• Title/Summary/Keyword: 화학반응론

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Carbothermic Reduction of Zinc Oxide with Iron Oxide (산화아연(酸化亞鉛)의 탄소열환원반응(炭素熱還元反應)에서 산화철(酸化鐵)의 영향(影響))

  • Kim, Byung-Su;Park, Jin-Tae;Kim, Dong-Sik;Yoo, Jae-Min;Lee, Jae-Chun
    • Resources Recycling
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    • v.15 no.4 s.72
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    • pp.44-51
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    • 2006
  • Most electric arc furnace dust (EAFD) treatment processes to recover zinc from EAFD employ carbon as a reducing agent for the zinc oxide in the EAFD. In the present work, the reduction reaction of zinc oxide with carbon in the present of iron oxide was kinetically studied. The experiments were carried out at temperatures between 1173 K and 1373 K under nitrogen atmosphere using a weight-loss technique. From the experimental results, it was concluded that adding the proper amount of iron oxide to the reactant accelerates the reaction rate of zinc oxide with carbon. This is because iron oxide in the reduction reaction of zinc oxide with carbon promotes the carbon gasification reaction. The spherical shrinking core model for a surface chemical reaction control was found to be useful in describing kinetics of the reaction over the entire temperature range. The reaction has an activation energy of 53 kcal/mol (224 kJ/mol) for ZnO-C reaction system, an activation energy of 42 kcal/mol (175 kJ/mol) for $ZnO-Fe_{2}O_{3}-C$ reaction system, and an activation energy of 44 kcal/mol (184 kJ/mol) for ZnO-mill scale-C reaction system.

Immunohistochemical Detection of p53, erbB-2 and CEA Oncoprotein in Lung Cancer; Clinical Correlations (폐암 환자에서 면역조직화학 염색을 통한 p53, erbB-2, CEA 종양단백 발현과 임상적 의의)

  • Jeong, Seong-Su;Kang, Dong-Won;Lee, Gyu-Seung;Ko, Dong-Seok;Suh, Jae-Chul;Kim, Geun-Hwa;Shin, Kyoung-Sang;Kim, Ju-Ock;Song, Gyu-Sang;Kim, Sun-Young
    • Tuberculosis and Respiratory Diseases
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    • v.45 no.4
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    • pp.766-775
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    • 1998
  • Background : The prognosis of patients with lung cancer is still poor. Lung cancer exhibits a variable clinical outcome, even in those patients with same stage. Numerous reports suggest that oncogene expression might playa role in explaining the variability of response and survival But many of these reports are still under debate. So we studied the clinical relevance of oncogene expression in Korean lung cancer patients. Immunohistochemistry of p53, erbB-2, CEA expression was performed. Method: From March, 1992 until March, 1997, 120 patients with lung cancer were reviewed. p53, erbB-2, and CEA expression were detected on paraffin-embedded tumor blocks with the use of monoclonal antibodies. The survival and response has correlated with the expressibility of p53, erbB-2, and CEA oncoprotein Results: Overall, the expression rates of p53, erbB-2, and CEA were 33.7%, 59.3%, and 32.6% respectively. Expression rates were not correlated to cell type or stage. Compared with response to chemotherapy, no correlation was found. The expression of p53, erbB-2, or CEA was not correlated with 2-year survival. With simultaneous applications of p53, erbB-2, and CEA, patients with 2 or more expressions also did not show poor response to chemotherapy. Conclusion: We conclude the p53, erbB-2, and CEA expression are clinically less useful in predicting response to chemotherapy or survival.

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Reevaluation of. the effect of Triton X-100 on the assay of superoxide radical by the nitrobluetetrazolium reduction method (NBT 환원방법에 의한 superoxide 라디칼의 검량에 미치는 Triton X-100 효과에 대한 재평가)

  • Kim, Hong-Suk;Chung, Soon-Kyu;Jung, Jin
    • Applied Biological Chemistry
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    • v.36 no.5
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    • pp.364-369
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    • 1993
  • Triton X-100 enhances to a marked extent the analytical sensitivity of the nitrobluetetrazolium (NBT) reduction method for the assay of superoxide$(O^-_{\.{^.2}})$ production. In the present work, it was attempted to elucidate the physicochemical nature of this Triton X-100 effect, focusing on not only the surfactant-caused stabilization of the water-insoluble formazan colloid but also the kinetic competition between the $NBT-O^-_{\.{^.2}}$ reaction and the autodisproportionation of concommitantly occuring in aqueous media. The measurements of formazan and $H_2O_2$ formed in a number of reaction systems, as prepared by vortex-mixing potassium superoxide dissolved in an aprotic solvent with aqueous solutions of NBT, revealed that Triton X-100 exerts its effect both through preventing formazan colloid from aggregation and thereby increasing the formazan absorbance and through suppressing the autodisproportionation reaction of $O^-_{\.{^.2}}$. It also turned out that the relative shares of the colloid stabilization effect and the kinetic effect in the contribution to the sensitivity amplification of the NBT method are dependent upon the reaction conditions, particulary the molar concentration ratio of NBT to $O^-_{\.{^.2}}$ in the reaction systems.

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A Study Based on Molecular Orbital Theory of Polymerization of Oxetane High Explosives (옥세탄 고폭 화약류의 중합반응에 관한 분자 궤도론적 연구)

  • Kim, Joon-Tae
    • Applied Chemistry for Engineering
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    • v.20 no.2
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    • pp.159-164
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    • 2009
  • Monomers of oxetane high explosives were theoretically examined in terms of reactivity, reaction mechanism and process of polymerization substituted by azido $(-CH_2N_3)$, nitrato $(-CH_2ONO_2)$ and hydrazino $(-CH_2N_2H_3)$ which belong to the 5th class hazardous materials and have explosiveness under acid catalyst using MINDO/3, MNDO, and AMI methods for formal charge, heat of formation, and energy level. Nucleophilicity and base of oxetane high explosives could be explained by negative charge size of oxetane oxygen atom and reactivity of oxetane in the growth stage of polymerization under acid catalyzer could be expected to be governed by positive charge size of axial carbon atom and low LUMO energy of electrophile. It could be estimated that carbenium ion was more beneficial in the conversion process of oxetane high explosives than that of stabilization energy (13.90~31.02 kcal/mole) of oxonium ion. In addition, concentration of oxonium ion and carbenium ion in equilibrium state influenced mechanism and it was also estimated that $S_N1$ mechanism reacts faster than that of $S_N2$ in prepolymer growth stage considering quick equilibrium based on form and calculation of polymerization under acid catalyzer.

Kinetic Study of Proton Exchange between Al($H_2O$)$_6^{3+}$ Ion and Bulk Water Molecules (Ⅰ) (Al($H_2O$)$_6^{3+}$ 이온과 물 용매 분자 사이에서의 수소 이온 교환의 반응속도론적 연구 (Ⅰ))

  • Moon-Hwan Cho;Jin-Ho Kim;Chang-Ju Yoon
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.436-442
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    • 1988
  • The $^1H-nmr$ lineshapes of $H_2O$ in the solution containing $Al^{3+}$ ion have been measured as a function of temperature and $H^+$-ion concentration. Above [$H^+$] = 0.06, the lineshape were analyzed by the uncoupled two-site exchange model. From the proton exchange rate between hexaaquaaluminium ion and bulk water as a function of H-ion concentration. These kinetic data could be fitted to a following linear rate law; that is; 1/${\tau}$ = k$_1$/12 + $k_2$[$H^+$]/6. The following proton exchange parameters were obtained; $k_1^{298}$ = 38.5s$^{-1}$ ${\{Delta}H_1^{\neq}$ = $42.9kJ mole^{-1}$ ${\{Delta}S_1^{\neq}$ = -48.6J $mole^{-1}K^{-1}$ $k_2^{298}$ = $172s^{-1}mole^{-1}$ ${\{Delta}H_2^{\neq}$ = 27.8kJ $mole^{-1}$ ${\{Delta}S_2^{\neq}$ = -90.3J $mole^{-1}K^{-1}$ These activation parameters are indicating an associative interchange, Ia, mechanism for the acid-hydrolysis of hexaaquaaluminium ion and the proton exchange between the hydration spheres of $Al^{3+}$ and $H^+$.

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반응성 고주파 마그네트론 스퍼터링 방법에 의한 AlN 압전 박막 증착 및 특성에 관한 연구

  • 황지현;권명회;김형택
    • Proceedings of the Korean Vacuum Society Conference
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    • 2000.02a
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    • pp.89-89
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    • 2000
  • AlN 박막은 Al과 N원자의 부분적 이온결합 특성을 가진 공유결합을 한 육방정계의 wurtzite 경정구조의 화합물 반도체로서, III-V족 반도체 중 가장 큰 에너지 갭(6.2 eV), 결정 구조적 이방성, 화학 양론적 결합구조, 높은 탄성종과 전달속도(약 10$\times$106 m/s)와 높은 열전도도, 고온 안정성, 가시광성.적외선 영역에서의 좋은 투과성과 높은 굴절률, 상온 대기압에서의 유일하게 안정적인 특성을 가지고 있어, 절연재료, 내열재료, 저주파 영역 센서의 압전 트랜스듀서, 광전소자, 탄성파 소자 및 내환경 소자, MIS소자 등으로 주목받고 있다. 본 연구에서는 BAW 공진기의 활용을 목적으로 반응성 마그네트론 스퍼터링 방법으로 AIN 압전박막을 제작하여, 증착 조건-질소 농도, 고주파 출력, 전체 스퍼터링 압력, 기판 온도-에 대한 박막의 특성을 조사하였다. AlN 박막의 c축 우선 방위 결정성 및 낮은 투과성, 적당한 굴절률의 특성이 BAW 공진기의 활용을 위한 요건이므로, 각각의 증착 조건하에 제작된 박막은 XRD의 $\theta$/2$\theta$ 스캔 회절상에 의한 결정성의 분석과 우선 성장 결정면의 rocking curve 및 XRD로 측정한 FWHM과 표준 편차로 결정성의 배열성과 소자 응용가능성을 조사하였다. 박막의 표면.단면 미세 구조 및 평활도는 SEM으로 관찰하였으며, Al-N 결합 상태는 XPS와 FT-IR로 분석 조사하였다. 제작된 AlN 박막의 결정성 분석 결과, c축 우선 방위 성장을 위한 스퍼터링 압력에 대한 임계 질소 농도와 임계 스퍼터링 압력이 관찰되었다. 전체 스퍼터링 압력이 6~8 mTorr의 범위에서 나타난 최소 임계질소 농도는 10%, 최대 임계 질소 농도는 60%이며, 4 m Torr 이하 10 m Torr 이상의 전체 스퍼터링 압력에서 박막의 우선 방위성장이 제재된다. 이는 AlN 박막이 형성에 관여하는 질소 이온 양의 충분한 형성에 필요로 하는 질소 가스의 유입량에 따른 것으로 판단된다. AlN 박막의 c축 결정면인 (002) 결정면의 성장을 유도하며 다른 방향으로의 성장을 제어하여 소자 활용에 유용한 박막을 제작하기 위한 고주파 출력은 300W 정도가 적당하며, 기판을 가열하지 않았을 때 낮은 투과도를 나타낸다. 본 연구에 의한 BAW 공진기 활용을 위한 AlN 압전박막의 제작을 위한 최적 증착 조건은 기판의 가열 없이 6~8 mTorr의 전체 스퍼터링 압력에 20~25%의 질소종도, 300W의 고주파 출력이다. 최적 조건에서의 AlN 박막은 약 0.19$^{\circ}$의 FWHM과 약 0.08$^{\circ}$의 표준편차를 가지며, 균일하고 조밀한 표면 미세구조와 주상정 구조의 측면구조, 파장에 대한 약 2.0의 굴절률, 낮은 투과도와 화학 양론적 구조를 가지는 우수한 박막이 형성되었다.

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Study on Preparation of Methyl N-Phenyl Carbamate by Oxidative Carbonylation of Aniline and Methanol (아닐린과 메탄올의 산화 카르보닐화에 의한 Methyl N-phenyl carbamate 제조 연구)

  • Roh, Jong-Seon;Lee, Kwan-Young;Kim, Tae-Soon;Chang, Tae-Seon;Yoon, Byung-Tae;Kim, Seong-Bo
    • Korean Chemical Engineering Research
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    • v.56 no.1
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    • pp.119-124
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    • 2018
  • The production of methyl N-phenyl carbamate by an oxidative carbonylation method of aniline and methanol is of great interest as an environmentally friendly process that can replace the monomer production process of a polymer produce using conventional phosgene. In this study, heterogeneous catalysts were prepared by using Y-zeolite, $SiO_2$, $Al_2O_3$ as support, and oxidative carbonylation continuous operation from aniline and methanol was attempted using the prepared heterogeneous catalyst. Batch reactor was used to determine the support, and various reaction conditions such as reaction temperature, reaction pressure, and effect of promoter were established using palladium catalyst. A reaction kinetics study was conducted under optimum reaction conditions. The basic data for carbamate process development were obtained by performing continuous operation for a long time under established reaction condition.

Kinetic Studies of Reaction of Transion Metal Ion with Macrocyclic Ligands. Containing Nitrogen and Oxygen Donor Atoms (전이금속 이온과 Macrocyclic Ligand 사이의 반응에 관한 속도론적 연구 질소원자와 산소원자를 포함하는 거대고리 리간드를 중심으로)

  • Kim Jin-Ho;Cho Moon-Hwan;Hyeoun Dong-Ho;Park Hyu-Bum;Kim Si-Joong;Lee Ihn-Chong
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.418-423
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    • 1990
  • The protonation constants for the macrocyclic ligands 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloeicosane (NdienOdienH$_4$), 1,12,15-triaza-3,4;9,10-dibenzo-5,8-dioxa cycloheptadecane (NdienOenH$_4$), and 1,15-diaza-3,4;12,13-dibenzo-5,8,11-trioxa cycloheptadecane (NenOdienH4) have been determined by the potentiometry in aqueous solutions (25$^{\circ}C$, I = 0.1, KNO$_3$). The stability constants for complexes formed in the aqueous solution (25$^{\circ}C$, I = 0.1, KNO$_3$) between the above ligands and the metal ions (Co(Ⅱ), Ni(Ⅱ), and Cu(Ⅱ)) have been measured by potentiometry. The rate of the ligand substitution reaction was measured spectrophotometrically by the addition of aqueous solutions of ethylenediamine to the solution of the complex. From the study of the temperature effect on the rate constant (k$_{obs}$), activation parameters (E$_a$,${\{Delta}H^{\neq}$, and ${\{Delta}S^{\neq}$) have been determined. The possible mechanism for the substitution reaction is proposed.

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Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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A Study on the Solvent Extraction Kinetics of Complex Nickel(Ⅱ) 8-Hydroxyquinolinate by Spectrophotometry (분광광도법에 의한 Ni(Ⅱ)-8-Hydroxyquinolinate의 용매추출 반응속도론)

  • Heung Lark Lee;Oh In-Gyung
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.540-545
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    • 1992
  • Kinetics and mechanism on the solvent extraction of nickel(Ⅱ) with 8-hydroxyquinoline (HOx) was studied spectrophotometrically. Absorbance variation was measured by changing the 8-hydroxyquinoline concentration in the chloroform organic phase and the pH values in the aquous phase. By analyzing absorbance data the reaction rate was found to be the first order for 8-hydroxyquinoline concentration and the inverse first one for [H$^+$]. Therefore the rate determining step of the extraction reaction is the formation of the one-to-one metal chelate NiOx$^+$ and the rate equation is as follows; -d[Ni$^{2+}$]/dt = k[Ni$^{2+}$][Ox$^-$] = k'[Ni$^{2+}$][HOx]$_0$/[H$^+$]. The value of k' was evaluated from the slope of plot of log [Ni$^{2+}$]$_0$/[Ni$^{2+}$]$_t$ versus time and the rate constant k was calculated according to the equation k' = k ${\times}$ K$_{HOx}$ / K$_{D,HOx}$. From the temperature dependence of the extraction rate, the activation energy E$_a$ = 6.26 kcal/mol is calculated, and activation parameters, ${\Delta}$G$^{\neq}_{298}$ = 6.59 kcal/mol, ${\Delta}$H$^{\neq}_{298}$ = 5.68 kcal/mol, ${\Delta}$S$^{\neq}_{298}$ = -3.09 eu/mol are estimated.

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