• Title/Summary/Keyword: chemical kinetics

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Kinetic Analysis for the Pyrolysis of Solid Refues Fuel Using Livestock Manure (축분 고형연료의 열분해 동역학 연구)

  • Jang, Eun-Suk;Song, Eunhye;Yoon, Jonghyuk;Kim, Young-Min
    • Applied Chemistry for Engineering
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    • v.31 no.4
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    • pp.443-451
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    • 2020
  • In this study, the physico-chemical properties and pyrolysis kinetics of livestock mature solid fuel were investigated to know its feasibility as a fuel. Ultimate and proximate analysis results showed that livestock mature solid fuel has high contents of volatile matter (64.94%), carbon (44.35%), and hydrogen (5.54%). The low heating value of livestock mature solid fuel (3880 kcal/kg) was also higher than the standard requirement of solid fuel (3000 kcal/kg). Thermogravimetic analysis results indicated that livestock mature solid fuel has three decomposition temperature regions. The first temperature zone (130~330 ℃) was consisted with the vaporization of extracts and the decomposition of hemicellulose and cellulose. The second (330~480 ℃) and third (550~800 ℃) temperature regions were derived from the decomposition of lignin and additional decomposition of carbonaceous materials, respectively. The activation energy derived from model free kinetic analysis results including Friedman, Flynn-Wall-Ozawa (FWO), and Kissinger-Akahira-Sunose (KAS) methods for the pyrolysis of livestock mature solid fuel was in the range of 173.98 to 525.79 kJ/mol with a conversion rate of 0.1 to 0.9. In particular, the activation energy increased largely at the higher conversion than 0.6. The kinetic analysis using a curve-fitting method suggested that livestock mature solid fuel was decomposed via a multi-step reaction which can be divided into five decomposition steps.

Effect of Sodium Hydroxide plus Hydrogen Peroxide Treated Mustard (Brassica campestris) Straw Based Diets on Rumen Degradation Kinetics (In sacco), Fermentation Pattern and Nutrient Utilization in Sheep

  • Mishra, A.S.;Misra, A.K.;Tripathi, M.K.;Santra, A.;Prasad, R.;Jakhmola, R.C.
    • Asian-Australasian Journal of Animal Sciences
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    • v.17 no.3
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    • pp.355-365
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    • 2004
  • Two experiments were conducted to determine the effect of alkaline hydrogen peroxide (AHP) treatment (1% NaOH+1.5% $H_2O_2$; 1 AHPMS, 2% NaOH+1.5% $H_2O_2$; 2AHPMS) on rate and extent of degradation of mustard straw (MS) in sacco in sheep, and its in vivo digestion and ruminal fermentation characteristics when fed to sheep with concentrate (200 g per sheep daily). The treatment of straw with 1 and 2% AHP increased its sodium content by 148 and 296% to that of untreated straw (UMS). There was significant decrease in NDF and hemicellulose contents of AHP treated straw and increase in cellulose and lignin contents. Phenolic acids like ferrulic, $\rho$-coumaric and o-coumaric significantly (p<0.001) reduced by AHP treatment of mustard straw. In first experiment the in sacco degradation of DM, OM and NDF was significantly (p<0.01) greater for 2 AHPMS than for UMS at all incubation periods. The disappearance of nutrient from 1 AHPMS and 2 AHPMS treated straws continue to increase up to 96 h whereas in UMS the peak disappearance was found at 48 h. By using the equation {(y=a+b) ($1-e^{-ct}$)} the degradation rates (c) for DM, OM, and NDF were significantly higher for UMS than AHP treated straws. Level of alkali (1 and 2%) had significant effect on degradation characteristics (a, b, c and $P_{0.05}$) of DM and NDF fraction of MS. However, the effect was not pronounced on OM fraction of MS. In feeding experiment, the intake of nutrients for DM, OM, cell wall constituents and energy was higher on 2 AHPMS, whereas no effect on the digestibility of these nutrients was observed. The apparent nitrogen retention was higher (p<0.05) both in 1 and 2 AHPMS groups. Water intake by animals was significantly increased due to AHP treated mustard straw feeding. Rumen liquor pH was higher in 2 AHPMS fed animals. The $NH_3-N$ of rumen liquor was not affected by feeding of AHP treated MS based diets. Total VFA concentration was significantly (p<0.01) higher in UMS fed group. The fractional out flow rate of DM was higher (p<0.05) in animals fed on 2 AHPMS diets compared to UMS and lAHPMS fed groups. The population of large holotrichs was higher (p<0.05) on AHP treated MS fed diets compared to UMS. The study indicated that treatment of mustard straw with AHP changed its chemical composition towards a better feed. The nutritive value of 2% AHP treated mustard straw was better in terms of dry matter intake and apparent nitrogen retention. The higher in sacco DM, OM and NDF disappearance however, was not confirmed by in vivo data in this study.

Kinetic Study on Preparation of Iron Fine Powders by Hydrogen Reduction of Ferous Chloride Vapor (염화물의 기상환원반응에 의한 미립질 철분말의 생성속도에 관한 연구)

  • Lee, Hwa-Yeong;Kim, Seong-Gyu
    • Korean Journal of Materials Research
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    • v.10 no.6
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    • pp.385-391
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    • 2000
  • A kinetic study on the preparation of iron powder by hydrogen reduction of ferrous chloride vapor has been carried out both experimentally and theoretically. For the preparation of iron powder, ferrous chloride was vaporized and transported to a reaction zone by Ar gas used as carrier. Ferrous chloride vapor and hydrogen were mixed and subject to a reduction reaction at high temperature to produce iron powder and HCI gas. Iron powder was collected with organic solvent at the end of reaction zone and HCI gas was also absorbed in a caustic soda solution to determine the conversion ratio of ferrous chloride. For the development of rate equations, a 1st-order reaction and equilibration of ferrous chloride vapor with Ar gas were assumed. According to the results, the rate constant, k could be expressed as $k=7,879exp(-53,840/RT)\textrm{dm}^3/mole.sec$ and the activation energy was found to be 53.84kJ/mole. From TEM observation, the particle size distribution of iron powder produced was found to be in the range of $0.1~1.0{\mu\textrm{m}}$ which was not significantly influenced by reaction temperature or gas flow rates.

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Silver nanowires and nanodendrites synthesized by plasma discharge in solution for the catalytic oxygen reduction in alkaline media

  • Kim, Hoe-Geun;Song, Myeon-Gyu;Kim, Dong-U;Lee, Sang-Yul
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2018.06a
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    • pp.62-62
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    • 2018
  • Pt is still considered as one of the most active electrocatalysts for ORR in alkaline fuel cells. However, the high cost and scarcity of Pt hamper the widespread commercialization of fuel cells. As a strong candidate for the replacement of Pt catalyst, silver (Ag) has been extensively studied due to its high activity, abundance, and low cost. Ag is more stable than Pt in the pH range of 8~14 as the equilibrium potential of Ag/Ag+ being ${\approx}200mV$ higher than that of Pt/PtO. However, Ag is the overall catalytic activity of Ag for oxygen reduction reaction(ORR) is still not comparable to Pt catalyst since the surface Ag atoms are approximately 10 times less active than Pt atoms. Therefore, further enhancement in the ORR activity of Ag catalysts is necessary to be competitive with current cutting-edge Pt-based catalysts. We demonstrate the architectural design of Ag catalysts, synthesized using plasma discharge in liquid phase, for enhanced ORR kinetics in alkaline media. An attractive feature of this work is that the plasma status controlled via electric-field could form the Ag nanowires or dendrites without any chemical agents. The plasma reactor was made of a Teflon vessel with an inner diameter of 80 mm and a height of 80 mm, where a pair of tungsten(W) electrodes with a diameter of 2 mm was placed horizontally. The stock solutions were made by dissolving the 5-mM AgNO3 in DI water. For the synthesis of Agnanowires, the electricfield of 3.6kVcm-1 in a 200-ml AgNO3 aqueous solution was applied across the electrodes using a bipolar pulsed power supply(Kurita, Seisakusyo Co. Ltd). The repetition rate and pulse width were fixed at 30kHz and 2.0 us, respectively. The plasma discharge was carried out for a fixed reaction time of 60 min. In case of Ag nanodendrites, the electric field of 32kVcm-1 in a 200-ml AgNO3 aqueous solution was applied and other conditions were identical to the plasma discharge in water in terms of electrode configuration, repetition rate and discharge time. Using SEM and STEM, morphology of Ag nanowires and dendrites were investigated. With 3.6 kV/cm, Ag nanowire was obtained, while Ag dendrite was constructed with 32 kV/cm. The average diameter and legth of Ag nanowireses were 50 nm and 3.5 um, and thoes values of Ag dendrites were 40 nm and 3.0 um. As a results of XPS analysis, the surface defects in the Ag nanowires facilitated O2 incorporation into the surface region via the interaction between the oxygen and the electron cloud of the adjacent Ag atoms. The catalytic activity of Ag for oxygen reduction reaction(ORR) showed that the catalytic ORR activity of Ag nanowires are much better than Ag nanodendrites, and electron transfer number of Ag nanowires is similar to that of Pt (${\approx}4$).

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Equilibrium, Kinetic and Thermodynamic Parameter Studies on Adsorption of Allura Red from Aqueous Solution by Granular Activated Carbon (입상활성탄에 의한 수용액으로부터 오로라 레드의 흡착에 대한 평형, 동력학 및 열역학 파라미터에 관한 연구)

  • Lee, Jong-Jib
    • Applied Chemistry for Engineering
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    • v.25 no.4
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    • pp.430-436
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    • 2014
  • Allura Red (AR) is a water-soluble harmful tar-based food colorant (FD & C Red 40). Batch adsorption studies were performed for the removal of AR using bituminous coal based granular activated carbon as adsorbent by varying the operation parameters such as adsorbent dosage, initial concentration, contact time and temperature. Experimental equilibrium adsorption data were analyzed by Langmuir, Freundlich and Temkin isotherms. The equilibrium process was described well by Freundlich isotherm. From determined separation factor ($R_L$), adsorption of AR by granular activated carbon could be employed as effective treatment method. Temkin parameter, B was determined to 1.62~3.288 J/mol indicating a physical adsorption process. By estimation of adsorption rate experimental data, the value of intraparticle diffusion rate constant ($k_m$) increased with the increasing adsorption temperature. The adsorption process were found to confirm to the pseudo second order model with good correlation. Thermodynamic parameters like change of free energy, enthalpy, and entropy were also calculated to predict the nature adsorption in the temperature range of 298~318 K. The negative Gibbs free energy change (${\Delta}G$ = -2.16~-6.55 kJ/mol) and the positive enthalpy change (${\Delta}H$ = + 23.29 kJ/mol) indicated the spontaneous and endothermic nature of the adsorption process, respectively.

A Study for Kinetics and Oxidation Reaction of Substituted Benzyl Alcohols Using (C10H8N2H)2Cr2O7 ((C10H8N2H)2Cr2O7를 이용한 치환 벤질 알코올류의 산화반응과 반응속도에 관한 연구)

  • Park, Young Cho;Kim, Young Sik;Kim, Soo Jong
    • Applied Chemistry for Engineering
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    • v.28 no.5
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    • pp.597-600
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    • 2017
  • $(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.

Characteristics of Isotherm, Kinetic, and Thermodynamic Parameters for Reactive Blue 4 Dye Adsorption by Activated Carbon (활성탄에 의한 Reactive Blue 4 염료의 흡착에 대한 등온선, 동력학 및 열역학적 특성)

  • Lee, Jong-Jib
    • Clean Technology
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    • v.26 no.2
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    • pp.122-130
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    • 2020
  • The isotherm, kinetic, and thermodynamic parameters of reactive blue 4 adsorbed by activated carbon were investigated for activated carbon dose, pH, initial concentration, contact time, and temperature data. The adsorption of the RB 4 dye by activated carbon showed a concave shape in which the percentage of adsorption increased in both directions starting from pH 7. The isothermal adsorption data were applied to Langmuir, Freundlich, and Temkin isotherms. Both Freundlich and Langmuir isothermal adsorption models fit well. From determined Freundlich separation factor (1/n = 0.125 ~ 0.232) and Langmuir separation factor (RL = 1.53 ~ 1.59), adsorption of RB 4 by activated carbon could be employed as an effective treatment method. The constant related to the adsorption heat (BT = 2.147 ~ 2.562 J mol-1) of Temkin showed that this process was physical adsorption. From kinetic experiments, the adsorption process followed the pseudo second order model with good agreement. The results of the intraparticle diffusion model showed that the inclination of the first straight line representing the surface diffusion was smaller than that of the second straight line representing the intraparticle pore diffusion. Therefore, it was confirmed that intraparticle pore diffusion is the rate-controlling step. The negative Gibbs free energy change (ΔG = -3.262 ~ -7.581 kJ mol-1) and the positive enthalpy change (ΔH = 61.08 kJ mol-1) indicated the spontaneous and endothermic nature of the adsorption process, proving this process to be spontaneous and endothermic.

Opto-Electrochemical Sensing Device Based on Long-Period Grating Coated with Boron-Doped Diamond Thin Film

  • Bogdanowicz, Robert;Sobaszek, Michał;Ficek, Mateusz;Gnyba, Marcin;Ryl, Jacek;Siuzdak, Katarzyna;Bock, Wojtek J.;Smietana, Mateusz
    • Journal of the Optical Society of Korea
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    • v.19 no.6
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    • pp.705-710
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    • 2015
  • The fabrication process of thin boron-doped nanocrystalline diamond (B-NCD) microelectrodes on fused silica single mode optical fiber cladding has been investigated. The B-NCD films were deposited on the fibers using Microwave Plasma Assisted Chemical Vapor Deposition (MW PA CVD) at glass substrate temperature of 475 ℃. We have obtained homogenous, continuous and polycrystalline surface morphology with high sp3 content in B-NCD films and mean grain size in the range of 100-250 nm. The films deposited on the glass reference samples exhibit high refractive index (n=2.05 at λ=550 nm) and low extinction coefficient. Furthermore, cyclic voltammograms (CV) were recorded to determine the electrochemical window and reaction reversibility at the B-NCD fiber-based electrode. CV measurements in aqueous media consisting of 5 mM K3[Fe(CN)6] in 0.5 M Na2SO4 demonstrated a width of the electrochemical window up to 1.03 V and relatively fast kinetics expressed by a redox peak splitting below 500 mV. Moreover, thanks to high-n B-NCD overlay, the coated fibers can be also used for enhancing the sensitivity of long-period gratings (LPGs) induced in the fiber. The LPG is capable of measuring variations in refractive index of the surrounding liquid by tracing the shift in resonance appearing in the transmitted spectrum. Possible combined CV and LPG-based measurements are discussed in this work.

Feasibility Study of Employing a Catalytic Membrane Reactor for a Pressurized CO2 and Purified H2 Production in a Water Gas Shift Reaction

  • Lim, Hankwon
    • Clean Technology
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    • v.20 no.4
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    • pp.425-432
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    • 2014
  • The effect of two important parameters of a catalytic membrane reactor (CMR), hydrogen selectivity and hydrogen permeance, coupled with an Ar sweep flow and an operating pressure on the performance of a water gas shift reaction in a CMR has been extensively studied using a one-dimensional reactor model and reaction kinetics. As an alternative pre-combustion $CO_2$ capture method, the feasibility of capturing a pressurized and concentrated $CO_2$ in a retentate (a shell side of a CMR) and separating a purified $H_2$ in a permeate (a tube side of a CMR) simultaneously in a CMR was examined and a guideline for a hydrogen permeance, a hydrogen selectivity, an Ar sweep flow rate, and an operating pressure to achieve a simultaneous capture of a concentrate $CO_2$ in a retentate and production of a purified $H_2$ in a permeate is presented. For example, with an operating pressure of 8 atm and Ar sweep gas for rate of $6.7{\times}10^{-4}mols^{-1}$, a concentrated $CO_2$ in a retentate (~90%) and a purified $H_2$ in a permeate (~100%) was simultaneously obtained in a CMR fitted with a membrane with hydrogen permeance of $1{\times}10^{-8}molm^{-2}s^{-1}Pa^{-1}$ and a hydrogen selectivity of 10000.

Miscibility and Properties of Ethyl-Branched Polyethylene/Ethylene-Propylene Rubber Blends (II) (에틸 가지화된 폴리에틸렌과 에틸렌-프로필렌 고무 블렌드의 혼화성과 물성(II))

  • Cho, Ur-Ryong
    • Elastomers and Composites
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    • v.37 no.2
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    • pp.79-85
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    • 2002
  • Ethyl-branched polyethylene [PE(2)] containing 2mole% ethyl branch and three ethylene-propylene rubbers (EPR's) having the same ethylene(E)-propylene(P) molar ratio(E/P=50/50) with different stereoregularity, that is, random EPR (r-EPR), alternating-EPR (alt-EPR) and isotactic-alternating-EPR (iso-alt-EPR) were mixed for the investigation or their properties depending on the stereoregularity. Crystallinity of the prepared blends decreased with increasing content of amorphous EPR because of a decrease in both the degree of annealing and kinetics of diffusion of the crystallizable polymer content. With blend composition, crystallinity was reduced with the stereoregularity in EPR. The thermodynamic interaction parameter(x) for the three blend systems approximately equals to zero near the melting point. These systems were determined to be miscible on a molecular scale near or above the crystalline melting point or the crystalline PE(2). From the measurement of $T_m$ vs. $T_c$, the behavior of PE(2) is mainly due to a diluent effect of EPR component. The spherulite size measured by small angle light scattering (SALS) technique depended upon blend composition, and stereoregularity of EPR. The size of spherulite was enlarged with the content of rubbery EPR and the decrease of stereoregularity in EPR.