• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.273-278
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• 1989

The gas-phase reactions of methyl formate with anions, $-NH_2,\;-OH,\;-CH_2CN$, are studied theoretically using the AM1 method. Stationary points are located by the reaction coordinate method, refined by the gradient norm minimization and characterized by the determination of Hessian matrix. Potential energy profiles and the stationary point structures are presented for all conceivable processes. Four reaction paths are found to be possible: formyl proton and methyl proton abstractions, carbonyl addition, and $S_N2$ process. For the most basic anion $-NH_2$ the proton abstraction path is favored, while in other case, $OH\;and\;-CH_2CN$, the carbonyl addition paths are favored. In all cases the $S_N2$ process is the most exothermic, but due to the relatively high activation barrier the process can be ruled out.

• Bulletin of the Korean Chemical Society
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• v.10 no.3
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• pp.292-297
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• 1989

In this work we have experimentally observed the physisorption isotherms for nitrogen, TMS, cyclohexane, benzene, and n-hexane adsorbed on flat aluminum foil surface and have analyzed them theoretically on the basis of the theory proposed by Chang et al. The results show that the theory by Chang et al. can provide a useful means to describe the physisorption of gases on uniform flat solid surface which is essentially important for analysis of the pore volume distribution in porous solid surface. We have also discussed the application of the results obtained in this work to the analysis of pore volume distribution in porous alumina we reported previously.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.343-347
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• 1990

A thermal decomposition of the tert-butoxy radical has been studied in the gas phase over the pressure range of 1-200 torr at $413_{\circ}K$ using di-tert-butyl peroxide + trimethylsilane mixtures. The relative rate constants were obtained by studying the competitive reactions between tert-butoxy radical decomposition 4(t-BuO·→ CH_3COCH_3 + CH_3·)$ and hydrogen abstraction reaction from trimethylsilane $(t-BuO·+ HSi(CH_3)_3 → t-BuOH + Si(CH_3)_3)·).$ The conventional RRKM calculations were carried out to compare the observed fall-off behavior of the decomposition rate constant $({\kappa}_d)$ with the theoretical predictions using reasonable values of input parameters. In all cases the calculated half-rate pressure $(P_{1/2})$ were significantly higher than those observed. The failure of RRKM to reproduce the fall-off behavior led us to suggest that not all of vibrational modes contribute to excitation (leading to decomposition) on the same time scale.

• Bulletin of the Korean Chemical Society
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• v.8 no.3
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• pp.155-157
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• 1987

Parameters of intraframework potential function suitable for aluminophosphate-5($AIPO_4-5$) are obtained by the constraint method. Using these parameters, we calculated the stabilization energies and their second derivatives of framework atoms and these values are compared with those of zeolite A. It is found that the oxygen atoms in $AIPO_4-5$ framework are more stable than those of zeolite A and that the aluminum atom is also more stable than that of zeolite A. On the other hand, the phosphorus atom in $AIPO_4-5$ framework, in which the silicon atoms of aluminosilicate are replaced by the phosphorus atom, is less stable than the silicon atom of aluminosilicate framework of dehydrated zeolite A.

• Analytical Science and Technology
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• v.21 no.1
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• pp.25-33
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• 2008

Organic disulfide compounds are having higher theoretical capacity than the conventional cathode material and are considered as the important storage material. Here, we are reporting the preparation of poly (2,2'-dithiodianiline) PDDA/multiwall carbon nanotubes, (MWCNTs) composites under different experimental conditions. Amine functionalized and unfunctionalized MWCNTs were independently used for the preparation of composites. Composites were prepared in the presence of cetyl trimethyl bromide (CTAB), a cationic surfactant, and also in the absence of CTAB. A physical mixture of PDTDA and MWCNTs was formed with unfunctionalized MWCNTs. Grafting of PDDA onto MWCNTs was performed by chemical oxidative polymerization of 2, 2'-dithiodianiline in the presence of amine functionalized MWCNTs. The composites of MWCNTs and PDTDA were characterized for structure, morphology and thermal properties through Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, scanning electron microscopy and UV-visible spectroscopy. The composite materials prepared by this method are expected to find applications as electrode materials for lithium batteries.

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2267-2273
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• 2011

A novel energetic material, 1-amino-1-(2,4-dinitrophenylhydrazinyl)-2,2-dinitroethylene (APHDNE), was synthesized by the reaction of 1,1-diamino-2,2-dinitroethylene (FOX-7) and 2,4-dinitrophenylhydrazine in N-methyl pyrrolidone (NMP) at 110 $^{\circ}C$. The theoretical investigation on APHDNE was curried out by B3LYP/6-311+$G^*$ method. The IR frequencies analysis and NMR chemical shifts were performed and compared with the experimental results. The thermal behavior of APHDNE was studied by DSC and TG/DTG methods, and can be divided into two crystal phase transition processes and three exothermic decomposition processes. The enthalpy, apparent activation energy and pre-exponential factor of the first exothermic decomposition reaction were obtained as -525.3 kJ $mol^{-1}$, 276.85 kJ $mol^{-1}$ and $10^{26.22}s^{-1}$, respectively. The critical temperature of thermal explosion of APHDNE is 237.7 $^{\circ}C$. The specific heat capacity of APHDNE was determined with micro-DSC method and theoretical calculation method, and the molar heat capacity is 363.67 J $mol^{-1}K^{-1}$ at 298.15 K. The adiabatic time-to-explosion of APHDNE was also calculated to be a certain value between 253.2-309.4 s. APHDNE has higher thermal stability than FOX-7.

• Applied Chemistry for Engineering
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• v.10 no.2
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• pp.310-318
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• 1999

The concentration breakthrough curves were examined to predict mass transfer coefficients of nitrogen and oxygen in adsorption column for design data of PSA process. Experimental breakthrough curves for bulk gas flow were compared with theoretical simulation results. For quantitative analysis of the adsorption, coupled Langmuir isotherm was considered and LDF model was used to describe the mass transfer effect. In the experimental and theoretical results, it was found that mass transfer coefficient was not affected by flow rate but strongly affected by pressure. As a result of this tendency, mass transfer resistance in this system was proved to belong to the macropore diffusion controlling region and the mass transfer coefficients could be expressed by exponential functions of pressure change. The mass transfer coefficients for one component, nitrogen or oxygen, were successfully applied to breakthrough curves for bulk mixed gases. The experimental curves were reasonably in consistent with the theoretical curves and the error time was less than 5 percent.

• Journal of the Korean Chemical Society
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• v.54 no.4
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• pp.387-394
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• 2010

The theoretical calculations for $B_nH_n$, $B_nH_{n+1}$, $B_nH_{n+2}$ (n = 3-6) have been considered at the B3LYP level of theory with the 6-311G$^*$ basis set. The optimized geometries, harmonic vibrational frequencies, and binding energies are evaluated to elucidate the thermodynamic stability and spectroscopic properties. The harmonic vibrational frequencies for the molecules considered in this study show all real numbers implying true minima and the binding energies are corrected using zero-point vibrational energies (ZPVE). The binding energies and average energies due to increasing of BH monomer are predicted.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.320-329
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• 1983

Effect of alkyl substitution on stabilization of $\alpha$-aminomethyl radicals, $CH_2NH_2$, has been investigated using MINDO/3-RHF method. Stabilization energies obtained from total energy of radicals indicated that the alkyl substitution decreases radical stability, which is in agreement with the ab initio MO results of Goddard but is contrary to trend shown by experimental results. It was also found that conformations of radicals were different from ab initio results. When, however, approximate account of electron correlation was made in the estimation of stabilization energies of radicals by assuming a proportionality between coulomb correlation and one center exchange integral, the order of radical stability was shown to agree to that found experimentally. It was therefore concluded that the main cause of discrepancy between theoretical and experimental order of stability of alkylsubstituted radicals is the failure of accounting electron correlation energies in the theoretical estimation.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.23-30
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• 1985

PMO expressions for ${\pi}^{\ast}$-${\pi}^{\ast}$ orbital interaction have been derived. Important differences between ${\pi}$-${\pi}$ and ${\pi}^{\ast}$-${\pi}^{\ast}$ interactions predicted by PMO expressions are : (ⅰ) energy splitting in ${\pi}^{\ast}$-${\pi}^{\ast}$ interaction will be greater than that in ${\pi}$-${\pi}$ interaction, (ⅱ) energy change due to interaction will be more destabilizing in ${\pi}^{\ast}$-${\pi}^{\ast}$ than in ${\pi}$-${\pi}$ interaction. These predictions were borne out in experimental data and in results of MO theoretical computations. It was pointed out that both STeO-3G and INDO-LCBO methods underestimate ${\pi}^{\ast}$-${\pi}^{\ast}$ orbital interaction and in order to estimate properly with MO theoretical calculation, use of split valence basis set is required.