• Korean Journal of Ecology and Environment
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• v.34 no.4 s.96
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• pp.261-266
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• 2001

Effects of elevated carbon dioxide ($CO_2$) on soil microbial processes were studied in a northern peatland. Intact peat cores with surface vegetation were collected from a northern Welsh fen, and incubated either under elevated carbon dioxide (700 ppm) or ambient carbon dioxide (350 ppm) conditions for 4 months. Higher algal biomass was found under the elevated $CO_2$ condition, suggesting $CO_2$ fertilization effect on primary production, At the end of the incubation, trace gas production and consumption were analyzed using chemical inhibitors. For methane ($CH_4$ ), methyl fluoride ($CH_3F$) was applied to determine methane oxidation rates, while acetylene ($C_2H_2$) blocking method were applied to determine nitrification and denitrification rates. First, we have adopted those methods to optimize the reaction conditions for the wetland samples. Secondly, the methods were applied to the samples incubated under two levels of $CO_2$. The results exhibited that elevated carbon dioxide increased both methane production (210 vs. $100\;ng\;CH_4 g^{-1}\;hr^{-1}$) and oxidation (128 vs. $15\;ng\;CH_4 g^{-1}\;hr^{-1}$), resulting in no net increase in methane flux. For nitrous oxide ($N_2O$) , elevated carbon dioxide enhanced nitrous oxide emission probably from activation of nitrification process rather than denitrification rates. All of these changes seemed to be substantially influenced by higher oxygen diffusion from enhanced algal productivity under elevated $CO_2$.

• 한국연소학회:학술대회논문집
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• 2006.04a
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• pp.149-156
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• 2006

Structure of edge flame established in a mixing layer, formed between two uniformly flowing pure $CH_4$ and pure $O_2$ streams, is numerically investigated by employing a detailed methane-oxidation mechanism. The numerical results exhibited the most outstanding distinction of using pure oxygen in the fuel-rich premixed-flame front, through which the carbon-containing compound is found to leak mainly in the form of CO instead of HC compounds, contrary to the rich $CH_4-air$ premixed flames in which $CH_4$ as well as $C_2H_m$ leakage can occur. Moreover, while passing through the rich premixed flame, a major route for CO production, in addition to the direct $CH_4$ decomposition, is found to be $C_2H_m$ compound formation followed by their decomposition into CO. Beyond the rich premixed flame front, CO is further oxidized into $CO_2$ in a broad diffusion-flame-like reaction zone located around moderately fuel-rich side of the stoichiometric mixture by the OH radical from the fuel-lean premixed-flame front. Since the secondary CO production through $C_2H_m$ decomposition has a relatively strong reaction intensity, an additional heat-release branch appears and the resulting heat-release profile can no longer be seen as a tribrachial structure.

• Journal of the Korean Society of Combustion
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• v.11 no.1
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• pp.19-26
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• 2006

Structure of edge flame established in a mixing layer, formed between two uniformly flowing pure $CH_4$ and pure $O_2$ streams, is numerically investigated by employing a detailed methane-oxidation mechanism. The numerical results exhibited the most outstanding distinction of using pure oxygen in the fuel-rich premixed-flame front, through which the carbon-containing compound is found to leak mainly in the form of CO instead of HC compounds, contrary to the rich $CH_4-air$ premixed flames in which $CH_4$ as well as $C_2H_m$ leakage can occur. Moreover, while passing through the rich premixed flame, a major route for CO production, in addition to the direct $CH_4$ decomposition, is found to be $C_2H_m$ compound formation followed by their decomposition into CO. Beyond the rich premixed flame front, CO is further oxidized into $CO_2$ in a broad diffusion-flame-like reaction zone located around moderately fuel-rich side of the stoichiometric mixture by the OH radical from the fuel-lean premixed-flame front. Since the secondary CO production through $C_2H_m$ decomposition has a relatively strong reaction intensity, an additional heat-release branch appears and the resulting heat-release profile can no longer be seen as a tribrachial structure.

• Korean Chemical Engineering Research
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• v.48 no.6
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• pp.776-783
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• 2010

Co and Ni catalysts supported on $Al_2O_3$ for partial oxidation of methane producing hydrogen were synthesized using impregnation to incipient wetness. The activities of these catalysts for the partial oxidation of methane was investigated at 1 atm and $CH_4/O_2=2.0$ in the temperature range of $450{\sim}650^{\circ}C$. The reaction activity of $Ni/Al_2O_3$ and $Co/Al_2O_3$ catalysts with different loading was investigated. And the beneficial effects of Ni addition to $Co/Al_2O_3$ and the promotional effects of Ce and La addition to $Ni/Al_2O_3$ and $Co/Al_2O_3$ were investigated. These catalysts were characterized by XRD and SEM/EDX. Comparing catalyst loadings, 10 wt% Co and 10 wt% Ni were found to be optimal at the experimental conditions. The 10 wt% $Ni/Al_2O_3$ and 10 wt% $Co/Al_2O_3$ catalysts in partial oxidation of methane showed $CH_4$ conversions and CO selectivity close to the thermodynamic equilibrium levels, but showed lower $H_2$ selectivity than equilibrium level. The addition of Ni to $Co/Al_2O_3$ exhibited higher $H_2$ selectivity but beneficial effect was not observed in the $CH_4$ conversion. Addition of Ce to $Co/Al_2O_3$ and addition of La to $Ni/Al_2O_3$ a improved the $CH_4$ conversion level and $H_2$ selectivity.

• Proceedings of the KSME Conference
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• 2000.04b
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• pp.949-955
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• 2000

Numerical study with detailed chemistry has been conducted to investigate the NOx formation and structure in $CH_4/Air-CO_2$ counterflow diffusion flames. The importance of radiation effect is identified and the role of $CO_2$ addition is addressed to thermal and chemical reaction effects, which can be precisely specified through the introduction of an imaginary species. Also NO separation technique is utilized to distinguish the contribution of thermal and prompt NO formation mechanisms. The results are as follows : The radiation effect is dominant at low strain rates and it is intensified by $CO_2$ addition. Thermal effect mainly contributes to the changes in flame structure and the amount of NO formation but the chemical reaction effect also cannot be neglected. It is noted that flame structure is changed considerably due to the addition of $CO_2$ in such a manner that the path of methane oxidation prefers to take $CH_4 {\rightarrow}CH_3{\rightarrow}C_2H_6{\rightarrow}C_2H_5$ instead of $CH_4 {\rightarrow}CH_3{\rightarrow}CH_2{\rightarrow}CH$. At low strain rate(a=10) the reduction of thermal NO is dominant with respect to reduction rate, but that of prompt NO is dominant with respect to total amount.

• Membrane and Water Treatment
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• v.8 no.2
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• pp.171-184
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• 2017

This study presents the effect of hydraulic retention time (HRT) on the characteristics of emission of three major greenhouse gases (GHGs) including $CH_4$, $CO_2$ and $N_2O$ during operation of a sequencing batch reactor for aerobic oxidation of methane with denitrification (AeOM-D SBR). Dissolved $N_2O$ concentration increased, leveled-off and slightly decreased as the HRT increased from 0.25 to 1d. Concentration of the dissolved $N_2O$ was higher at the shorter HRT, which was highly associated with the lowered C/N ratio. A longer HRT resulted in a higher C/N ratio with a sufficient carbon source produced by methanotrophs via methane oxidation, which provided a favorable condition for reducing $N_2O$ formation. With a less formation of the dissolved $N_2O$, $N_2O$ emission rate was lower at a longer HRT condition due to the lower C/N ratio. Opposite to the $N_2O$ emission, emission rates of $CH_4$ and $CO_2$ were higher at a longer HRT. Longer HRT resulted in the greater total GHGs emission as $CO_2$ equivalent which was doubled when the HRT increased from 0.5d to 1.0 d. Contribution of $CH_4$ onto the total GHGs emission was most dominant accounting for 98 - 99% compared to that of $N_2O$ (< 2%).

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.

• Bulletin of the Korean Chemical Society
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• v.24 no.1
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• pp.60-64
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• 2003

The reactions of $[Pt(dppf)Cl_2]$ with thiophenol (PhSH), 1-propanethiol (n-PrSH), and 1,3-propanedithiol $(HSCH_2CH_2CH_2SH)$ gave the corresponding Pt-dppf-di(thiolato) compounds, $[Pt(dppf)(SPh)_2]\;(1),\;[Pt(dppf)(S-n-Pr)_2]\;(2),\;and [Pt(dppf)(SCH_2CH_2CH_2S)]\;(3)$, respectively. All products are monomeric and 4-coordinate square-planar compounds and were structurally characterized by X-ray diffraction. Electrochemical measurements (cyclovoltammograms) revealed that the oxidation potential of the dppf ligand appears to depend on the type of the group on the thiolato ligand.

• Proceedings of the Korean Environmental Sciences Society Conference
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• 2018.10a
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• pp.130-130
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• 2018

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.953-958
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• 2010

A laser ablation-molecular beam/reflectron time-of-flight mass spectrometric technique was used to investigate the ion-molecule reactions that proceed within $Ti^+(CH_3COCH_3)_n$ heterocluster ions. The reactions of $Ti^+$ with $CH_3COCH_3$ clusters were found to be dominated exclusively by an oxidation reaction, which produced $TiO^+(CH_3COCH_3)_n$ clusters. These ions were attributed to the insertion of a $Ti^+$ ion into the C=O bond of the acetone molecule within the heteroclusters, followed by $C_3H_6$ elimination. The mass spectra also indicated the formation of minor sequences of heterocluster ions with the formulas $Ti^+(C_3H_4O)(CH_3COCH_3)_n$ and $TiO^+(OH)(CH_3COCH_3)_n$, which could be attributed to C-H bond insertion followed by $H_2$ elimination and to the sequential OH abstraction by the $TiO^+$ ion, respectively. Density functional theory calculations were carried out to model the structures and binding energies of both the association complexes and the relevant reaction products. The reaction pathways and energetics of the $TiO^+\;+\;CH_2CHCH_3$ product channel are presented.