• Title/Summary/Keyword: chemical kinetics

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Feasibility of Mineral Carbonation Technology as a $CD_{2}$ Storage Measure Considering Domestic Industrial Environment (국내 산업 여건을 고려한 $CD_{2}$ 저장 방안으로서 광물 탄산화 기술의 타당성)

  • Han, Kun-Woo;Rhee, Chang-Houn;Chun, Hee-Dong
    • Korean Chemical Engineering Research
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    • v.49 no.2
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    • pp.137-150
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    • 2011
  • $CO_{2}$ mineral carbonation technology, fixation technology of $CO_{2}$ as carbonates, is considered to be an alternative to the $CO_{2}$ geological storage technology, which can perform small- or medium-scale $CO_{2}$ storage. We provide the current R&D status of the mineral carbonation with special emphasis on the technical and economical feasibility of $CO_{2}$ mineral carbonation taken into consideration of the domestic geological and industrial environment. Given that the domestic industry produces relatively large amount of the industrial by-products, it is expected that the technology play a pivotal role on the $CO_{2}$ reduction countermeasure, reaching the potential storage capacity to 12Mt-$CO_{2}$/yr. The economics of the overall process should be improved via the development of advanced technologies on the pretreatment of raw materials, method/solvents for metal extraction, enhanced kinetics of carbonation reactions, heat integration, and the production of highly value-added carbonates.

Kinetics and Mechanism for Aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3^-$, NO$_2$, NCS$^-$, H$_2$O} in Hg$^{2+}$ Aqueous Solution ($Hg^{2+}$ 수용액 내에서 cis-[Co(en)$_2$YCl]$^{r+}$ (Y = $NH_3$, NO$_2^-$, NCS$^-$, $H_2O$)의 아쿠아 반응속도와 반응메카니즘)

  • Byung-Kak Park;Joo-Sang Lim
    • Journal of the Korean Chemical Society
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    • v.32 no.5
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    • pp.476-482
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    • 1988
  • Kinetic studies and theoretical investigations were made to illustrate the mechanism of the aquation of cis-[Co(en)$_2$YCl]$^{r+}$ (Y = NH$_3$, NO$_2^-$, NCS$^-$, $H_2O$) in $Hg^{2+}$ aqueous solution UV/vis-spectrophotometrically. The aquation of cis-[Co(en)$_2$YCl]$^{r+}$ have been found to be the second order for overall reaction as first order for each of substrate and Hg$^{2+}$+ catalyst. The reaction rate was increased in the order of Y=NH$_3$ < NCS$^-$- < $H_2O$ < $NO_2^-$, which are neighboring group of Cl. The step of bond formation was found to be the rate determining one, because the net charge of central metal ion run parallel with the observed rate constant. On the basis of rate determining step, kinetic data and the observed activation parameters, we have proposed the Id mechanism for the reaction system. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation.

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Kinetics of the Reaction of Benzyl Chlorides with Pyridine in Methanol Solvent under High Pressure (고압하의 메탄올 용매내에서 염화벤질류와 피리딘과의 반응에 대한 반응속도론적 연구)

  • Oh Cheun Kwon;Young Cheul Kim;Jin Burm Kyong;Kee Joon Choi
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.413-418
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    • 1987
  • Rates of the reaction for p-nitro benzyl chloride, benzyl chloride and p-methyl benzyl chloride with pyridine in methanol solvent have been measured by an electric conductivity method at 40$^{\circ}$C and 50$^{\circ}$C under various pressures (1∼2000bar). Pseudo first-order rate constants and second-order rate constants were determined. Rates of these reactions were increased in the order p-NO$_2$ < p-H < p-CH$_3$ and increased with temperature, pressure and concentration of pyridine. From those rate constants, the activation parameters were evaluated. The activation volume and the activation compressibility coefficient are both negative values, but the activation enthalpy is positive and the activation entropy is large negative value. From the evaluation of the ground state and transition state which was resulted from substituents and pressure, it was found that this reaction proceeds through S$_N$2 reaction, and S$_N$2 fashion is slightly disappeared as pressure increases.

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Micelles in Physical Chemistry Laboratory. Surfactant Catalyzed Oxidation of Glycine by Acidic Permanganate

  • Pare, Brijesh;Kaur, Parwinder;Bhagwat, V.W.;Fogliani, Charles
    • Journal of the Korean Chemical Society
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    • v.48 no.2
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    • pp.195-202
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    • 2004
  • Micellar catalysis is an essential part of theoretical and experimental curricular. The sodium dodecylsulfate (SDS) catalyzed reaction between glycine and potassium permanganate in acidic medium is an ideal kinetic experiment for the secondary and undergraduate physical chemistry laboratory, to show the effect of micellar catalysis on rate of the reaction. The reaction is conducted both with and without SDS to observe the rate enhancement in the presence of surfactant. To show surfactant catalysis a plot between k and [SDS] is plotted. As surfactant catalysis is observed even before the critical micelle concentration of SDS, this pre-micellar catalysis can be understood in the light of positive co-operativity. The value of positive cooperative index (n) has been found to be 2.37. Further, dependence of the reaction rate on substrate and oxidant concentrations is also discussed. The reaction follows pseudo-first-order kinetics. The overall reaction is second order, with first-order dependence on both glycine and permanganate concentrations. The theory of surfactant catalysis is also discussed. With the conditions specified in the experiment, total reaction times are in 3~4 hours lab session, thus allowing several data sets to be acquired in a single laboratory period. Preparation of solutions and procedure is also given in detail.

Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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Effects of Temperature and Pressure on the Reaction of [Pt(dien)X]$^+$ with ${NO_2}^-$ Aqueous Solutions (수용액에서 [Pt(dien)X]$^+$${NO_2}^-$와의 치환반응에 미치는 온도 및 압력변화)

  • Sang Oh Oh;Sang Hyup Lee;Hwan Jin Yeo;Jong Wan Lim;Du Hwan Jo
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.371-378
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    • 1989
  • Kinetics of the substitution reaction of [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) with NO2- in aqueous solution were investigated by a spectrophotometric method at $20-35^{\circ}C$ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]$^+$ follow the order ($Cl^-$ > $Br^-$ > $I^-$). Activation volumes (${\mid}{\Delta}V^{\neq}{\mid}$) were large negative values and decreased with raising temperature. First ($k_1$) and second($k_2$) order rate constants of these reactions were determined at $25^{\circ}C$ and both $k_1$ and $k_2$ were increased with raising pressure and activation volumes (${\Delta}{V_1}^{\neq}$, ${\Delta}{V_2}^{\neq}$) for the $k_1$ and $k_2$ path were large negative values respectively. The $k_1$ and $k_2$ of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of $k_1$ and $k_2$ path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]$^+$ with ${NO_2}^-$ proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.

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Wavelength-resolved Thermoluminescence of Chemical-vapor-deposited Diamond Thin Film (화학증착된 다이어몬드 박막의 파장 분해된 열자극발광)

  • Cho, Jung-Gil;Yi, Byong-Yong;Kim, Tae-Kyu
    • Progress in Medical Physics
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    • v.12 no.1
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    • pp.1-8
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    • 2001
  • Diamond thin films were synthesized by a chemical vapor deposition (CVD). Raman spectrum showed the diamond line at 1332 $cm^{-1}$ / and x-ray diffraction pattern exhibited a strong (111) peak of diamond. The scanning electron microscopy analysis showed that the CVD diamond thin film was grown to be unepitaxial crystallites with pyramidal hillocks. A wavelength-resolved thermoluminescence (TL) of the CVD diamond thin film irradiated with X-rays showed one peak at 430 nm around 560 K. The glow curve of the CVD diamond thin film produced one dominant 560-K peak that was caused by first-order kinetics. Its activation energy and the escape frequency were calculated to be 0.92 ~ 1.05 eV and 1.34 $\times$ 10$^{7}$ sec$^{-1}$ , respectively. The emission spectrum at 560 K was split into 1.63-eV, 2.60-eV, and 3.07-eV emission bands which is known to be attribute to silicon-vacancy center, A center, and H3 center, respectively.

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Synthesis and Characterization of Biodegradable MethoxyPoly(ethylene glycol)-Poly$(\varepsilon-caprolactone-co-L-lactide)$ Block Copolymers (메톡시폴리(에틸렌 글리콜)-폴리(카프로락톤-co-L-락타이드) 공중합체의 합성 및 특성 분석)

  • Hyun Hoon;Cho Young Ho;Jeong Sung Chan;Lee Bong;Kim Moon Suk;Khang Gilson;Lee Hai Bang
    • Polymer(Korea)
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    • v.30 no.1
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    • pp.28-34
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    • 2006
  • A series of methoxypoly(ethylene glycol) $(MPEG)-poly(\varepsilon-co-L-lactide)$ (PCLA) diblock copolymers were synthesized by ring-opening polymerization of a mixture of $\varepsilon-caprolactone$ and L-lactide with different ratios in the presence of $Sn(Oct)_2$. The characterization of MPEG-PCLA diblock copolymers were examined by $^1H-NMR$, GPC, DSC, and XRD. Kinetic study on ring-opening polymerization of monomer mixtures was carried out in various conditions such as a variation with polymerization time, amount of catalyst, and temperature. The highest conversion obtained in 1.2 ratic of initiator venn catalyst at $110\;^{\circ}C$. The biodegradable characterization of MPEG-PCLA diblock copolymers in aqueous solution was carried out by using GPC for $1\~14$ weeks. The biodegradability of MPEG-PCLA diblock copolymers increased as the L-lactide content of diblock copolymers increased. In conclusion, we confirmed the dependence of polymerization rate according to various conditions. In addition, we can control the biodegradability of MPEC-PCLA diblock copolymers by changing the ratio of PCL and PLA block segment.

Preparation and Characterization of Anion Exchange Membrane Based on Crosslinked Poly(2,6-dimethyl-1,4-phenylene oxide) with Spacer-type Conducting Group (Spacer-type 전도기가 도입된 가교형 poly(2,6-dimethyl-1,4-phenylene oxide) 음이온 교환막의 제조 및 특성평가)

  • Lim, Haeryang;Kim, Tae-Hyun
    • Membrane Journal
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    • v.27 no.5
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    • pp.425-433
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    • 2017
  • As the problems related to the environmental pollution such as carbon dioxide emission are emerging, the need for the renewable energy and environmentally friendly energy is getting intense. Fuel cells are eco-friendly energy generation devices that generate electrical energy and produce water as a sole by-product. Compared to the traditional proton exchange membrane fuel cell (PEMFC), anion exchange membrane alkaline fuel cell (AEMAFC) has a main advantage of possibility to use low cost metal catalysts due to its faster kinetics. The AEM, which conducts $OH^-$ ions, should possess high ion conductivity as well as high chemical stability at high pH conditions. We hereby introduce a crosslinked poly(2,6-dimethyl-1,4-phenylene oxide) having a spacer-type conducting group as novel AEM, and report a high ion conductivity ($67.9mScm^{-1}$ at $80^{\circ}C$) and mechanical properties (Young's modulus : 0.53 GPa) as well as chemical stability (6.8% IEC loss at $80^{\circ}C$ for 1,000 h,) for the developed membrane.

Hydrogenation Characteristics of Aromatics in Residue Oil of Naphtha Cracking on Pt/Pd Impregnated Mesoporous Molecular Sieve (메조포러스 분자체에 담지된 Pt/Pd 촉매상에서 납사분해 잔사유의 방향족 화합물 수소화 특성)

  • Choi, Jong Hwa;Jeong, Soon Yong;Oh, Sung-Geun
    • Korean Chemical Engineering Research
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    • v.43 no.6
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    • pp.675-682
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    • 2005
  • Al containing mesoporous molecular sieve (Al-MMS) was synthesized by hydrolysis of $H_2SiF_6$ and $Al(NO_3)_3{\cdot}9H_2O$. The material obtained was characterized by XRD, $N_2$-physisorption. The specific surface area was $981m^2/g$, and the average pore size was uniformity $39{\AA}$. It was confirmed that the acidity of Al-MMS was milder than that of zeolite Y based on the results of $NH_3$-TPD. Active materials, Pt and Pd, were loaded on Al-MMS in order to examine the feasibility of using Al-MMS as a catalyst support in the hydrogenation of aromatic compounds included in the residue oil of a naphtha cracker. The hydrogenation activity of PtPd/Al-MMS has been studied by following the kinetics of the hydrogenation of naphthalene, and by comparing the kinetic parameters obtained with Pt and Pd catalysts supported on the other mesoporous material support and commercial conventional support materials. PtPd/Al-MMS catalyst shows the highest activity of hydrogenation and sulfur resistance. The high activity of PtPd/Al-MMS was confirmed again in the hydrogenation of PGO (pyrolized gas oil), which is residue oil obtained from a naphtha cracker. Therefore, PtPd/Al-MMS can be applied to the hydrogenation of aromatic compounds included in the residue oil of a commercial naphtha cracker commericially.