• Bulletin of the Korean Chemical Society
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• v.13 no.6
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• pp.642-647
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• 1992

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

• Journal of the Korean Chemical Society
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• v.30 no.2
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• pp.195-200
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• 1986

MO studies have been carried out on 1,5-hydrogen shifts between tautomeric forms (6${\pi}$ system) of ${\beta}$-diketones, ${\beta}$-thioxoketones and ${\beta}$-dithioketones by determining transition state and analyzing structural stability effects on the activation barriers using MNDO method. The barrier was found to increase with the stability of the ground state having greater charge separation and with the increase (less stabilization) in the one electron energy ${\Delta}(2\sum\limits^{occ}{\varepsilon}i)^{\neq}$ in the activation process.

• Journal of the Korean Chemical Society
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• v.31 no.5
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• pp.419-424
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• 1987

Kinetic studies on the solvolysis of para-methyl benzyl nitrate and benzyl nitrate were carried out in aqueous methanol, ethanol, acetonitrile, acetone, tetrahydrofuran and dioxane mixtures at 60$^{\circ}$C. The rates were faster in protic solvent mixtures than in aprotic solvent mixtures. This was considered in the light of transition state stabilization by hydrogen bonding solvation of protic solvent mixtures. Grunwald-Winstein equation, extended Grunwald-Winstein equation and correlation between E$_T$(30) and rate constant were applied in order to discuss the transition state variations caused by changing benzyl substituents and solvents. The results showed that strong electrophilic assistance of solvent is operative in the the water-rich solvents.

• Nano
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• v.13 no.12
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• pp.1850141.1-1850141.11
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• 2018

Sodium ion batteries based on the more sodium source reserve than that of lithium have been designed as promising alternatives to lithium ion batteries. However, several problems including unsatisfied specific capacity and serious cyclic stability must be solved before the reality. One of the effective approaches to solve the abovementioned problems is to search for suitable anode materials. In this work, we designed and prepared $FeSe_2$ nanoflakes via a simple hydrothermal method which can be adjusted in composition by Fe precursor. As a potential anode for sodium storage, the optimized $FeSe_2$ electrode was further evaluated in different electrolytes of $NaClO_4$ in propylene carbonate/fluoroethylene carbonate and $NaCF_3SO_3$ in diethylene glycol dimethyl ether. The capacity was about $470mAh\;g^{-1}$ and $535mAh\;g^{-1}$ at $0.5A\;g^{-1}$, respectively, in the voltage between 0.5 V and 2.9 V in the cycle of stabilization phase. Superior performance both in capacity and in stability was obtained in ether-based electrolyte, which affords the property without plugging the intermediates of transition metal dichalcogenides during charge/discharge processes.

• Journal of the Korean Chemical Society
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• v.24 no.4
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• pp.288-294
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• 1980

Methanolysis rate constants were determined for $CH_3O(CO)Cl,\;CH_3S(CO)Cl\;and\;CH_3S(CS)Cl\;in\;CH_3OH-CH_3CN$ mixtures. Results show that the rates are not predominantly influenced by the bulk solvent properties but are partly influenced by specific electrophilic solvation.Polarity of the solvent is not a dominant factor but it nevertheless plays a role in charge stabilization of the $S_N1$ like transition state. The methanolysis proceeds through $S_N1$ mechanism for $CH_3S(CS)Cl$ for which both specific solvation of leaving group by methanol and charge stabilization by a high dielectric medium are important, while for $CH_3O(CO)Cl\;methanolysis occurs\;via\;S_N2$ mechanism in which both of the solvent effects are unimportant.

• Applied Biological Chemistry
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• v.37 no.3
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• pp.189-193
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• 1994

The hydrolysis of fungicidal N-[1-(benzotriazol-1-yl)benzyl]aniline (BBA) molecule in the presence of cationic cetyltrimethylammonium bromide (CTABr) and anionic sodium laurylsulfate (NaLs) micellar solutions has been studied kinetically. The Micellar catalysis effect shows that the rate is slightly accelerated by the addition of the anionic NaLs at high pH and the binding constant (Ks) is $1.45{\times}10^4M^{-1}$. This result presumably is due to the electrostatic stabilization by the anionic micelle of the developing carbocation in the transition state rather than the hydrophobic character (${\pi}$: 4.93) of (BBA).

• Bulletin of the Korean Chemical Society
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• v.18 no.8
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• pp.868-873
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• 1997

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

• Nuclear Engineering and Technology
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• v.56 no.2
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• pp.655-665
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• 2024

The objective of the present experimental study is to investigate the effect of inlet throttling on the thermohydraulic stability of a large scale water-based Reactor Cavity Cooling System (RCCS). The test was performed using the water-based Natural convection Shutdown heat removal Test Facility (NSTF) at Argonne, which represented a ½ axial scale and 12.5° sector slice of the full scale Framatome 625 MW_t SC-HTGR RCCS concept. A two-phase steady state was first established through direct condensate refill, followed by increased inlet throttling over 10 stages, corresponding to a loss coefficient K over the range of 0.05-653. With the inlet throttling gradually increased, the system experienced a unique transition process between stabilization and destabilization. Through a stability analysis, three instability mechanisms were identified in the present test, including a compound mechanism due to both natural circulation oscillations (NCOs) and density wave oscillations (DWOs), Type-II DWOs, and geysering.

• Journal of the Korean Chemical Society
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• v.50 no.4
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• pp.291-297
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• 2006

The equilibrium structures, relative energies and NBO analyses for the possible conformations and transition states which can exist on the internal rotation of CPDFB and CPCFB molecules have been investigated using DFT and ab initio methods with various basis sets. The interaction between bonding orbital ((C1-C3, C2-C3)) and antibonding orbital (n*(B9) and *(B9-Cl11)) was the main characteristic hyperconjugation in both molecules. In addition, the stabilization energy of CPDFB was 6.63kcal/mol and that of CPCFB was 6.97(E-form)/6.79(Z-form) kcal/mol for each conformation. The rotational barriers by internal rotation of BF2- and BFCl- functional groups were evaluated to be 5.3~6.7kcal/mol and 5.7~6.5kcal/mol respectively, which showed good agreement with the experimental values reported by previous dynamic NMR study. Finally, Z-form was more stable than E-form by 0.2 kcal/mol in CPCFB molecule and therefore Z-form was confirmed as global minimum.

• Journal of the Korean Society for Aeronautical & Space Sciences
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• v.48 no.9
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• pp.681-689
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• 2020

This paper presents methods and results of both flight test examining roll angle estimation performance of slowly rolling munition forced to spin in the air, and fabricating a replica of guided munition. Guided munition was deployed from multi rotor type UAV mother ship whose altitude and velocity was conveyed to it as initial state. Flight test scenario is composed of a sequence of munition drop(deployment), munition spin, roll angle estimation and stabilization. Munition was deployed from mother ship at around 200m high with horizontal velocity of 15m/s, and was made spun using internal reaction wheel. Performance analysis on roll angle estimation is provided in comparison with commercial aerospace graded GPS/INS. Moreover, several mechanisms that rotates munition using reaction wheel, and actual product that realizes one of them are introduced.