• Title/Summary/Keyword: $N_2O$ 촉매 분해

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Mechanism on the Hydrolysis of Cinnamonitrile in Strong Acid (强酸性 溶液中에서 Cinnamonitrile의 加水分解 反應메카니즘)

  • Ki-Sung Kwon;Nack-Do Sung;Tae-Rin Kim;Jeon, Yong Gu
    • Journal of the Korean Chemical Society
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    • v.28 no.6
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    • pp.418-424
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    • 1984
  • Rate constants for the hydrolysis of cinnamonitrile in the concentration range of 1 ∼ 5M of perchloric acid at 25$^{\circ}$C have been determined by UV spectrophotometry and from the Bunnett equations, hydration parameters (${\omega}$ = 9.8, ${\omega}^*$ = 0.42 & ${\phi}$=1.6) were obtained. CNDO/2 MO calculations were performed to determine relative stability, net charges, and overlap population of various conformational isomers. The results show that the (E)-planar is more stable than the (Z)-planar and protonation is favored on the nitrogen atom. On the basis of above findings, the acid hydrolysis is initiated by the protonation of the nitrogen atom of cinnamonitrile and then water molecule acting as nucleophile and as a proton transfer agent in the rate determining step. In the transition state of the acid hydrolysis, nucleophilic addition of water molecule occurs by sigma approach to the positively charged $C_7({\alpha}$) atom of the conjugate acid. As the results, we may conclude that the hydrolysis of cinnamonitrile in the strong acidic media proceeds through the A-2 type mechanism.

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The Effects on Alkoxy Group and Catalyst in Hydrolysis of Silicon Alkoxide System (Silicon Alkoxide계 가수분해에서 Alkoxy Group과 촉매의 첨가에 대한 영향)

  • ;;Sumio Sakka
    • Journal of the Korean Ceramic Society
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    • v.24 no.6
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    • pp.561-571
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    • 1987
  • In case of glass ceramics and powder preparation from the metalakoxide solutions, metalakoxide solutions with a various species of alkoxy groups have unique characteristics. Therefore, in this study, the mixing ability of homogeneous sol, gel morphology and physical properties of gels were investigated by the changes in terms of the different four alkoxy groups, CH3-, C2H5-, i-C3H7-n-C4H9-, along with the catalyst for the purpose of the observation about the homogenous transition range from sol to gel. As a result, when the fixed condition was mol ratio of H2O/Si(OR)4=2.0 and variables were batch composition and addition amount of catalyst, the characteristics of Tetra-normal-Butoxysilane and Tetra-iso-propoxysilane systems had very narrow sol-gel conversion region than Tetramethoxysilane and Tetraethoxysilane system. And silicon-alkoxide, systems having narrow sol-gel conversion region were enlarged by addition of catalyst. In viewpoint of the weight loss of gel produced by hydrolysis of silicon alkoxide systems with different four alkoxy groups, the amounts of weight loss of gel containing large molecular alkoxy groups were much more than those of small molecular alkoxy group.

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Preparation of PMSQ/TiO2 Composite Fine Powder by Sol-Gel Process (Sol-Gel Process를 이용한 PMSQ/TiO2 복합 미립자의 합성)

  • Lee, Dong Hyun;Koo, Sangman
    • Applied Chemistry for Engineering
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    • v.9 no.5
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    • pp.634-638
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    • 1998
  • Monodisperse, spherical $PMSQ/TiO_2$ composite fine powders were prepared by modified sol-gel process where 300 nm $TiO_2$ fine powders were used as seed particles for hetero-condensation with hydrolyzed MTMS (Methyltrimethoxysilane). The reaction was carried out under $N_2$ atmosphere at ambient temperature using $NH_3$ as a catalyst. Methanol was used as a solvent. Powder was obtained by the filtration of the solution with a glass filter and washing with acetone. The stirring rate, reaction temperature, $[H_2O]/[MTMS]$ and $[MTMS]/[TiO_2]$ ratio were varied to investigate shapes and sizes of particles. Monodisperse particles of $1-2{\mu}m$ diameter were obtained with [MTMS]=0.2 M, $[NH_3]=0.6M$, $[H_2O]/[MTMS]=100$, $[MTMS]/[TiO_2]=10-50$ at ambient temperature with mild stirring condition. These composite particles had a contact angle of almost 180 degree contact angle with water, which proves their excellent hydrophobicity. The study of UV absorption spectra showed that they have UV protecting effect.

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Study on Hydrogen Production and CO Oxidation Reaction using Plasma Reforming System with PEMFC (고분자 전해질 연료전지용 플라즈마 개질 시스템에서 수소 생산 및 CO 산화반응에 관한 연구)

  • Hong, Suck Joo;Lim, Mun Sup;Chun, Young Nam
    • Korean Chemical Engineering Research
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    • v.45 no.6
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    • pp.656-662
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    • 2007
  • Fuel reformer using plasma and shift reactor for CO oxidation were designed and manufactured as $H_2$ supply device to operate a polymer electrolyte membrane fuel cell (PEMFC). $H_2$ selectivity was increased by non-thermal plasma reformer using GlidArc discharge with Ni catalyst simultaneously. Shift reactor was consisted of steam generator, low temperature shifter, high temperature shifter and preferential oxidation reactor. Parametric screening studies of fuel reformer were conducted, in which there were the variations of the catalyst temperature, gas component ratio, total gas ratio and input power. and parametric screening studies of shift reactor were conducted, in which there were the variations of the air flow rate, stema flow rate and temperature. When the $O_2/C$ ratio was 0.64, total gas flow rate was 14.2 l/min, catalytic reactor temperature was $672^{\circ}C$ and input power 1.1 kJ/L, the production of $H_2$ was maximized 41.1%. And $CH_4$ conversion rate, $H_2$ yield and reformer energy density were 88.7%, 54% and 35.2% respectively. When the $O_2/C$ ratio was 0.3 in the PrOx reactor, steam flow ratio was 2.8 in the HTS, and temperature were 475, 314, 260, $235^{\circ}C$ in the HTS, LTS, PrOx, the conversion of CO was optimized conditions of shift reactor using simulated reformate gas. Preheat time of the reactor using plasma was 30 min, component of reformed gas from shift reactor were $H_2$ 38%, CO<10 ppm, $N_2$ 36%, $CO_2$ 21% and $CH_4$ 4%.

A Study on the Hydrolysis of Sarin and Soman by Merrifield-Type Diaminatedpolystyrene-Cu (II) Heterogeneous Polymers (Merrifield-Type Diaminatedpolystyrene-Cu (II) 불균일 촉매에 의한 Sarin과 Soman 분해반응 연구)

  • 정우영;계영식
    • Journal of the Korea Institute of Military Science and Technology
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    • v.3 no.1
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    • pp.164-175
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    • 2000
  • Three compounds of Cu(II)-loaded N,N,N'-trimethylethylenediaminated Merrifield-type polymers were synthesized with yields higher than 80%, and the hydrolysis reaction rates of O-isopropylmethyl-phosphonofluoridate(GB) and O-pinacolylmethylphosphonofluoridate (GD) catalyzed by them have been surveyed. GB and GD hydrolysis by Cu(II)-loaded polymers occurs via intermediate complex mechanism where rapid equilibrium to form intermediate complex between substrate and Cu(II)-loaded polymers($K_f$) is followed by rate determining hydrolysis step($k_1$). The measured activation parameters for $k_1$ are ${\Delta}H^{\ddag}$ : $17.75{\pm}0.98kJ/mol$ ${\Delta}S^{\ddag}$ / : $-218.42{\pm}3.35J/mol$ K, $E^{\circ}_a$ : $20.22{\pm}0.98kJ/mo1$ for GB and ${\Delta}H^{\ddag}$ / : $11.16{\pm}1.15kJ/mol,$${\Delta}S^{\ddag}$ /: $-258.57{\pm}3.93J/mol$ K, $E^{\circ}_a$ : $13.64{\pm}1.15 kJ/mol$ for GD. Standard enthalpy/entropy changes corresponding to the intermediate complex formation constant $K_f$ are ${\Delta}H^{\circ}$ : $37.05{\pm}2.19 kJ/mo1,$$ {\Delta}S^{\circ}$ : $163.12{\pm}7.49 J/mol$ K and ${\Delta}H^{\circ}$ : 418.59{\pm}2.04 kJ/mol,$ ${\Delta}S^{\circ}$ : 4111.92{\pm}6.98 J/mol$ K for GB and GD, respectively, The electron push-pull mechanism by Cu(II)-loaded polymers lowers the P-F bond breaking energy(~400 kJ/mol) to less than 1/20 compared to the case in which no Cu(II)-loaded resin presents. Analysis of $K_f$ and 4k_1$ over pH=6.5~8.0 range suggest that the GB and GD hydrolysis occurs intramolecularily with $pK_a$ =7.29 for ligated $H_2O$ and $t_{1/2}$=36.9 sec, $pK_a$ = 7.06 and $t_{1/2}$=177.7 sec for GB and GD, respectively.

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Changes in Sink capacity and Source Activity of Rice Cultivars in Response to Shift of Heading date (벼 품종들의 출수기에 따른 동화산물 생산능력 및 수용기관 크기 변화)

  • Lee, Sok-Young;Kwon, Yong-Woong
    • KOREAN JOURNAL OF CROP SCIENCE
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    • v.40 no.2
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    • pp.260-267
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    • 1995
  • In temperate zone planting rice at different date subjects the Crop to different climatic condition. The present study aimed at comparison of the change in source-sink relationship of the Japonica(J) and that of IndicaxJaponica(I$\times$J) type rice cultivars caused by shift of heading date. Two J- and two I$\times$J-type cultivars were made to head on August 16, August 26, and September 5. Sink capacity was changed by shift of heading date in different mode between the types of cultivars. In both types major determinant of sink capacity was number of effective tillers, and the number of spikelets per panicle was the minor. In J-type earlier planting/heading was beneficial to increased panicle numbers and this was due mainly to a larger diurnal difference in temperature. I$\times$J-type cultivars favored a higher daily mean temperature to increase the sink capacity. The ability of source at heading, in terms of leaf area per panicle, chlorophyll content per spiklet, photosynthetic ability of leaves per unit area at 25$\^{\circ}C$, carbohydrate and N contents of leaves, was not so different among different heading dates in both types. However, the source activity was governed principally by temperature during grain filling. The J-type cultivars headed on Sept. 5 and I$\times$J-type cultivars headed later than August 16 could not have had sufficient source activity in grain filling due to lower temperature.

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Effects of Water Quality Improvement by Porosity of Fill Materials in Mattress/Filter System (Mattress/Filter 채움재의 공극률에 따른 하천수질 개선효과)

  • Ko, Jin Seok;Lee, Sung Yun;Heo, Chang Hwan;Jee, Hong Kee
    • KSCE Journal of Civil and Environmental Engineering Research
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    • v.26 no.1B
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    • pp.51-60
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    • 2006
  • Water quality improvement in mattress/filter system using porous material like slag from industrial activity and zeolite that has been studied for environment improvement and pollution abatement is very useful in polluted stagnant stream channel. Slag is consisted of CaO, $SiO_2$, $Al_2O_3$ and $Fe_2O_3$. Slag with large specific surface area of porosity has been used such as sludge settling and adsorptive materials. Because slag is porous, it can be used for purification filter. As slag is used as filled materials of mattress/filter system and the system has good advantages for the waste water treatment, water recycling, and the improvement of water quality at the same time and so on. Because zeolite has much advantage of cation exchange, adsorption, catalyst and dehydration characteristics, It is used for environment improvement of livestock farms, treatment of artificial sewage and waste water, improvement of drinking water quality, radioactive waste disposal and radioactive material pollution control. In this study, according to verifying effects of water quality improvement of fill materials by porosity that 38.6%, 45.8% and 49.8% respectively in the stagnant stream channel, water quality monitoring of inflow and outflow was conducted on pH, DO, BOD, COD, SS, T-N and T-P. Mattress/filter system was able to accelerate water quality improvement by biofilter as waste water flows through gap of mattress/filter fill materials and by contact catalysis, absorption, catabolism by biofilm. Mattress/filter system used slag and zeolite forms biofilm easily and accelerates adsorption of organic matter. As a result, mattress/filter system increases water self-purification and accelerates water quality improvement available for stream water clean-up.

Rapid Detection Methods for Biogenic Amines in Foods (식품 내 바이오제닉아민 신속검출기술 개발 동향)

  • Lee, Jae-Ick;Kim, Young-Wan
    • Korean Journal of Food Science and Technology
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    • v.44 no.2
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    • pp.141-147
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    • 2012
  • Biogenic amines have been used as chemical indicators to estimate bacterial spoilage of foods, particularly fish and fish products, cheese, and fermented foods. So far many chromatography methods have been developed to detect biogenic amines in foods. Although these instrumental analyses exhibit good sensitivity, they cannot be used as rapid detection methods due to the chemical treatment of the samples and the time-consuming process involved. For the rapid and simple detection of biogenic amines, enzyme linked immunosorbent assay kits are commercially available. In addition, analytical systems with enzyme-based amperometric biosensor detection have been increasingly developed. The biosensors used to detect the biogenic amines are based on the action of either amine oxidases or amine dehydrogenases that catalyzes the oxidative deamination of biogenic amines to the corresponding aldehydes and ammonia. This review mainly focused on the principle, development, and applications of the detection methods for rapid detection of biogenic amines in foods.