• 제목/요약/키워드: Rate Determining Step

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Development of Kiln Schedules to Eliminate the Development of Internal Checking in Radiata Pine Boards

  • Kang, Ho-Yang;Booker, R.E.
    • 한국가구학회지
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    • 제19권2호
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    • pp.116-123
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    • 2008
  • Kiln schedule development was based on two schedule phases, the first being to determine the maximum safe kiln temperature during the check prone initial stage of drying, with the second stage determining how to accelerate drying once the danger of checking had passed. This was achieved by using 38 mm thick boards which were pre-screened for susceptibility to internal checking, and then drying matched sample boards over a range of kiln temperatures. Research has shown that below 50% MC there is no further risk of internal checking. However, difference in drying rate due to board width and the increased occurrence of wet patches in wide boards means that it is essential to modify the basic schedule according to the maximum board width. A condition of 52/40 $^{\circ}C$ was selected for the checking-free initial kiln drying step and a 5-step kiln-schedule dried the boards from 109% to 8% MC for 72.5 hours without internal checking.

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Kinetic Study on Nucleophilic Displacement Reactions of Y-Substituted-Phenyl 2-Methylbenzoates with Cyclic Secondary Amines in Acetonitrile: Effects of Modification of 2-MeO in Benzoyl Moiety by 2-Me on Reactivity and Reaction Mechanism

  • Lee, Ji-Youn;Kim, Mi-Yeon;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권12호
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    • pp.3795-3799
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    • 2013
  • The second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of Y-substituted-phenyl 2-methylbenzoates (6a-e) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. Comparison of the $k_N$ values for the reactions of 4-nitrophenyl 2-methylbenzoate (6d) with those reported previously for the corresponding reactions of 4-nitrophenyl 2-methoxybenzoate (5) reveals that 6d is significantly less reactive than 5, indicating that modification of 2-MeO in the benzoyl moiety of 5 by 2-Me (i.e., $5{\rightarrow}6d$) causes a significant decrease in reactivity. This supports our previous report that aminolysis of 5 proceeds through a six-membered cyclic intermediate, which is highly stabilized through intramolecular H-bonding interactions. The Br${\o}$nsted-type plot for the reactions of 6d with a series of cyclic secondary amines is linear with ${\beta}_{nuc}=0.71$, which appears to be a lower limit of ${\beta}_{nuc}$ for a stepwise mechanism with breakdown of an intermediate ($T^{\pm}$) being rate-determining step (RDS). The Br${\o}$nsted-type plot for the reactions of 6a-e with piperidine is curved, i.e., the slope of Br${\o}$nsted-type plot (${\beta}_{lg}$) decreases from -1.05 to -0.41 as the leaving-group basicity decreases. The nonlinear Br${\o}$nsted-type plot has been taken as evidence for a stepwise mechanism with a change in RDS (e.g., from the $k_2$ step to the $k_1$ process as the leaving-group basicity decreases). Dissection of $k_N$ into the microscopic rate constants associated with the reactions of 6a-e with piperidine (e.g., $k_1$ and $k_2/k_{-1}$ ratio) also supports the proposed mechanism.

구리(Ⅱ)-아민류착물에 의한 과산화수소의 분해반응속도와 메카니즘 (Rates and Mechanism of Decomposition of Hydrogen Peroxide by Copper(Ⅱ)-Amines Complexes)

  • 김선덕;신윤열;박정은;김창수
    • 대한화학회지
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    • 제37권2호
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    • pp.199-205
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    • 1993
  • 구리-아민류착물에 의한 과산화수소의 초기분해속도를 pH7.3~11.8 범위에서 측정하였다. 과산화수소의 분해속도는 pH에 따라 증가하였다가 감소하였다. 이들 실험결과에 일치하는 가능한 메카니즘이 제안되었다. 이 메카니즘은 과산화수소와 구리-아민류착물의 탈양성첨가를 거친 다음에 속도 결정단계에서 퍼옥소구리착물이 생성되는 반응과정과 일치한다.

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3차 아민의 4차화 반응에 관한 연구 (제 5 보). 페나실 아렌술포네이트류에 의한 피리딘의 4차화반응 (Studies on the Quaternization of Tertiary Amine (V). The Quaternization of Pyridine with Phenacyl Arenesulfonates)

  • 이오석
    • 대한화학회지
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    • 제31권3호
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    • pp.280-286
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    • 1987
  • 페나실 치환 벤젠술포네이트류와 피리딘의 반응속도를 아세토니트릴과 메탄올 용매속에서 각각 35, 45, 그리고 $55^{\circ}C$에서 전기전도도법으로 측정하였다. 이탈기 내의 치환기 효과는 치환기의 전자끌기 능력이 클수록 반응이 빨라지므로써 이탈기의 이탈 능력이 반응속도에 직접 영향을 미쳤다. 또한 양성자성 용매인 메탄올과 비양성자성 용매인 아세토니트릴에서의 반응을 비교한 결과 수소결합을 통한 특성 용매화가 작용되고 있음을 알수 있었다. 그러므로 이 반응에서 피리딘이 기질의 카르보닐기에 속도 결정 단계로 첨가되는 메카니즘을 배제시킬수 있었다

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막여과지에 대한 이트륨-90의 흡착 반응속도에 관한 연구 (Adsorption Kinetics of Carrier-Free Yttrium-90 on Membrane Filters)

  • 제원목
    • 대한화학회지
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    • 제16권1호
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    • pp.1-5
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    • 1972
  • The adsorption kinetics on a membrane filter have been studied by an introduction of acid or alkali in yttrium-90 solution. The change of the adsorption in the filtration process was determined by the filtrate activities with using a microsyringe filter holder connected with a syringe. The over all reaction rate obeyed a reversible first order reaction, and the rate constants thus obtained, showed the values of $k_1$ = 0.12 $sec^{-1}$ and $k_1'$ = 0.039 $sec^{-1}$. As a result of the present studies, it would be reasonable that the rate determining step of the adsorption reaction was the hydrolysis reaction of the adsorbed yttrium ions.

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畜舍의 換氣量 決定을 위한 새로운 換氣그래프 開發 (Development of New Conceptual Ventilation Graphs for Mechanically Ventilated Livestock Buildings)

  • 최홍임;김우중;김현태
    • 한국농공학회지
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    • 제33권3호
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    • pp.91-100
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    • 1991
  • Since ventilation in livestock buildings is critical for indoor air quality, the first step in designing environmental control is to determine required ventilation rate. The purpose of the study was to suggest a conceptually new ventilation graph for determining minimum/maximum ventilation rate based on the conservation law of the thermal energy and mass in livestock buildings. PC-based programs coded with PASCAL language, [RVALUE] for overall thermal resistance of composite structural walls/ceilings, [POLYNOM] for coefficients values of animal's sensible heat equation were involved in developing a computer program, [VENTGRPH] for the determination of ventilation rate. It would be useful for design, for such a program would permit the designer to explore various design options and immediately, see the result in terms of its effect on minimum ventilation rates.

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C3S-C3A계의 초기 수화반응 특성에 미치는 석고의 영향 (I) (Effect of Gypsum on the Characteristics of Early Hydration of the System C3S-C3A (I))

  • 신규연;한기성
    • 한국세라믹학회지
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    • 제26권4호
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    • pp.514-520
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    • 1989
  • The early hydration characteristics according to the C3S/C3A ratio and presence of gypsum, in order to establish the hydration mechanism of the system C3S-C3A, have been studied. The rate of C3S dissolution in the system C3S-Gypsum was higher than that in the system C3S. Consequently, the induction period was reduced and the rate of Ca(OH)2 formation in the accleration period was increased. The hydration of C3S in the system C3S-C3A was retarded because Al3+ in the liquid phase originating from the hydration of C3A was incorporated into calcium hydrosilicates formed. The retardation phenomenon of C3S hydration was not appeared in the system C3S-C3A-gypsum because the reaction of monosulfate formation became the rate-determining step.

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Nickel-Phthalocyanine 생성의 반응속도론적 연구 (Kinetics of the Formation of Nickel-Phthalocyanine)

  • 배국진;한치선
    • 대한화학회지
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    • 제16권2호
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    • pp.84-92
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    • 1972
  • A mechanism for the ring formation of nickel phthalocyanine (Ni-Pc) has been proposed based on chemical kinetics. The effect of the catalyst on the rate was examined, and ammonium molybdate has been found to be the most effective. The reaction order of the ring formation was determined to be of the 1st order over all, with only the concentration of urea affecting the rate of the ring formation. All the results including thermodynamic parameters support a conclusion that the rate-determining step seems to be the enolization of the urea-catalyst transition complex, followed by fast decomposition of the tautomeric enolized urea into ammonia and isocyanic acid. These intermediates then reacted with the phthalic anhydride to form imino and diimino-phthalimide, which condense to form nickel phthalocyanine in the presence of the nickel cation.

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The Oxidation of Hydrazobenzene Catalyzed by Cobalt Complexes in Nonaqueous Solvents

  • Kim, Stephen S.B.;Hommer, Roger B.;Cannon, Roderick D.
    • Bulletin of the Korean Chemical Society
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    • 제27권2호
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    • pp.255-265
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    • 2006
  • The oxidation of hydrazobenzene by molecular oxygen in the polar solvent methanol is catalysed by a Schiff's base complex Co(3MeOsalen) which is a synthetic oxygen carrier. The products are trans-azobenzene and water. The rate of the reaction has been studied spectrophotometrically and the rate law established. A mechanism involving a ternary complex of catalyst, hydrazobenzene and molecular oxygen has been proposed. The kinetic studies show that a ternary complex $CoL{\cdot}H_2AB{\cdot}O_2$ is involved in the rate determining step. The reactions are summarised in a catalytic cycle. The kinetic data suggest that a ternary complex involving Co(3MeOsalen), triphenyl-phosphine and molecular oxygen is catalytically acive species but at higher triphenylphosphine concentrations the catalyst becomes inactive. The destruction of the catalytic activity could be due to the catalyst becoming coordinated with triphenyl phosphine at both z axis sites of the complex e.g. Co (3MeOsalen)$(PPh_3)_2$.

MCFC의 예비 개질 반응 메커니즘 연구 (Study of reaction mechanism in pre-reforming for MCFC)

  • 이우형;박용기
    • 산업진흥연구
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    • 제3권2호
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    • pp.1-8
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    • 2018
  • 본 연구에서는 탄화수소 개질을 위한 예비 개질기에서 에탄의 반응 메커니즘과 이에 적합한 반응속도식에 대한 연구를 수행하였다. 반응 mechanism 분석을 통해 ethane의 개질 반응 중 (CO2+H2,C2H6+H2,C2H6+H2O)3개의 반응이 진행되는 것을 확인할 수 있었으며, 각각의 반응 속도 (CO2+H2($r=3.42{\times}10-5molgcat.-1\;s-1$), C2H6+H2($r=3.18{\times}10-5mol\;gcat.-1s-1$), C2H6+H2O($r=1.84{\times}10-5mol\;gcat.-1s-1$)) 를 구하였다. 이를 통해 C2H6+H2O반응이 rate determining step (RDS)임을 확인하고, Langmuir-Hinshelwood model (L-H model)을 통해 이 반응의 반응식을 r=kS*(KAKBPC2H6PH2O)/(1+KAPC2H6+KBPH2O)2 (KA=2.052,KB=6.384,$kS=0.189{\times}10-2$)로 나타낼 수 있었다. 이렇게 얻어진 반응식은 반응 메커니즘을 고려하지 않고 유도된 power rate law와 비교하였으며, power rate law는 좁은 농도 변화 영역 (ethane 약 2.5-4%, water 약 60-75%)에서는 비교적 유사한 fitting이 이루어졌지만, 넓은 농도 변화영역에서는 반응 mechanism을 토대로 얻은 L-H model 반응식이 실험값과 더 유사한 값을 보이는 것을 확인하였다.