• Journal of the Korean Society of Marine Environment & Safety
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• v.18 no.2
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• pp.139-144
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• 2012

A numerical simulation has been performed to investigate effects of toluene mixing on soot formation in pure ethylene opposed-flow nonpremixed flame. Mixture ratios of toluene were 3%, 5%, 10%, and 20%. Senkin code for 0-D simulation and oppdif code for 1-D simulation based on CHEMKIN III were utilized. 0-D results by senkin showed that concentrations of methyl radicals and benzene were increased with increasing toluene mixture ratio. This implied that the mixing of toluene in pure ethylene diffusion flame produces more PAHs and soot than those of pure ethylene flame. 1-D result of 10 % toluene reaction by oppdif code showed that production rate for H radical was a crucial factor for benzene formation. These results imply that methyl radical, benzene and H radical play a important role on soot formation in diffusion flames.

• Journal of the Korean Chemical Society
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• v.26 no.1
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• pp.1-6
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• 1982

The addition of thiophenol to ${\alpha}$-methylstyrene has been studied MO theoretically using CNDO/2 method. Although overall reaction proceeds in two steps i.e., (1) decomposition of thiophenol to give phenylthiyl radical and (2) addition of the radical to ${\alpha}$-methylstyrene to give a new monomer radical, theoretical results suggested that the phenylthiyl radical formation step, (1), was the dominant process in determining the rate of addition; this was the rationale behind the negative ${\rho}$ value obtained experimentally from the Hammett plots for substituents on the thiyl radicals. The departure from a linear Hammett plot for addition of ${\rho}$-chlorophenylthiyl and m-trifluoromethyl phenylthiyl to ${\rho}$-methoxy-${\alpha}$-methylstyrene could be explained as a result of an increased contribution of the addition step, (2) to the overall reaction rate.

• Journal of the Korean Society of Combustion
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• v.4 no.2
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• pp.51-62
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• 1999

NOx formation in turbulent flames is strongly coupled with temperature, superequilibrium concentration of O radical, and residence time. This implies that in order to accurately predict NO level, it is necessary to develop sophisticated models able to account for the complex turbulent combustion processes including turbulence/chemistry interaction and radiative heat transfer. The present study numerically investigates the turbulent nonpremixed hydrogen jet flames using the laminar flamelet model. Flamelet library is constructed by solving the modified Peters equations and the turbulent combustion model is extended to nonadiabatic flame by introducing the enthalpy defect. The effects of turbulent fluctuation are taken into account by the presumed joint PDFs for mixture fraction, scalar dissipation rate, and enthalpy defect. The predictive capability of the present model has been validated against the detailed experimental data. Effects of nonequilibrium chemistry and radiative heat loss on the thermal NO formation are discussed in detail.

• 한국연소학회:학술대회논문집
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• 1999.10a
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• pp.93-104
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• 1999

NOx formation in turbulent flames is strongly coupled with temperature, superequilibrium concentration of O radical, and residence time. This implies that in order to accurately predict NO level, it is necessary to develop sophisticated models able to account for the complex turbulent combustion processes including turbulence/chemistry interaction and radiative heat transfer. The present study numerically investigates the turbulent nonpremixed hydrogen jet flames using the laminar flamelet model. Flamelet library is constructed by solving the modified Peters equations and the turbulent combustion model is extended to nonadiabatic flame by introducing the enthalpy defect. The effects of turbulent fluctuation are taken into account by the presumed joint PDFs for mixture fraction, scalar dissipation rate, and enthalpy defect. The predictive capability of the present model has been validated against the detailed experimental data. Effects of nonequilibrium chemistry and radiative heat loss on the thermal NO formation are discussed in detail.

• The Korean Journal of Pharmacology
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• v.21 no.1
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• pp.12-26
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• 1985

The generation of $O^{-}_{2}{\cdot}$ and its toxic effects were studied with rat brain mitochondria. The production of $O^{-}_{2}{\cdot}$ from mitochondria in the presence of succinate and antimycin was demonstrated by SOD-inhibitable reduction of NBT. Although succinate can support the $O^{-}_{2}{\cdot}$ formation, the highest rate needs antimycin indicating that blockade of electron flow in the respiratory chain augments the univalent reduction of molecular oxygen. Under this condition, $H_2O_2$ was also observed to be produced. But its formation appears to be derived from the dismutation of the primary product, $O^{-}_{2}{\cdot}$ since the rate of $H_2O_2$ production was markedly decreased by NBT and ferricytochrome c. The $O^{-}_{2}{\cdot}$ and $H_2O_2$ produced were able to cause toxic actions to mitochondrial and extra-mitochondrial components as shown by lipid peroxidation of mitochondrial membrane, and inactivation and lysis of isocitrate dehydrogenase and erythrocytes added to the medium, respectively. In all the toxic actions observed, $Fe^{++}$ was required. It appears that in the toxic actions $OH{\cdot}$ generated from the iron-catalyzed Haber-Weiss reaction acts as a mediator. This was supported by the finding that mitochondria in the presence of succinate and antimycin produced ethylene from methional, and $Fe^{++}$ added increased the ethylene production. The observed toxic actions of mitochondrial $O^{-}_{2}{\cdot}$ may provide evidence supporting a potential role of mitochondria as a source of oxygen radicals to cause tissue damage.

• Transactions of the Korean Society of Automotive Engineers
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• v.15 no.5
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• pp.86-96
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• 2007

A direct-injection stratified-charge(DISC) engine has been considered as a promising alternative in spite of high unburned hydrocarbon emission levels during light load operation. In this paper investigation is made to characterize formation and combustion processes of stratified mixture charge in a simple constant volume combustion chamber. Both experimental and numerical analyses are performed for fluid and combustion characteristics with 3 different induction types for rich, homogeneous and lean mixture conditions. The commercial code FIRE is applied to the turbulent combustion process in terms of measured and calculated pressure traces and calculated distributions of mean temperature, OH radical and reaction rate. It turns out that the highest combustion rate occurs for the rich state condition at the spark ignition location due to existence of stoichiometric mixture and timing.

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.857-860
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• 1994

We have calculated the ${\pi}$-electron density, atom self-polarizability, and free valence on each atom of N-(2-chlorobenzyl)-pyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-2-chloropyridinium salts using a simple Huckel method in order to discuss their intramolecular photocyclization reaction in a qualitative method. Our calculation qualitatively predicts that photocyclization occurs through forming radicals as a reaction intermediate by breaking a C-Cl bond after photoexcitation into a triplet state via intersystem crossing from an initially excited singlet state. We noticed that this C-Cl bond breaking is aided by ${\pi}$-complex formation between a chlorine atom and the ${\pi}$ -electrons of the neighboring ring in the triplet state and a stronger ${\pi}$-complex bond makes C-Cl bond breaking, i.e., radical formation, much easier. A chlorine atom will form a stronger ${\pi}$ -complex bond to a benzyl ring of N-(benzyl)-2-chloropyridinium than a pyridinium ring of N-(2-chlorobenzyl)-pyridinium because the former can donate its ${\pi}$-electron more easily than the latter. The chlorine at position 15 of N-(2-chlorobenzyl)-2-chloropyridinium salt in the excited state also provides its ${\pi}$-electron to the benzyl ring. So this ${\pi}$-electron can increase the bond strength of the $\pi-complex.$ Therefore, the strength of ${\pi}$-complex follows the order of N-(2-chlorobenzyl)-2-chloropyridinium, N-(benzyl)-2-chloropyridinium, and N-(2-chlorobenzyl)-pyridinium salts and thus the radical formation rate. This provides us with an intramolecular photocyclization reaction rate of the same order as given above.

• Rapid Communication in Photoscience
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• v.3 no.4
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• pp.70-72
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• 2014

Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.

• Transactions of the Korean hydrogen and new energy society
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• v.18 no.2
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• pp.157-163
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• 2007

During PEMFC operation, low current and low humidity conditions accelerate the degradation of perfluorosulfonic acid membrane. But, there have been no studies that clearly explain why these conditions accelerate the membrane degradation. In this study, the hydrogen permeability through the membrane, I-V polarization of MEA, fluoride emission rate(FER) in effluent water were measured during cell operation under low current densities and low relative humidity(RH). The experimental results were evaluated with oxygen radical mechanism the most commonly known for membrane degradation. It seems that low RH of anode is a good condition for $H{\cdot}$ radical formation on the Pt catalyst and the low current condition accelerates the $H{\cdot}$ to form $HO_2{\cdot}$ radical attacking the polymer membrane.

• Journal of Environmental Science International
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• v.19 no.9
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• pp.1143-1152
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• 2010

The purpose of this study is to degradation of Rhodamine B (RhB, dye) and N, N-Dimethyl-4-nitrosoaniline (RNO, indicator of the electro-generation of OH radical) in solution using boron doped diamond (BDD) electrode. The effects of applied current (0.2~1.0 A), electrolyte type (NaCl, KCl, and $Na_2SO_4$) and electrolyte concentration (0.5~3.0 g/L), solution pH (3~11) and air flow rate (0~4 L/min) were evaluated. Experimental results showed that RhB and RNO removal tendencies appeared with the almost similar thing, except of current. Optimum current for RhB degradation was 0.6 A, however, RNO degradations was increased with increase of applied current. The RhB and RNO degradation of Cl type electrolyte were higher than that of the sulfate type. The RhB and RNO degradation were increased with increase of NaCl concentration and optimum NaCl dosage was 2.5 g/L. The RhB and RNO concentrations were not influenced by pH under pH 7. Optimum air flow rate for the oxidants generation and RhB and RNO degradation were 2 L/min. Initial removal rate of electrolysis process was expressed Langmuir - Hinshelwood equation, which is used to express the initial removal rate of UV/$TiO_$2 process.