• Bulletin of the Korean Chemical Society
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• v.35 no.9
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• pp.2717-2722
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• 2014

The reaction mechanism between azacyclopropenylidene and epoxypropane has been systematically investigated employing the second-order M${\o}$ller-Plesset perturbation theory (MP2) method to better understand the reactivity of azacyclopropenylidene with four-membered ring compound epoxypropane. Geometry optimization, vibrational analysis, and energy property for the involved stationary points on the potential energy surface have been calculated. It was found that for the first step of this reaction, azacyclopropenylidene can insert into epoxypropane at its C-O or C-C bond to form spiro intermediate IM. It is easier for the azacyclopropenylidene to insert into the C-O bond than the C-C bond. Through the ring-opened step at the C-C bond of azacyclopropenylidene fragment, IM can transfer to product P1, which is named as pathway (1). On the other hand, through the H-transferred step and subsequent ring-opened step at the C-N bond of azacyclopropenylidene fragment, IM can convert to product P2, which is named as pathway (2). From the thermodynamics viewpoint, the P2 characterized by an allene is the dominating product. From the kinetic viewpoint, the pathway (1) of formation to P1 is primary.

• Korean System Dynamics Review
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• v.14 no.4
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• pp.63-89
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• 2013

The purpose of this paper is to explain the entropic measures could cause the organization to increase the entropy. The organization as an open system has a tendency to input new energy to adapt itself to the change in its surroundings. This intention of inputting energy into organization is based on the second law of thermodynamics, the laws of entropy.Entropy is a measure of disorder, or a measure of progressing towards thermodynamic equilibrium. The entropy of an isolated system increases. Organizations have to open to their environment, have to do something to reduce their entropy. But, this attempt to reduce entropy entails another entropy. This study shows the side effects by giving examples of illegal receipt of worker's compensation insurance. The implications through the cases of illegal receipt of workers' compensation are as follows. Firstly, organizational policy is that inaction in itself may be the best policy, unless we always think the action best. Secondly, public organization should be careful in substituting business management in the private sector such as customer satisfaction(CS) for the value in public sector. Thirdly, the setting the expiration date of organizational policy could be the way to slow down the degree of entropy.

• Bulletin of the Korean Chemical Society
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• v.33 no.6
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• pp.1913-1918
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• 2012

The nitramine explosives with $-NH_2$ and -F groups were optimized to obtain their molecular geometries and electronic structures at DFT-B3LYP/6-31+G(d) level. The theoretical molecular density (${\rho}$), heat of formation (HOF), detonation velocity ($D$) and detonation pressure ($P$), estimated using Kamlet-Jacobs equations, showed that the detonation properties of these compounds were excellent. Based on the frequencies scaled by 0.96 and the principle of statistic thermodynamics, the thermodynamic properties were evaluated, which were respectively related with the temperature. The simulation results reveal that 1,3,5,7-tetranitro-1,3,5,7-tetrazocan-2-amine (molecule B1) performs similarly to the famous explosive HMX, and 2-fluoro-1,3,5-trinitro-1,3,5-triazinane (molecule C1) and 2-fluoro-1,3,5,7-tetranitro-1,3,5,7-tetrazocane (molecule D1) outperform HMX. According to the quantitative standard of energetics and stability as an HEDC (high energy density compound), molecules C1 and D1 essentially satisfy this requirement. These results provide basic information for molecular design of novel high energetic density compounds.

• Macromolecular Research
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• v.11 no.5
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• pp.303-310
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• 2003

The phase behavior of binary blends of dimethylpolycarbonate-tetramethyl polycarbonate (DMPCTMPC) copolycarbonates and styrene-acrylonitrile (SAN) copolymers has been examined and then compared with that of DMPC/TMPC/SAN ternary blends having the same chemical components and compositions except that the DMPC and TMPC were present in the form of homopolymers. Both binary and ternary blends were miscible at certain blends compositions, and the miscible blends showed the LCST-type phase behavior or did not phase separated until thermal degradation temperature. The miscible region of binary blends is wider than that of the corresponding ternary blends. Furthermore, the phase-separation temperatures of miscible binary blends are higher than those of miscible ternary blends at the same chemical compositions. To explain the destabilization of polymer mixture with the increase of the number of component, interaction energies of binary pairs involved in these blends were calculated from the phase separation temperatures using lattice-fluid theory and then the phase stability conditions for the polymer mixture was analyzed with volume fluctuation thermodynamics.

• Geomechanics and Engineering
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• v.35 no.6
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• pp.593-601
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• 2023

In this paper, an analytical solution of large-strain cylindrical cavity expansion in compaction grouting problem under temperature field is given. Considering the stress increment caused by temperature, the analytical solution of cavity expansion under traditional isothermal conditions is improved by substituting the temperature stress increment into the cavity expansion analysis. Subsequently, combined with the first law of thermodynamics, the energy theory is also introduced into the cylindrical cavity expansion analysis, and the energy dissipation solution of cylindrical cavity expansion is derived. Finally, the validity and reliability of solution are proved by comparing the results of expansion pressure with those in published literatures. The results show that the dimensionless expansion pressure increases with the increase of temperature, and the thermal response increases with the increase of dilation angle. The higher the exothermic temperature of grouting slurry, the greater the plastic deformation energy of the surrounding soil, that is, the greater the influence on the surrounding soil deformation and the surrounding environment. The proposed solution not only enrich the theoretical system of cavity expansion, but also can be used as a theoretical tool for energy geotechnical engineering problems, such as CPT, nuclear waste disposal, energy pile and chemical grouting, etc.

• Journal of the Korean Chemical Society
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• v.56 no.4
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• pp.431-439
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• 2012

Dissipative particle dynamics (DPD) was carried out to study the nucleation and crystal growth process of $CeO_2$ nanoparticles in different alcohol aqueous solutions. The results showed that the nucleation and crystal growth process of $CeO_2$ can be classified into three stages: nuclei growth, crystal stabilization and crystal aggregation except the initial induction stage, which could be reproduced by collecting simulation results after different simulation time. Properly selecting the sizes of $CeO_2$ and water bead was crucial in the simulation system. The influence of alcohol type and content in solutions, and precipitation temperature on the particle dimension were investigated in detail and compared with the experimental results. The consistency between simulation results and experimental data verify that the simulation can reproduce the macroscopic particle aggregation process. The effect of solvent on the nucleation and crystal growth of $CeO_2$ nanoparticles are different at three stages and can not be simply described by Derjaguin-Landau-Verwey-Overbeek (DLVO) theory or nucleation thermodynamics theory. Our work demonstrated that DPD methods can be applied to study nanoparticle forming process.

• Journal of the Korean Vacuum Society
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• v.16 no.1
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• pp.15-22
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• 2007

We present the morphological evolution at different source powers in the ion-enhanced etching of GaAs(100) in $BCl_3-Cl_2$ plasma. With little ion bombardment at floating potential, the surface develops <110< ridges and {111} facets, as it does in purely chemical etching. The morphology develops in less than 1 minute and grows bigger over time. The etched surfaces show different morphologies at different source powers with constant pressures of gases. Lowe. source power (100 W) produces poorly developed crystallographic surfaces while higher source power (900 W) produces well developed crystallographic surfaces. This is attributed to the availability of excited reactive species(chlorine atoms) depending on source powers. With more concentration of the reactive species at higher source powers, the surface of GaAs(100) would be a surface that is expected from thermodynamics while the surface morphology would be determined by sputtering in the lack of reactive species. Statistical analysis of the surfaces, based on scaling theory, revealed two spatial exponents: one(smaller than one) is formed by atomic scale mechanisms, the other(larger than one) is formed by larger scale mechanisms which is believed to develop facets.

• Journal of the Korean Vacuum Society
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• v.16 no.4
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• pp.250-261
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• 2007

We present the morphological evolution at different source powers in the ion-enhanced etching of GaAs(100) in $BCl_3-Cl_2$ plasma. With little ion bombardment at floating potential, the surface develops <110> ridges and {111} facets, as it does in purely chemical etching. Higher source power (900 W) produces well developed crystallographic surfaces while lower source power (100 W) produces poorly developed crystallographic surfaces. This is attributed to the availability of excited reactive species (chlorine atoms) depending on source powers. With more concentration of the reactive species at higher source powers, the surface of GaAs(100) would be a surface that is expected from thermodynamics while the surface morphology would be determined by sputtering in the lack of reactive species. Statistical analysis of the surfaces, based on scaling theory, revealed two spatial exponents: one (smaller than one) is formed by atomic scale mechanisms, the other (larger than one) is formed by larger scale mechanisms which is believed to develop facets. When samples are biased, the surfaces experienced bombardment resulting in suppression of ridge formation at high source power and islands formation at low source power.

• Proceedings of the Korean Vacuum Society Conference
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• 2016.02a
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• pp.246-246
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• 2016

Tungsten-nitrogen (W-N) co-doping has been known to enhance the photocatalytic activity of anatase titania nanoparticles by utilizing visible light. The doping effects are, however, largely dependent on calcination or annealing conditions, and thus, the massive production of quality-controlled photocatalysts still remains a challenge. Using density functional theory (DFT) thermodynamics and time-dependent DFT (TDDFT) computations, we investigate the atomic structures of N doping and W-N co-doping in anatase titania, as well as the effect of the thermal processing conditions. We find that W and N dopants predominantly constitute two complex structures: an N interstitial site near a Ti vacancy in the triple charge state and the simultaneous substitutions of Ti by W and the nearest O by N. The latter case induces highly localized shallow in-gap levels near the conduction band minimum (CBM) and the valence band maximum (VBM), whereas the defect complex yielded deep levels (1.9 eV above the VBM). Electronic structures suggest that substitutions of Ti by W and the nearest O by N improves the photocatalytic activity of anatase by band gap narrowing, while defective structure degrades the activity by an in-gap state-assisted electron-hole recombination, which explains the experimentally observed deep level-related photon absorption. Through the real-time propagation of TDDFT (rtp-TDDFT), we demonstrate that the presence of defective structure attracts excited electrons from the conduction band to a localized in-gap state within a much shorter time than the flat band lifetime of titania. Based on these results, we suggest that calcination under N-rich and O-poor conditions is desirable to eliminate the deep-level states to improve photocatalysis.

• Polymer(Korea)
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• v.26 no.2
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• pp.245-252
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• 2002

Thermodynamics and gas transport properties of polymethylmethacrylate (PMMA) blends with polyvinylmethylether (PVME) containing various amount of poly (styrene-b-methylmethacrylate) copolymer (P(S-b-MMA)) as a compatibilizer were studied. To extract interaction energies of binary pairs involved in the blends from the phase separation temperatures using an equation-of-state theory, PVME blends with methylmethacrylate copolymers containing various amount of styrene (SMMA) were prepared. PVME formed miscible blends with methylmethacrylate copolymers containing more than 70 wt% styrene and these miscible blonds showed a LCST-type phase separation behavior. Based on the interaction information obtained here, P(S-b-MMA) copolymer was added to the PMMA/PVME blends to enhance their compatibility. The average diameter of the dispersed rubber particles was gradually decreased for the blends of containing P(S-b-MMA) from 0 to 5 phr and then leveled off at a fixed size. At a fixed bland composition, the gas permeation was also increased as the P(S-b-MMA) content increased from 0 to 5 phr and then leveled off when the P(S-b-MMA) content was higher than 5 phr.