• Title/Summary/Keyword: 총괄반응속도

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Kinetics for Reduction of trans-[Co(en)$_2$(NO$_2$)Cl]$^+$ and [Fe(H$_2$O)$_6$]$^{2+}$ in Acidic Solution (산성용액내에서 trans-[Co(en)$_2$(NO$_2$)Cl]$^+$ 와 [Fe(H$_2$O)$_6$]$^{2+}$ 와의 산화환원반응에 대한 속도론적 연구)

  • Park Byung-Kak;Woo Tae-Ha;Lim Joo-Sang;Song Yeung-Dae
    • Journal of the Korean Chemical Society
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    • v.34 no.5
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    • pp.460-464
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    • 1990
  • Proton behavior was investgated for the redox reaction of trans-[$Co(en)_2(NO_2)Cl]^+$ with aqueous Fe(II) in acidic solution by UV/vis-spectrophotometric method. The reaction order of proton is first one and the rate constant(k$_H^+$) is 6.7 ${\times}\;10^{-1}L^2/mol^2{\cdot}min$. The values of $E_a$, ${\{Delta}H^{\neq}$, ${\{Delta}S^{\neq}$ are 14.5 Kcal/mol, 13.8 Kcal/mol and -18.3e.u., respectively. As the result of analysis of kinetic data, it has been found that this reaction proceeds through inner-sphere mechanism.

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Kinetic Study for Aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ in $Hg^{2+}$ Aqueous Solution ($Hg^{2+}$수용액에서 $cis-[Co(en)_2(NH_3)Cl]^{2+}$의 아쿠아반응에 대한 속도론적 연구)

  • Byung-Kak Park;Gil-Jun Lee;Jae-Weon Lee;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.3
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    • pp.227-232
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    • 1988
  • A kinetic study was made to determine the mechanism of the aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}\;in\;Hg^{2+}$ aqueous solution. The progress of reaction was followed UV/vis-spectrophotometrically by a measurement of the absorbance at a specific wave length (530nm) of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ as a function of time. The experimental results have shown that the reaction rate is dependent upon the concentration of $Hg^{2+}$ that act as a catalyst. And it was found that the overall reaction proceed with second order, first order with respect to Co(III) complex and $Hg^{2+}$. Activation parameters, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$, were obtained as 12.9 kcal/mol and -19.3 e.u., respectively. We have proposed a plausible reaction mechanism which is consistent with the observed rate equation.

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Characteristics of Copper-catalyzed Cyanide Decomposition by Electrolysis (전해법에 의한 구리함유 시안의 분해특성)

  • Lee Jin-Yeung;Yoon Ho-Sung;Kim Sung-Don;Kim Chul-Joo;Kim Joon-Soo;Han Choon;Oh Jong-Kee
    • Resources Recycling
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    • v.13 no.1
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    • pp.28-38
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    • 2004
  • The characteristics of cyanide decomposition in aqueous phase by electric oxidization have been explored in an effort to develop a process to recycle waste water. Considering current efficiency and voltage, the free cyanide decomposition experiment by electric oxidization indicated that 5 V of voltage and copper catalytic Cu/CN mole ratio 0.05 was the most appropriate condition, where current efficiency was 26%, and decomposition speed was 5.6 mM/min. High voltage and excess copper addition increased decomposition speed a little bit but not current efficiency. The experiment of free cyanide density change proves that high density cyanide is preferred because speed and current efficiency increase with density. Also, the overall decomposition reaction could be represented by the first order with respcect to cyanide with the rate constant of $1.6∼7.3${\times}$10^{-3}$ $min^{-1}$ The mass transfer coefficient of electric oxidization of cyanide came out as $2.42${\times}$10^{-5}$ $min^{-1}$ Furthermore, the Damkohler number was calculated as 5.7 in case of 7 V and it was found that the mass transfer stage was the rate determining step.

Removal of Cd(II) by Cation Exchange Resin in Differential Bed Reactor (미분층반응기에서 양이온 교환수지에 의한 카드뮴(II)의 제거)

  • Kim, Jong-Tae;Chung, Jaygwan G.
    • Journal of Korean Society of Environmental Engineers
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    • v.22 no.7
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    • pp.1193-1203
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    • 2000
  • In this study, in order to remove Cd(II) from aqueous solutions, strongly acidic cation exchange resin(SK1B) by Diaion Co. was employed as an adsorbent. Experiments were mainly performed in two parts at room temperature($25{\pm}5^{\circ}C$) : batch tests and adsorption kinetics tests. In batch tests adsorption equilibrium time, pH effects, temperature effects, several adsorption isotherms, and finally desorption tests were examined. In differential bed tests, an optimum flow rate and an overall adsorption rate were obtained. In the batch experiment, adsorption capability increased with pH and became constant above pH 6 and adsorption quantity increased with temperature. Batch experimental data found that Freundlich and Sips adsorption isotherms were more favorable than Langmuir adsorption isotherm over the range of concentration (5~15ppm). The desorbent used in the desorption test was hydrochloric acid solution with different concentrations(0.01~2N). The degree of regeneration increased with concentration of desorbent and decreased slightly with the number of regeneration. In the continuous flow process using a differential bed reactor, the optimum flow rate was $564m{\ell}/min$ above which the film diffusion resistance was minimized. The overall adsorption rate for the removal of Cd(II) by cation exchange resin was found as follows ; $r=1.3785C_{fc}^{1.2421}-2.0907{\times}10^{0.0746C_i}\;q_e^{0.0121C_i-0.0301}$

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Experimental Study of Char Oxidation and Kinetic Rate in O2/CO2 and O2/N2 Environments (O2/CO2조건과 O2/N2조건에서의 촤 연소특성 및 산화 반응성에 관한 실험적 연구)

  • Kim, Song-Gon;Lee, Cheon-Seong;Lee, Byoung-Hwa;Song, Ju-Hun;Chang, Young-June;Jeon, Chung-Hwan
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.34 no.12
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    • pp.1101-1109
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    • 2010
  • We investigated the combustion rate and kinetic rate of char when burning in oxygen-enriched atmospheres with either an $N_2$ or $CO_2$ bath gas in a drop tube furnace. The experiments were performed with sub-bituminous coal (Adaro) and bituminous coal (Coal valley) under atmospheric pressure conditions. Two different coals were investigated over 12 to 30 vol% oxygen and furnace temperatures of 900, 1100, and $1300^{\circ}C$. For both coals, the particle temperature and overall reaction rate are lower in the $CO_2$ bath gas. However, analysis of single-particle data shows that the surface-specific burning rate of char oxidation is similar in both gases. In addition, the kinetic rate and activation energy for each coal were similar for both gases. Generally, the particle temperature and overall reaction rate of sub-bituminous coal are higher than those of bituminous coal.

Synthesis of High Purity p-Phenylenediamine from p-Nitroaniline by Catalytic Hydrogenation (Pd/C촉매하 파라니트로아닐린 수소첨가에 의한 고순도 파라페닐렌디아민의 합성공정)

  • Cho, Chul Kun;Chung, Kwang Bo
    • Applied Chemistry for Engineering
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    • v.10 no.8
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    • pp.1210-1215
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    • 1999
  • Optimum conditions of the hydrogenation of PNA to pure PPD were determined in a three-phase slurry reactor with suspended Pd/C catalyst particles. Minimization of mass transfer resistances at the interfaces of both gas-liquid and liquid-catalyst particles and control of overall reaction rate on catalyst surface leaded to decrease the hydrogen starvation on reaction active sites and to reduce the side reactions during hydrogenation. The optimum temperature, pressure, and catalysst concentration were confirmed to be in the range of $60^{\circ}C$, 60~70 psig, and 1~2 g-cat/L, respectively. Reaction rate was zero order with respect to the concentration of PNA and 1st order with respect to the pressure of hydrogen(P). Overall rate expression of the reaction was $R_A=6.44{\times}10^6{\cdot}H{\cdot}P{\cdot}m{\cdot}$exp(-4659/T) where H is constant, m is concentration of catalyst, and T is temperature.

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The Kinetics of Transesterification between Dimethylterephthalate and 1,3-Propanediol (디메틸 테레프탈레이트와 1,3-프로판디올 사이의 에스테르교환반응에 관한 연구)

  • Na, Sang-Kuwon;Kong, Byeong-Gi;Choi, Chang-Yong;Kim, Jung-Gyu;Hong, Wan-Hae;Nah, Jae-Woon
    • Polymer(Korea)
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    • v.29 no.1
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    • pp.41-47
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    • 2005
  • The transesterification of dimethyl terephthalate (DMT) with 1,3-propanediol (PDO) was investigated in the presence of catalyst, titanium (IV) butoxide (TBO), at 175~190 $^{\circ}C$ . The degree of transesterification reaction was measured by the output of methanol which was distilled from the reactor. The amount of methanol increased as the reaction temperature, molar ratio and catalyst concentration increased. The observed overall rate of the transesterification was third order; first order with respect to DMT, PDO, and the concentration of catalyst, respectively. Using calculated rate constants, the activation energy for transesterification was 26.93 kcal/mole. The melting temperature of bis(2-hydroxytrimethyl) terephthalate (BHTMT) was 85.2$^{\circ}C$ and heat of fusion 141.3 J/g.

Reduced Chemical Kinetic Mechanism for Premixed CO/H2/Air Flames ([ CO/H2/Air ] 예혼합 화염에 대한 준총괄 화학반응 메커니즘)

  • Jang, Kyoung;Cha, Dong-Jin;Joo, Yong-Jin;Lee, Ki-Yong
    • Transactions of the Korean Society of Mechanical Engineers B
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    • v.32 no.2
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    • pp.133-140
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    • 2008
  • A reduced chemical kinetic mechanism is developed in order to predict the flame phenomena in premixed $CO/H_2/Air$ flames at atmospheric pressure, aimed at studying the coal gas combustion for the IGCC applications. The reduced mechanism is systematically derived from a full chemical kinetic mechanism involving 11 reacting species and 66 elementary reactions. This mechanism consists of four global steps, and is capable of explicitly calculating the concentration of 7 non-steady species and implicitly predicting the concentration of 3 steady state species. The fuel blend contains two fuels with distinct thermochemical properties, whose contribution to the radical pool in the flame is different. The flame speeds predicted by the reduced mechanism are in good agreement with those by the full mechanism and experimental results. In addition, the concentration profiles of species and temperature are also in good agreement with those by the full mechanism.

Solvent Extraction of Cu(II) by 2,4-Heptadione in Chloroform (2, 4-Heptadione에 의한 Cu(II)의 용매추출특성)

  • Shin, Jeong-Ho;Jeong, Kap-Seop;Lee, Sang-Hoon;Park, Sang-Wook;Park, Dae-Weon
    • Applied Chemistry for Engineering
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    • v.4 no.4
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    • pp.672-682
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    • 1993
  • 2, 4-Heptadione(abbreviated to 24HTD) was synthesized from methylpropyl ketone and ethyl acetate with sodium amide, and the equilibrium and the kinetic characteristics of copper extraction by 24HTD-chloroform were investigated. Equilibrium constants such as the dissociation constant and the distribution coefficient of 24HTD and the stability constant of the 24HTD-Cu chelate were evaluated from the spectrophotometry, and the overall equilibrium constant of the extraction was also determined. The extracted species of the 24HTD-Cu chelate was found to be $CuR_2$ and the initial rate of the extraction of coupper by 24HTD in chloroform was expressed by $R_0=k[\bar{HR}]([Cu^{2+}]/[H^+])^{0.5}$.

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Optimum Process Condition by Experimental Design Method for the Synthesis of Methylchlorosilanes(MCS) (실험계획법에 의한 메틸염화실란 합성의 최적공정조건)

  • Cho, Chul Kun;Han, Kee Do
    • Applied Chemistry for Engineering
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    • v.9 no.3
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    • pp.394-398
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    • 1998
  • An optimum synthetic condition was studied for the MCS used as a silicone monomer. The contact mixture was made from the four component catalyst system($CuCl/ZnCl_2/Sn/Cd$) and silicon particles. The contact mass was used for a series of experiments with methyl chloride, which were designed and done to explore the optimum condition for MCS synthesis by an experimental design method. The optimum temperature and MeCl flow rate, which were obtained using 50g contact mass at 60rpm and 1 atm, were in the range of $300-305^{\circ}C$ and of 70-80ccm. Also a continuous run was performed to confirm the conditions. The results showed that the average reaction rate and selectivity were 170(g-MCS/hr.kg-Si) and 0.05 respectively at 67% conversion of MeCl and 92% silicon utilization rate. Also the parameters of overall reaction rate equation and a total pressure were estimated on the basis of the results of the continuous run.

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