• 제목/요약/키워드: kinetic equation

검색결과 527건 처리시간 0.022초

니켈로 코팅된 영가금속을 이용한 염소계 페놀화합물의 반응경로 및 반응율 평가 (Reductive Degradation Kinetics and Pathways of Chlorophenolic Organic Pollutants by Nickel-Coated Zero Valent Iron)

  • 신승철;김영훈;고석오
    • 대한환경공학회지
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    • 제28권5호
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    • pp.487-493
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    • 2006
  • 본 연구에서는 지하수에 존재하는 다양한 클로로페놀류 화합물을 제거하기 위하여 니켈로 코팅된 영가철을 이용하여 적용 타당성을 검토하였다. 다섯가지 종류의 클로로페놀 화합물을 대상으로 처리효과를 평가하였으며 중간 생성물을 분석하였다. 실험결과를 이용하여 개질된 영가철에 의한 반응경로 및 반응율을 평가하기 위하여 수치해석적 방법을 적용하였다. 개질된 영가철에 의한 오염물의 제거는 반응계수를 기준으로 2-CP>4-CP>2,4-DCP>2,4,6-TCP>2,6-DCP의 순서를 나타내었다. 수치해석 결과 각 클로로페놀 화합물의 탈염소화 반응은 연속적 단계와 평행적 단계를 거쳐 최종 생성물인 페놀화합물에 도달되는 결과를 보여주었다.

Applications of Third Order Models in Solvolytic Reaction of Aliphatic Substituted Acyl Derivatives in 2,2,2-Trifluoroethanol-Ethanol Systems

  • Ryu, Zoon-Ha;Lim, Gui-Taek;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • 제24권9호
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    • pp.1293-1302
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    • 2003
  • Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide의 가수분해 반응메카니즘에 관한 반응속도론적 연구 (Kinetic Studies on the Mechanism of Hydrolysis of 4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide)

  • 김태린;정동인;변상용
    • 대한화학회지
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    • 제40권12호
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    • pp.733-740
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    • 1996
  • 4'-[N-(9-Acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) 의 가수분해속도상수를 25.deg.C의 수용액속에서 자외선 분광법으로 측정하여 넓은 pH에서 잘 맞는 반응속도식을 구하였다. pH에 따르는 속도상수의 변화, Bronsted plot, 가수분해 생성물을 확인, 일반염기 및 치환기 효과 등으로부터 실험 사실에 잘 맞는 반응메카니즘을 제안하였다. 즉 pH 3.00 이하에서는 acridinyl기의 질소에 양성자가 첨가된 다음 quinonoid의 4'-위치에 물의 첨가가 일어나 가수분해가 진행되며, pH 3.00-9.00 사이에서는 물분자와 수산화 음이온의 첨가가 경쟁적으로 일어나 반응이 진행되었고, pH 9.00이상에서는 수산화 음이온의 농도에만 비례함을 알았다.

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${\beta},\;{\beta}$-Diethoxycarbonylstyrene 유도체에 대한 3-Mercaptopropionic Acid의 친핵성첨가반응에 관한 반응속도론적 연구 (Kinetic Studies on the Nucleophilic Addition of 3-Mercaptopropionic Acid to ${\beta},\;{\beta}$-Diethoxycarbonylstyrene Derivatives)

  • 김태린;최윤정;정명숙
    • 대한화학회지
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    • 제33권1호
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    • pp.127-134
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    • 1989
  • ${\beta},\;{\beta}$-diethoxycarbonylstryene 유도체(H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$), 3,4,5-methylenedioxy)에 대한 3-mercaptopropionic acid의 친핵성 첨가반응 속도상수를 자외선 분광법으로 측정하여 넓은 pH 범위에서 적용될수 있는 속도식을 구하였다. pH에 따르는 속도상수의 변화, 일반염기촉매작용등을 바탕으로 이 첨가반응 메카니즘을 제안하였다. 즉 pH 6.0 이하에서는 중성인 3-mercaptopropionic acid 분자의 첨가로 이 반응이 시작되며 pH 6.0∼8.0영역에서는 이 중성분자와 황화음이온의 첨가가 경쟁적으로 일어나며, pH 8.0이상에서는 황화음이온에 의해서만 첨가반응이 진행된다.

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DMF 수용매에서 벤질알코올에 의한 바나듐(V)의 환원반응속도와 메카니즘 (Rates and Mechanism of the Reduction of Vanadium(V) by Benzyl Alcohol in Aqueous Dimethylformamide)

  • 김창수;이우식
    • 대한화학회지
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    • 제32권3호
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    • pp.179-185
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    • 1988
  • 과염소산이 존재하는 디메틸포름아미드 수용액에서 벤질알코올과 VO_2\;^+$를 반응시키면 $VO^{2+}$와 벤즈알데히드를 생성한다. 이때 생성물인 $VO^{2+}$와 벤즈알데히드는 적외선 분광광도법과 기체크로마토그래피법으로 확인하였다. 벤질알코올에 의한 VO_2\;^+$의 환원반응에 대한 속도론적 연구는 분광광도법으로 행하였다. 이 반응에 대한 실험속도식은 다음과 같이 나타낼 수 있으며 속도결정단계는 $VO^{2+}$$C_6H_5CHOH$의 생성과정이다. $-d[VO_2\;^+]/dt=2\{\\{k_O+k_H[HClO_4]\}\[VO_2\;^+][C_6H_5CH_2OH]$이 반응의 활성화파라미터는 ${\Delta}H^{\neq}=13.32{\pm}1.73\;kcalmol^{-1}$ 이고 ${\Delta}S^{\neq}$$-31.02{\pm}0.09\;calmol^{-1}K^{-1}$이다.

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고해상도 X-ray CT 를 이용한 토양표면 피막의 공극율 및 포화수리전도도 측정 (Saturated Hydraulic Conductivity of Surface Seals Estimated from Computed Tomography-Measured Porosity)

  • 이상수;;;;;옥용식
    • 한국환경농학회:학술대회논문집
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    • 한국환경농학회 2011년도 30주년 정기총회 및 국제심포지엄
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    • pp.207-222
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    • 2011
  • Relationships between soil saturated hydraulic conductivity ($K_s$) and porosity (${\phi}$) have been developed over many years; however, use of these relationships for evaluating rain-induced seals is limited mainly because of difficulties in estimating seal pore-size characteristics. The objectives of this study were to evaluate the $K_s$ of soil surface seals over a range of thicknesses, where seal thickness was determined using a High-Resolution-Computed-Tomography (HRCT) scanner, and to investigate relationships between $K_s$ and ${\phi}$ of developing seals in samples with equivalent diameters (e.d.) ${\geq}15\;{\mu}m$. A Mexico silt loam soil was packed to a bulk density (${\rho}_b$) of $1.1\;Mg\;m^{-3}$ in cylinders 160-mm i.d. by 160-mm long and subjected to $61-mm\;h^{-1}$ simulated rainfall having a kinetic energy (KE) of $25\;J\;m^{-2}\;min^{-1}$ for 7.5, 15, 30, and 60 min to create a range in seal development. Thicknesses of the seal layers were determined by analysis of HRCT images of seals. The $K_s$ values of the seals were estimated using an effective $K_s$ value ($K_{s-eff}$). The $K_s-{\phi}$ relationship was described by a Kozeny and Carmen equation, $K_s=B{\phi}^n$; where B and n are empirical constants and n = 31. This approach explained 86% of the variation between $K_s$ and ${\phi}$ within the soil seals. Knowledge of surface seal information and hydraulic conductivity can provide useful information to use in management of sites prone to sealing formation.

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쌀 보리 및 겉 보리 취반에 대한 역학적 연구 (Kinetic Studies on Cooking of Naked and Covered Barley)

  • 김혜란;김성곤;최홍식
    • 한국식품과학회지
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    • 제12권2호
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    • pp.122-125
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    • 1980
  • 표준 도정한 쌀 보리(품종 세도하다까) 및 겉 보리 (수원 18호)의 취반에 대한 기작을 연구하였다. 취반 (취반 온도 $90^{\circ}{\sim}120^{\circ}C$) 후 입자의 경도는 texturometer로 측정하였다. 쌀 보리나 겉 보리는 비슷한 취반양상을 보이며 고온($110^{\circ}C$이상)에서는 갈변 현상과 동시에 입자 자체는 붕괴하면서도 연화도는 계속 증가하였다. 취반 속도는 1차 반응의 식으로 표시될 수 있었으며 취반의 활성화 에너지는 $100^{\circ}C$ 이하에서는 약 16,000cal/mole, $100^{\circ}C$ 이상에서는 약 9,500 cal/mole이었다. 보리의 취반 과정은 다음의 두 기작으로 설명할 수 있었다. 즉 취반 온도 $100^{\circ}C$ 이하에서는 보리의 성분 및 물에 의한 화학 반응이, 취반 온도 $100^{\circ}C$이하에서는 보리의 성분 및 물에 의한 화학 반응이, 취반 온도 $100^{\circ}C$ 이상에서는 취반된 부분으로부터 취반되지 않은 부분 (즉 반응이 진행되고 있는 부분)으로의 물의 확산 속도가 취반 속도를 제한하였다.

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

  • 이기창;윤철훈;류정욱;이석우;정덕채
    • 한국응용과학기술학회지
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    • 제8권2호
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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.

Cu-Zr-Al-Be 비정질합금의 결정화거동 및 속도론 (Crystallization Behavior and Kinetics of Cu-Zr-Al-Be Bulk Metallic Glass)

  • 김유찬;에릭플러리;석현광;차필령;이진규;이재철
    • 대한금속재료학회지
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    • 제46권6호
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    • pp.338-344
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    • 2008
  • The crystallization kinetics of the $Cu_{43}Zr_{43}Al_7Be_7$ bulk metallic glass were studied by differential scanning calorimetry(DSC) in the continuous heating and isothermal annealing modes. Only one major peak could be detected on the DSC traces of $Cu_{43}Zr_{43}Al_7Be_7$ bulk amorphous alloy, and the activation energy for crystallization corresponding to the peak determined by the Kissinger method was resulted of 239 kJ/mol. The isothermal kinetic, analyzed by the Johnson-Mehl-Avrami equation yielded values for the Avrami exponents in the range 1.69 to 2.37, which implied a crystallization governed by a three-dimensioned growth. Primary phases were essentially the cubic structure CuZr together with the $Cu_{10}Zr_7$ phase. At higher temperature, the CuZr disappeared while the $Cu_{10}Zr_7$ became predominant. After long term annealing at 731 K, the phases were $Cu_{10}Zr_7$, $Cu_2ZrAl$ and $Al_3Zr_5$.

Geometrically nonlinear thermo-mechanical analysis of graphene-reinforced moving polymer nanoplates

  • Esmaeilzadeh, Mostafa;Golmakani, Mohammad Esmaeil;Kadkhodayan, Mehran;Amoozgar, Mohammadreza;Bodaghi, Mahdi
    • Advances in nano research
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    • 제10권2호
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    • pp.151-163
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    • 2021
  • The main target of this study is to investigate nonlinear transient responses of moving polymer nano-size plates fortified by means of Graphene Platelets (GPLs) and resting on a Winkler-Pasternak foundation under a transverse pressure force and a temperature variation. Two graphene spreading forms dispersed through the plate thickness are studied, and the Halpin-Tsai micro-mechanics model is used to obtain the effective Young's modulus. Furthermore, the rule of mixture is employed to calculate the effective mass density and Poisson's ratio. In accordance with the first order shear deformation and von Karman theory for nonlinear systems, the kinematic equations are derived, and then nonlocal strain gradient scheme is used to reflect the effects of nonlocal and strain gradient parameters on small-size objects. Afterwards, a combined approach, kinetic dynamic relaxation method accompanied by Newmark technique, is hired for solving the time-varying equation sets, and Fortran program is developed to generate the numerical results. The accuracy of the current model is verified by comparative studies with available results in the literature. Finally, a parametric study is carried out to explore the effects of GPL's weight fractions and dispersion patterns, edge conditions, softening and hardening factors, the temperature change, the velocity of moving nanoplate and elastic foundation stiffness on the dynamic response of the structure. The result illustrates that the effects of nonlocality and strain gradient parameters are more remarkable in the higher magnitudes of the nanoplate speed.