• Title/Summary/Keyword: Initial pressure of mixture

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Pressure Effects on the Aquation of $cis-[Co(en)(NH_3)_2Cl_2]Cl$ in Acetone-Water Mixtures (아세톤-물 혼합용매에서 $cis-[Co(en)(NH_3)_2Cl_2]Cl$의 수화반응에 미치는 압력의 영향)

  • Jong-Jae Chung;Byung-Hwan Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.472-477
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    • 1985
  • The rates for the aquation of $cis-[Co(en)(NH_3)_2Cl_2]Cl in acetone-water mixtures have been measured at various pressures and temperatures by the electric conductivity method. The rate constant measured at 25$^{\circ}$C in pure water solvent is 3.47 ${\times}10^{-4}$/sec. Rate constants are increased with increasing temperature, and decreased with increasing pressure and mole fraction of acetone. Activation volumes and other activation parameters are calculated from these rate constants. The activation volumes are all positive and lie in the limited range +2.82~+$8.2cm^3$/mole. The rate constants in aqueous acetone solution are analyzed with the solvent compositions. Plots of log $k_{obs}$ vs. Grunwald-Winstein Y values show that log $k_{obs}$ varies linearly and the gradients are about 0.25. The applications of a free energy cycle relating the process initial state ${\to}$ transition state in water to that in acetone-water mixture show that the changes in solvation of the transition state have a dominant effect on the rate. From these results the aquation of this complex would be discussed in terms of dissociative mechanism ($I_d$).

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Kinetic Investigation of CO2-CH4 Reaction over Ni/La2O3 Catalyst using Photoacoustic Spectroscopy

  • Oh, Hyun-Jin;Kang, Jin-Gyu;Heo, Eil;Lee, Sung-Han;Choi, Joong-Gill
    • Bulletin of the Korean Chemical Society
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    • v.35 no.9
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    • pp.2615-2620
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    • 2014
  • Ni/$La_2O_3$ with a high dispersion was prepared by reduction of $La_2O_3$ perovskite oxide to examine the catalytic activity for the $CO_2-CH_4$ reaction. The Ni/$La_2O_3$ catalyst was found to be highly active for the reaction. The ratios of $H_2$/CO were measured in a flow of the reaction mixture containing $CO_2/CH_4$/Ar using an on-line gas chromatography system operated at 1 atm and found to be varied with temperature between 0.66 and 1 in the temperature range of $500-800^{\circ}C$. A kinetic study of the catalytic reaction was performed in a static reactor at 40 Torr total pressure of $CO_2/CH_4/N_2$ by using a photoacoustic spectroscopy technique. The $CO_2$ photoacoustic signal varying with the concentration of $CO_2$ during the catalytic reaction was recorded as a function of time. Rates of $CO_2$ disappearance in the temperature range of $550-700^{\circ}C$ were obtained from the changes in the $CO_2$ photoacoustic signal at early reaction stage. The plot of ln rate vs. 1/T showed linear lines below and above $610^{\circ}C$. Apparent activation energies were determined to be 10.4 kcal/mol in the temperature range of $550-610^{\circ}C$ and 14.6 kcal/mol in the temperature range of $610-700^{\circ}C$. From the initial rates measured at $640^{\circ}C$ under various partial pressures of $CO_2$ and $CH_4$, the reaction orders were determined to be 0.43 with respect to $CO_2$ and 0.33 with respect to $CH_4$. The kinetic results were compared with those reported previously and used to infer a reaction mechanism for the Ni/$La_2O_3$-catalyzed $CO_2-CH_4$ reaction.

Determination of Aldehydes in Tap Water by Reverse Phase Liquid Chromatography (역상 액체 크로마토그래피에 의한 수도수 중 알데하이드류의 정량)

  • Choi, Yong Wook;Choi, Yun Jung
    • Journal of the Korean Chemical Society
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    • v.43 no.4
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    • pp.438-446
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    • 1999
  • The optimum analytical method of aldehydes, ozone by-products, was established by reverse phase liquid chromatography. Six aldehydes including formaldehyde, acetaldehyde, acrolein, propionaldehyde, butylaldehyde and benzaldehyde, and one ketone including acetone were selected as aldehyde test samples through preliminary experiments. Such analytical conditions as the pH of citrate buffer solution, reaction temperature, reaction time, and concentration of DNPH, the component and composition of desorption solvent were optimized. As the result, pH 3.0 of citrate buffer solution, 40$^{\circ}C$ of reaction temperature, 15 minutes of reaction time, and 0.012% of DNPH concentration were chosen as optimum conditions. Aldehydes-DNPH derivatives in water were concentrated on $C_18$ Sep-Pak cartridge and followed by elution of their derivatives fraction with THF/ACN(70/30) mixture, and showed recoveries of the range from 87 to 107%. Separation condition on Nova-Pak $C_18$ column with low pressure gradient elution from ACN/MeOH/water(30/10/60) of an initial condition to 80% ACN of a final condition was found to give a good resolution within 20 minutes of run time. 86% to 103% of recovery for aldehydes using this method was similar to that for aldehyde using EPA Method 554 which is ranged from 84% to 103%.

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Separation and Recovery of $SF_6$ Gas from $N_2/SF_6$ Gas Mixtures by using a Polymer Hollow Fiber Membranes (고분자 중공사 분리막을 이용한 $N_2/SF_6$ 혼합가스로부터 $SF_6$의 분리 및 회수)

  • Lee, Hyun-Jung;Lee, Min-Woo;Lee, Hyun-Kyung;Lee, Sang-Hyup
    • Journal of Korean Society of Environmental Engineers
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    • v.33 no.1
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    • pp.47-53
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    • 2011
  • $SF_6$ (Sulfur hexafluoride) possesses high GWP (Global Warming Potential) as sepcified by the IPCC (Intergonvernmental Panel of Climate Change). Recently, the recovery-separtion of $SF_6$ research area, including permeation properties studies using various membrane's materials and the practical operation of recovery-separtion using membrane of waste $SF_6$ gas is in the initial state. The separation efficiency of a single $SF_6$ and waste $SF_6$ mixture was evaluated using a PSF (polysulfone), PC (tetra-bromo polycarbonate) and PI (polyimide) hollow fiber membranes. According to the results of single gases permeation properties, PI membrane has the highest permselectivity of $N_2$ gas in $N_2/SF_6$ gas. Under the condition of P=0.5 MPa, the highest concentration of recovered $SF_6$ is 95.6 vol % in the separation experiment of $SF_6/N_2$ mixture gas by PC membrane. Under the operation pressure of P=0.3 MPa at a fixed retentate flow rate fixed of 150 cc/min, the maximum recovery efficiency of $SF_6$ is up to 97.8% by PSF membrane. From the results above, it is thought that the separation and recovery technique of $SF_6$ gas using membrane will be used as the representative eco-technology in the $SF_6$ gas treatment in the future.

Study on Nucleation and Evolution Process of Ge Nano-islands on Si(001) Using Atomic Force Microscopy (AFM을 이용한 Si (001) 표면에 Ge 나노점의 형성과 성장과정에 관한 연구)

  • Park, J.S.;Lee, S.H.;Choia, M.S.;Song, D.S.;Leec, S.S.;Kwak, D.W.;Kim, D.H.;Yang, W.C.
    • Journal of the Korean Vacuum Society
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    • v.17 no.3
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    • pp.226-233
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    • 2008
  • The nucleation and evolution process of Ge nano-islands on Si(001) surfaces grown by chemical vapor deposition have been explored using atomic force microscopy (AFM). The Ge nano-islands are grown by exposing the substrates to a mixture of gasses GeH4 and H2 at pressure of 0.1-0.5Torr and temperatures of $600-650^{\circ}C$. The effect of growth conditions such as temperature, Ge thickness, annealing time on the shape, size, number density, and surface distribution was investigated. For Ge deposition greater than ${\sim}5$ monolayer (ML) with a growth rate of ${\sim}0.1ML/sec$ at $600^{\circ}C$, we observed island nucleation on the surface indicating the transition from strained layer to island structure. Further deposition of Ge led to shape transition from initial pyramid and hut to dome and superdome structure. The lateral average size of the islands increased from ${\sim}20nm$ to ${\sim}310nm$ while the number density decreased from $4{\times}10^{18}$ to $5{\times}10^8cm^{-2}$ during the shape transition process. In contrast, for the samples grown at a relatively higher temperature of $650^{\circ}C$ the morphology of the islands showed that the dome shape is dominant over the pyramid shape. The further deposition of Ge led to transition from the dome to the superdome shape. The evolution of shape, size, and surface distribution is related to energy minimization of the islands and surface diffusion of Ge adatoms. In particular, we found that the initially nucleated islands did not grow through long-range interaction between whole islands on the surface but via local interaction between the neighbor islands by investigation of the inter-islands distance.