• 공업화학
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• 제10권2호
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• pp.293-298
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• 1999

Fluoran계 감열색소의 중간체인 2-Methyl-4-methoxydiphenylamine(MMDPA)을 합성하는 촉매반응의 반응기구를 규명하고 반응조건을 최적화하였다. 반응물질로서는 2-methyl-4-methoxyaniline(MMA), 3-methyl-4-nitroanisole(MNA), 그리고 cyclohexanone의 혼합물을 사용하였으며, 5 wt % Pd/C를 촉매로 사용하였다. 반응실험은 reflux condenser가 부착된 개방형 slurry reactor에서 진행시켰으며, 생성물은 GC/MS와 NMR에 의해서 분석하였다. 반응조건을 최적화 시킨 결과 xylene용매 속에서 0.01 gmoles MMA 투입기준으로 MMA : MNA : cyclohexanone = 1 : 2 : 150의 반응물조성, $160^{\circ}C$의 반응온도, 0.5 g 촉매량 조건에서 8~10시간 경과 후 90 mole %의 MMDPA수율을 얻을 수 있었다. MMA와 cyclohexanone간의 축합반응에 의해 생성된 중간생성물의 탈수소화 반응단계가 총괄반응을 율속함을 알 수 있었다. MNA를 MMA와 함께 반응물에 투입함으로써 hydrogen transfer반응에 의하여 총괄반응속도와 MMDPA수율이 증대되었다. 반응물에 과량으로 투입된 cyclohexanone은 MMA와의 축합반응을 촉진시키는 역할을 하였다.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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• pp.3588-3592
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• 2010

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2-pyridyl X-substituted benzoates 8a-e with a series of alicyclic secondary amines in $H_2O$ at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 8a-e are slightly smaller than the corresponding reactions of 4-nitrophenyl X-substituted benzoates 1a-e (e.g., $kN^{1a-e}/k_N^{8a-e}$ = 1.1 ~ 3.1), although 2-pyridinolate in 8a-e is ca. 4.5 $pK_a$ units more basic than 4-nitrophenolate in 1a-e. The Br$\o$nsted-type plot for the aminolysis of 8c (X = H) is linear with $\beta_{nuc}$ = 0.77 and $R^2$ = 0.991 (Figure 1), which is typical for reactions reported previously to proceed through a stepwise mechanism with breakdown of a zwitterionic tetrahedral intermediate $T^{\pm}$ being the rate-determining step (RDS), e.g., aminolysis of 4-nitrophenyl benzoate 1c. The Hammett plot for the reactions of 8a-e with piperidine consists of two intersecting straight lines (Figure 2), i.e., $\rho$ = 1.71 for substrates possessing an electron-donating group (EDG) while $\rho$ = 0.86 for those bearing an electron-withdrawing group (EWG). Traditionally, such a nonlinear Hammett plot has been interpreted as a change in RDS upon changing substituent X in the benzoyl moiety. However, it has been proposed that the nonlinear Hammett is not due to a change in RDS since the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with $\rho$ = 0.85 and r = 0.62 ($R^2$ = 0.995, Figure 3). Stabilization of substrates 8a-e in the ground state has been concluded to be responsible for the nonlinear Hammett plot.

• 한국세라믹학회지
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• 제27권1호
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• pp.79-85
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• 1990

A study on the oxidation of SiO2 sensing layer was done at 950, 1000, 105$0^{\circ}C$ under dry O2 atmosphere. The rate determining step around the oxide layer thickness, 1000$\AA$ was different with the oxidation temperature, as follows ; ⅰ) linear growth at 95$0^{\circ}C$ and ⅱ) parabolic growth at 100$0^{\circ}C$ and 105$0^{\circ}C$. The flatness of SiO2 film was observed within $\pm$1% and surface state charge density was reduced by annealing in N2 atmosphere. Finally, pH sensitivity of SiO2 film, in the range of pH 3-9, was 20mV/pH.

• 한국잠사곤충학회지
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• 제42권1호
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• pp.1-5
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• 2000

To investigate the possibility of crypreservation of mulberry seeds in liquid nitrogen(LN$_2$), characteristics of the seeds were examined after picking mulberry syncarps and drying-heat treatment. Storage in LN$_2$has the potential of providing indifinite preservation of valuable seed germplasm. Determining the tolerance of seeds among given cultivars to LN$_2$cooling and subsequent rewarming is the first step to establishing the feasibility of LN$_2$storage. Seeds of 4 mulberry varities were treated to LN$_2$(-196$\^{C}$) for 24 hours after drying heat treatment. Seed moisture content of Daeryukppong was the highest. As moisture content of mulberry seed was below 1%, storage in LN$_2$was safe. And drying heat treatment for 60 minutes was suitable to prevent decreased germination rate and germination vigor of seeds. The seeds of Cheongilppong were unsuibable to cryopreserve in LN$_2$for longterm storage.

• Bulletin of the Korean Chemical Society
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• 제29권1호
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• pp.38-42
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• 2008

The voltammetic behavior of Vitamin B6 (VB6) was studied at a glassy carbon electrode in phosphate buffers using cyclic, linear sweep and differential pulse voltammetry. The oxidation process was shown to be irreversible over the entire pH range studied (4.0-10.0) and was adsorption controlled. The adsorption amount of VB6 on the glassy carbon electrode was examined by chronocoulometry and the value of n, product of transfer coefficient and number of electrons transferred in the rate determining step, was determined from Tafel plot. VB6 was determined by differential pulse voltammetry and the peak current was found linearly with its concentration in the range of 3 10-7-2 10-4 mol L-1. The detection limit was 1 10-7 mol L-1. The procedure was successfully applied for the assay of VB6 in tablets.

• 대한전기학회논문지:전력기술부문A
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• 제52권6호
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• pp.316-324
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• 2003

This paper applied Elite-based Simplex-GA hybrid approach combined with Muptipop-GA (ESGA) to determining the location, size and number of capacitors to improve voltage profile and minimize power losses in unbalanced distribution systems. One of the main obstacles in applying GA to complex problems has been the high computational cost due to their slow convergence rate. To alleviate this difficulty, ESGA approach was developed that combines Elite-based Simplex-GA hybrid approach with Muptipop-GA. The objective function formulated consists of two terms: cost for energy losses and cost related to capacitor purchase and capacitor installation. The cost function associated with capacitor placement is considered as a step function due to banks of standard discrete capacities. Its efficiency was proved through the application in IEEE 13 bus and 34 bus test systems and was compared with several methods using GA.

• Bulletin of the Korean Chemical Society
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• 제23권5호
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• pp.715-720
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• 2002

Kinetic studies of the reaction of Z-aryl cyclobutanecarboxylates with X-pyridines in acetonitrile at $55.0^{\circ}C$ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterion ic tetrahedral intermediate, T $\pm$ . These mechanistic conclusions are drawn based on (i) the large magnitude of ${\rho}X$ and $\rhoZ$, (ⅱ) the positive sign of ${\rho}XZ$ and the larger magnitude of $\rhoXZ$ than normal SN2 processes, (ⅲ) a small positive enthalpy of activation, ${\Delta}H{\neq}$, and a large negative, ${\Delta}S{\neq}$, and lastly (iv) adherence to the reactivity-selectivity principle (RSP) in all cases.

• 한국표면공학회지
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• 제41권6호
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• pp.279-286
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• 2008

Numerical analysis is done to investigate which would be the most influencing process parameter in determining the uniformity of deposition thickness in TiN ICP-CVD(inductively coupled plasma chemical vapor deposition). Two configurations of ICP antenna are modeled; side and top planar. Side and top gas inlets are considered with each ICP antenna geometries. Precursor for TiN deposition was TDMAT(Tetrakis Diethyl Methyl Amido Titanium). Two step volume dissociation of TDMAT is used and absorption, desorption and deposition surface reactions are included. Most influencing factors are H and N concentration dissociated by electron impact collisions in plasma volume which depends on the relative positions of gas inlet and ICP antenna generated hot plasma region. Low surface recombination of N shows hollow type concentration, but H gives a bell type distribution. Film thickness at substrate edges is sensitive to gas flow rate and at high pressures getting more dependent on flow characteristics.

• 대한화학회지
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• 제32권6호
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• pp.567-574
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• 1988

바나듐(IV)촉매가 존재하는 물 및 알코올 수용매에서 과산화수소에 의한 디메틸술폭시드의 산화반응은 디메틸술폭시드와 산농도에 각각 일차의존성임을 보여주었다. 이 산화반응의 속도 결정단게는 황이 바나듐(V)-과산화물의 O-O결합에 대하여 친핵적 공격을 함으로서 디메틸술폭시드가 산화되는 과정임을 제시한다.

• Bulletin of the Korean Chemical Society
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• 제31권11호
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• pp.3366-3370
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• 2010

The specific rates of solvolysis of t-butyl fluoroformate (1) have been measured at $40.0^{\circ}C$ in 21 pure and binary solvents. These give a satisfactory correlation over the full range of solvents when the extended Grunwald-Winstein equation, with incorporation of the solvent nucleophilicity and the solvent ionizing power, is applied. The actual values are very similar to those obtained in earlier studies of the solvolyses of isopropyl chloroformate and ethyl chlorothioformate in the more ionizing and least nucleophilic solvents, which are believed to proceed by an ionization pathway. The small negative values for the entropies of activation are consistent with the ionization nature of the proposed rate-determining step. These observations are also compared with those previously reported for the corresponding primary and secondary alkyl haloformate esters.