• Bulletin of the Korean Chemical Society
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• v.25 no.10
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• pp.1463-1464
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• 2004

• Bulletin of the Korean Chemical Society
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• v.33 no.4
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• pp.1199-1203
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• 2012

Catalytic filters consisting of Ni nanoparticle and carbon fiber with different oxidation states of Ni (either metallic or oxidic) were prepared using a chemical vapor deposition process and various post-annealing steps. CO oxidation reactivity of each sample was evaluated using a batch type quartz reactor with a gas mixture of CO (500 mtorr) and $O_2$ (3 torr) at $300^{\circ}C$. Metallic and oxidic Ni showed almost the same CO oxidation reactivity. Moreover, the CO oxidation reactivity of metallic sample remained unchanged in the subsequently performed second reaction experiment. We suggested that metallic Ni transformed into oxidic state at the initial stage of the exposure to the reactant gas mixture, and Ni-oxide was catalytically active species. In addition, we found that CO oxidation reactivity of Ni-oxide surface was enhanced by increase in the $H_2O$ impurity in the reactor.

• Bulletin of the Korean Chemical Society
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• v.17 no.7
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• pp.604-607
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• 1996

Semiempirical PM3 MO calculations are applied to estimate both 1-atom (X=S,O,C) and 3-substituent (Y=R, CH2R, SR, CH2SR) effects on the reactions of some 1-atom-replaced and 3-substituted cephem-like β-lactam compounds of thiacephems, oxacephems, and carbacephems. Stabilization energy (SE) of the reaction intermediate for the reaction with a hydroxyl ion can be used to evaluate the facility of a reaction and selected as a chemical reactivity index. With the 1-atom effect only, the SE values obtained imply that thiacephems are generally more reactive than the other two cephem-like molecules and the reactivity order is thiacephems>oxacephems>carbacephems. When it comes to the 3-substituent (Y=R, CH2R, SR, CH2SR) effect, chemical reactivity can be best realized by using a 3-substituted thiacephem molecule capable of giving a resonance-stabilized and electron-rich leaving group after the reaction with a nucleophile. SE values, however, decrease in most cases when an additional intervening ethylene group is present (Y=CH2R, CH2SR). The overall 3-substituent reactivity tendency is SR>CH2SR>R>CH2R.

• Bulletin of the Korean Chemical Society
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• v.33 no.3
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• pp.1020-1028
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• 2012

This work compares various models for geminate reversible diffusion influenced reactions. The commonly utilized contact reactivity model (an extension of the Collins-Kimball radiation boundary condition) is augmented here by a volume reactivity model, which extends the celebrated Feynman-Kac equation for irreversible depletion within a reaction sphere. We obtain the exact analytic solution in Laplace space for an initially bound pair, which can dissociate, diffuse or undergo "sticky" recombination. We show that the same expression for the binding probability holds also for "mixed" reaction products. Two different derivations are pursued, yielding seemingly different expressions, which nevertheless coincide numerically. These binding probabilities and their Laplace transforms are compared graphically with those from the contact reactivity model and a previously suggested coarse grained approximation. Mathematically, all these Laplace transforms conform to a single generic equation, in which different reactionless Green's functions, g(s), are incorporated. In most of parameter space the sensitivity to g(s) is not large, so that the binding probabilities for the volume and contact reactivity models are rather similar.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.219-224
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• 2011

The new MPV type reagent, Al-trifluoromethanesulfonyldiisobutylalane ($DIBAO_3SCF_3$), has been prepared and its reducing characteristics in the reduction of selected organic compounds containing representative functional groups have been examined, and compared its reactivity with that of Al-methanesulfonyldiisobutylalane ($DIBAO_3SCH_3$) in order to understand the fluorine-substituent effect on its reactivity. In general, the reactivity of $DIBAO_3SCF_3$ appears to be much higher than that of $DIBAO_3SCH_3$, apparently due to the acidity increase by the electron-withdrawing fluorine-substituent. The reagent reduced aldehydes and ketones readily, but showed a perfect selectivity in the reduction of $\alpha,\beta$-unsaturated aldehydes and ketones to produce the corresponding allylic alcohols in an absolutely 100% purity. In addition, the reagent achieved the regioselective cleavage of phenyl- or/and alkyl-substituted epoxides to the less substituted alcohols in a perfect regioselectivity. Moreover, the reagent also showed an high stereoselectivity in the reduction of substituted cycloalkanones to produce the thermodynamically more stable alcohol epimers exclusively.

• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.384-388
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• 2013

Fluorine-doping on the $Li_{1+x}Mn_{1.9-x}Al_{0.1}O_4$ spinel cathode materials is found to alter crystal shape, and enhance initial interfacial reactivity and solid electrolyte interphase (SEI) formation, leading to improved initial coulombic efficiency in the voltage region of 3.3-4.3 V vs. Li/$Li^+$ in the room temperature electrolyte of 1 M $LiPF_6$/EC:EMC. SEM imaging reveals that the facetting on higher surface energy plane of (101) is additionally developed at the edges of an octahedron that is predominantly grown with the most thermodynamically stable (111) plane, which enhances interfacial reactivity. Fluorine-doping also increases the amount of interfacially reactive $Mn^{3+}$ on both bulk and surface for charge neutrality. Enhanced interfacial reactivity by fluorine-doping attributes instant formation of a stable SEI layer and improved initial cyclic efficiency. The data contribute to a basic understanding of the impacts of composition on material properties and cycling behavior of spinel-based cathode materials for lithium-ion batteries.

• Journal of the Korean Chemical Society
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• v.7 no.4
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• pp.288-292
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• 1963

The rates of reaction of various Korean anthracites with carbon dioxide were measured at temperatures ranging from $850^{\circ}C$ to $1100^{\circ}C$ with coal -6, +8 sieve size and the residence time of reactant gas in the fixed coal bed 14.0 to 15.0 seconds. The primary variables studied were the coal sources and temperature. The reactivity was considerably varies with the coal sources and the general trends show that the reactivity sharply increases with increasing reaction temperature except the Yongwol coal where the increase is not so sharp, which is considered to be due to high reactivity and high-pore structure of the coal. It was also found that a straight line was produced when a logarithm of the rate constant is plotted against the reciprocal of the absolute temperature up to 1000^${\circ}C$, but above that temperature it deviates from linearity. The information obtained will be of value in the design of the coal gasifier using Korean anthracites.

• Journal of the Korean Institute of Gas
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• v.27 no.3
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• pp.108-115
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• 2023

Although hydrazine is an excellent liquid propellant, caution is required during storage and handling due to its high toxicity and reactivity. Safety guidelines should be established in consideration of the chemical reactivity by unintended leakage. In this study, the status of hydrazine facilities at launch site and safety standards for storing and handling were investigated and then, the reactivity between chemicals and hydrazine was analyzed. As a result of the analysis, hydrazine has reactivity with the exception of fuel oil. This paper emphasizes the imperative nature of constructing a dedicated hydrazine storage facility. Ensuring compatibility between hydrazine and the materials used in storage containers and handling equipment is crucial to prevent undesired reactions that could compromise safety. It was intended to be used as basic data to secure the range safety when handling hydrazine.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2335-2339
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• 2013

Relative reactivity of various Al-substituted dialkylalans ($AlR_2(X)$) in reduction of acetone has been studied with density functional theory and MP2 method. Formation of the alan dimers and the alan-acetone adduct, and the transition state for the Meerwein-Ponndorf-Verley (MPV) type reduction of the adduct were calculated to figure out the energy profile. Formation of dimeric alans is highly exothermic. Both the relative free energies for acetone-alan adduct formation and the TS barriers for the MPV type reduction with respect to alan dimers and acetone were calculated and they show the same trend. Based on these energetic data, relative reactivity of alans is expected to be; $AlR_2(Cl)$ > $AlR_2(OTf)$ > $AlR_2(O_2CCF_3)$ > $AlR_2(F)$ > $AlR_2(OMs)$ > $AlR_2(OAc)$ > $AlR_2(OMe)$ > $AlR_2(NMe_2)$. The energy profile is relatively well correlated with the experimental order of the reactivity of Al-substituted dialkylalans. It is noted that the substituents of alans have initial effects on the relative free energies for the carbonyl-adduct formation. Therefore, an $AlR_2(X)$ which forms a more stable carbonyl-adduct is more reactive in carbonyl reduction.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.279-283
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• 1984

${\beta}$-Substituent effect on the reactivity of retro-ene decarboxylation of but-3-enoic acid was investigated theoretically. It was found that charge effect is important not only through ${\pi}$-electron transfer as has been claimed to rationalize experimental results but also through polarization as found for the $CH_3$ substituent. The reactivity was not determined by the charge effect alone but the HOMO-LUMO energy gap was also found to affect the reactivity. In general it was confirmed that the greater the ${\pi}$-electron donating power of the substituent, the greater is the reactivity.