• Title/Summary/Keyword: Reaction parameter

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$Hg^{2+}$-promoted Aquation and Chelation of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = Amines) Complexes ($Hg^{2+}$에 의한 cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = 아민류) 착물의 아쿠아화 및 킬레이트화 반응)

  • Chang Eon Oh;Doo Cheon Yoon;Bok Jo Kim;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.565-578
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    • 1992
  • It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

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Simultaneous determination of preservatives in sausages using liquid chromatography with electrospray ionization tandem mass spectrometry (LC-MS/MS를 이용한 소시지 중 보존료 동시분석)

  • Koh, Ba-Ra-Da;Kim, Ji-Yeon;Jang, Mi-Sun;Seo, Doo-Ri;Jung, Bo-Ram;Shin, Ji-Hyun;Lim, Jin-Taek;Kim, Yong-Hwan;Kim, Eun-Sun
    • Korean Journal of Veterinary Service
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    • v.38 no.2
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    • pp.127-136
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    • 2015
  • A simultaneous determination method was developed for nine preservatives (benzoic acid, sorbic acid, dehydroacetic acid, methyl-, ethyl-, isopropyl-, propyl-, isobutyl- and butyl-parabens) in sausage by liquid chromatography with electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS). Each parameter was established by multiple reaction monitoring in negative mode. Separation was achieved on a phenyl-hexyl ($2.5{\mu}m$, $2.1{\times}150mm$, Waters) with A-20 mM ammonium acetate containing 0.1% acetic acid in water, B-Acetonitrile as mobile phase with gradient mode at a flow rate of 0.3 mL/min. The developed method was validated for specificity, linearity, accuracy and precision in sausages samples. Linearity was over 0.998 with calibration curve of the mixed standards. The mean recoveries from sausages fortified at the level of 2.0~10.0 mg/L were in range of 98.60~109.16% with RSDs lower than 8.93%. The limits of detection (LOD) and the limits of quantification (LOQ) were in the range between 0.0003~0.085 mg/L and 0.01~0.257 mg/L, respectively. Intra-day precision and inter-day precision were 0.45~6.16% and 2.81~13.33%, respectively. Using presently developed determination method, 33 field sausage samples from Gwangju city in Korea were screened over nine preservatives. As a result, no preservatives were detected in all samples.

Thermal and Mechanical Evaluation of Environmental Barrier Coatings for SiCf-SiC Composites (SiCf-SiC 복합재료의 내환경 코팅 및 열, 기계적 내구성 평가)

  • Chae, Yeon-Hwa;Moon, Heung Soo;Kim, Seyoung;Woo, Sang Kuk;Park, Ji-Yeon;Lee, Kee Sung
    • Composites Research
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    • v.30 no.2
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    • pp.84-93
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    • 2017
  • This study investigates thermal and mechanical characterization of environmental barrier coating on the $SiC_f-SiC$ composites. The spherical environmental barrier coating (EBC) powders are prepared using a spray drying process for flowing easily during coating process. The powders consisting of mullite and 12 wt% of Ytterbium silicate are air plasma sprayed on the Si bondcoat on the LSI SiC fiber reinforced SiC composite substrate for protecting the composites from oxidation and water vapor reaction. We vary the process parameter of spray distance during air plasma spray of powders, 100, 120 and 140 mm. After that, we performed the thermal durability tests by thermal annealing test at $1100^{\circ}C$ for 100hr and thermal shock test from $1200^{\circ}C$ for 3000 cycles. As a result, the interface delamination of EBC never occur during thermal durability tests while stable cracks are prominent on the coating layer. The crack density and crack length depend on the spray distance during coating. The post indentation test indicates thermal tests influence on the indentation load-displacement mechanical behavior.

Analysis on the Frumkin Adsorption Isotherm of the Over-Potentially Deposited Hydrogen (OPD H) at the Polycrystalline Ni | Alkaline Aqueous Electrolyte Interface Using the Phase-Shift Method

  • Chun Jang H.;Jeon Sang K.
    • Journal of the Korean Electrochemical Society
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    • v.4 no.4
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    • pp.146-151
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    • 2001
  • The Frumkin adsorption isotherm of the over-potentially deposited hydrogen (OPD H) for the cathodic $H_2$ evolution reaction (HER) at the poly-Ni|0.05M KOH aqueous electrolyte interface has been studied using the phase-shift method. The behavior of the phase shift $(0^{\circ}\leq{\phi}\leq90^{\circ})$ for the optimum intermediate frequency corresponds well to that of the fractional surface coverage $(1\geq{\theta}\geq0)$ at the interface. The phase-shift method, i.e., the Phase-shift profile $(-{\phi}\;vs.\;E)$ for the optimum intermediate frequency, can be used as a new method to estimate the Frumkin adsorption isotherm $(\theta\;vs.\;E)$ of the OPD H for the cathodic HER at the interface. At the poly-Ni|0.05M KOH aqueous electrolyte interface, the rate (r) of change of the standard free energy of the OPD H with $\theta$, the interaction parameter (g) for the Frumkin adsorption isotherm, the equilibrium constant (K) for the OPD H with $\theta$, and the standard free energy $({\Delta}G_{\theta})$ of the OPD H with ${\theta}$ are $24.8kJ mol^{-1},\;10,\;5.9\times10^{-6}{\leq}K{\leq}0.13,\;and\;5.1\leq{\Delta}G_{\theta}\leq29.8kJ\;mol^{-1}$. The electrode kinetic parameters $(r,\;g,\;K,\;{\Delta}G_{\theta})$ depend strongly on ${\theta} (0{\leq}{\theta}{\leq}1)$.

Optimization of Roasted Perilla Leaf Tea Using Response Surface Methodology (반응표면분석을 이용한 들깨잎차 볶음처리의 최적화)

  • Han, Ho-Suk;Park, Jung-Hye;Choi, Hee-Jin;Sung, Tae-Su;Woo, Hi-Seob;Choi, Cheong
    • Applied Biological Chemistry
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    • v.47 no.1
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    • pp.96-106
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    • 2004
  • Response surface methodology (RSM) was applied in roasting processes of perilla leaves to develop a high quality perilla leaf tea. The Hunter color parameters and electron donating ability were monitored to optimize organoleptic properties of perilla leaf tea. The roasting processes were based on the central composite design with primary variables-roasting temperature $(140{\sim}220^{\circ}C)$, time $(5{\sim}25)$, and reaction variables-sensory test, electron donating ability. From the variables, the roasting condition was optimized using statistical analysis system (SAS) program as developing the functional tea using perilla leaf. Hunter color L and b values of the powdered samples increased with the roasting processes, but Hunter color a value decreased. Electron donating ability was influenced by roasting temperature (p<0.01) and time (p<0.01), and optimum condition selected was at $220^{\circ}C$ for 15 min with coefficient of determinations $(R^2)$ above 0.98. After preference test of perilla leaf tea using parameter of taste, color, and flavor, we can estimate that the optimal roasting condition of preilla leaf for function tea manufacturing are $210{\sim}220^{\circ}C$ for $10{\sim}20$ min by response surface methodology (RSM). Tyrosinase, xanthine oxidase and electron donating ability were 10.14, 14.37 and 59.19% of perilla leaf tea.

Kinetics and Mechanism of Hydrolysis of Insecticidal Imidacloprid (살충성 Imidacloprid의 가수분해 반응 메카니즘)

  • Yu, Sung-Jae;Kang, Moon-Sung;Sung, Nack-Doo
    • Applied Biological Chemistry
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    • v.40 no.1
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    • pp.53-57
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    • 1997
  • The rate of hydrolysis of insecticidal 1-(6-chloro-3-pyridylmethyl) -2-nitro-iminoimidazolidine (common name; imidacloprid) have been investigated in 15%(v/v) aqueous dioxane at $45^{\circ}C$. From the kinetics and non-kinetics data such as pH-effect, solvent effect(m=0.04, n=0.30 IT m<${\Delta}H^{\neq}=16.14kcal{\cdot}mol^{-1}\;&\;{\Delta}S^{\neq}=-0.03e.u.$), rate equation ($k_{obs.}=4.56{\times}10^{-3}[OH^-]$) and analysis of hydrolysis product, 1-(6-chloro-3-pyridylmethyl-2)-imidazolidinon, the hydrolysis mechanism of imidacloprid is proposed that the specific base catalyzed hydrolysis($K_{OH^-}$) through nucleophilic addition-elimination ($Ad_N-E$) mechanism proceed via intermediate, 1-(6-chloro-3- pyridylmethyl)-2-hydroxy-2-imidazolidinylisonitraminate (I) and ${\beta}$-3-(6-chloro-3-pyridylmethyl)aminoethyl-1-nitrourea(III). And the half-life(t1/2) of hydrolytic degradation at pH 8.0 and $45^{\circ}C$ was about 4.5 months.

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Analysis of Photoluminescence of Eu3+ in YOBr and Investigation of Critical Distance (YOBr:Eu3+ 형광체의 발광특성과 임계거리 연구)

  • Kim, Gyeong Hwa;Park, Jong Gyu;Park, Hui Dong;Han, Jeong Hwa
    • Journal of the Korean Chemical Society
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    • v.45 no.6
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    • pp.570-576
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    • 2001
  • The europium doped yttrium oxybromide phosphors were synthesized by solid-state reaction method. The YOBr: $Eu^{3+}$ phosphor showed a strong and narrow red emission band at 621 nm and maximum emission intensity obtained when 0.05 mol Eu ions were doped. The red emission of $Eu^{3+}$ originated from $^5D_0$ ${\rightarrow}$ $^7F_2$electric dipole transition. In order to investigate on photoluminescence behavior, several experimental skills and numerical fittings are conducted to the YOBr: $Eu^{3+}$ phosphor. The emission spectrum was measured in the UV range and then decay curve of $^5D_0$ ${\rightarrow}$ $^7F_j$transitions was examined. The energy interaction type of YOBr: $Eu^{3+}$ phosphor was dipole-dipole interaction. In addition to the calculating by critical concentration, the critical distance ($R_0$) was calculated by decay curve fitting parameter from Inokuti-Hirayamas equation, and spectral overlap method. The critical distance was 17.03, 10.51 and 7.18$\AA$ for those methods, respectively. As considering systematic error of measurements, these values are within the same order, so that the above fitting methods are plausible and recommendable.

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Development and Validation of Urea- SCR Control-Oriented Model for NOX and NH3 Slip Reduction (NOX 및 NH3 Slip 저감을 위한 Urea-SCR 제어기반 모델 개발 및 검증)

  • Lee, Seung Geun;Lee, Seang Wock;Kang, Yeonsik
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.39 no.1
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    • pp.1-9
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    • 2015
  • To satisfy stricter $NO_X$ emission regulations for light- and heavy-duty diesel vehicles, a control algorithm needs to be developed based on a selective catalytic reaction (SCR) dynamics model for chemical reactions. This paper presents the development and validation of a SCR dynamics model through test rig experiments and MATLAB simulations. A nonlinear state space model is proposed based on the mass conservation law of chemical reactions in the SCR dynamics model. Experiments were performed on a test rig to evaluate the effects of the $NO_X$ and $NH_3$ concentrations, gas temperature, and space velocity on the $NO_X$ conversion efficiency for the urea-SCR system. The parameter values of the proposed SCR model were identified using the experimental datasets. Finally, a control-oriented model for an SCR system was developed and validated from the experimental data in a MATLAB simulation. The results of this study should contribute toward developing a closed-loop control strategy for $NO_X$ and $NH_3$ slip reduction in the urea-SCR system for an actual engine test bench.

Effect of irradiation and LDPE content on crystal formation of PP (PP의 결정형성에 대한 조사가교와 LDPE 함량의 영향)

  • Dahal, Prashanta;Kim, Youn Cheol
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.15 no.6
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    • pp.4039-4045
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    • 2014
  • The crystallization behavior of irradiated polypropylene (PP) and the blend is an important parameter for polymer processing. Blends of PP/low density polyethylene (LDPE) with different LDPE contents were prepared by melt mixing in a twin screw extruder. The effect of the LDPE content on the irradiation effectiveness of the PP/LDPE blend with trimethylolpropane-trimetacrylate (TMPTMA) as a crosslinking co-agent was investigated in conjunction with the LDPE loading in the blend. The non-isothermal crystallization and crystal structure were measured by DSC, X-ray diffraction (XRD), and polarized optical microscopy (POM). A decrease in the melting temperature of PP was observed due to irradiation, which may be due to the PP chain scissioning effect of irradiation. The Ozawa component n represents a rod shaped, disc shaped and sphere-shaped geometry of the crystal if the value corresponds to 2, 3 and 4, respectively. Based on Ozawa analysis, the values of n were 3.8 and 2.3 for the pure PP and PP blends with 30 wt% LDPE, respectively. The fact that the crystal geometry of PP changed from spherical to disc and rod shaped was confirmed by Ozawa analysis and POM. The ${\beta}$ form XRD peak of the PP/LDPE blend at $16.1^{\circ}$ disappeared after irradiation due to the crosslinking reaction.

Motility Analysis of Gate Myocardium SPECT Image Using Left Ventricle Myocardium Model (좌심실 심근 모델을 이용한 게이트 심근 SPECT 영상의 운동성 분석)

  • 손병환;김재영;이병일;이동수;최흥국
    • Journal of Korea Multimedia Society
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    • v.6 no.3
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    • pp.444-454
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    • 2003
  • An analysis of heart movement is to estimate a role which supplies blood in human body. We have constructed a left ventricle myocardium model and mathematically evaluated the motion of myocardium. The myocardial motility was visualized using some parameters about cardiac motion. We applied the myocardium model in the gated myocardium SPECT image that showed a cardiac biochemical reaction, and analyzed a motility between the gated myocardium SPECT image and the myocardium model. The myocardium model was created of the based on three dimensional super-ellipsoidal model that was using the sinusoidal function. To express a similar form and motion of the left ventricle myocardium, we calculated parameter functions that gave the changing of motion and form. The LSF algorithm was applied to the myocardium gated SPECT image data and the myocardium model, and finally created a fitting model. Then we analyzed a regional motility direction and size of the gated myocardium SPECT image that was constructed on a fitting model. Furthermore, we implemented the Bull's Eye map that had evaluated the heart function for presentation of regional motility. Using myocardium's motion the evaluation of cardiac function of SPECT was estimated by a contraction ability, perfusion etc. However, it is not any estimation about motility. So, We analyzed the myocardium SPECT's motility of utilizing the myocardium model. We expect that the proposed algorithm should be a useful guideline in the heart functional estimation.

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