• Title/Summary/Keyword: Kinetic studies

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Nucleophilic Substitution at a Carbonyl Carbon Atom(VI)

  • Lee, Hai-Whang;Lee, Ikchoon
    • Nuclear Engineering and Technology
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    • v.7 no.4
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    • pp.311-316
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    • 1975
  • Kinetic studies on the halide exchange reactions of substituted benzoyl chlorides have been carried out. The experimental result has been explained reasonably in terms of HSAB principle and EH-Theory, and addition elimination mechanism has been proposed for this type of reaction.

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Kinetic Studies on the Reaction of the Heterobimetallic Anion, $(OC)_5CrMn(CO)_5{^-}M^+\;(M^+=Na^+,\;PPN^+)$ with Allyl Bromide

  • Park, Yong K.;Kim, Gyu S.;Song, Gwan O.
    • Bulletin of the Korean Chemical Society
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    • v.16 no.4
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    • pp.310-315
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    • 1995
  • The heterobimetallic anion, (OC)5CrMn(CO)5-M+ (M+=Na+, PPN+), which has a donor-acceptor metal-metal bond1, was reacted with allyl bromide to yield BrCr(CO)5- and Mn(CO)5(CH2CHCH2). The reaction mechanism has been proposed in terms of the consecutive reaction pathway in which Cr(CO)5(THF) is an important intermediate leading to the corresponding product. Counterion effect on this reaction was also evaluated and the results were compared with those of the corresponding reaction of the mononuclear carbonyl anion, Mn(CO)5-.

Kinetic Characterization of Brain Distribution for KR-31378 in Rats

  • Kim, Ji-Hye;Shim, Chang-Koo;Chung, Suk-Jae
    • Proceedings of the PSK Conference
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    • 2002.10a
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    • pp.421.2-421.2
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    • 2002
  • Recent studies show that KR-31378 [(2S.3SAR)-N"-cyano-N-(6-amino-3A-dihydro-3-hydroxy-2-methyl-2-dimethoxymethyl-2H-benzopyran-4-yl)-N${\cdots}$-benzylguanidine] has the neuroprotective effect as evidenced by the limitation of the size of infarct of the ischemia-reperfusion injury after an administration of KR-31378. In the literature. however. kinetics of KR-31378 distribution into the brain has not been systematically studied. (omitted)

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Photolysis Improvement of Toluene in 50%TiO2/6%WO3 Sol Solutions Sensitized by Acetone (50%TiO2/6%WO3 졸 용액에서의 톨루엔 처리에 대한 아세톤의 광활성 증가효과)

  • Shin, Hye-Seung;Kim, Jae-Hyoun
    • Journal of Environmental Health Sciences
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    • v.38 no.3
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    • pp.261-268
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    • 2012
  • Objectives: The photocatalytic degradation of toluene in a batch mode photoreactor for the purpose of the hazardous waste treatment was investigated. Methods: Kinetic experiments using a low pressure mercury lamp (Lambda Scientific Pty Ltd, 50 Watt) emitting both UV and visible light were performed at $31^{\circ}C$ over toluene concentrations ranging from 10 to 50 mg/l in water with $50%TiO_2/6%WO_3$ (TW) concentration of 1 g/l at a pH of 6. Results: Kinetic studies showed that $50%TiO_2/6%WO_3$ (TW) photocatalyst was highly active in toluene degradation; we observed that 99% of the pollutant was degraded after six hours under visible irradiation; furthermore, we observed that adsorption onto TW catalyst was responsible for the decrease of toluene with pseudo-first order kinetics. It was also found that oxygen as a radical source in the sol medium played a significant role in affecting the photodegradation of toluene, especially with a two-fold elevation. This increase was achieved by a more than four-fold elevation of the photodegradation of toluene in the presence of acetone than without, presumably via an energy transfer mechanism. Conclusions: We concluded that photodegradation in acetone and oxygen molecules along with TW was an effective method for the removal of toluene from wastewater.

Kinetics and Mechanism of the Benzylaminolysis of O,O-Diphenyl S-Aryl Phosphorothioates in Dimethyl Sulfoxide

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.5
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    • pp.1625-1629
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    • 2011
  • Kinetic studies of the reactions of O,O-diphenyl Z-S-aryl phosphorothioates with X-benzylamines have been carried out in dimethyl sulfoxide at 55.0 $^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}_X$) and Bronsted [log $k_2$ vs $pK_a(X)$] plots for substituent X variations in the nucleophiles are biphasic concave downwards with a maximum point at X = H, and the unusual positive ${\rho}_X$ and negative ${\beta}_X$ values are obtained for the strongly basic benzylamines. The sign of the cross-interaction constant (${\rho}_{XZ}$) is negative for both the strongly and weakly basic nucleophiles. Greater magnitude of ${\rho}_{XZ}$ value is observed with the weakly basic nucleophiles (${\rho}_{XZ}$ = -2.35) compared to with the strongly basic nucleophiles (${\rho}_{XZ}$ = -0.03). The deuterium kinetic isotope effects ($k_H/k_D$) involving deuterated benzylamines [$XC_6H_4CH_2ND_2$] are primary normal ($k_H/k_D$ > 1). The proposed mechanism is a concerted $S_N2$ involving a frontside nucleophilic attack with a hydrogen bonded, four-center-type transition state for both the strongly and weakly basic nucleophiles. The unusual positive ${\rho}_X$ and negative ${\beta}_X$ values with the strongly basic benzylamines are rationalized by through-space interaction between the ${\pi}$-clouds of the electron-rich phenyl ring of benzylamine and the phenyl ring of the leaving group thiophenoxide.

Comparison of the Kinetic Behaviors of Fe2O3 Spherical Submicron Clusters and Fe2O3 Fine Powder Catalysts for CO Oxidation

  • Yoo, Seung-Gyun;Kim, Jin-Hoon;Kim, Un-Ho;Jung, Jin-Seung;Lee, Sung-Han
    • Bulletin of the Korean Chemical Society
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    • v.35 no.5
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    • pp.1379-1384
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    • 2014
  • ${\alpha}-Fe_2O_3$ spherical particles having an average diameter of ca. 420 nm and ${\alpha}-Fe_2O_3$ fine particles (< 10 ${\mu}m$ particle size) were prepared to examine as catalysts for CO oxidation. Kinetic studies on the catalytic reactions were performed in a flow reactor using an on-line gas chromatography system operated at 1 atm. The apparent activation energies and the partial orders with respect to CO and $O_2$ were determined from the rates of CO disappearance in the reaction stage showing a constant catalytic activity. In the temperature range of $150-275^{\circ}C$, the apparent activation energies were calculated to be 13.7 kcal/mol on the ${\alpha}-Fe_2O_3$ spherical submicron clusters and 15.0 kcal/mol on the ${\alpha}-Fe_2O_3$ fine powder. The Pco and $Po_2$ dependencies of rate were investigated at various partial pressures of CO and $O_2$ at $250^{\circ}C$. Zero-order kinetics were observed for $O_2$ on both the catalysts, but the reaction order for CO was observed as first-order on the ${\alpha}-Fe_2O_3$ fine powder and 0.75-order on the ${\alpha}-Fe_2O_3$ spherical submicron clusters. The catalytic processes including the inhibition process by $CO_2$ on the ${\alpha}-Fe_2O_3$ spherical submicron powder are discussed according to the kinetic results. The catalysts were characterized using XRD (X-ray powder diffraction), FE-SEM (field emission-scanning electron microscopy), HR-TEM (high resolution-transmission electron microscopy), and $N_2$ sorption measurements.

A Study on Oxidative Degradation of Chlorophenols by Heat Activated Persulfate (열적활성화된 과황산에 의한 염화페놀의 산화분해특성 연구)

  • Son, JiMin;Kwon, Hee-Won;Hwang, Inseong;Kim, Jeong-Jin;Kim, Young-Hun
    • Journal of Environmental Science International
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    • v.29 no.1
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    • pp.69-77
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    • 2020
  • Oxidative degradation of phenol, three monochlorophenols (2-chlorophenol, 2-CP; 3-chlorophenol, 3-CP; 4-chlorophenol, 4-CP), four dichlorophenols (2,3-dichlorophenol, 2,3-DCP; 2,4-dichlorophenol, 2,4-DCP; 2,5-dichlorophenol, 2,5-DCP; 2,6-dichlorophenol, 2,6-DCP), and two trichlorophenols (2,4,5-trichlorophenol, 2,4,5-TCP; 2,4,6-trichlorophenol, 2,4,6-TCP) was conducted with heat activated persulfate. As the number of chlorinations increased, the reaction rate also increased. The reaction rate was relatively well fitted to the zero-order kinetic model, rather than the pseudo-first order kinetic model for the reactions at 60 ℃, which can be explained by insufficient activation of the persulfate at 60 ℃, and the oxidation reaction of 2,4,6-TCP at 70 ℃ was relatively well fitted to the pseudo-first order kinetic model. The oxidation reaction rate generally increased with increase of persulfate concentration in the solution. 2,6-dichloro-2,5-cyclohexadiene-1,4-dione was found as a degradation product in a GC/MS analysis. This compound is a non-aromatic compound, and one chlorine was removed. This result is similar to the result of previous studies. The current study proved that heat activated persulfate activation could be an alternative remediation technology for phenol and chlorophenols in soil and groundwater.

Biodegradation Kinetics of Nonylphenol Ethoxylates by Pseudomonas sp. (Pseudomonas sp.에 의한 Nonylphenol Ethoxylates의 Kinetics)

  • 김수정;이종근;이상준
    • Journal of Environmental Science International
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    • v.2 no.4
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    • pp.271-278
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    • 1993
  • Optimal biodegradation kinetics models to the initial nonylphenol ethoxylates-30 concentration were investigated and had been fitted by the linear regression. Microorganisms capable of degrading nonylphenol ethoxylates-30 were isolated from sewage near Ulsan plant area by enrichment culture technique. Among them, the strain designated as EL-10K had the highest biodegradability and was identified as Pseudomonas from results of taxonomical studies. The optimal conditions for the biodegradation were 1.0 g/ι of nonylphenol ethoxylates-30 and 0.02 g/ι of ammonium nitrate at pH 7.0 and 3$0^{\circ}C$. The highest degradation rate of nonylphenol ethoxylates-30 was about 89% for 30 hours incubation on the optimal condition. Biodegradation data were fit by linear regression to equations for 3 kinetic models. The kinetics of biodegradation of nonylphenol ethoxylates was best described by first order model for 0.1 $\mu\textrm{g}$/ι nonylphenol ethoxylates-30 ; by Monod no growth model and Monod with growth model for 0.5 $\mu\textrm{g}$/mι and 1.0, 5.0 $\mu\textrm{g}$/mι, respectively.

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Equilibrium, Kinetics and Thermodynamics Studies about Adsorption of Safranin by Granular Activated Carbon (입상 활성탄에 의한 Safranin의 흡착에 관한 평형, 동력학 및 열역학에 관한 연구)

  • Lee, Jong Jib
    • Applied Chemistry for Engineering
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    • v.26 no.5
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    • pp.581-586
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    • 2015
  • Adsorption of Safranin using granular activated carbon from aqueous solution was investigated. Batch experiments were carried out as a function of adsorbent dose, initial concentration, contact time and temperature. The equilibrium adsorption data were fitted to Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. Based on an estimated Langmuir separation factor, $R_L=0.183{\sim}0.254$ and a Freundlich separation factor, 1/n = 0.518~0.547, this process could be employed as an effective treatment method. Adsorption data were also modeled using the pseudo-first and second-order kinetic equations. It was shown that the pseudo-second-order kinetic equation could best describe the adsorption kinetics. The negative Gibbs free energy (${\Delta}G=-3.688{\sim}-7.220kJ/mol$) and positive enthalpy (${\Delta}H=33.126kJ/mol$) indicated that the adsorption process was spontaneous and endothermic.