• Bulletin of the Korean Chemical Society
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• v.29 no.9
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• pp.1769-1773
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• 2008

fThe kinetics and mechanism of the reactions of Y-O-aryl phenylphosphonochloridothioates with X-pyridines are investigated in acetonitrile at 35.0 ${^{\circ}C}$. The negative value of the cross-interaction constant, $\rho$XY = −0.46, indicates that the reaction proceeds by concerted $S_N2$ mechanism. The observed $k_H/k_D$ values involving d-5 pyridine ($C_5D_5N$) nucleophiles are greater than unity (1.05-1.11). The net primary deuterium kinetic isotope effects, $(k_H/k_D)_{net}$ = 1.28-1.35, excluding the increased $pK_a$ effect of d-5 pyridine are obtained. The transition state with a hydrogen bond between the leaving group Cl and the hydrogen (deuterium) atom in the C-H(D) is suggested for the studied reaction system.

• Journal of the Korean Chemical Society
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• v.62 no.4
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• pp.265-268
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• 2018

The solvolyses of anthraquinone-2-carbonyl chloride (1) were studied kinetically in 27 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolyses of anthraquinone-2-carbonyl chloride (1) obtained the l value of $2.11{\pm}0.11$, the m value of $0.54{\pm}0.06$, and the correlation coefficient of 0.955. The solvolysis reaction of 1 might proceed via an associative $S_N2$ mechanism enhancing bond making than bond breaking in the transition state (TS). This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.27).

• Journal of the Korean Chemical Society
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• v.65 no.5
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• pp.309-312
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• 2021

The solvolysis of (1s)-(+)-menthyl chloroformate (1) were studied kinetically in 28 pure and various mixed solvents. The analysis using the extended Grunwald-Winstein equation in the solvolysis of 1 obtained the l value of 2.46 ± 0.18, the m value of 0.91 ± 0.07, and the correlation coefficient of 0.950. The solvolysis of 1 might proceed via an associative S_N2 mechanism enhancing bond making than bond breaking in the transition state (TS). The value of l/m is 2.7 within the ranges of value found in associative S_N2 reaction. This interpretation is further supported by a relatively large solvent kinetic isotope effect (SKIE, 2.16).

• Bulletin of the Korean Chemical Society
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• v.33 no.8
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• pp.2769-2772
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• 2012

• Proceedings of the Korean Nuclear Society Conference
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• 1999.05a
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• pp.325-325
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• 1999

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3783-3786
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• 2011

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.975-978
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• 2009

• Journal of the Korean Chemical Society
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• v.47 no.3
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• pp.191-198
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• 2003

The pairwise energy model (PEM) assumes that the cross section for the reaction cross section for the reaction A+BC$\{leftrightarrow}$B+C, where B and C are isotopes of hydrogen, depends on only the pairwise relative energy Es between A and B. Until now, the PEM has been used to interpret theoretically the isotope effect for the reactions such as $O(^3P)+HD,\;Ar^++(H_2,\;D_2,and\;HD)$. In this paper we carry out extensive quasiclassical trajectory calculations for the three possible reactions $Cl+H_2$ and HD and show that the PEM works very well at high energy. In particular we are able to accurately predict the intramolecular isotope effect at high energy for the reaction of Cl+HD using only the cross section data for $Cl+H_2$. To understand that the PEM works so well at high energy, the internal energy distributions for the products are examined. The distributions for three reactions are different at a fixed relative collision energy E but are approximately same at a fixed pairwise energy Es. This suggests that the PEM works very well at high energy. We believe the conclusions reached here will apply to other A+BC systems.

• Progress in Superconductivity and Cryogenics
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• v.17 no.3
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• pp.23-27
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• 2015

Quadruple magnet is an essential component for the accelerator, and the field uniformity in the good field region reflects the quality of quadruple magnet. In this paper, the total magnetic field B was separated into the coil-induced magnetic field $B_s$ and the iron-induced magnetic field $B_c$ to explain why the total magnetic field B has some inhomogeneity. Using Fourier analysis, harmonic components of $B_s$, $B_c$ and B have been analyzed at good field region, respectively. The harmonics of multipole magnet and Fourier analysis are helpful to show the uniformity of magnetic field. Several geometries of yoke and coils were defined to analyze the effect on field uniformity of an HTS quadruple magnet. By the analysis, it was found that the sixth harmonics which is the main factor of field inhomogeneity can be reduced to zero. It means that the sixth harmonics of the magnetic field B can be removed by adjusting the geometry of the magnet pole and the position of coils. We expect that this result can effectively improve the uniformity of an HTS quadruple magnet.

• Mass Spectrometry Letters
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• v.3 no.2
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• pp.54-57
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• 2012

Mass spectrometric analysis was carried out using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) for the precise and accurate determination of the isotope ratios of ultratrace levels of uranium dissolved in 3% $HNO_3$. We used the certified reference material (CRM) 112-A at a trace level of 100 pg/mL for the uranium isotopic measurement. Multiple collectors were utilized for the simultaneous measurement of uranium isotopes to reduce the signal uncertainty due to variations in the ion beam intensity over time. Mass bias correction was applied to the measured U isotopes to improve the precision and accuracy. Furthermore, elemental standard solution with certified values of platinum, iridium, gold, and thallium dissolved in 3% $HNO_3$ were analyzed to investigate the formation rates of the polyatomic ions of $Ir^{40}$ $Ar^+$, $Pt^{40}$ $Ar^+$, $Tl^{40}$ $Ar^+$, $Au^{40}$ $Ar^+$ for the concentration range of 50-400 pg/mL. Those polyatomic ions have mass-to-charge ratios in the 230-245 m/z region that it would contribute to the increase of background intensity of uranium, thorium, plutonium, and americium isotopes. The effect of the polyatomic ion interference on uranium isotope measurement has been estimated.