values of $k_f$ and $k_r$ are $(3.78 {\pm} 0.61) {\times} 10^{-4}M^{-1}s^{-1}$ and $(6.93 {\pm} 2.39) {\times} 10^{-4}s^{-1}$, respectively. Activation parameters are ${\Delta}H^* = 50.71{\pm}6.91 kJmol^{-1}$ and ${\Delta}S^* = -121.65JK^{-1}mol^{-1}$. The mechanism is proposed and discussed.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.3
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• pp.1027-1034
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• 2010

Effects of inorganic nano-powders on the polymerization and thermal degradation kinetics as well as the mechanical properties of polyurethane nano-composites were studied by both the measurement of polymerization temperature as a function of time and non-isothermal thermogravimetric analysis (TGA) as well as the Instron test. As the results from polymerization studies, the reaction rates of MMT-filled PU composites were faster than those of Ce500-filled ones, and moreover, the activation energies using Kissinger method for the thermal degradation of composites were calculated as 139.34 kJ/mol for the Ce500-filled PU composites and 91.12 kJ/mol for MMT-filled one, respectivel, exhibiting that MMT nano-powder seemed to be acting as the catalyst for both polymerization and degradation of PU composites. UTM result, however, showed that tensile strength at break of MMT-filled composites was much higher than that of Ce500-filled ones above the concentrations range of 5 phr in the composites.

• Bulletin of the Korean Chemical Society
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• v.4 no.1
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• pp.3-9
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• 1983

Lithium n-butylborohydride was prepared from borane-dimethylsulfide (BMS) and n-butyllithium, and the approximate rates and stoichiometrics of its reactions with selected organic compounds containing representative functional groups were studied in THF at room temperature. Phenol and benzenetiol liberated hydrogen quickly and quantitatively, and the reactions of primary alcohols, 2,6-di-ter-butylphenol and 1-hexanethiol liberated hydrogen quantitatively within 3 hrs, whereas the reactions of secondary and tertiary alcohols were very slow. Aldehydes and ketones were reduced rapidly and quantitatively to the corresponding alcohols. Cinnamaldehyde utilized 1 equiv. of hydride rapidly, suggesting the reduction to cinnamyl alcohol. Carboxylic acids evolved 1 equiv. of hydrogen rapidly and further reduction was not observed. Anhydrides utilized 2 equiv. of hydride rapidly but further hydride uptake was very slow, showing a half reduction. Acid chlorides were reduced to the alcohol stage very rapidly. All the esters examined were reduced to the corresponding alcohol rapidly. Lactones were also reduced rapidly. Expoxides took up 1 equiv. of hydride at a moderate rate to be reduced to the corresponding alcohols. Nitriles and primary amides were inert to this hydride system, whereas tertiary amide underwent slow reduction. Nitroethane and nitrobenzene were reduced slowly, however azobenzene and azoxybenzene were quite inert. Cyclohexanone oxime evolved 1 equiv. of hydrogen rapidly, but no further reduction was observed. Phenyl isocyanate and pyridine N-oxide were proceeded slowly, showing 1.74 and 1.53 hydride uptake, respectively in 24 hours. Diphenyl disulfide was reduced rapidly, whereas di-n-butyl disulfide, sulfone and sulfonic acids were inert or sluggish. n-Hexyl iodide and benzyl bromide reacted rapidly, but n-octyl bromide, n-octyl chloride, and benzyl chloride reacted very slowly.

• Bulletin of the Korean Chemical Society
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• v.16 no.9
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• pp.819-823
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• 1995

Thin films of two kinds of Prussian Blue (PB)-modified, using iron(Ⅲ) complex instead of conventional FeCl3, were prepared on a gold substrate and these films were able to be electrochemically reduced in potassium nitrate solution. In case of PB-modified films prepared from Fe(Ⅲ)-ethylenediamine-N,N'-diacetic acid (FeEN3+)/K3Fe(CN)6 solution, the mid-peak potential was 0.156 V in 0.1 M KNO3 and it was found that potassium ion migrates into or out of the film during the electrolysis. These films were shown to be electrochromic. These films exhibited smaller peak separation than those formed from Fe(Ⅲ)-tartaric acid (FeTA3+)/K3Fe(CN)6 system. The diffusion coefficient of Fe(CN)63-/4- redox couple, evaluated using the fabricated Au rotating disc electrode(rde) previously reported, was in good agreement with the existing data. Two experimental procedures, including the voltammetry at relatively low scan rates and the rde study, have been used in order to characterize the electrode kinetics. The electrode kinetics of some redox couples (FeEN2+-FeEN3+ and FeTA2+-FeTA3+) on both PB-modified thin films and bare Au electrode were studied using a Au rde. In all cases the rate constants of electron transfer obtained with the PB-modified film electrodes were only slightly less than those obtained for the same reaction on bare Au disc electrodes. The conductivities, as determined from the slopes of the i-V curves for a ca. 1 mm sample for dried PB-modified potassium-rich and deficient bulk samples pressed between graphite electrodes, were 6.21 × 10-7 and 2.03 × 10-7(Ω·cm)-1, respectively.

• Bulletin of the Korean Chemical Society
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• v.10 no.4
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• pp.382-388
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• 1989

The approximate rates and stoichiometry of the reaction of excess potassium tri-sec-butylborohydride ($K_s-Bu_3BH$) with selected organic compounds containing representative functional groups were determined under the standard conditions (0$^{\circ}C$, THF) in order to define the characteristics of the reagent for selective reductions. Primary alcohols evolve hydrogen in 1 h, but secondary and tertiary alcohols and amines are inert to this reagent. On the other hand, phenols and thiols evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to the corresponding alcohols. Reduction of norcamphor gives 99.3% endo- and 0.7% exo-isomer of norboneols. The reagent rapidly reduces cinnamaldehyde to the cinamyl alcohol stage and shows no further uptake of hydride. p-Benzoquinone takes up one hydride rapidly with 0.32 equiv hydrogen evolution and anthraquinone is cleanly reduced to the 9,10-dihydoxyanthracene stage. Carboxylic acids liberate hydrogen rapidly and quantitatively, however further reduction does not occur. Anhydrides utilize 2 equiv of hydride and acyl chlorides are reduced to the corresponding alcohols rapidly. Lactones are reduced to the diol stage rapidly, whereas esters are reduced moderately (3-6 h). Terminal epoxides are rapidly reduced to the more substituted alcohols, but internal epoxides are reduced slowly. Primary and tertiary amides are inert to this reagent and nitriles are reduced very slowly. 1-Nitropropane evolves hydrogen rapidly without reduction and nitrobenzene is reduced to the azoxybenzene stage, whereas azobenzene and azoxybenzene are inert. Cyclohexanone oxime evolves hydrogen without reduction. Phenyl isocyanate utilizes 1 equiv of hydride to proceed to formanilide stage. Pyridine and quinoline are reduced slowly, however pyridine N-oxide takes up 1.5 equiv of hydride in 1 hr. Disulfides are rapidly reduced to the thiol stage, whereas sulfide, sulfoxide, sulfonic acid and sulfone are practically inert to this reagent. Primary alkyl bromide and iodide are reduced rapidly, but primary alkyl chloride, cyclohexyl bromide and cyclohexyl tosylate are reduced slowly.

• Bulletin of the Korean Chemical Society
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• v.12 no.6
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• pp.686-691
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• 1991

Emission quenching of photoexcited tris(${\alpha},{\alpha} '$-diimine)-ruthenium(II) complex cations, $RuL_3^{2+}$ (L: 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine; 4,4'-diphenyl-2,2'-bipyridine; 1,10-phenanthroline; 5-methyl-1,10-phenanthroline; 5,6-dimethyl-1,10-phenanthroline or 4,7-diphenyl-1,10-phenanthroline) by $Cu^{2+}$, dimethylviologen $(MV^{2+})$, nitrobenzene (NB), and oxygen was studied in aqueous homogeneous and sodium dodecyl sulfate (SDS) micellar solutions. The apparent bimolecular quenching rate constants $k_q$ were determined from the quenching data and life-times of $^{\ast}RuL_3^{2+}$. In homogeneous media, the quenching rate was considerably slower than that for the diffusion-controlled reaction. The decreasing order of quenching activity of quenchers was $NB>O_2>MV^{2+}>Cu^{2+}$. The rate with $Cu^{2+}$ was faster as the reducing power of $^{\ast}RuL_3^{2+}$ is greater. On the other hand, the rates with NB and $O_2$ were faster as the ligand is more hydrophobic. This was attributed to the stabilization of encounter pair by van der Waals force. The presence of SDS enhanced the rate of quenching reactions with $Cu^{2+}$ and $MV^{2+}$, whereas it attenuated the quenching activity of NB and $O_2$ toward $RuL_3^{2+}$. The binding affinity of quenchers to SDS micelle and binding sites of the quenchers and $RuL_3^{2+}$ in micelle appear to be important factors controlling the micellar effect on the quenching reactions.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.36 no.3
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• pp.241-248
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• 2023

The value of experimentally obtained data becomes highest when they are properly analyzed based on valid logics. Many physical and chemical properties such as electrical and magnetic properties, chemical reaction rates, etc. are known to be thermally activated; thus, a proper understanding of thermally-activated processes is of importance. However, there are still a number of papers published with falsely analyzed data. In this contribution, we would like to revisit the meaning of thermally-activated processes, and then reanalyze a data set published misinterpreted. By showing a step-by-step procedure for the reanalysis, we would like to help researchers who may come across such data in the future not to make mistakes in their analysis.

• Environmental Engineering Research
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• v.10 no.5
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• pp.213-226
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• 2005

To treat wastewater efficiently by a one-step process of nitrogen removal, a new bacterial strain producing $N_2$ gas from ${NH_4}^+$ under an aerobic condition was isolated and identified. The cell was motile and a Gram-negative rod, and usually occurred in pairs. By 16S-rDNA analysis, the isolated strain was identified as Enterobacter asburiae with 96% similarity. The isolate showed that the capacity of $N_2$ production under an oxic condition was approximately three times higher than that under an anoxic condition. Thus, the consumption of ${NH_4}^+$ by the isolate was significantly different in the metabolism of $N_2$ production under the two different environmental conditions. The optimal conditions of the immobilized isolate for $N_2$ production were found to be pH 7.0, $30^{\circ}C$ and C/N ratio 5, respectively. Under all the optimum reaction conditions, $N_2$ production by the immobilized isolate resulted in reduction of ORP with both the consumption of DO and the drop of pH. The removal efficiencies of $COD_{Cr}$, and TN were 56.1 and 60.9%, respectively. The removal rates of $COD_{Cr}$, and TN were the highest for the first 2.5 hrs with the removal $COD_{Cr}/TN$ ratios of 32.1, and afterwards the rates decreased as reaction proceeded. For application of the immobilized isolate to a practical process of ammonium removal, a continuous operation was executed with a synthetic medium of a low C/N ratio. The continuous bioreactor system exhibited a satisfactory performance at 12.1 hrs of HRT, in which the effluent concentrations of ${NH_4}^+$-N was measured to be 15.4 mg/L with its removal efficiency of 56.0%. The maximum removal rate of ${NH_4}^+$-N reached 1.6 mg ${NH_4}^+$-N/L/hr at 12.1 hrs of HRT(with N loading rate of $0.08\;Kg-N/m^3$-carrier/d). As a result, the application of the immobilized isolate appears a viable alternative to the nitrification-denitrification processes.

• Journal of the Institute of Electronics Engineers of Korea SD
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• v.41 no.6
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• pp.25-31
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• 2004

In this paper, we introduce kinetic Monte Carlo (kMC) methods for simulating diffusion process in nano-scale device fabrication. At first, we review kMC theory and backgrounds and give a simple point defect diffusion process modeling in thermal annealing after ion (electron) implantation into Si crystalline substrate to help understand kinetic Monte Carlo methods. kMC is a kind of Monte Carlo but can simulate time evolution of diffusion process through Poisson probabilistic process. In kMC diffusion process, instead of. solving differential reaction-diffusion equations via conventional finite difference or element methods, it is based on a series of chemical reaction (between atoms and/or defects) or diffusion events according to event rates of all possible events. Every event has its own event rate and time evolution of semiconductor diffusion process is directly simulated. Those event rates can be derived either directly from molecular dynamics (MD) or first-principles (ab-initio) calculations, or from experimental data.