• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2929-2933
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• 2010

Pseudo-first-order rate constants ($k_{obsd}$) have been measured for nucleophilic substitution reactions of 2-pyridyl benzoate 5 with alkali metal ethoxides (EtOM, M = Li, Na, K) in anhydrous ethanol. The plots of $k_{obsd}$ vs. $[EtOM]_o$ are curved upwardly but linear in the excess presence of 18-crown-6-ether (18C6) with significant decreased $k_{obsd}$ values in the reaction with EtOK. The $k_{obsd}$ value for the reaction of 5 with a given EtONa concentration decreases steeply upon addition of 15-crown-5-ether (15C5) to the reaction medium up to ca. [15C5]/$[EtONa]_o$ = 1, and remains nearly constant thereafter, indicating that $M^+$ ions catalyze the reaction in the absence of the complexing agents. Dissection $k_{obsd}$ into $k_{EtO^-}$- and $k_{EtOM}$, i.e., the second-order rate constants for the reaction with the dissociated $EtO^-$ and the ion-paired EtOM, respectively has revealed that ion-paired EtOM is 3.2 - 4.6 times more reactive than dissociated $EtO^-$. It has been concluded that $M^+$ ions increase the electrophilicity of the reaction center through a 6-membered cyclic transition state. This idea has been examined from the corresponding reactions of 4-pyridyl benzoate 6, which cannot form such a 6-membered cyclic transition state.

• Journal of Environmental Science International
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• v.21 no.7
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• pp.845-853
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• 2012

Diethyl phthalate (DEP) is widely spread in the natural environment as an endocrine disruption chemicals (EDs). Therefore, in this study, ultrasound (US) and ultraviolet (UVC), including various applied power density (10-40 W/L), UV wavelengths (365 nm, 254 nm and 185 nm) and frequencies (283 kHz, 935 kHz) were applied to a DEP contaminated solution. The pseudo-first order degradation rate constants were in the order of $10^{-1}$ to $10^{-4}\;min^{-1}$ depending on the processes. Photolytic and sonophotolytic DEP degradation rate also were high at shortest UV wavelength (VUV) due to the higher energy of photons, higher molar absorption coefficient of DEP and increased hydroxyl radical generation from homolysis of water. Sonolytic DEP degradation rate increased with increase of applied input power and the dominant reaction mechanism of DEP in sonolysis was estimated as hydroxyl radical reaction by the addition of t-BuOH, which is a common hydroxyl radical scavenger. Moreover, synergistic effect of were also observed for sonophotolytic degradation with various UV irradiation.

• Proceedings of the Korean Society of Soil and Groundwater Environment Conference
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• 2005.04a
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• pp.53-56
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• 2005

A Laboratory study was conducted to evaluate the kinetics of oxidation of trichloroethylene (TCE) in groundwater by potassium permanganate $(KMnO_4)$, Consumption of permanganate by TCE and aquifer materials was also evaluated to obtain an appropriate injection rate of $KMnO_4$. TCE degradation by $KMnO_4$ in the absence of aquifer material showed effective with pseudo-first order rate constant, $k_{obs}=1.8110^{-3}\;s^{-1}\;at\;KMnO_4=500mg/L$. TCE oxidation by $KMnO_4$ was found to be second order reaction and the rate constant, $k=0.65{\pm}0.08\;M^{-1}s^{-1}$, was independent of pH changes. $KMnO_4$ consumption rate by groundwater sampled from field site was not significant, indicating that groundwater containing negligible amount of dissolved organic matter does not have any influence on the $KMnO_4$ degradation. Meanwhile, aquifer materials from field site were actively reacted with permanganate, resulting in the significant consumption of $KMnO_4$. It might be attributed to the existence of metal oxides in aquifer materials, Based on the rate constants obtained from this study, appropriate injection rate of permanganate and TCE removal rate in groundwater could be estimated.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.673-677
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• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1789-1793
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the reactions of 5-nitro-8-quinolyl nicotinate (4) and 5-nitro-8-quinolyl isonicotinate (5) with alkali metal ethoxides (EtOM; M = K, Na and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plots of $k_{obsd}$ vs. [EtOM] curve slightly upward for the reactions with EtOK and EtONa but are linear for the reactions with EtOLi and for those with EtOK in the presence of 18-crown-6-ether. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ and ion-paired EtOM, respectively) has revealed that the reactivity increases in the order $EtO^-{\approx}EtOLi$ < EtOK < EtONa for the reactions of 4 and EtOLi < $EtO^-$ < EtOK < EtONa for the reactions of 5. Comparison of the kinetic results for the reactions of 4 and 5 with those reported previously for the corresponding reactions of 5-nitro-8-quinolyl benzoate (2) and picolinate (3) has revealed that the esters possessing a pyridine ring (i.e., 3-5) are significantly more reactive than the benzoate ester 2 due to the presence of the electronegative N atom (e.g., 2 << 3 < 4 < 5). It has been concluded that $M^+$ ion catalyzes the reactions of 3-5 by increasing the electrophilicity of the reaction center through a five-membered cyclic transition state (TS) for the reaction of 3 and via a four-membered cyclic TS for the reactions of 4 and 5.

• Membrane Journal
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• v.14 no.4
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• pp.275-288
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• 2004

Carbon dioxide was absorbed into water-in-oil (w/o) emulsion composed of aqueous 2-amino-2-methyl-1-propanol (AMP) droplets as a dispersed phase and benzene solutions of polybutene and polyisobutylene as a continuous phase in a flat-stirred vessel to investigate the effect of non-Newtonian rheological behavior on the rate of chemical absorption of $CO_2$, where the reaction between $CO_2$ and AMP in the aqueous phase was assumed to be a pseudo-first-order reaction. It was expressed that PIB with elastic property made the rate of chemical absorption of $CO_2$ accelerated by comparison of mass transfer coefficient of $CO_2$ in the non-Newtonian liquid with that in the Newtonian liquid.

• Bulletin of the Korean Chemical Society
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• v.33 no.9
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• pp.3009-3016
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• 2012

This study evaluated the use of iron-impregnated SBA-15 (Fe/SBA-15) as a catalyst for the oxidative degradation of persistent phenol analogues, such as 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP) and 2,4,6-trichlorophenol (2,4,6-TCP) in water. The oxidation reactions were carried out with reaction time, concentration of the phenols, amount of the catalysts, reaction temperature, pH of the reaction mixture as the process variables with or without using hydrogen peroxide as the oxidizing agent. The conversion achieved with Fe/SBA-15 at 353 K for 2-CP, 4-CP, 2-NP, 4-NP, 2,4,6-TCP was 80.2, 71.2, 53.1, 62.8, 77.3% in 5h with a reactant to $H_2O_2$ mole ratio of 1:1, and 85.7, 65.8, 61.9, 63.7, 78.1% in the absence of $H_2O_2$, respectively. The reactions followed pseudo first order kinetics. The leachability study indicated that the catalyst released very little iron into water and therefore, the possibility of secondary pollution is negligible.

• Journal of Korea Soil Environment Society
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• v.4 no.1
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• pp.97-108
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• 1999

Reduction 2, 4, 6-trinitrotoluene by zero valent iron was studied in a batch reactor under anoxic conditions. Results showed that the removal of trinitrotoluene (TNT)followed a pseudo-first order reaction and the rate was linearly dependent on the available reactive surfau area of the zero valent iron surface area, resulting a rate constant of 0.0981min$^{1}m$$^{-2}m$. High concentrations of the final product, presumably triaminotoluene which needs to be treated by other means, accumulated in the solution. However , little amount of TAT was extracted from the metal surface by using acetonitrile or phosphate buffered water (pH 7.0). Other common major intermediate in biological TNT degradation, a group of aminodinitrotoluenes, was not detected in the solution. Therefore, it is postulated that the reduction of nitro group by $Fe^0$ occurs simultaneously in all three positions and a TNT reduction model by zero valent iron was suggested.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1749-1753
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• 2014

Pseudo-first-order rate constants ($k_{obsd}$) have been measured spectrophotometrically for the nucleophilic substitution reaction of Y-substituted-phenyl picolinates (7a-f) with potassium ethoxide (EtOK) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. The plot of $k_{obsd}$ vs. [EtOK] curves upward while the plot of $k_{obsd}/[EtO^-]_{eq}$ vs. $[EtO^-]_{eq}$ is linear with a positive intercept in all cases. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOK}$ (i.e., the second-order rate constants for the reactions with the dissociated $EtO^-$ ion and ion-paired EtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated $EtO^-$. The ${\sigma}^{\circ}$ constants result in a much better Hammett correlation than ${\sigma}^-$ constants, indicating that the reaction proceeds through a stepwise mechanism in which departure of the leaving group occurs after the rate-determining step (RDS). $K^+$ ion catalyzes the reaction by increasing the electrophilicity of the reaction center through formation of a cyclic transition state (TS). The catalytic effect decreases as the substituent Y becomes a stronger electron-withdrawing group (EWG). Development of a positive charge on the N atom of the picolinyl moiety through resonance interactions is responsible for the decreasing $K^+$ ion catalysis.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.29 no.1B
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• pp.97-103
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• 2009

The decompostion characteristics of NAPL TCE in cement/slag/Fe(II) system were studied with various TCE concentration and amounts of binders (cement/slag) For analyses of the TCE degradation by cement/slag/Fe(II), TCE solution injected using gas-tight syringe after TCE solution dissolved a methanol. Initial concentrations of TCE are 0.42 mM, NAPL condition 11.7 mM and saturated condition 16.8 mM respectively. The result showed that the cases of 8.4 mM and 4.2 mM are decreased 88% of total TCE concentration within 18 days. NAPL condition 11.7 mM was decreased 84% within 50 days and saturated condition 16.8 mM was decreased 60% of total TCE concentration within 60 days respectively. This showed that degradations of TCE in various concentrations were in one kind reaction as pseudo-first-order. TCE was dissolved as aqueous solution before degraded. The reaction rate was increased $0.12day^{-1}$, $0.24day^{-1}$, $0.31day^{-1}$ when the mass of media 0.1, 0.2, 0.3 S/L rate was increased. TCE reaction speed is affected by cement/slag surface ares in this system. When HDTMA, experimental facter, was added, TCE decomposition rate was high despite the high concentration of NAPL. and The decompostion characteristics of NAPL TCE in cement/slag/Fe(II) system were studied by using modeling.