• Journal of the Korean Chemical Society
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• v.43 no.1
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• pp.85-91
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• 1999

The second order rate constants for the hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates (2,4-$(NO_2)_2$, 4-$NO_2$, 4-CN, 4-Cl, 4-H)in 20% dioxane-water (v/v) have been determined by UV/Vis spectrophotometric method at various temperatures. The activation parameters (Ea, ${\Delta}H^{\neq}$,${\Delta}S^{\neq}$) were calculated from the rate constants and the reaction constant ($\rho$) was also estimated by Hammett equation. The activation entropies of the title reactions show considerably negative values, this result is not consistent with a dissociative mechanism (EA) in which a positive or a slightly negative value of the entropy of activation should be expected. Further, kinetic evidence for an associative mechanism (AE) was obtained from the linear free energy relationship. By the results of kinetic study for the alkaline hydrolysis of substituted phenyl N,N-diethyl-P-benzylphosphonamidates, it may be concluded that these reactions proceed through an associative mechanism.

• Journal of the Korean Chemical Society
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• v.40 no.12
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• pp.733-740
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• 1996

The rate constants for the hydrolysis of 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide(AMQD) were determined by ultraviolet visible spectrophotometer in water at $25^{\circ}C.$ The rate equation which could be applied over wide pH ranges were obtained. On the basis of pH-rate profile, Bronsted plot, hydrolysis product analysis, general base catalysis and substituent effect, the plausible hydrolysis mechanism was proposed: Below pH 3.00, the hydrolysis reaction was proceeded by the attack of water to 4'-position of quinonoid after protonation at nitrogen of acridinyl and between pH 3.00 and 9.00, the addition of water and hydroxide occurred competitively. However, above pH 9.00, the rate constants were dependent upon only the concentration of hydroxide ion.

• Journal of Korean Society of Environmental Engineers
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• v.33 no.3
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• pp.157-161
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• 2011

This study investigated decomposition the pathway and characteristics of fenitrothion, which is applied on the golf course for pesticide, by ZVI in batch reactor. The removal efficiencies of the pure fenitrothion and the commercial fenitrothion in Smithion by ZVI were compared. The fenitrothion was converted to 3-Methyl-4-nitrophenol and 4-Amino-m-cresol by ZVI. The fenitrothion decomposition rate by ZVI could be expressed by the first order reaction. As increasing the ZVI dosages, the first order rate constants and removal efficiencies increased. The surface area normalized rate constants for the pure fenitrothion and the commercial fenitrothion were 0.0398 and 0.1312 ($L/m^2{\cdot}hr$), respectively. The decomposition of the commercial fenitrothion in Smithion was faster than that of the pure fenitrothion by ZVI, the surfactant in Smithion lead to enhances solubility of fenitrothion and disperse ZVI.

• Journal of the Korean Chemical Society
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• v.19 no.2
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• pp.123-129
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• 1975

The rate constants of the hydrolysis of phenylvinylsulfone were determined by ultraviolet spectrophotometry at various pH and a rate equation which can be applied over wide pH range was obtained. The reaction mechanism of hydrolysis of phenylvinylsulfone and especially the catalytic contribution of hydroxide ion which did not study carefully before in acidic media, can be fully explained by the rate equation obtained. The rate equation reveals that: below pH 7, the reaction is initiated by the addition of water molecule to phenylvinylsulfone. At above pH 9, the overall rate constant is only dependent upon the concentration of hydroxide ion.

• Journal of Food Hygiene and Safety
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• v.14 no.3
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• pp.249-254
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• 1999

The present study was performed to investigate biodegradation rate of BPMC(2-sec-butylphenyl methyl carbamate) and chlorothalonil. In the biodegradation test of two pesticides by the modified river die-away method from June 17 to August 22, 1998, the biodegradation rate constants and half-life were determined in Nakdong(A) and Kumho River(B). Bio- degradation rate of BPMC was 27% in A sampling point, 40% in B sampling point after 7 days. Biodegradation rate constants and half-life of BPMC were 0.0460 and 15.1 days in A sampling point, 0.0749 and 9.3 days in B sampling point, respectively. Biodegradation rate of chlorothalonil was 100% in A and B sampling points after 7 days. Biodegradation rate constants and half-life of chlorothalonil were 0.1416 and 4.9 hours in A sampling point, 0.1803 and 3.8 hours in B sampling point, respectively. Biodegradation rate of chlorothalonil was faster than that of BPMC. Correlation analysis between biodegradation rate constants of pesticides and water quality(DO, BOD, SS, ABS, $NH_3-N\;and\;NO_3-N$) showed significant correlation with BOD, SS and $NH_3-N$. Furthermore, regression analysis with BOD, SS and $NH_3-N$ as independent variable and biodegradation rate constant as independent variable showed a significant linear equation. These results suggested that BPMC and chlorothalonil were mainly degraded by biodegradation, and the difference in biodegradation of two pesticides was due to difference of water quality.

• 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.

• Journal of the Korea Organic Resources Recycling Association
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• v.15 no.3
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• pp.113-120
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• 2007

Anaerobic batch tests were performed to evaluate the characteristics of methane production from piggery manure such as the ultimate methane yield (UMY), the kinetic constant and the maximum methane production rate. The kinetic behavior of anaerobic degradation of piggery manure was assumed as a first order reaction. The UMY, the first order kinetic constant and the maximum methane production rate were 0.27~0.44L $CH_4/gVS$, $0.161{\sim}0.280d^{-1}$ and 0.043~0.120L $CH_4/d$, respectively. Reactor of piggery manure as the self-seed source of anaerobic digestion resulted in longer acclimation time than reactors seeded with anaerobic digested sludge (ADS). But there was no little difference in the UMY between the two seed materials. The anaerobic digestion can be effective for the treatment of piggery manure containing high concentration of solids, the two-stage anaerobic digestion is, however, thought to be more effective than the traditional single one.

• Journal of the Korean Chemical Society
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• v.44 no.2
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• pp.120-126
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• 2000

The rate constants for the hydrolysis of 2-phenyl-4H,5H-3-methyl-3-thiazolinium perchlorate(PTP) derivatives were detemined by the use of ultraviolet visible spectrophotometer in water. The rate equations which could be applied over a wide pH ranges were obtained. On the basis of rate equation, hydrolysis product analysis, general base catalysis, and substituent effect, a plausible mechanism of the hydrolysis is proposed: Below pH 4.0, the reaction is initiated by addition of water, while above pH 9.0, Michael type nucleophilic addition takes place. In the pH range of $4.5{\sim}8.0$, these two reactions appear to occur competitively.

• Applied Chemistry for Engineering
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• v.18 no.5
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• pp.415-423
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• 2007

Pyrolysis characteristics of sawdust and rice husk as biomass resources in a thermogravimetric analysis were determined. Experiments were carried out with a linear heating rate under inert atmosphere of $N_2$ gas. Pyrolysis of the biomass can be classified as a lower temperature reaction zone where the major component of holocellulose is thermally decomposed and a high temperature reaction zone where lignin is thermally decomposed. The obtained data was analyzed by the two-step consecutive reaction model. Activation energies of sawdust and rice husk are found to be respectively 82.5 kJ/mol and 85.1kJ/mol in the low temperature zone according to the first order reaction model and 19.7 kJ/mol, 22.0 kJ/mol in the high temperature zone according to the three-way transport model. The reaction rate constant with variation of heating rate can be well predicted by the kinetic compensation relation of Gaur-Reed.

• Journal of computational fluids engineering
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• v.13 no.4
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• pp.50-57
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• 2008

The prediction of hydrate pellet decomposition characteristics is required to design the regasification process of GTS (gas to solid) technology, which is considered as an economic alternative for LNG technology to transport natural gas produced from small and stranded gas wells. Mathematical model based on the conservation principles, the phase equilibrium relation, equation of gas state and phase change kinetics was set up and numerical solution procedure employing volume averaged fixed grid formulation and extended enthalpy method are implemented. Initially, porous methane hydrate pellet is at uniform temperature and pressure within hydrate stable region. The pressure starts to decrease with a fixed rate down to the final pressure and is kept constant afterwards while the bounding surface of pellet is heated by convection. The predicted convective heat and mass transfer accompanied by the decomposed gas flow through hydrate/ice solid matrix is reported focused on the comparison of spherical and cylindrical pellets having the same effective radius.