• Title/Summary/Keyword: Hydrolysis Reaction

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Kinetics and Reaction Mechanism for Alkaline Hydrolysis of Y-Substituted-Phenyl Diphenylphosphinates

  • Hong, Hyo-Jeong;Lee, Jieun;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.34 no.7
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    • pp.2001-2005
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    • 2013
  • The second-order rate constants ($k_{OH^-}$) for the reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $OH^-$ in $H_2O$ at $25.0{\pm}0.1^{\circ}C$ have been measured spectrophotometrically. Comparison of $k_{OH^-}$ with $k_{EtO^-}$ (the second-order rate constants for the corresponding reactions with $EtO^-$ in ethanol) has revealed that $EtO^-$ is less reactive than $OH^-$ although the former is ca. 3.4 $pK_a$ units more basic than the latter, indicating that the reactivity of these nucleophiles is not governed by their basicity alone. The Br${\o}$nsted-type plot for the reactions of 4a-4i with $OH^-$ is linear with ${\beta}_{lg}$ = -0.36. The Hammett plot correlated with ${\sigma}^-$ constants results in a slightly better correlation than that correlated with ${\sigma}^{\circ}$ constants but exhibits many scattered points. In contrast, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ${\rho}$ = 0.95 and r = 0.55. The r value of 0.55 implies that a negative charge develops partially on the O atom of the leaving group. Thus, the reactions of 4a-4i with $OH^-$ have been concluded to proceed through a concerted mechanism.

Fabrication of R-plane Sapphire wafer for Nonpolar a-plane GaN (비극성 a-GaN용 R-면 사파이어 기판의 제조)

  • Kang, Jin-Ki;Kim, Jung-Hwan;Kim, Young-Jin
    • Journal of the Microelectronics and Packaging Society
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    • v.18 no.3
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    • pp.25-32
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    • 2011
  • We have studied on the slicing and polishing processes of R-plane sapphire wafers for the substrates of UHB nonpolar a-plane GaN LED. The fabrication conditions of the R-plane and c-plane wafers were influenced by the large anisotropic properties (mechanical properties) of the sapphire. The slicing process was more affected by the anisotropic properties of R-plane than the polishing process. When the slicing direction was $45^{\circ}$ to the a-flat, the slicing time was shorter and the quality of as-slicing wafers was better than the slicing direction of normal to the a-flat. The MRR(Material removal rate) of mechanical polishing processes such as lapping and DMP(Diamond mechanical polishing) did not show significant differences between the R-plane and c-plane. The MRR of the c-plane was about two times higher than that of R-planes at the CMP(Chemical mechanical polishing) process due to the formation of hydrolysis reaction layers on the surface of the c-plane.

Control of Reactive Dividing Wall Column for the Recovery of Lactic Acid (젖산회수를 위한 분리벽형 반응증류탑의 제어)

  • Choi, Yu-Mi;Woo, Dae-Sik;Cho, Hoon;Han, Myung-Wan
    • Korean Chemical Engineering Research
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    • v.49 no.3
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    • pp.306-313
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    • 2011
  • Lactic acid is widely used in the food, chemical and pharmaceutical industries, and there is an increasing demand for lactic acid as the raw material of polylactic acid, which is a biodegradable polymer. The presence of high boilers and non volatility of lactic acid makes the separation of lactic acid very difficult job. Esterification of lactic acid with methanol followed by hydrolysis of the separated methyl lactate was employed for the recovery of lactic acid. Reactive dividing wall column was proposed for the simultaneous reaction and separation. The intensified process poses a challenging control problem. Dynamic characteristics of the proposed process were examined and control systems were proposed to get a stable control performance for a disturbance in feed. Control performances of the proposed control systems were compared.

Physico-Chemical Pretreatment of Herbaceous Biomass by Organosolv Flow-Through Process (초본계 바이오매스의 물리-화학적 유기용매 전처리 공정)

  • Kim, Jun Seok
    • Korean Chemical Engineering Research
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    • v.56 no.4
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    • pp.441-446
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    • 2018
  • Herbaceous biomass is easier at chemical conversion than woody biomass. However, pretreatment must be needed because it has substantially lignin. Organsolv is good at fractionation of enzymatic hydrolysis inhibitors such as lignin and it is reusable by distillation when it has low molecular weight. Flow-through process can prevent recondensation of fractionated components and easily separate liquid from the biomass. In this study, the pretreatment was performed for decreasing additional process by using ethanol without catalyst because this process has a lot of operation expense at bio-alcohol production process. Flow-through pretreatment was performed at $150{\sim}190^{\circ}C$ with 30~99.5 wt% ethanol during 20~60 minutes. Also the phsyco-chemical pretreatment was performed for decreasing reaction time and temperature.

Synthesis and Mechanical, Dyeable Properties of Polyurethane with the Chain Extender Containing Tertiary Amine (3차 아민계 쇄연장제를 이용한 폴리우레탄 수지의 합성과 기계적, 염색 특성)

  • Noh, Si-Tae;Kim, Pyung-Jun;Jung, Chang-Nam
    • Applied Chemistry for Engineering
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    • v.7 no.2
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    • pp.341-349
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    • 1996
  • To improve the dyeability of polyurethane (PU) resin, low molecular weight diols containing dye site in the molecular structure was added as a chain-extender. PU resin were synthesized with the variations in the chain extender, polyol type, and hard segment/soft segment (HS/SS) ratio. When HS/SS ratio is 1.4 and dimethylolpropionic acid(DMPA) or N-butyldiethanolamine (BDEA) was used as a chain extender, because of heterogeneity of reaction mechanical properties were diminished. But when N-methyldiethanolamine (MDEA) was used as a DCE, and HS/SS ratio lowed to 1.3, mechanical properties and dyeability improved. In particular, when linear type 1,4-BD was formulated with MDEA, hydrolysis resistance and mechanical properties of PTMG type PU was improved. And initial elasticity, tensile strength and elongation could be controlled by the variation of HS/SS ratio, DCE mixing ratio of 1,6-HD or NPG.

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Property and Catalytic Activity of Heteropoly Acid Supported on MCM-41, 48 Mesoporous Material and SiO2 (MCM-41, 48 메조포러스 물질 및 SiO2에 담지한 헤테로폴리산의 특성 및 촉매적 활성)

  • Park, Jung-Woo;Kim, Beom-Sik;Lee, Jung-Min;Lee, Kwan-Young
    • Applied Chemistry for Engineering
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    • v.10 no.7
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    • pp.1020-1027
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    • 1999
  • Heteropoly acid(HPW) catalysts supported on three different carriers, an amorphous silica, MCM-41 and MCM-48, with different loadings and calcination temperatures have been prepared and characterized by X-ray diffraction, nitrogen physorption, infrared spectroscopy, and $^{31}P$ magic angle spinning NMR. From the result of IR and NMR, it was shown that HPW retains the Keggin structure on the supported catalysts. No HPW crystal phase was developed even at HPW loadings as high as 35 wt % on the MCM-41 and 65 wt % MCM-48. Thus, HPW appeared to form finely dispersed species. In the hydrolysis reaction of di, bis, tri-pentaerythritol, HPW/MCM-41, 48 exhibited higher catalytic activity than $HPW/SiO_2$ or HPW.

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Properties of Pepsin Inhibitor Produced by Actinomycetes sp. GF 155-2 (Actinomyces sp. GF155-2가 생산하는 Pepsin 저해물질의 성질)

  • 박석규;성낙계;노종수;김양우;조영숙
    • Microbiology and Biotechnology Letters
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    • v.18 no.5
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    • pp.496-500
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    • 1990
  • When pepsin was used at a concentration of 8 mglml for hydrolysis of 0.02% casein, inhibitory activity of this inhibitor was proportional to a inhibitor concentration of 20 ${\mu}g$/ml, and fifty percent inhibition ($IC_{50}$) was observed to be 15 ${\mu}g$/ml. The inhibitor was pH-stable at pH range of 5-9 at $100^{\circ}C$ for 10 minutes and thermo-stable at pH 7.0 at $100^{\circ}C$ to give 100% activity for 20 minutes. The formation of pepsin-inhibitor complex was confirmed by sephadex 6-25 gel filtration and type of inhibition was determined as non-competitive inhibition by Lineweaver-Burk plot. The inhibitor strongly inhibited acid proteases such as pepsin and renin, and it was soluble in methanol very well. On TLC analysis of silicagel 60 using various sohent systems, the inhibitor gave a single spot at Rf range 0.4-0.6. From the result of IR spectrum and color reaction (Rydon-Smith, Biuret), this inhibitor was considered as peptide substance. Melting point and elemental contents were 220-$230^{\circ}C$, and C 50.61%-H 8.02%-N 9.34% (found), respectively.

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Clarification of Fruit Juice by the Use of Polygalacturonase and Gelatin (Polygalacturonase와 젤라틴을 병용한 과실쥬스의 청징화)

  • Hur, Byung-Suk;Kim, Ze-Uook
    • Applied Biological Chemistry
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    • v.32 no.4
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    • pp.367-373
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    • 1989
  • The effect of gelatin concentration, pH of fruit juice and other factors for the enzymatic clarification of fruit juice by the use of polygalacturonase was studied. The proper addition of gelatin was much effected on clarification by polygalacturonase and optimum concentrations of gelatin for the enzymatic clarification of Zugaru juice, Magnolia Gold juice, Golden Delicious juice, Jonagold juice, Jonathan juice, Campbell Early juice were 0.04, 0.01% 0.02%, 0.06% 0.01%, and 0.04%, respectively. Optimum pH for the clarification by the use of polygalacturonase and gelatin was $3.2{\sim}3.5$ contrary to optimum pH 4.8 of polygalacturonase for the hydrolysis of pectic acid. At the reaction temperature of $45^{\circ}C$ and polygalacturonase concentration of 0.01mg/ml, fruit juices were completely clarified by optimum addition of gelatin for 60min.

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Characteristics of Polyimide-silica Hybrid Materials Prepared from Alkoxide Precursor Using Sol-gel Process (졸-겔법을 이용하여 알콕사이드 전구체로부터 합성된 Polyimide-silica 혼성체의 특성)

  • Kim, Byoung-Woo;Lee, Sung-Hwan;Kim, Sung-Wan;Park, Jae-Hyun;Kim, Jun-Ho;Park, Seong-Soo;Park, Hee-Chan
    • Journal of the Korean Ceramic Society
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    • v.39 no.11
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    • pp.1063-1068
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    • 2002
  • Polyimide/silica(PI/silica) hybrid materials having physical or chemical bonds between the PI and silica network were prepared using sol-gel process through hydrolysis and polycondensation of tetraethoxysilane with the polyamic Acid(PAA) or end-capped PAA solution. PAA solution was synthesized by ring opening reaction of pyromellitic dianhydride and oxydianiline monomers in dimethyl acetamide solution. End-capped PAA solution was synthesized by the addition of 3-aminopropyltriethoxysilane in PAA solution. PI/silica hybrid samples were characterized by infrared spectroscopy, differential thermogravimetry, X-ray diffractometry, scanning electron microscopy, and tensile tester. It has been demonstrated that the properties of hybrid samples were affected by the silica content and the bond type between PI and silica.

Photoaddition Reactions of Silyl Ketene Acetals with Aromatic Carbonyl Compounds: A New Procedure for β-Hydroxyester Synthesis

  • Yoon, Ung-Chan;Kim, Moon-Jung;Moon, Jae-Joon;Oh, Sun-Wha;Kim, Hyun-Jin;Mariano, Patrick S.
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1218-1242
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    • 2002
  • Photochemical reactions of aromatic carbonyl compounds with silyl ketene acetals have been explored. Irradiation of acetonitrile or benzene solutions containing aryl aldehydes or ketones in the presence of silyl ketene acetals is observed to promo te formation of ${\beta}-hydroxyester$, 2,2-dioxyoxetane and 3,3-dioxyoxetane products. The ratios of these photoproducts, which arise by competitive single electron transfer (SET) and classical Paterno-Buchi mechanistic pathways, is found to be dependent on the degree of methyl-substitution on the vinyl moieties of the ketene acetals in a manner which reflects expected alkyl substituent effects on the oxidation potentials of these electron rich donors. An analysis of the product distribution arising by irradiation of a solution containing butyrophenone (6) and the silyl ketene acetal 9, derived from methyl isobutyrate, provides an estimate of the rate constants for the competitive Norrish type Ⅱ, SET and Paterno-Buchi processes occuring. Finally, sequences involving silyl ketene acetal-aryl aldehyde or ketone photoaddition followed by 2,2-dioxyoxetane hydrolysis represent useful procedures for Claisen-condensation type, ${\beta}-hydroxyester$ synthesis.