• Title/Summary/Keyword: 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.
    • Journal of the Korea Furniture Society
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    • v.19 no.2
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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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    • v.34 no.12
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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.

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

  • Sun-Deuk Kim;Yun-Yeol Shin;Jeong-Eun Park;Chang-Su Kim
    • Journal of the Korean Chemical Society
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    • v.37 no.2
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    • pp.199-205
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    • 1993
  • The decomposition of hydrogen peroxide by copper-amines complexes was studied in the pH range of 7.3∼11.3 by measuring the rate of the decreasing concentration of $H_2O_2$. Decomposition rate of hydrogen peroxide increased with increasing pH, and then decreased with increasing pH successively. The mechanism for this type of reaction involves the formation of peroxo complexes in the rate-determining step preceding deprotonation of hydrogen peroxide and copper-amines complexes.

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

  • Lee, Oh-Seuk
    • Journal of the Korean Chemical Society
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    • v.31 no.3
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    • pp.280-286
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    • 1987
  • The effect of substituent inleaving group on the rates of reactions of phenacyl substituted-benzenesulfonates with pyridine was determined conductometrically in acetonitrile and in methanol at 35, 45, and $55^{\circ}C$, respectively. The reaction rate became faster in proportion to electron-attracting ability of substituent, which indicates that the substituent in leaving group can directly control reaction rate. It was shown that the specific to the carbonyl carbon as the rate-determining step.

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

  • Won Mok Jae
    • Journal of the Korean Chemical Society
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    • v.16 no.1
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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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Development of New Conceptual Ventilation Graphs for Mechanically Ventilated Livestock Buildings (畜舍의 換氣量 決定을 위한 새로운 換氣그래프 開發)

  • Choi, Hong-Lim;Kim, Woo-Joong;Kim, Hyeon-Tae
    • Magazine of the Korean Society of Agricultural Engineers
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    • v.33 no.3
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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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Effect of Gypsum on the Characteristics of Early Hydration of the System C3S-C3A (I) (C3S-C3A계의 초기 수화반응 특성에 미치는 석고의 영향 (I))

  • 신규연;한기성
    • Journal of the Korean Ceramic Society
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    • v.26 no.4
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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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Kinetics of the Formation of Nickel-Phthalocyanine (Nickel-Phthalocyanine 생성의 반응속도론적 연구)

  • Bae, Kook-Jin;Hahn, Chi-Sun
    • Journal of the Korean Chemical Society
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    • v.16 no.2
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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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    • v.27 no.2
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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)$(PPh_3)_2$.

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

  • Lee, Woo-Hyung;Park, Yong-Ki
    • Industry Promotion Research
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    • v.3 no.2
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    • pp.1-8
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    • 2018
  • In this study, the reaction mechanism of ethane and the reaction rate equation suitable for hydrocarbon reforming were studied. Through the reaction mechanism analysis, it was confirmed that three reactions (CO2 + H2, C2H6 + H2, C2H6 + H2O) proceed during the reforming reaction of ethane, each reaction rate (CO2+H2($r=3.42{\times}10-5molgcat.-1\;s-1$), C2H6+H2($r=3.18{\times}10-5mol\;gcat.-1s-1$), C2H6+H2O($r=1.84{\times}10-5mol\;gcat.-1s-1$)) was determined. It was confirmed that the C2H6 + H2O reaction was a rate determining step (RDS). And the reaction equation of this reaction can be expressed as r = kS * (KAKBPC2H6PH2O) / (1 + KAPC2H6 + KBPH2O) (KA = 2.052, KB = 6.384, $kS=0.189{\times}10-2$) through the Langmuir-Hinshelwood model. The obtained equation was compared with the derived power rate law without regard to the reaction mechanism and the power rate law was relatively similar fitting in the narrow concentration change region (about 2.5-4% of ethane, about 60-75% of water) It was confirmed that the LH model reaction equation based on the reaction mechanism shows a similar value to the experimental value in the wide concentration change region.