• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4185-4190
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• 2011

The nucleophilic substitution reactions of ethylene phosphorochloridate (1c) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $5.0^{\circ}C$. The anilinolysis rate of 1c involving a cyclic five-membered ring is four thousand times faster than its acyclic counterpart (1a: diethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}=+30\;cal\;mol^{-1}K^{-1}$ compared to negative value of 1a (${\Delta}S^{\neq}=-45\;cal\;mol^{-1}K^{-1}$) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=27.7\;kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=8.3\;kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. The free energy correlations exhibit biphasic concave upwards for substituent X variations in the X-anilines with a break point at X = 3-Me. The deuterium kinetic isotope effects are secondary inverse ($k_H/k_D$ < 1) with the strongly basic anilines and primary normal ($k_H/k_D$ > 1) with the weakly basic anilines and rationalized by the TS variation from a dominant backside attack to a dominant frontside attack, respectively. A concerted $S_N2$ mechanism is proposed and the primary normal deuterium kinetic isotope effects are substantiated by a hydrogen bonded, four-center-type TS.

• Journal of the Korean Applied Science and Technology
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• v.8 no.1
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• pp.59-67
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• 1991

The reactions of semicarbazide hydrochloride with aliphatic and alicyclic ketones were studied kinetically at 15, 25, 35 and 45$^{\circ}C$ in 20% ethanol solution buffered at pH 2.9. The rate of cyclohexanone semicarbazone formation is 5.5 times as fast as that of cyclopentanone semicarbazone, while 3-pentanone semicarbazone is 4.7 times as slow as that of 2-pentanone, The activation energy of cyclohexanone, 2-pentanone, 2 hexanone, cyclopentanone, 4-methyl-2-pentanone and 3-pentanone semicarbazone formation are calculated 5.08, 7.52, 8.79, 9.59, 9.49, 11.59, respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ion but neutral molecules being progressed hydrogen bond between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst and concerted nucleophilic attack of free base on the carbonly compound. Dependence on pH of the rate of 2-pentanone semicarbozone formation is linear relationship below pH 4.60 and above pH 5.60. As a result of studing citric acid catalysis, second order constants increase linearly with citric acid concentration. As the catalyst concentration is varied from 0.025 to 0.10 mol/1 at pH 2.90, the rate constants increase 1.4 times, but slight increase is observed at pH 5.60. Conclusively, the rate-determining step is formation of tetrahedral interemediate below pH 4.65 and dehydration between pH 5.60 and pH 7.11. It is concluded that the formation reaction of cyclohexanone semicarbazone is faster than cyclopentanone semicarbazone due to the steric strain in the process of forming tetrahedral intermediate.

• Journal of Hydrogen and New Energy
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• v.29 no.2
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• pp.197-204
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• 2018

In the present study, unsteady flow analysis has been conducted to investigate the blade forces and wake flow around a hybrid street-lamp having a vertical-axis small wind turbine and a photovoltaic panel. Uniform velocities of 3, 5 and 7 m/s are applied as inlet boundary condition. Relatively large vortex shedding is formed at the wake region of the photovoltaic panel, which affects the increase of blade torque and wake flow downstream of the wind turbine. It is found that blade force has a good relation to the variation of the angle of attack with the rotation of turbine blades. Variations in the torque on the turbine blade over time create a cyclic fluctuation, which can be a source of turbine vibration and noise. Unsteady fluctuation of blade forces is also analyzed to understand the nature of the vibration of a small wind turbine over time. The detailed flow field inside the turbine blades is analyzed and discussed.

• Journal of Hydrogen and New Energy
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• v.25 no.2
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• pp.151-160
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• 2014

CL-SPEEK/Cs-TPA/$CeO_2$ composite membrane was prepared for polymer electrolyte membrane water electrolysis (PEMWE). In order to improve the electrochemical, mechanical, durabilities and electrocatalytic characteristics, engineering plastic of polyether ether ketone (PEEK) as polymer matrix was sulfonated and the organic-inorganic blend composite membranes was prepared by loading cesium-substituted tungstophosphoric acid (Cs-TPA) by titration method with cross-linking agent contents of 0.01mL. Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the PEMWE circumstance and to increase the duration of the membrane. CL-SPEEK/$Cs_{(1)}$-TPA/CeriaIn conclusion, 1% membrane showed the optimum results such as 0.119 S/cm at $80^{\circ}C$ of proton conductivity and 62MPa of tensile strength.

• Journal of Hydrogen and New Energy
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• v.25 no.1
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• pp.1-10
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• 2014

Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance and to increase the duration of the membrane. In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) and the organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted phophomolybdic acid(Cs-MoPA) with cross-linking agent contents of 0.01mL. In conclusion, CL-SPEEK/$Cs_{(2.5)}$-MoPA/ceria(1%) membrane showed the optimum results such as 0.1095S/cm of proton conductivity at $80^{\circ}C$, 2.906meq./g-dry-membrane of ion exchange capacity and mechanical characteristics, and 49.73MPa of tensile strength which were better than Nafion 117 membrane.

• Journal of Hydrogen and New Energy
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• v.23 no.5
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• pp.437-447
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• 2012

Ceria ($CeO_2$) was used to scavenge free radicals which attack the membrane in the polymer electrolyte membrane water electrolysis (PEMWE) circumstance and to increase the duration of the membrane. In order to improve the electrochemical, mechanical and electrocatalytic characteristics, engineering plastic of the sulfonated polyether ether ketone (SPEEK) as polymer matrix was prepared in the sulfonation reaction of polyether ether ketone (PEEK) and the organic-inorganic blended composite membranes were prepared by sol-gel casting method with loading the highly dispersed ceria and cesium-substituted tungstophosphoric acid (Cs-TPA) with cross-linking agent contents of 0.01 mL. In conclusion, CL-SPEEK/Cs-TPA/ceria (1%) membrane showed the optimum results such as 0.130 S/cm of proton conductivity at $80^{\circ}C$, 2.324 meq./g-dry-membrane of ion exchange capacity and mechanical characteristics, and 65.03 MPa of tensile strength which were better than Nafion 117 membrane.

• Korean Chemical Engineering Research
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• v.44 no.6
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• pp.597-601
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• 2006

The degradation of the Nafion membrane by oxygen radical (OH, $HO_2$) was investigated in Polymer electrolyte membrane fuel cell (PEMFC). Nafion membrane was degraded in Fenton solution consisted with hydrogen peroxide (10-30％) and ferrous ion (1-4 ppm) at $80^{\circ}C$. After degradation in Fenton solution, C-F, S-O and C-O chemical bonds of membrane were broken by oxygen radical attack. Breaking of C-F bond reduced the mechanical strength of Nafion membrane, and hence induced pinholes, resulting in increase of $H_2$ crossover through the membrane. Decomposition of S-O and C-O bonds decreased the ion exchange capacity of the electrolyte membrane. The performance of unit cell composed the membrane, which was degraded in 30％ $H_2O_2$ with 4ppm $Fe^{2+}$ solution for 48 hr, was about half times as low as one with normal membrane.

• Journal of the Korean Chemical Society
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• v.50 no.5
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• pp.369-373
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• 2006

Arylation reactions of styrene catalyzed by Pd(CF3CO2)2-sulfides and Pd(CF3CO2)2-phosphines were investigated. The yield of trans-stilbene, the main product, increased as the basicity of the substituents on the aryl groups of the phosphines increased and the steric hindrance of the substituents decreased. The mechanism of the aryl migration of arylphosphines to styrene is proposed to involve the electrophilic attack of Pd to the phenyl group on the phosphines. The phosphine systems were found to be more effective than the sulfide ones.

• Journal of Sensor Science and Technology
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• v.16 no.2
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• pp.97-103
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• 2007

Crystallized carbon nitride film that has many stable physical and/or chemical properties has been expected potentially by a new electrical material. However, one of the most significant problems degrading the quality of carbon nitride films is an existence of N-H and C-H bonds from the deposition environment. The possibility of these reactions with hydroxyl group in carbon nitride films, caused by a hydrogen attack, was suggested and proved in our previous reports that this undesired effect could be applied for fabricating micro-humidity sensors. In this study, MIS capacitor and MIM capacitor with $5{\mu}m{\times}5{\mu}m$ meshes were fabricated. As an insulator, carbon nitride film was deposited on a $Si_{3}N_{4}/SiO_{2}/Si$ substrate using reactive magnetron sputtering system, and its dielectric constant, C-V characteristics and humidity sensing properties were investigated. The fabricated humidity sensors showed a linearity in the humidity range of 0 %RH to 80 %RH. These results reveal that MIS and MIM $CN_{X}$ capacitive humidity sensors can be used for Si based micro-humidity sensors.

• The Korean Journal of Zoology
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• v.7 no.2
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• pp.1-5
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• 1964

Carbonyl compounds, glycine, ammonia, carbon dioxide and hydrogen have been identified in gamma-irradiated oxygenated aqueous solutions of triglycine. The reactions occurring in this system are postulated only by representing the initial process and the final products. The triglycine molecule undergoes a reaction to form an intermediate giving rise to carbonyl compounds and acid amides. These compounds are decomposed to acetamide, glycine, glyoxylic acid, formic acid, oxalic acid, ammonia, and carbon dioxide by free radical attack in the primary and/or secondary reactions. It is also possible that the unrecognized reactions may give rise to products formed by radical-radical combinations. Satisfactory material balance for all the products have to wait until the completion of a study now in progress.ogress.