• Title/Summary/Keyword: Chemical reaction kinetics

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Phase Distribution and Interface Chemistry by Solid State SiC/Ni Reaction

  • Lim, Chang-Sung;Shim, Kwang-Bo;Shin, Dong-Woo;Auh, Keun-Ho
    • The Korean Journal of Ceramics
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    • v.2 no.1
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    • pp.19-24
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    • 1996
  • The phase distribution and interface chemistry by the solid-state reaction between SiC and nickel were studied at temperatures between $550 \;and\; 1250^{\circ}C$ for 0.5-100 h. The reaction with the formation of silicides and carbon was first observed above $650^{\circ}C$. At $750^{\circ}C$, as the reaction proceeded, the initially, formed $Ni_3Si_2$ layer was converted to $Ni_2$Si. The thin nickel film reacted completely with SiC after annealing at $950^{\circ}C$ for 2 h. The thermodynamically stable $Ni_2$Si is the only obsrved silicide in the reaction zone up to $1050^{\circ}C$. The formation of $Ni_2$Si layers with carbon precipitates alternated periodically with the carbon free layers. At temperatures between $950^{\circ}C$ and $1050^{\circ}C$, the typical layer sequences in the reaction zone is determined by quantitative microanalysis to be $SiC/Ni_2$$Si+C/Ni_2$$Si/Ni_2$$Si+C/…Ni_2$Si/Ni(Si)/Ni. The mechanism of the periodic band structure formation with the carbon precipitation behaviour was discussed in terms of reaction kinetics and thermodynamic considerations. The reaction kinetics is proposed to estimate the effective reaction constant from the parabolic growth of the reaction zone.

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Photoinduced Intramolecular Substitution Reaction of Aryl Halide with Carbonyl Oxygen of Anide Group

  • Park, Yeong-Tae;Song, Myong-Geun;Kim, Moon-Sub;Kwon, Jeong-Hee
    • Bulletin of the Korean Chemical Society
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    • v.23 no.9
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    • pp.1208-1254
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    • 2002
  • Photoreaction of N-(o-halophenyl)acetamide in basic acetonitrile produces an intramolecular substituted product, 2-methylbenzoxazole in addition to reduced product, acetanilide, whereas photoreaction of N-(o-halobenzyl) acetamide affords a reduced product, N-benzylacetamide only. On the basis of preparative reaction, kinetics, and UV/vis absorption behavior, an electrophilic aromatic substitution of aryl halide with oxygen of its amide bond are proposed.

Reactions in Surfactant Solutions(V): Dephosphorylation of p-Nitrophenyldiphenylphosphinate by Benzimidazole Catalyzed with Ethyltri-n-octylammonium Bromide

  • 홍영석;이정근;김현묵
    • Bulletin of the Korean Chemical Society
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    • v.18 no.12
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    • pp.1260-1264
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    • 1997
  • The phase-transfer reagent (PTC), ethyl tri-n-octylammonium bromide (ETABr), strongly catalyzes the reaction of p-nitrophenyldiphenylphosphinate (p-NPDPIN) with benzimidazole (BI) and its anion (BI-). In ETABr solutions, the dephosphorylation reactions exhibit higer than first order kinetics with respect to the nucleophile, BI, and ETABr, suggesting that reactions are occuring in small aggregates of the three species including the substrate, whereas the reaction of p-NPDPIN with OH- is not catalyzed by ETABr. This behavior for the drastic rate-enhancement of the dephosphorylation is refered as 'aggregation complex model' for reactions of hydrophobic organic phosphinates with benzimidazole in hydrophobic quarternary ammonium salt solutions.

Study on Desorption Reaction of VOC Produced from Manufacturing of Chemical Products (화학제품 제조업에서 발생한 VOC의 탈착반응 연구)

  • Park, Kuny-Ik;Yoon, Sung-Min;Kim, Joo-Yeon;Kil, In-Sub;Park, Hi-Jae;Rhee, Young-Woo
    • Applied Chemistry for Engineering
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    • v.21 no.5
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    • pp.505-508
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    • 2010
  • The characteristics of desorption reaction for spent activated carbon produced from the manufacture of other chemical products in Shiwha/Banwal industrial complex were investigated. TGA (Thermogravimetric Analyzer) was used to study for characteristics of desorption and kinetics. Then Friedman method and Freeman-carroll method were used to find the activation energy and the order of reaction. Activation energy by Friedman method was 24.82~46.49 kJ/moL. And then activation energy and order of reaction by Freeman-carroll method were 8.77~32.26 kJ/moL and 0.11~1.69.

The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea for Benzoyl Styrene Derivatives (Benzoyl styrene유도체에 대한 Thiourea의 친핵성 첨가반응 메카니즘과 그 반응속도론적 연구)

  • Lee, Ki-Chang;Yoon, Chul-Hun;Hwang, Sung-Kwy;Ryu, Jung-Uk
    • Journal of the Korean Applied Science and Technology
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    • v.12 no.2
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    • pp.107-113
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    • 1995
  • Benzoyl styrene derivatives were synthesized by Claisen-Schmidt condensation. It was measured that nucleophilic addition of thiourea for benzoyl styrene made use of ultraviolet spectrophotometery at a wide pH $1.0{\sim}13.0$ range in 5% $dioxane-H_2O$ at $40^{\circ}C$. On the basis of general base catalysis, substitutent effect, and confirmation of addtion reaction product, the nucleophilic addtion kinetics of thiourea for benzoylstyrene derivatives were measured by pH change. It maybe concluded that a part was unrelated to pH and another part was in proportion to concentration of hydroxide ion : Above pH 10.0. It was in propotion to concentration of hydroxide ion, a part having no concern with pH was added to the neutral thiourea molecule. From the results of measurement the reaction rate and there findings, nucleophilic addition of thiourea to benzoylstyrene derivative was proposed a fitting mechanism.

Cinnamic Acid Derivatives VI, The Kinetics and Mechanism of the Nucleophilic Addition of Thiourea to Cinnamenylisophorone Derivatives (신남산 유도체 VI. Cinnamenylisophorone 유도체에 대한 Thiourea의 친핵성 첨가반응메카니즘과 그 반응속도론적 연구)

  • Jung, Duck-Chae;Lee, Ki-Chang;Hwang, Young-Hyun;Ryu, Jung-Wook;Yun, Cheol-Hun
    • Journal of the Korean Applied Science and Technology
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    • v.10 no.2
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    • pp.65-72
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    • 1993
  • The kinetics of the addition of thiourea to cinnamenylisophorone derivatives(X : H, p-Br, $p-CH_3$ $m-CH_3$, $p-OCH_3$) was investigated using ultraviolet spectrophotometry in 20%(v/v) dioxane-$H_2O$ 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 of cinnamenylisophorone derivatives. Hammett constant was plotted. As the result, the rate of uncleophilic addition of thiourea to cinnamenylisophorone derivatives was facilitated by electron donating group. It was found that addition of neutral thiourea which was not dissociated at the pH $1.0{\sim}9.0$ was proceeded, the reaction was proceeded by addition of dissociated anion of thiourea above the pH 10.0. On the basis of this kinetic study, the reaction mechanism of nucleophilic addition of thiourea was investigated.

Kinetics of nitrification and acrylamide biodegradation by Enterobacter aerogenes and mixed culture bacteria in sequencing batch reactor wastewater treatment systems

  • Madmanang, Romsan;Jangkorn, Siriprapha;Charoenpanich, Jittima;Sriwiriyarat, Tongchai
    • Environmental Engineering Research
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    • v.24 no.2
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    • pp.309-317
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    • 2019
  • This study evaluated the kinetics of acrylamide (AM) biodegradation by mixed culture bacteria and Enterobacter aerogenes (E. aerogenes) in sequencing batch reactor (SBR) systems with AQUASIM and linear regression. The zero-order, first-order, and Monod kinetic models were used to evaluate the kinetic parameters of both autotrophic and heterotrophic nitrifications and both AM and chemical oxygen demand (COD) removals at different AM concentrations of 100, 200, 300, and 400 mg AM/L. The results revealed that both autotrophic and heterotrophic nitrifications and both AM and COD removals followed the Monod kinetics. High AM loadings resulted in the transformation of Monod kinetics to the first-order reaction for AM and COD removals as the results of the compositions of mixed substrates and the inhibition of the free ammonia nitrogen (FAN). The kinetic parameters indicated that E. aerogenes degraded AM and COD at higher rates than mixed culture bacteria. The FAN from the AM biodegradation increased both heterotrophic and autotrophic nitrification rates at the AM concentrations of 100-300 mg AM/L. At higher AM concentrations, the FAN accumulated in the SBR system inhibited the autotrophic nitrification of mixed culture bacteria. The accumulation of intracellular polyphosphate caused the heterotrophic nitrification of E. aerogenes to follow the first-order approximation.

The Decomposition Kinetics of PET Microfiber Fabrics by Saturated CaO/Ethylene glycol Solution (CaO/Ethylene glycol 용액에 의한 Polyester섬유의 분해에 관한 연구)

  • Yoon, Jong Ho;Huh, Man Woo;Kim, Kyung Jae
    • Textile Coloration and Finishing
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    • v.9 no.3
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    • pp.18-26
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    • 1997
  • Polyester microfiber fabrics were decomposed at 100, 110, and 12$0^{\circ}C$ in saturated CaO/ethylene glycol solutions(CaO/EG), and the characteristics of decomposition kinetics were discussed in comparison to those by hot aqueous hydroxide solution(NaOH). The Arrhenius pre-exponential factor(A) was 9.17x $10^{14}$/M $sec^{-1}$and the activation energy($E_{a}$) was 8.19kcal/mol. While the A value was 1.947x $10^{14}$/M $sec^{-1}$ and the ($E_{a}$ value was about 15~19kcal/mol in NaOH-PET decomposition reaction. The much higher A value of the CaO/EG-PET decomposition reaction means that CaO/EG-PET decomposition reaction will occur in a less selective fashion in comparison to the NaOH-PET decomposition reaction. On the other hand, the lower ($E_{a}$) value of the CaO/EG-PET decomposition reaction than that of the NaOH-PET decomposition reaction means that CaO/EG-PET decomposition reaction is less sensitive on the variation of temperature than NaOH-PET decomposition reaction.

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Temperature-dependent studies on catalytic hydrosilation of polyalkylsiloxane using NMR

  • Sul, Hyewon;Lee, Tae Hee;Lim, Eunsoo;Rho, Yecheol;Kim, Chong-Hyeak;Kim, Jeongkwon
    • Analytical Science and Technology
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    • v.30 no.4
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    • pp.213-219
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    • 2017
  • Polyalkylsiloxane has been spotlighted in pressure-sensitive adhesive (PSA) application due to excellent physical properties and good biocompatibility. Thermal behaviour of polyalkylsiloxane mixtures, such as thermal stability and heat flow, were studied using TG-DTA during catalytic hydrosilation. To understand reaction kinetics of cross-linking, catalytic hydrosilation of polyalkylsiloxane was monitored using variable temperature nuclear magnetic resonance (VT-NMR) as increased temperature. The formation of cross-linking bond $Si-CH_2-CH_2-Si$ was directly observed using distortionless enhanced by polarization transfer (DEPT) technique. Successfully polyalkylsiloxane PSA samples exhibited excellent adhesion properties by cross-linking reaction.

A Study on the Catalytic Oxidation Reaction of Carbon Monoxide with Nickel Oxide (NiO 촉매에 의한 CO 산화반응에 관한 연구)

  • Jae Shi Choi;Keu Hong Kim
    • Journal of the Korean Chemical Society
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    • v.13 no.4
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    • pp.241-247
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    • 1969
  • The catalytic reaction between carbon monoxide and oxygen was investigated with the various nickel oxide catalysts at different partial pressures of carbon monoxide and oxygen and at reaction temperatures in the region of 120$^{circ}$to 250$^{circ}C$. The reaction has the highest rate with the nickel oxide catalyst which is sintered at low temperature. A reaction mechanism to explain the data is derived. From the Arrhenius equation, the activation energies in the region of experimental temperatures are found to be from 5.49 to 9.15 kcal/mole. The concentration of excess oxygen in the nickel oxide seems to vary according to the sintering temperatures and periods and is the controlling factor in determining the type of kinetics followed by the catalytic reaction.

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