• Bulletin of the Korean Chemical Society
• /
• 제35권6호
• /
• pp.1754-1758
• /
• 2014

The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at $35.0^{\circ}C$. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ${\rho}_{XY}$) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

• E2M - 전기 전자와 첨단 소재
• /
• 제6권1호
• /
• pp.63-68
• /
• 1993

CO$_{2}$기체의 운동량변환, 진동여기, 전자여기 및 전리충돌 단면적의 결정은 온도 293[.deg.K], 상대전계의 세기 E/N은 1.0[Td].leq.E/N.leq.200[Td]의 범위에서 볼츠만 방정식을 Backward-Prolongation 방법으로 해석하여 전자 이동속도의 계산값을 산출하고 이것을 M. T. Elford에 의해 실험적으로 측정된 이동속도의 값과 비교하였다. 본 연구에서 운동량변환충돌단면적은 Hake & Phelps의 값을 기초로 하였으며 온도 293[.deg.K], 상대전계의 세기 E/N은 3.0[Td].leq.E/N.leq.50[Td]인 범위 전자에너지분포함수 및 전자특성에너지는 상대전계의 세기 E/N이 1.0[Td].leq.E/N.leq.200[Td]인 범위에서 산출하였다.

• Bulletin of the Korean Chemical Society
• /
• 제32권7호
• /
• pp.2199-2202
• /
• 2011

The electronic properties of altretamine(2,4,6-tris [dimethylamino]-1,3,5-triazine) adsorbed on epitaxial graphene (EG) were investigated by core-level photoemission spectroscopy (CLPES) in conjunction with low energy electron diffraction (LEED). We found that altretamine molecule adsorbed onto interface layer (S1) of graphene as we confirm decrement of S1 peak using CLPES and haziness of LEED pattern. Moreover, the measured work function changes verified that increased adsorption of the altretamine on graphene layer showed n-type doping characteristics due to charge transfer from altretamine to graphene through the nitrogens. Two distinct nitrogen bonding feature associated with the N 1s peak was clearly observed in the core-level spectra indicating two different chemical environments.

• Journal of Advanced Marine Engineering and Technology
• /
• 제24권6호
• /
• pp.139-146
• /
• 2000

The development of high performance materials is very important subject in order to enhance the properties of bearings whose role is to transfer energy harmoniously by reducing the problem of friction and wear down, etc. between the interacting solid surfaces in relative motion under high loads in comply with mechanical operating mechanism of engines. In this study, several (100-x)Al-xSn coating films (where x=85, 75, 65 atomic % at Al) on substrates which are abt. 2mm thickenss of Kelmet layer sintered back steel were prepared by using RF sputtering system. These coating films were observed the morphology by SEM(Scanning Electron Microscope) and investigated the crystal structure by XRD(X-ray Diffractor) for their properties. And friction coefficient of these films was measured by ball-on-disc tester for their tribological properties. From the experimental results, it was shown that high performance properties of bearing can be improved greatly by controlling the composition and morphology of material surface with effective use of the plasma-assisted sputtering process.

• Bulletin of the Korean Chemical Society
• /
• 제35권1호
• /
• pp.111-116
• /
• 2014

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. $$-\frac{d[CAT]}{dt}=\frac{kK_1[RNHCl][SA]}{K_1+[H^+]}$$ (1) All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be $(61.67{\pm}0.47)kJmol^{-1}$ and $(-62.71{\pm}2.48)kJmol^{-1}$ respectively employing Eyring equation.

• Bulletin of the Korean Chemical Society
• /
• 제34권2호
• /
• pp.453-459
• /
• 2013

In phtosynthetic light harvesting complexes, the electronic transition energies of chlorophylls are influenced by the Coulombic interaction with nearby molecules. Variation of the interactions caused by structural inhomogeneity in biological environment results in a distribution of disordered electronic transition energies of chlorophylls. In order to provide a practical guide to predict qualitative tendency of such distribution, we model four porphyrin derivatives including chlorophyll a molecule interacting with an external positive charge and calculate their transition energies using the time dependent density functional method. It is found that ${\pi}-{\pi}^*$ transition energies of the molecules are generally blue-shifted by the charge because this stabilizes occupied molecular orbitals to a greater extent than unoccupied ones. Furthermore, new transitions in the visible region emerge as a result of the red-shift in energy of an unoccupied Mg orbital and it is suggested that light-induced electron transfer may occur from the tetrapyrrole ring to the central magnesium when the molecules are interacting with a positive charge.

• 세라미스트
• /
• 제22권2호
• /
• pp.170-181
• /
• 2019

All-solid-state batteries have received increasing attention because of their high safety aspect and high energy and power densities. However, the inferior solid-solid interfaces between solid electrolyte and active materials in electrode, which cause high interfacial resistance, reduce ion and electron transfer rate and limit battery performance. Recently, spark plasma sintering is emerging as a promising technique for fabricating solid electrolytes and composite-electrodes. Herein, this paper focuses on the overview of spark plasma sintering to fabricate solid electrolytes and composite-electrodes for all-solid-state batteries. In the end, future opportunities and challenges associated with SPS technique for all-solid-state batteries are described.

• Bulletin of the Korean Chemical Society
• /
• 제19권1호
• /
• pp.86-93
• /
• 1998

Trans-4-(9-anthrylethenyl)-4'-methyl-2,2'-bipyridine(t-aemb) and its bipyridyl Ru complex $[Ru(bpy)_2(t-aemb)](PF_6)_2$ (bpy=2,2'-bipyridine) 1 have been prepared and their excited state properties have been studied. t-Aemb exhibits solvent-dependent fluorescence and efficient trans→cis photoisomerization. 1 shows very weak fluorescence and its photochemically reactive. Fluorescence is wavelength-dependent. While the excitation into the MLCT band makes the complex fluorescent, direct absorption by the t-aemb ligand leads to the photoreaction of t-aemb ligand and no fluorescence is observed. 1 is considered to behave in part as bichromophoric molecule in which $[Ru(bpy)_3](PF_6)_2$ and anthryl group are covalently linked by ethenyl linkage. Because anthryl moiety is not effectively conjugated with bipyridylethenyl moiety due to steric hindrance, weak fluorescence can be explained due to the efficient energy or electron transfer.

• Bulletin of the Korean Chemical Society
• /
• 제7권3호
• /
• pp.186-190
• /
• 1986

Effects of substituents in the nucleophile(X), the substrate(Y) and the leaving group(Z) on the structure of $S_N2$ transition states have been analyzed by considering effects of four components, electrostatic($E_{es}$), exchange repulsion ($E_{ex}$), polarization($E)_{pl}$) and charge transfer($E_{ct}$) terms, of interaction between the reactants on the degree of bond making and bond breaking. Prediction of net effects of all substituents(X, Y and Z) on the degree of bond making were found to be clearcut whereas the effect of an electron withdrawing group on the substrate (Y = EWG) on the degree of bond breaking was complex; the substituent(Y = EWG) is normally carbon-leaving group($C^{\ast}$-L) bond tightening($E_{pl}$ dominance) but becomes $C^{\ast}$-L bond loosening when the bond is strongly antibonding ($E_{ct}$ dominance). Our model calculations on the reaction of $CH_2XNH_2$ with $YCH_2COOCH_2Z$ using energy decomposition scheme have confirmed that predictions based on our analysis are correct.

• 한국재료학회지
• /
• 제29권3호
• /
• pp.183-188
• /
• 2019

Flexible dye-sensitized solar cells using binder free $TiO_2$ paste for low temperature sintering are developed. In this paste a small amount of titanium gel is added to a paste of $TiO_2$ nanoparticle. Analysis of titanium gel paste prepared at $150^{\circ}C$ shows that it has a pure anatase phase in XRD and mesoporous structure in SEM. The formation of the titanium gel 1-2 nm coated layer is confirmed by comparing the TEM image analysis of the titanium gel paste and the pristine paste. This coating layer improves the excited electron transfer and electrical contact between particles. The J-V curves of the organic binder DSSCs fabricated at $150^{\circ}C$ shows a current density of $0.12mA/cm^2$ and an open-circuit voltage of 0.47 V, while the titanium gel DSSCs improves electrical characteristics to $5.04mA/cm^2$ and 0.74 V. As a result, the photoelectric conversion efficiency of the organic binder DSSC prepared at low temperature is as low as 0.02 %, but the titanium gel paste DSSCs has a measured effciency of 2.76 %.