• Journal of the Korean Chemical Society
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• v.13 no.3
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• pp.215-219
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• 1969

The kinetics of the reaction of m-or p-substituted benzyl bromides with thiourea in methanol at 35.0$^{\circ}$were determined by an electric conductivity method. According to a plot of log k against the Hammett substituent constants, C-Br bond cleavage in benzyl bromide is postulated to be a rate determining step at the SN2 reaction of benzyl bromide with thiourea. Both electron-donating substituents and electron-withdrawing substituents quantitatively affected the rate of reaction, but each in a different manner. A mechanistic possibility was proposed to account for the results. Some activation parameters were also calculated.

• Bulletin of the Korean Chemical Society
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• v.13 no.1
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• pp.32-36
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• 1992

The gas-phase pyrolysis reactions of 2-alkoxypyrimidines(II), 2-alkoxypyrazines(III), 4-ethoxypyrimidine(IV) and 3-ethoxypyridazine(V) are investigated theoretically using the AM1 MO method. These compounds pyrolyze in a concerted retro-ene process with a six-membered cyclic transition state (TS). The relative order of reactivity if (IV)>(II)>(III)>(V), which can be rationalized by the two effects arising from electron-withdrawing power of the aza-substituent: (ⅰ) Electron withdrawal from the C-O bond accelerates the rate and (ⅱ) electron withdrawal from the $N^1$-atom, that is participating in the six-membered TS, deactivates the reaction. We are unable to explain the experimental result of the greatest reactivity for pyridazine, (V), with our AM1 results. The reactivity increase accompanied by successive methylation of the ethoxy group, ethoxytert-butoxy, is due to a release of steric crowding in the activation process.

• Proceedings of the Materials Research Society of Korea Conference
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• 2009.05a
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• pp.29.1-29.1
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• 2009

Fabrication of good quality P-type GaN remained as a challenge for many years which hindered the III-V nitrides from yielding visible light emitting devices. Firstly Amano et al succeeded in obtaining P-type GaN films using Mg doping and post Low Energy Electron Beam Irradiation (LEEBI) treatment. However only few region of the P-GaN was activated by LEEBI treatment. Later Nakamura et al succeeded in producing good quality P-GaN by thermal annealing method in which the as deposited P-GaN samples were annealed in N2 ambient at temperatures above $600^{\circ}C$. The carrier concentration of N type and P-type GaN differs by one order which have a major effect in AlGaN based deep UV-LED fabrication. So increasing the P-type GaN concentration becomes necessary. In this study we have proposed a novel method of activating P-type GaN by electrochemical potentiostatic method. Hydrogen bond in the Mg-H complexes of the P-type GaN is removed by electrochemical reaction using KOH solution as an electrolyte solution. Full structure LED sample grown by MOCVD serves as anode and platinum electrode serves as cathode. Experiments are performed by varying KOH concentration, process time and applied voltage. Secondary Ion Mass Spectroscopy (SIMS) analysis is performed to determine the hydrogen concentration in the P-GaN sample activated by annealing and electrochemical method. Results suggest that the hydrogen concentration is lesser in P-GaN sample activated by electrochemical method than conventional annealing method. The output power of the LED is also enhanced for full structure samples with electrochemical activated P-GaN. Thus we propose an efficient method for P-GaN activation by electrochemical reaction. 30% improvement in light output is obtained by electrochemical activation method.

• Polymer(Korea)
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• v.33 no.5
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• pp.501-508
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• 2009

The thermal degradation experiment of sodium salt of poly (${\gamma}$-glutamic acid) (PGGNa) has been carried out in both its solid phase and solution phase at the range of $57{\sim}120^{\circ}C$ and their molecular weight decreasing effect was analyzed as a function of time by means of viscometry and light scattering. Based on the solid phase degradation results, it was supposed that the bond scission rate in a polymer chain kept constant and that the bond scission was occurred on a randomly located position in a polymer chain. For the degradation in solution phase, it was also found that all data at various temperatures were dropped on a single master curve when the reduced time $t/t^*$ was used in the plot of the reciprocal intrinsic viscosity (or molecular weight). This degradation curve in solution phase could be expressed as the sum of a single exponential and a linear equation and especially, the single exponential character appeared only at the beginning stage. The activation energy was measured as $107{\sim}115$ kJ/mol in this study and agreed with the literature values.

• Fire Science and Engineering
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• v.29 no.2
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• pp.25-32
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• 2015

The improved thermal stability and anti-oxidation properties of lyocell fiber were studied based on flame retardant treatment by using $Na_3PO_4$ solution. The optimized conditions of flame retardant treatment were studied on various concentrations of $Na_3PO_4$ and the mechanism was proposed through experimental results of thermal stability and anti-oxidation. The integral procedural decomposition temperature (IPDT), limiting oxygen index (LOI) and activation energy ($E_a$) increased 30, 160% respectively via flame retardant treatment. It is noted that thermal stability and anti-oxidation improved based on char and carbon layer formation by dehydrogenation and dissociation of C-C bond resulting the hindrance of oxygen and heat energy into polymer resin. The optimized conditions for efficient flame retardant property of lyocell fiber were provided using $Na_3PO_4$ solution and the mechanism was also studied based on experimental results such as initial decomposition temperature (IDT), IPDT, LOI and $E_a$.

• Journal of the Korean Chemical Society
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• v.46 no.3
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• pp.187-193
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• 2002

The reaction rates of substituted 6-chloroquinoline with p-substituted benzoyichorides $p-CH_3,$ p-H, $p-NO_2$ have been measured by conductometry in acetonitrile, and the constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ${\Delta}V^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$, ${\Delta}G^{\neq}$) and the pressure dependence of Hammett p values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substiuents in substrate $(p-NO_2)$ with 6-chloroqinoline. When the activation volume and the activation entropy are all negative And the Hammett p values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical $S_N2$ reaction mechanism and "associative $S_N2$" in bond formation favored with increasing pressures.

• Journal of the Korean Chemical Society
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• v.47 no.3
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• pp.206-212
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• 2003

The reaction rates of substituted quinolines (6-Clqui., qui.) with p-substituted benzoylchlorides $(p-CH_3,\;p-H,\;p-NO_2)$ have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10, 15, 20, $25^{\circ}C$) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters $(Ea,\;{\Delta}V^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}, \;{\Delta}G^{\neq})$and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron acceptor substituents in substrate $(p-NO_2)$ with quinoline. The activation volume and the activation entropy are all negative. And the Hammett p values are negative for nucleophile ${\rho}_X$ and positive for the substrate ${\rho}_Y$ over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed through a typical $S_N2$ reaction mechanism and "associative $S_N2$" favoring bond formation with increasing pressures.

• Journal of the Korean Chemical Society
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• v.40 no.7
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• pp.483-491
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• 1996

Dieis-Alder reaction between cyclopentadiene and 5-membered ring compounds which have exo-cyclic double bond has been studied using the PM3 method. Transition states do not show large geometrical change with the variation of dienophiles. Two isomers are possible due to the rotation of the exo-cyclic double bond of a dienophile. The reactivity for the formation of different products are explained using the FMO energy gap. The exo and endo selectivity of the reaction has been also studied from the correlation between the deformation energy and the activation barrier. Minimum energy reaction path is discussed using the Curtin-Hammett principle.

• Journal of the Korean Chemical Society
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• v.25 no.6
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• pp.376-382
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• 1981

The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

• Bulletin of the Korean Chemical Society
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• v.8 no.4
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• pp.242-246
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• 1987

The hydrogen abstraction reactions of $SiH_4, SiH_2Cl_2 \;and\; SiHCl_3$ by ground state chlorine atoms generated photochemically from chlorine molecules have been studied at temperatures between 15 and $100^{\circ}C.$ The absolute rates for the reactions have been obtained by a competition technique using ethane as a competitor. The rate expressions ($in cm^3/mol/s$) are found to conform to an Arrhenius rate law: $k_{SiH_4} = (7.98 {\pm} 0.42) {\times} 10^{13}$ exp $[-(1250 {\pm}20)/T].$ $k_{SiH_2Cl_2} = (2.25 {\pm} 0.12) {\times} 10^{15}$ exp[-(1010 ${\pm}$ 10)/T]. $k_{SiHCl_3} = (9.04 {\pm} 0.28) {\times} 10^{14}\; exp[-(1200 {\pm} 10)/T].$ The activation energies obtained from this study represent the same trend as with the carbon analogues, while this trend was not found with respect to the bond dissociation energies among silicon compound homologues. These anomalous behaviors were interpreted in terms of electronic effects and of the structural differences between these compounds.