• Title/Summary/Keyword: 겉보기 반응속도 상수

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Effect of Solution Temperature and Bath Concentration on the Kinetics with Dissolution Reaction of Zinc-Ferrite (Zinc-ferrite의 용해 속도론에 미치는 황산 용액의 온도와 농도의 영향)

  • Oh Iee-Sik;Kim Chun-Jo
    • Resources Recycling
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    • v.12 no.4
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    • pp.30-37
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    • 2003
  • A kinetics study on the dissolution reaction of zinc-ferrite has been made with aqueous sulfuric acid in various temperature and concentration. Fraction reacted(R) and apparent rate constant(K) increased with increasing temperature and concentration of sulfuric acid solution. The rate of dissolution is shown by $1-(1-K)^{1/3}=Kt$ for the initial stage of the reaction in aqueous sulfuric acid, where K is apparent rate constant, R is fraction reacted and t is reaction time, respectively. Activation energy associated with reaction was determined to be 16.3 kcal/mole. The dissolution of zinc-ferrite in sulfuric acid solution is dissolved by sto-ichiometric composition, but Fe and Zn did not dissolved, respectively.

The Effect of Crystallization Condition on the Crystallization Rate of Zeolite A (제올라이트 A의 결정화 속도에 대한 결정화 조건의 영향)

  • Chung, Kyeong-Hwan;Seo, Gon
    • Applied Chemistry for Engineering
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    • v.4 no.1
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    • pp.94-102
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    • 1993
  • The effects of temperature and of $Na_2O$ and $SiO_2$ contents on the crystallization of zeolite A were studied, by examining crystallization curves and particle size distributions of final products at various crystallization conditions. Crystallization process could be simulated adopting the assumptions of constant linear growth rate and equilibrium between amorphous solid phase and soluble species. Rate constants were determined by comparing the simulated crystallization curves with experimental data. Rate constant for linear growth increased with temperature and crystallization rate at different mole ratio of $Na_2O/H_2O$ correlated reasonably well with increase of soluble species. The rate constant of crystallization did not increase with increase in mole ratio of $Na_2O/H_2O$, but the rate of nuclei formation and the fraction of soluble species were enhanced. The rate constants for linear growth of zeolite A were determined as $0.07{\sim}0.24{\mu}m{\cdot}min^{-1}$ at these experimental conditions Apparent activation energy was estimated as $49kJ{\cdot}mol^{-1}$.

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Kinetics Study of the Reaction of Bromine with Phenylhydrazine in Sulfuric Acid Media (페닐히드라진과 브롬의 반응메카니즘에 관한 연구)

  • Park Byoung Bin;Park Il H.;Kong Young Kun;Choi Q. Won
    • Journal of the Korean Chemical Society
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    • v.21 no.4
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    • pp.227-234
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    • 1977
  • The reaction of phenylhydrazine with bromine in sulfuric acid solution has been studied kinetically. The pseudo-second-order rate constant is approximately inversely proportional to hydrogen-ion concentration when the concentration of sulfuric acid is lower than 1M. arom the study of the effect of potassium bromide concentration on the rate constant, it is concluded that both neutral bromine and tribromide ion participate in the reaction, the rate constants in 0.01M $H_2SO_4$ being $5{\times}10^5M^{-1},sec^{-1}\;and\;0. 7{\times}10^5M^{-1},sec^{-1}$, respectively at $20^{\circ}C$. The pseudo-second-order rate constant of 2.4-dinitrophenylhydrazine-bromine reaction is independent of hydrogen ion concentration. From the KBr addition experiment, the rate constants for $Br_2\;and\;Br_3^-$ were obtained as $1.2{\times}10^5M^{-1},sec^{-1}\;and\;2.0{\times}10^4M^{-1},sec^{-1}$, respectively.

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Effects of Medium on Nucleophilic Substitution Reactions (I). Methanolysis of t-Butylbromide and Benzoylchloride in Methanol-Acetonitrile Mixtures (친핵치환반응에 미치는 용매효과 (제1보) 메탄올-아세토니트릴 혼합용매에서 t-Butylbromide 및 Benzoylchloride 의 가메탄올 분해반응)

  • Hai Whang Lee;Sangmoo La;Ikchoon Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.115-120
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    • 1980
  • A kinetic study of the methanolysis of t-butylbromide and benzoylchloride in methanol-acetonitrile mixtures is reported. First order rate constants for the methanolysis of t-butyl bromide show maximum at $X_{MeOH}$=0.75∼0.9 and 25∼$50^{\circ}C$. Apparent second order rate constants for the methanolysis of benzoylchloride also show maximum at $X_{MeOH}$= 0.6∼0.95 and 12∼$26^{\circ}C$. The maximum rate is ascribed to the solvent structure change; the addition of acetonitrile to methanol perturbs the methanol structure increasing the free methanol molecules available to stabilize the transition state for the methanolysis of t-butylbromide and benzoylchloride. It has been shown that methanol acts as nucleophilic and electrophilic catalyst upon methanolysis of t-butylbromide and as electrophilic catalyst upon methanolysis of benzoylchloride.

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Modeling on the Sorption Kinetics of Lead and Cadmium onto Natural Sediments (퇴적물에서의 납과 카드뮴의 흡착 동력학 모델링)

  • Kwak, Mun-Yong;Ko, Seok-Oh;Park, Jae-Woo;Jeong, Yeon-Gu;Shin, Won-Sik
    • Korean Journal of Ecology and Environment
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    • v.39 no.4 s.118
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    • pp.450-461
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    • 2006
  • In this study, sorption kinetics of lead (Pb) and cadmium (Cd) onto coastal sediments were investigated at pH 5.5 using laboratory batch adsorbers. Four different models: one-site mass transfer model (OSMTM), pseudo-first-order kinetic model (PFOKM) ,pseudo-second-order kinetic model (PSOKM) and two compartment first-order kinetic model (TCFOKM) were used to analyze the sorption kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM, PFOKM and PSOKM in describing sorption kinetics of Pb and Cd onto sediments. Most sorption of Pb and Cd was rapidly completed within the first three hours, followed by slow sorption in the subsequent period of sorption. All models predicted that the sorbed amount at the apparent sorption ($q_{e,s}$) equilibria increased as the CEC and surface area of the sediments increased, regardless of initial spiking concentration ($C_0$) and heavy metal and the sediment type. The sorption rate constant ($k_s,\;hr^{-1}$) in OSMTM also increased as the CEC and BET surface area increased. The rate constant of pseudo-first-order sorption ($k_{p1,s},\;hr^{-1}$) in PFOKM were not correlated with sediment characteristics. The results of PSOKM analysis showed that the rate constant of pseudo-second-order sorption ($k_{p2,s},\;g\;mmol^{-1}\;hr^{-1}$) and the initial sorption rate ($v_{o,s},\;mg\;g^{-1}\;hr^{-1}$) were not correlated with sediment characteristics. The fast sorption fraction ($f_{1,s}$) in TCFOKM increased as CEC and BET surface increased regardless of initial aqueous phase concentrations. The sorption rate constant of fast fraction ($k_{1,s}=10^{0.1}-10^{1.0}\;hr^{-1}$) was much greater than that of slow sorption fraction ($k_{2,s}=10^{-2}-10^{-4}\;hr^{-1}$) respectively.

Reduction of High Explosives (HMX, RDX, and TNT) Using Micro- and Nano- Size Zero Valent Iron: Comparison of Kinetic Constants and Intermediates Behavior (마이크로와 나노 철을 이용한 고성능 화약물질(HMX, RDX 및 TNT)의 환원처리: 중간산물의 거동과 도역학 상수의 비교)

  • Bae, Bum-Han
    • Journal of Soil and Groundwater Environment
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    • v.11 no.6
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    • pp.83-91
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    • 2006
  • Reduction kinetics and the behaviour of intermediate of three high explosives (HMX, RDX, and TNT) were studies in batch reactors using nano- or micro- size zero valent iron(nZVI or mZVI) as reducing agent. The kinetic constants normalized by the mass of iron ($k_M$) or by the surface area ($k_{SA}$) were measured and compared along with the changes in the concentrations of intermediates. Results showed that $k_M$ and $k_{SA}$ values were not suitable to fully explain the behaviour of mother compounds and reduced intermediates in the batch reactor. The concentrations of initial explosives degradation products, such as nitroso-RDXs, nitroso-HMXs, and hydroxylamino-TNTs, were higher in mZVI treated reactor than in nZVI treated reactor, whereas more reduced polar intermediates such as TAT were accumulated in the nZVI reactor. Therefore, a new parameter, which accounted for the intermediates reduction, needs to be developed.

Permeability of Silver Sulfadiazine through Crosslinked Chitosan Matrices (가교키토산 매트릭스를 통한 Silver Sulfadiazine의 투과)

  • Nah, Jae Woon
    • Journal of the Korean Chemical Society
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    • v.40 no.9
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    • pp.640-648
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    • 1996
  • Crosslinked chitosan was prepared from chitin after reaction with epichlorohydrin followed by deacetylation at C2-position. Epidermal releasing polymeric matrix was prepared after swelling crosslinked chitosan with distilled water and adding silver sulfadiazine and glycerine as a plasticiser. The release behavior of silver sulfadiazine from polymeric matrix was studied in pH 7.4 phosphate buffer solution by varing the drug content, glycerine concentration, and the thickness of the matrix. The drug release time was delayed by increasing the content of silver sulfadiazine and the thickness of the matrix, whereas decreased as glycerine concentration increased. The apparent constant(K) of release rate was independent upon the matrix thickness, but was proportional to the content of drug or glycerine of crosslinked chitosan matrix. These results indicated that chitosan matrix showed some potential as a drug delivery system for transdermal therapeutic application.

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Sorption Kinetics of Hydrophobic Organic Compounds in Wetland Soils (습지 토양에서 소수성 유기화합물질의 흡착 동력학)

  • Park, Je-Chul;Shin, Won-Sik
    • Korean Journal of Ecology and Environment
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    • v.36 no.3 s.104
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    • pp.295-303
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    • 2003
  • Sorption kinetics of hydrophobic organic compounds (chlorobenzene and phenanthrene) in natural wetland soils was investigated using laboratory batch adsorbers. One -site mass transfer model (OSMTM) and two compartment first-order kinetic model (TCFOKM) were used to analyze sorption kinetics. Analysis of OSMTM reveals that apparent sorption equilibria were obtained within 10 to 75 hours for chlorobenzene and 2 hours for phenanthrene, respectively. For chlorobenzene, the sorption equilibrium time for surface soil was longer than that of deeper soil presumably due to physico-chemical differences between the soils. For phenanthrene, however, no difference in sorption equilibrium time was observed between the soils. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM in describing sorption kinetics, The fraction of fast sorption ($f_1$) and the first-order sorption rate constants for fast ($k_1$)and slow ($k_2$) compartments were determined by fitting experimental data to the TCFOKM. The results of TCFOKM analysis indicate that the sorption rate constant in the fast compartment($k_1$) was much greater than that of slow fraction($k_2$) . The fraction of the fast sorption ($f_1$) and the sorption rate constant in the fast compartment($k_1$) were increasing in the order of increasing $k_{ow}$, phenanthrene > chlorobenzene. The first-order sorption rate constants in the fast ($k_1$) and slow ($k_2$) compartments were found to vary from $10^{-0.1}\;to\;-10^{1.0}$ and from $10^{-4}\;to-10^{-2}$, respectively.

Synthesis of Poly(oxyethylene-co-adipate)-diol from Adipic Acid and Polyethylene Glycols: Effect of Catalyst Concentration (아디프산과 폴리에틸렌글리콜로부터 폴리(옥시에텔렌-아디페이트)-디올 공중합체 합성: 촉매농도의 영향)

  • Jung, Yong-Sung;Lee, Sang-Ho
    • Elastomers and Composites
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    • v.49 no.2
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    • pp.110-116
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    • 2014
  • We investigated the effect of the concentration of stannous 2-ethylhexanoate catalyst on the esterification rate between adipic acid (AA) and each of two PEG oligomers, diethylene glycol (DEG) and polyethylene glycol (PEG600). The concentration of the catalyst was varied from 0.15 to 2.0 wt.%. To attach hydroxy group to each end of the poly(oxyethylene-co-adipate) synthesized from AA and the PEGs, the esterification was performed with excessive PEG oligomers ([PEG]/[AA]=2) at $170^{\circ}C$. The degree of polymerization of the poly(oxyethylene-co-adipate)diol products were three. The apparent rate constant ($k_{app}$) of the esterification between AA and DEG shows the first order dependency on the catalyst concentration ($k_{app}=0.88[C_{cat}]$), whereas the $k_{app}$ of the esterification between AA and PEG600 has a relation of $k_{app}=0.123[C_{cat}]^{0.55}$ with the catalyst concentration. It is expected that the rate of esterification between AA and DEG has a non-linear dependency on the catalyst concentration as the catalyst concentration approaches to 0.22M.

Photo- and Sonic Degradation of Endosulfans(α, β, and sulfate) in Aqueous Solution (엔도설판류의 광 및 초음파분해)

  • Kwon, Sung Hyun;Kim, Jong Hyang;Cho, Daechul
    • Korean Chemical Engineering Research
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    • v.45 no.5
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    • pp.460-465
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    • 2007
  • Endosulfan-${\alpha}$ endosulfan-${\beta}$ and endosulfan-sulfate, which are classified as pesticides, were degraded by use of UV energy and ultrasonic irradiation. The degradation residuals were analysed by gas chromatography with an electron capture detector and TOC (total oragnic carbon) analysis. The reactions were conducted in a quartz annular reactor equipped with a low pressure mercury multilamp (8Wx2) and a sonic generator. All the aqueous solutions were concentrated as 10 mg/L initially. Endosulfans were degraded each to result in 48.2% (${\alpha}$), 50.0% (${\beta}$) and 76.5% (sulfate) of removal efficiency by UV energy, and 66.9% (${\alpha}$), 55.8% (${\beta}$) and 72.7% (sulfate) by ultrasonic irradiation, respectively. In contrast to the results of the single-component solutions, degradation of the endosulfan-sulfate was greatly suppressed to result in the lowest degradation rate and removal efficiency in the three-component solutions. This finding suggests that there should be a reversible reaction with a substantially low equilibrium constant between endosulfan-${\alpha}$ or -${\beta}$ and -sulfate in the coexistence of the three endosulfans. TOC data showed the endosulfans were decomposed by 20%~40% toward complete mineralization, producing a quantity of intermediates induced by the radical reactions. We found that all the decay reactions considered in this study nicely fell into pseudo first-order rate.