• Title/Summary/Keyword: H1-H2

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One-pot Four Component Reaction of Unsymmetrical 1-Methylbarbituric Acid with BrCN and Various Aldehydes in the Presence of Et3N and/or Pyridine

  • Jalilzadeh, Mohammad;Pesyan, Nader Noroozi
    • Journal of the Korean Chemical Society
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    • v.55 no.6
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    • pp.940-951
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    • 2011
  • Reaction of 1-methylpyrimidine-(1H,3H,5H)-2,4,6-trione (1-MBA 1) as an unsymmetrical barbituric acid with cyanogen bromide and various aldehydes in the presence of triethylamine and/or pyridine afforded diastereomeric mixtures of new class of heterocyclic stable 5-aryl-1,1'-dimethyl- and 5-aryl-3,1'-dimethyl-1H,1'H-spiro[furo[2,3-d]pyrimidine-6,5'-pyrimidine]2,2',4,4',6'(3H,3'H,5H)-pentaones which are dimeric forms of 1-methyl barbiturate at the range of $0^{\circ}C$ to room temperature. In the reaction of some aldehydes with 1-MBA and BrCN were afforded a mixture of diastereomers. Another two aldehydes such as 4-cyano- and 2-hydroxybenzaldehydes gave exclusively two diastereomers in which binded to the salt of triethylammonium hydrobromide by intermolecular H-bond in ratio of 1:1. 4-Hydroxybenzaldehyde and 2-pyridinecarbaldehyde gave exclusively one diastereomer under the same condition. Aldehydes possessing strong electron-donor were produced exclusively two geometric isomers of Knoevenagel adduct (E- and Z-isomers). The structures of compounds were deduced by $^1H$ NMR, $^{13}C$ NMR and FT-IR spectroscopy. Mechanism of the formation is discussed.

The Complexes of Aromatic Amines with Iodine or Iodine Monochloride in Carbon Tetrachloride (방향족아민과 요오드 또는 일염화요오드 사이의 錯物에 관한 연구)

  • Choi, Sang-Up;Lee, Bu-Yong
    • Journal of the Korean Chemical Society
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    • v.11 no.3
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    • pp.100-104
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    • 1967
  • The systems of aromatic amines such as aniline, N,N-dimethylaniline and N,N-diethylaniline with iodine or iodine monochloride in carbon tetrachloride have been examined spectrophotometrically. The results indicate the formation of one to one molecular complexes. The equilibrium constants obtained at room temperature for formation of the complexes are as follows: $C_6H_5NH_2{\cdot}I_2\;2.05$, $C_6H_5N(CH_3)_2{\cdot}I_2\;15.2$, $C_6H_5N(C_2H_5)_2{\cdot}I_2\;35.5$, $C_6H_5NH_2{\cdot}ICl\;18.5$, $C_6H_5N(CH_3)_2{\cdot}ICl\;25.6$, and $C_6H_5N(C_2H_5)_2\;42.0$ l $mole^{-1}$.

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Treatment Characteristics of Trichloroethylene(TCE) by Oxidation and Reduction with Nanoscale Zero-valent Iron (나노영가철의 산화·환원에 의한 트리클로로에틸렌 처리특성)

  • Park, Young-Bae;Jung, Yong-Jun;Choi, Jeong-Hak;Moon, Boung-Hyun
    • Journal of Environmental Science International
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    • v.23 no.5
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    • pp.903-910
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    • 2014
  • This study examined the treatment characteristics of hard-to-degrade pollutants such as TCE which are found in organic solvent and cleaning wastewater by nZVI that have excellent oxidation and reduction characteristics. In addition, this study tried to find out the degradation characteristics of TCE by Fenton-like process, in which $H_2O_2$ is dosed additionally. In this study, different ratios of nZVI and $H_2O_2$, such as 1.0 mM : 0.5 mM, 1.0 mM : 1.0 mM, and 1.0 mM : 2.0 mM were used. When 1.0 mM of nZVI was dosed with 1.0 mM of $H_2O_2$, the removal efficiency of TOC was the highest and the first order rate constant was also the highest. When 1mM of nZVI was dosed with 0.5 mM of $H_2O_2$, the first order rate constant and removal efficiency were the lowest. The size of first order rate constant and removal efficiency was in the order of nZVI 1.0 mM : $H_2O_2$ 1.0 mM > nZVI 1.0 mM : $H_2O_2$ 2.0 mM > nZVI 1.0 mM : $H_2O_2$ 0.5 mM > $H_2O_2$ 1.0 mM > nZVI 1.0 mM. It is estimated that when 1.0 mM of nZVI is dosed with 1.0 mM of $H_2O_2$, $Fe^{2+}$ ion generated by nZVI and $H_2O_2$ react in the stoichiometric molar ratio of 1:1, thus the first order rate constant and removal efficiency are the highest. And when 1.0 mM of nZVI is dosed with 2.0 mM of $H_2O_2$, excessive $H_2O_2$ work as a scavenger of OH radicals and excessive $H_2O_2$ reduce $Fe^{3+}$ into $Fe^{2+}$. As for the removal efficiency of TOC in TCE by simultaneous dose and sequential dose of nZVI and $H_2O_2$, sequential dose showed higher first order reaction rate and removal efficiency than simultaneous dose. It is estimated that when nZVI is dosed 30 minutes in advance, pre-treatment occurs and nanoscale $Fe^0$ is oxidized to $Fe^{2+}$ and TCE is pre-reduced and becomes easier to degrade. When $H_2O_2$ is dosed at this time, OH radicals are generated and degrade TCE actively.

Effects of Simulated Acid Rain on Soil Chemical Properties (인공산성비 처리가 토양의 화학적 성질에 미치는 영향)

  • Ryu, Kwan-Shig
    • Korean Journal of Soil Science and Fertilizer
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    • v.31 no.4
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    • pp.400-406
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    • 1998
  • To investigate the effect of simulated acid rain on the change in soil chemical properties, simulated acid rain of different pH was applied to the three soils of different texture. Simulated acid rain of pH 4.0 and 6.0 did not greatly change the soil pH, while simulated acid rain of pH 2.0 decreased greatly the soil pH. Decrease in soil pH were in the order of sandy loam > loam > clay loam, while increase in exchangeable acidity was in the order of clay loam > loam > sandy loam. Amount of nutrients leached downward due to the penetration of simulated acid rain into the soil was in the order of Ca > K > Mg. Exchangeable Al was not detected when soil acidity dropped to pH 5 and exchangeable acidity increased within a range of CEC. A total 1200mm of simulated acid rain(pH 3.0) can load $12kg\;ha^{-1}$ of $H^+$ ion, $128kg\;ha^{-1}$ of sulfur, $56kg\;ha^{-1}$ of nitrogen. The acidity of simulated acid rain pH 3.0 can be neutralized by addition of $444kg\;ha^{-1}$ of slaked lime. The amount of leached bases were equivalent to 923, 1731 and $1608kg{\cdot}ha^{-1}$ in sandy loam, loam and clay loam soil respectively.

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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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Volumetric Behaviour of Binary Liquid Mixtures at a Temperature of 303.15 K

  • Wahab, Mohammad A.;Ali, M. Azhar;Mottaleb, Mohammad A.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.7
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    • pp.953-956
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    • 2002
  • Excess molar volumes (Vm E ) of binary liquid mixtures: xC6H5CH3 + (1-x1)CH3CN or + (1-x1)C6H5NO2, or + (1-x1)C2H5NO2 have been determined as a function of mole fraction of C6H5CH3 (x) at a temperature of 303.15 K over a entire range of composition. The densities of the binary liquid mixtures were determined by pycnometrically. The VmE values of the mixtures have been found to be negative over the whole composition in order of C6H5CH3 + C6H5NO2, < C6H5CH3 + CH3CN, and < C6H5CH3 + C2H5NO2. The negative magnitude of VmE suggests the presence of intermolecular interaction in the three binary liquid mixtures.

Corrosion of Fe-2%Mn-0.5%Si Steels at 600-800℃ in N2/H2O/H2S Atmospheres

  • Kim, Min-Jung;Park, Sang-Hwan;Lee, Dong-Bok
    • Journal of the Korean institute of surface engineering
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    • v.44 no.5
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    • pp.201-206
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    • 2011
  • Fe-2%Mn-0.5%Si alloys were corroded at 600, 700 and $800^{\circ}C$ for up to 70 h in 1 atm of $N_2$ gas, or 1 atm of $N_2/H_2O$-mixed gases, or 1 atm of $N_2/H_2O/H_2S$-mixed gases. Oxidation prevailed in $N_2$ and $N_2/H_2O$ gases, whereas sulfidation dominated in $N_2/H_2O/H_2S$ gases. The oxidation/sulfidation rates increased in the order of $N_2$ gas, $N_2/H_2O$ gases, and, much more seriously, $N_2/H_2O/H_2S$ gases. The base element of Fe oxidized to $Fe_2O_3$ and $Fe_3O_4$ in $N_2$ and $N_2/H_2O$ gases, whereas it sulfidized to FeS in $N_2/H_2O/H_2S$ gases. The oxides or sulfides of Mn or Si were not detected from the XRD analyses, owing to their small amount or dissolution in FeS. Since FeS was present throughout the whole scale, the alloys were nonprotective in $N_2/H_2O/H_2S$ gases.

Temperature and Ligand Effects on the Eu(Ⅲ) Emission Spectra in the Aqueous Solution (수용액에서의 Eu(Ⅲ) 착물의 형광스펙트럼에 영향을 미치는 온도 및 리간드 효과에 관한 연구)

  • Lee, In Suk;Kim, Geon
    • Journal of the Korean Chemical Society
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    • v.34 no.6
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    • pp.548-554
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    • 1990
  • Temperature effects on the fluorescence emission spectra of 0.01 M Eu(III) ion with ClO$_4$, Cl$^-$, NO$_3$ were studied. Relative intensity change of hypersensitive band ($^5D0\; {\to}\;^7F_2$) and nonhypersensitive band ($^5D0 \;{\to}\;^7F_1$) was quite remarkable with temperature and ligand. The relative intensity change was interpreted as the change of formation constant and used to calculation the enthalpy change of $Eu(H_2O)_X^{3+}$+ to EuL(H$_2O)_{X-1}^{2+}$ complex. $\Delta{H}$ of $Eu(H_2O)_X^{3+}$ to EuCl(H$_2O)_{X-1}^{2+}$ was roughly 15 kJ/mol and temperature independent, but $\Delta{H}$ of EuNO$_3(H_2O)_{X-1}^{2+}$ was changed with temperature; -11 kJ/mol at 25$^{\circ}C$ and 47 kJ/mol at 250$^{\circ}C$.

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Two-dimensional Zinc Coordination Polymer Based Paddle-Wheel Type Secondary Building Units of $Zn_2(CO_2R)_4$: [Zn(ATP)(DMF)] $(ATP=2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2;\;DMF\;=\;N,\;N-dimethylformamide)$ (Paddle-wheel유형의 2차 쌓음 단위 $Zn_2(CO_2R)_4$에 기초한 2차원 아연 배위 고분자: [Zn(ATP)(DMF)] $(ATP=2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2;\;DMF\;=\;N,\;N-dimethylformamide)$)

  • Min Dongwon;Lee Hee K.;Lee Soon W.
    • Korean Journal of Crystallography
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    • v.15 no.2
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    • pp.78-82
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    • 2004
  • The solvothermal reaction of zinc(H) nitrate $(Zn(NO_3)_2\;{\cdot}\;6H_2O)$ with $ATP(2-aminoterephthalate,\;H_2N-C_6H_3-1,4-(COO)_2)$ in a mixture of solvents of DMF and ethanol, in the presence of benzene, gave a 2 dimensional zinc polymer [Zn(ATP) (DMF)] (1). X-ray structure determination revealed that two zinc metals and four ATP ligands form the paddle-wheel SBUs, which are linked by the ATP ligands to give a 2-D square-grid network. Each square grid has approximate dimensions of $11.1\times11.1\;{\AA}$ based on Zn metals. Benzene was required to produce high-quality crystals of polymer 1.

Analysis and Comparison of Cerebroside Components from Soybean Fermented Foods (대두발효식품 Cerebroside의 구성성분 분석 및 비교)

  • 이은열;김희숙
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.31 no.2
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    • pp.177-183
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    • 2002
  • Cerebroside fatty acids, sugars and long-chain sphingoid bases in raw soybean and soybean fermented foods (chongkukjang and deunjang) were analyzed using gas chromatography-mass spectrometry (GC-MS) and high-pH anion exchange chromatography with pulsed amerometric detection (HPAEC-PAD). Fatty acids of acid-hydrolyzed cerebrosides were derivatized to O-TMS methylester and analysed. The major fatty acids in raw soybean and chongkukjang cerebrosides were identified as 2-hydroxyhexadecanoic acid (16 : 0h), 2-hydroxydocosanoic acid (22 : 0h) and 2-hydroxytetracosanoic acid (24 : 0h). In the case of deunjang cerebroside, 24 : 0h (40.9%) and 22 : 0h (23.4%) were major fatty acids, but 16 : 0h, 23 : 0h, 25 : 0h and 26 : 0h were also detected. Long-chain sphingoid bases of acid-hydrolyzed cerebrosides from raw soybean, chongkukjang and deunjang consisted primarily of 4-tracts, 8-tracts-sphingadienine (dihydroxy base, d18 : 2$\Delta$$^{4trans, 8trans}$) and sis-tracts isomers of 4-hydroxy-sphingenine (trihydroxy base, tl8:1$\Delta$$^{4trans or cis}$) with much less amounts of phytosphingosine (tl8: 0) and isomers of sphingenine (d18 : 1). Although deunjang is a soybean food fermented by fungi and microorganisms for a long period, 2-hydroxyoctadec-3-enoic acid (18 : 1h) and branched 9-methyl-4,8-sphingadienine known as compositional cerebroside fatty acids in Aspergillus species were not detected. Mass spectrum for sugar derivatives in cerebrosides of soybean foods including raw soybean and fermented soybean showed that C-1 of glucose moiety was linked to ceramide backbone as like a monoglucosylceramide.