• Title/Summary/Keyword: Hydrolysis Reaction

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Synthesis of Monodispersed Zirconia Powder by Hydrolysis of Zirconium Alkoxides (알콕사이드의 가수분해법에 의한 단분산 지르코니아 분체의 합성)

  • Rhee Jhun;Jo, Dong-Soo
    • Journal of the Korean Ceramic Society
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    • v.28 no.2
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    • pp.167-175
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    • 1991
  • In synthesizing hydrated zirconia powder by hydrolysis of Zr-alkoxides using ethanol as mutual solvent, three experimental parameters, namely, concentration of alkoxides and hydrolysis water and addition rate of hydrolysis water were varied systematically. Spherical, monodispersed, nonagglomerated and submicrometer sized powders were prepared at 0.3 M of Zr(n-OPr)4 and 0.05M of Zr(n-OBu)4 with wide ranges of hydrolysis water conditions i.e. 0.5-2.0M concentration and 1-20ml/min addition rate. During the hydrolsis, careful attention have to be paid to maintain homogeneous reaction by controlling the agitation of the reactant and the addition of the hydrolysis water. For more improved condition of monodispersity it was found that the key point is to shorten the self-nucleation time within several seconds as rapid as possible. In both alkoxides system, with higher concentration of alkoxide and hydrolysis water and with slow addition rate of hydrolysis water, hydrated zirconia powders synthesized showed tendency to fall in worse powder conditions.

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Study on the Hydrolysis Kinetics of Xylan on Different Acid Catalysts (다양한 산 촉매에서 자이란 가수분해 특성)

  • Na, Byeong-Il;Lee, Jae-Won
    • Korean Chemical Engineering Research
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    • v.52 no.2
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    • pp.226-232
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    • 2014
  • In this study, we investigated kinetic model for the acid-catalyzed xylan hydrolysis at temperature $120{\sim}150^{\circ}C$. Also, we analyzed the kinetic parameters for xylose production and furfural decomposition. The hydrolysis of xylan and the degradation of xylose were promoted by high reaction temperature and acid concentration. The optimal hydrolysis condition for the highest reaction rate constants ($k_1$) was different depending on the acid catalysts. Among sulfuric, oxalic and maleic acid, the xylan reaction rate constants ($k_1$) to xylose had the highest value of $0.0241min^{-1}$ when 100 mM sulfuric acid was used at $120^{\circ}C$. However, sulfuric acid induced more xylose degradation compared to oxalic and maleic acid hydrolysis. The activation energy for xylan degradation was the highest when sulfuric acid was used.

Burke-Schumann analysis of silica formation by hydrolysis in an external chemical vapor deposition process (외부 화학증착 공정에서의 가수분해반응으로 인한 실리카 생성에 대한 버크-슈만 해석)

  • Song, Chang-Geol;Hwang, Jeong-Ho
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.20 no.5
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    • pp.1671-1678
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    • 1996
  • In external chemical vapor deposition processes including VAD and OVD the distribution of flame-synthesized silica particles is determined by heat and mass transfer limitations to particle formation. Combustion gas flow velocities are such that the particle diffusion time scale is longer than that of gas flow convection in the zone of particle formation. The consequence of these effects is that the particles formed tend to remain along straight smooth flow stream lines. Silica particles are formed due to oxidation and hydrolysis. In the hydrolysis, the particles are formed in diffuse bands and particle formation thus requires the diffusion of SiCl$\_$4/ toward CH$\_$4//O$\_$2/ combustion zone to react with H$\_$2/O diffusing away from these same zones on the torch face. The conversion kinetics of hydrolysis is fast compared to diffusion and the rate of conversion is thus diffusion-limited. In the language of combustion, the hydrolysis occurs as a Burke-Schumann process. In selected conditions, reaction zone shape and temperature distributions predicted by the Burke-Schumann analysis are introduced and compared with experimental data available. The calculated centerline temperatures inside the reaction zone agree well with the data, but the calculated values outside the reaction zone are a little higher than the data since the analysis does not consider diffusion in the axial direction and mixing of the combustion products with ambient air. The temperatures along the radial direction agree with the data near the centerline, but gradually diverge from the data as the distance is away from the centerline. This is caused by the convection in the radial direction, which is not considered in the analysis. Spatial distribution of silica particles are affected by convection and diffusion, resulting in a Gaussian form in the radial direction.

Cinnamic Acid Derivatives V. the Kinetics and Mechanism of the Hydrolysis of Cinnamenylisophorone Derivatives (신남산 유도체 V. Cinnamenylisophorone 유도체의 가수분해 반응에 대한 메카니즘과 그 반응속도론적 연구)

  • Lee, Ki-Chang;Yun, Cheol-Hun;Ryu, Jung-Wook;Lee, Seok-Woo;Jung, Duk-Chal
    • Journal of the Korean Applied Science and Technology
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    • v.8 no.2
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    • pp.161-167
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    • 1991
  • The kinetics of hydrolysis of cinnamenylisophorone derivatives (${rho}-H,\;{rho}-Br,\;P-Cl,\;{rho}-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-$H_2O$ at 25$^{\circ}C$. A rate equation which can be applied over wide pH range (pH $1.0{\sim}13.0$) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral $H_2O$ molecule which does not dissociated at below pH 9.0, and in the range of pH $9.0{\sim}11.0$ this reaction occurs by $H_2O$ or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.

Single-stranded DNA Enhances the Rate of Product Release During Nucleotide Hydrolysis Reaction by T7 DNA Helicase

  • Kim, Dong-Eun;Jeong, Yong-Joo
    • Bulletin of the Korean Chemical Society
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    • v.27 no.10
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    • pp.1618-1622
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    • 2006
  • Bacteriophage T7 gp4A' is a ring-shaped hexameric DNA helicase that catalyzes duplex DNA unwinding using dTTP hydrolysis as an energy source. To investigate the effect of single-stranded DNA (ssDNA) on the kinetic pathway of dTTP hydrolysis by the T7 DNA helicase complexed with ssDNA, we have first determined optimal concentration of long circular M13 single-stranded DNA and pre-incubation time in the absence of $Mg^{2+}$ which is necessary for the helicase-ssDNA complex formation. Steady state dTTP hydrolysis in the absence of $Mg^{2+}$ by the helicase-ssDNA complex provided $k_{cat}$ of $8.5\;{\times}\;10^{-3}\;sec^{-1}$. Pre-steady state kinetics of the dTTP hydrolysis by the pre-assembled hexameric helicase was monitored by using the rapid chemical quench-flow technique both in the presence and absence of M13 ssDNA. Pre-steady state dTTP hydrolysis showed distinct burst kinetics in both cases, indicating that product release step is slower than dTTP hydrolysis step. Pre-steady state burst rates were similar both in the presence and absence of ssDNA, while steady state dTTP hydrolysis rate in the presence of ssDNA was much faster than in the absence of ssDNA. These results suggest that single-stranded DNA stimulates dTTP hydrolysis reaction by T7 helicase by enhancing the rate of product release step.

Temperature-Dependent Hydrolysis Reactions of U(VI) Studied by TRLFS

  • Lee, J.Y.;Yun, J.I.
    • Journal of Nuclear Fuel Cycle and Waste Technology
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    • v.1 no.1
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    • pp.65-73
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    • 2013
  • Temperature-dependent hydrolysis behaviors of aqueous U(VI) species were investigated with time-resolved laser fluorescence spectroscopy (TRLFS) in the temperature range from 15 to $75^{\circ}C$. The formation of four different U(VI) hydrolysis species was measured at pHs from 1 to 7. The predominant presence of $UO{_2}^{2+}$, $(UO_2)_2(OH){_2}^{2+}$, $(UO_2)_3(OH){_5}^+$, and $(UO_2)_3(OH){_7}^-$ species were identified based on the spectroscopic properties such as fluorescence wavelengths and fluorescence lifetimes. With an increasing temperature, a remarkable decrement in the fluorescence lifetime for all U(VI) hydrolysis species was observed, representing the dynamic quenching behavior. Furthermore, the increase in the fluorescence intensity of the further hydrolyzed U(VI) species was clearly observed at an elevated temperature, showing stronger hydrolysis reactions with increasing temperatures. The formation constants of the U(VI) hydrolysis species were calculated to be $log\;K{^0}_{2,2}=-4.0{\pm}0.6$ for $(UO_2)_2(OH){_2}^{2+}$, $log\;K{^0}_{3,5}=-15.0{\pm}0.3$ for $(UO_2)_3(OH){_5}^+$, and $log\;K{^0}_{3,7}=-27.7{\pm}0.7$ for $(UO_2)_3(OH){_7}^-$ at $25^{\circ}C$ and I = 0 M. The specific ion interaction theory (SIT) was applied for the extrapolation of the formation constants to infinitely diluted solution. The results of temperature-dependent hydrolysis behavior in terms of the U(VI) fluorescence were compared and validated with those obtained using computational methods (DQUANT and constant enthalpy equation). Both results matched well with each other. The reaction enthalpies and entropies that are vital for the computational methods were determined by a combination of the van't Hoff equation and the Gibbs free energy equation. The temperature-dependent hydrolysis reaction of the U(VI) species indicates the transition of a major U(VI) species by means of geothermal gradient and decay heat from the radioactive isotopes, representing the necessity of deeper consideration in the safety assessment of geologic repository.

Supercritical Water Hydrolysis of Waste Logs after Oak Mushroom Production (초임계수를 이용한 표고버섯 골목의 가수분해)

  • Koo, Bon-Wook;Lee, Jae-Won;Choi, Joon-Weon;Choi, Don-Ha;Choi, In-Gyu
    • Journal of the Korean Wood Science and Technology
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    • v.34 no.6
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    • pp.81-95
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    • 2006
  • In order to investigate the possibility of waste logs after oak mushroom production as a source of an alternative energy and to obtain the fundamental data of supercritical water hydrolysis that has been paid attention as a new saccharification method of lignocellulosics, supercritical water hydrolysis of normal log woods (Quercus acutissima Carruth) and waste logs was carried out. With the increase of reaction time and temperature, the color of the degradation products has been dark and the degradation rate and the crystalline index increased. However the increase of reaction pressure affected the color of the degradation products and the degradation rate at only low reaction temperature. In the early stage of the reaction, the degradation of hemicellulose was progressed, while in the late stage, the cellulose was degraded. The increase of reaction time and reaction temperature (less than $415^{\circ}C$) improved the sugar yield, while at high temperature(more than $415^{\circ}C$), the sugar yield was decreased. Based on the result of the sugar yield, the optimal hydrolysis condition of Q. acutissima Carruth by supercritical water was determined to be $415^{\circ}C$, 60 seconds and 230 pressure bar with the sugar yield of 2.68% (w/w). At the optimal condition, the supercritical water hydrolysis of waste logs after the mushroom production was carried out and the sugar yield was increased to 358% (w/w). The major degradation products of waste logs by supercritical water hydrolysis were 1,1'-oxybis-benzene and 1,2-benzendicarboxylic acid by the GC-MS analysis. At the reaction condition with low degradation rate, the fatty acids such as pentadecanoic acid, 14-methyl-heptadecanoic acid were identified. With the increase of the reaction temperature and time, the amounts of phenol and benzene were increased, but the reaction pressure did not affect the kinds of degradation products. Holocellulose content was 60.6~79.2% in the water insoluble residue and the monosaccharide yield of the water insoluble residue was 49.2~675% by the acid hydrolysis. The monosaccharide yield of water-soluble portion was increased largely by the second hydrolysis using dilute acid.

A Study on Heat Transfer Characteristics according to Thermal Hydrolysis Reaction of Poultry Slaughter Waste (도계폐기물의 열가수분해 반응에 따른 열전달 특성 연구)

  • Song, Hyoung Woon;Jung, Hee Suk;Kim, Choong Gon
    • Journal of the Korea Organic Resources Recycling Association
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    • v.23 no.4
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    • pp.95-103
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    • 2015
  • The purpose of this study was performed to quantitatively measure the thermal conductivity of poultry slaughter waste with variation of reaction temperature for optimal design of thermal hydrolysis reactor. We continuously quantified the thermal conductivity of dehydrated sludge related to the reaction temperature. As the reaction temperature increased, the dehydrated sludge is thermally liquefied under high temperature and pressure by the thermal hydrolysis reaction. Therefore, the bond water in the sludge cells comes out as free water, which changes the dehydrated sludge from a solid phase to slurry of a liquid phase. As a result, the thermal conductivity of the its sludge was more than 2.11 times lower than that of the water at $20^{\circ}C$. However, the thermal conductivity of the sludge approached to $0.677W/m{\cdot}^{\circ}C$ of water at $200^{\circ}C$, experimentally substantiating liquefaction of the dehydrated sludge. Therefore, we confirmed that the change in physical properties due to thermal hydrolysis appears to be an important factor for heat transfer efficiency. And the thermal conductivity function related to reaction temperature was derived to give the boundary condition for the optimal design of the thermal hydrolysis reactor. The consistency of the calculated function was 99.69%.

Generation of Hydrogen from Hydrolysis Reaction of NaBH4 Using Sea Water (바닷물을 이용한 NaBH4 가수분해에 의한 수소발생)

  • Lee, Daewoong;Oh, Sohyeong;Kim, Junseong;Kim, Dongho;Park, Kwon-Pil
    • Korean Chemical Engineering Research
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    • v.57 no.6
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    • pp.758-762
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    • 2019
  • Sodium borohydride,$NaBH_4$, has many advantages as hydrogen source for portable proton exchange membrane fuel cells (PEMFC). When PEMFC is used for marine use, $NaBH_4$ hydrolysis using seawater is economical. Therefore, in this study, hydrogen was generated by using seawater instead of distilled water in the process of hydrolysis of $NaBH_4$. Properties of $NaBH_4$ hydrolysis reaction using activated carbon supported Co-B/C catalyst were studied. The yield of hydrogen decreased as $NaBH_4$ concentration and NaOH concentration were increased during $NaBH_4$ hydrolysis using sea water. At higher concentrations of $NaBH_4$ and NaOH, byproducts adhered to the surface of the catalyst after hydrolysis reaction using sea water, reduced hydrogen yield compared to distilled water. The activation energy of $NaBH_4$ hydrolysis is 59.3, 74.4 kJ/mol for distilled water and sea water, respectively. In order to increase the hydrogen generation rate in seawater as high as distilled water, the reaction temperature has to be increased by $80^{\circ}C$ or more.

Optical Resolution of Racemic Ibuprofen by Candida Rugosa Lipase Catalyzed esterification (Candida Rugosa Lipase에 의한 Ibuprofen 에스테르화 반응과 광학분할)

  • 홍중기;김광제;소원욱;문상진;이용택
    • KSBB Journal
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    • v.17 no.6
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    • pp.543-548
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    • 2002
  • The enantioselective esterification of racemic ibuprofen catalyzed by a Candida rugosa lipase was studied according to reaction conditions such as a lipase concentration, reaction temperature, alcohol chain length and alcohol concentration. The S-(+)-ibuprofen alkyl esters prepared were converted to S-(+)-ibuprofen by hydrolysis with sulfuric acid as a catalyst. High conversions in the esterifications were obtained at 60$^{\circ}C$ and an equimolar ratio of octanol to ibuprofen. The initial reaction rate of the esterification decreased with increasing octanol concentration. Conversion and initial reaction rate increased with increasing alcohol chain length. Values of enantiomeric excess(ee) according to esterification reaction conditions did not change below 60$^{\circ}C$. On the other hand, values of conversion and ee for the chemical hydrolysis of S-(+)-ibuprofen alkyl esters were independent of alcohol alkyl chain length. Optical resolution of racemic ibuprofen was achieved by lipase catalyzed esterification and chemical hydrolysis. The separation method provided a high yield and enantioselectivity for the production of S-(+)-ibuprofen from racemic ibuprofen.