Development and Application of a Landfill Gas Migration Model

박유철,이강근,박철휘,김용우,Park, Yu-Chul,Lee, Kang-Kun,Park, Chul-Hwi,Kim, Yong-Woo The Korean Society of Economic and Environmental G 1996 자원환경지질 Vol.29 No.3

numerical model is developed to estimate gas flow in the landfill site. Darcy's law, the mass conservation law, and the ideal gas state equation are combined to compose the governing equation for the steady-state and transient-state gas flows. The finite element method (FEM) is used as the numerical solution scheme. Two-dimensional radial symmetric triangular ring element is used to discretize the simulation domain. The steady state model developed in this study is compared with AIRFLOW that is a commercial model developed by Hydrologic Inc. Mass balance test is performed on the transient gas flow simulation. The developed model is applied to analyze the gas extraction experiment performed by Daewoo Institute of Construction Technology at the Nanjido landfill in 1993. The developed model was registered at Korea Computer Program Protection Foundation.

Ni(II)-$N_4$ 착이온의 낮은 스핀상태 ($D_{4h}$)와 높은 스핀상태 ($O_h$)간의 평형 ($N_4$ : 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene)

박유철,변종철,유만수,Yu-Chul Park,Jong-Chul Byun,Mahn-Su Yu 대한화학회 1989 대한화학회지 Vol.33 No.6

물, 아세토니트릴, 아세톤 및 니트로메탄에서 Ni(II)-tetraamine 착물(tetraamine=2.12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17)2,11,13,15-pentaene)의 화학평형을 분광광도법을 이용하여 각각 관찰하였다. Ni(II)-tetraamine 착이온의 낮은 스핀($D_{4h}$) 구조와 높은 스핀($O_h$)구조간의 평형이 물, 아세토니트릴, 아세톤 용액에서는 나타났지만 니트로메탄 용액에서 나타나지 않았다. 평형상수와 반응엔탈피 및 반응엔트로피는 착물의 전자스펙트럼에 대한온도의 영향을 분석하므로써 결정하였다. $O_h$ 구조인 triplet 화학종의 형성은 발열과정으로 나타났었다. $D_{4h}$와 $O_h$간의 평형에 대한 용매와 전해질의 영향은 용매의 유전상수와 반응엔트로피로 설명할 수 있었다. The chemical equilibria of Ni(II)-tetraamine (tetraamine = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-11,3,1-heptadeca-1(17),2,11,13,15-pentaene) complex ion in water, acetonitrile, acetone and nitromethane were investigated using spectrophotometric method, respectively. The equilibria between low-spin ($D_{4h}$) and high-spin ($O_h$) structures of Ni-tetraamine complex ion were presented in water, acetonitrile and acetone, but not in nitromethane. The eqilibrium constants, the reaction enthalpies and the reaction entropies were determined from analysis of the temperature dependence of the electronic spectra. The formation of the triplet species ($O_h$) was found to be exothermic. The solvent and electrolyte effects on the equilibrium constants could be explained by the dielectric constants of solvents and the reaction entropies.

Methalloporphyrin(MTPP 및 M(o-Cl)TPP)과 염기성리간드(L)간의 화학평형. (M = $Zn^{2+},\;Cu^{2+},\;Ni^{2+}$:TPP = tetraphenylporphyrin, (o-Cl)TPP = tetrakis (ortho-chlorophenyl)porphyrin: L = imidazole, pyridine,1-methylimidazole, 2,6-lutidine)

박유철,김성수,나훈길,Yu Chul Park,Seong Su Kim,Hun Gil Na 대한화학회 1991 대한화학회지 Vol.35 No.5

The axial ligations of nitrogenous bases (pyridine, imidazole, 1-methylimidazole and 2,6-lutidine) to Zn(II)-, Cu(II)-, and Ni(II)-tetrakis(o-chlorophenyl)porphyrin(o-ClTPP), and -tetraphenylporphyrin (TPP) were investigated in organic solvents $(CH_2Cl_2,\;C_6H_6,\;CH_3NO_2,\;(CH_3)_2CO,\;CHCl_3,\;DMF\;and\;DMSO)$ and at 0.01M of ionic strength. The equilibrium constants for the ligation reactions of methalloporphyrins were determined using spectrophotometric method at 15∼35${\circ}C$. In case of M(II)-TPP the equilibrium constants K were considerably larger than those of M(II)-(o-Cl)TPP, depending on steric effect of the porphyrin. The linear relationships between logK of the axial ligation and $pK_a$ of nitrogenous base were shown in M(II)-TPP, but not in M(II)-(o-Cl)TPP. The stabilities of MTPP(L) were controlled by the reation enthalpy and entropy, while those of M(o-Cl)TPP almost by the reaction entropy. The coordinating power of solvent to the methalloporphyrin were also studied in $CHCl_3,\;(CH_3)_2CO$, DMF and DMSO. From those results the solvent effects on the equilibrium constants were discussed.

[Cu(dl-trans-[14]-diene)]$^{2+}$ 착이온과 음이온 (S$_2O_3^{2-},\;SCN^-,\;I^-$ 및 NO$_2^-$)간의 화학반응에 대한 열역학적 성질 (${\Delta}G;\;{\Delta}H;\;{\Delta}V$)

박유철,변종철,Yu Chul Park,Jong Chul Byun 대한화학회 1985 대한화학회지 Vol.29 No.3

The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]$^{2+}$ and L$^{n-}$(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$) ions were studied by the spectrophotometric method in the range of 15 to 35$^{\circ}C$ and 1 to 1500bar. The equilibrium constants(K) for L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at 25$^{\circ}C$ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S$_2$O$_3^{2-}$, SCN$^-$ and I$^-$ except NO$_2^-$ ion were exothermic. The volume changes of reaction(${\Delta}$V) had positive values for all the used anions. The values of ${\Delta}$V in cm$^3$/mole for S$_2$O$_3^{2-}$ ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and L$^{n-}$ was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S$_2$O$_3^{2-}$ ion. [Cu(dl-trans-[14]-diene)]$^{2+}$ 착이온과 음이온(L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$)사이의 화학평형 관계를 온도 15 ~ 35$^{\circ}C$, 압력 1 ~ 1500bar 범위에서 분광광도법으로 연구하였다. S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ 및 NO$_2^-$일때 평형상수 K는 25$^{\circ}C$, 1500bar에서 각각 3.0, 1.9, 0.6 및 0.5이었다. K값은 온도와 압력이 증가함에 따라 감소하였다. K에 대한 온도 영향으로 부터 열역학적 파라메터(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$)를 계산하였으며, 이 결과 NO$_2^-$이온을 제외한 다른 이온(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$)에서는 모두 발열반응으로 나타났다. K에 대한 압력 영향에서 얻은 반응체적변화(${\Delta}$V)는 각 음이온에서 모두 양의 값이었다. S$_2$O$_3^{2-}$ 이온일 때 1,500, 1,000 및 1,500bar에서의 ${\Delta}$V(cm$^3$/mole)는 각각 26,22,19 및 16이었고, 상압에서 S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ 및 NO$_2^-$이온일 때 ${\Delta}$V(cm$^3$/mole)는 각각 26, 30, 64 및 45이었다. S$_2$O$_3^{2-}$이온인 경우 Fuoss식에 의하여 계산한 평형상수와 실험치를 비교하여 Cu(Ⅱ) 착이온과 L$^{n-}$간의 결합성을 고찰하였다.

Ga(Ⅲ), In(Ⅲ) 및 Tl(Ⅲ) 금속이온을 포함한 Metalloporphyrin 착물의 촉매적 특성

박유철,나훈길,김성수,Park, Yu Chul,Na, Hun Gil,Kim, Seong Su 대한화학회 1995 대한화학회지 Vol.39 No.5

The catalytic oxidations of several olefins in $CH_2Cl_2$ have been investigated using non-redox metalloporphyrin (M=Ga(III), In(III), Tl(III)) complexes as catalyst and sodium hypochlorite as terminal oxidant. Porphyrins were $(p-CH_3O)TPP,\;(p-CH_3)TPP,\;TPP,\;(p-F)TPP,\;(p-Cl)TPP\;and\;(F_20)TPP$ (TPP=tetraphenylporphyrin), and olefins were $(p-CH_3O)-,\;(p-CH_3)-,\;(p-H)-,\;(p-F)-,\;(p-Cl)-\;and\;(p-Br)styrene$styrene and cyclopentene and cyclohexene. The substrate conversion yield was discussed according to the substituent effects of metalloporphyrin and substrate, and the radius effect of non-redox metal ion. The conversion yield of substrate by changing the substituent of TPP increased in the order of $p-CH_3O$ < $p-CH_3$ < H < p-F < p-Cl, which was consistent with the sequence of $4{\sigma}$ values of TPP. But the substituent effect of substrate on the conversion yield decreased with increasing the ${\sigma}^+$ values on substrates in the order of p-CH3O > p-CH3 > H > p-Cl > p-Br. For the oxidation of several olefins, the complexes of In(III)- and Tl(III)-porphyrins turned out to be more active catalysts than Ga(III)-porphyrin.

Simulation of Groundwater Flow in Fractured Porous Media using a Discrete Fracture Model

박유철,이강근,Park, Yu-Chul,Lee, Kang-Kun The Korean Society of Economic and Environmental G 1995 자원환경지질 Vol.28 No.5

Groundwater flow in fracture networks is simulated using a discrete fracture (DF) model which assume that groundwater flows only through the fracture network. This assumption is available if the permeability of rock matrix is very low. It is almost impossible to describe fracture networks perfectly, so a stochastic approach is used. The stochastic approach assumes that the characteristic parameters in fracture network have special distribution patterns. The stochastic model generates fracture networks with some characteristic parameters. The finite element method is used to compute fracture flows. One-dimensional line element is the element type of the finite elements. The simulation results are shown by dominant flow paths in the fracture network. The dominant flow path can be found from the simulated groundwater flow field. The model developed in this study provides the tool to estimate the influences of characteristic parameters on groundwater flow in fracture networks. The influences of some characteristic parameters on the frcture flow are estimated by the Monte Carlo simulation based on 30 realizations.

몇가지 $d^8$ 전이금속-디포스핀 착물 ($MCl_2PP$)의 합성과 촉매적 응용 (M = $Ni^{2+}$, $Pd^{2+}$, $Pt^{2+}$, $Au^{3+}$ ; PP = diphosphines)

박유철,김경채,조영제,Park Yu-Chul,Kim Kyung-Chae,Cho Young-Jae 대한화학회 1992 대한화학회지 Vol.36 No.5

디포스핀을 포함한 몇가지 $d^8$ 전이금속착물$(MCl_2PP)$은 출발물질 $K_nMCl_m$을 사용하여 합성하였다. 중심금속(M)은 Ni(II), Pd(II), Pt(II), Au(III)이며, 디포스핀(PP)은 bis(diphenylphosphino)methane(dppm), bis(diphenylphosphino)ethane(dppe), bis(diphenylphosphino)propane (dppp) 및 bis(diphenylphosphino)ethylene(dppety)이었다. 착물의 조성이나 특성은 원소분석과 $^1H-NMR$, $^{31}P-NMR$ 및 UV-Visible 스펙트럼을 이용하여 확인하였다. 이들 착물의 촉매적 활성은 3(2H)-furanone 및 cyclic carbonate 생성반응에 대하여 각각 조사하였다. 2-methyl-3-butyn-2-ol로부터 생성물 3(2H)-furanone을 얻은 반응 (1)에서 Ni(II)-, Pd(II)-diphosphine 착물은 좋은 촉매적 효과를 나타내었다. 그러나 이들 diphosphine 착물들은 cyclic carbonate 생성반응 (2)에 대해 촉매제로서의 활성을 거의 나타내지 않았다.

아세톤-물 혼합용매에서 trans-$[Co(en)_2Cl-2]^+$, trans-$[Co(N-eten)_2Cl-2]^+$, trans-$[Co(N-meen)_2Cl_2]^+$, trans-$[Co(tn)_2Cl_2]^+$ 착이온의 가용매 분해반응에 대한 압력과 용매조성의 영향. 반응메카니즘과 자유에너지 변화사이클 및 Excess 자유에너지

박유철,조영제,Yu-Chul Park,Young-Je Cho 대한화학회 1985 대한화학회지 Vol.29 No.6

아세톤-물 혼합용매에서 trans-$[Co(AA)_2Cl_2]^+$ 착이온의 가용매분해반응속도를 전도도법과 분광광도법을 사용하여 1~2000bar의 압력범위ㅣ에서 측정하였다. 여기서 AA는 에틸렌디아민(en), N-에틸에틸렌디아민(N-eten), N-메틸에틸렌디아민(N-meen)과 트리메틸렌디아민(tn)을 각각 의미한다. 속도상수에 대한 압력의 영향으로부터 구한 활성화 체적은 AA가 en, N-eten, N-meen 및 tn 일때 각각 -0.2∼0.9 $cm^3mole^{-1}$, -0.2∼0.6 $cm^3mole^{-1}$, -0.8∼6.0 $cm^3mole^{-1}$, 0.7∼7.0$cm^3mole^{-1}$이었다. 이들 착이온의 가용매분해반응성은 excess 자유에너지와 자유에너지 사이클로부터 얻을 결과를 비교하여 검토하였다. 가용매분해반응성은 압력이 감소할수록, 그리고 아세톤의 함량이 증가할수록 $S_N1$ 경향성이 증가하였다. 또한 가용매 분해반응의 메카니즘에 미치는 하전분리 효과도 고찰하였다. The rates of solvolysis of trans-$[Co(AA)_2Cl_2]^+$ in which AA indicates ethylenediamine(en), N-ethylethylenediamine (N-eten), N-methylethylenediamino (N-meen) and trimethylenediamine(tn) respectively have been investigated using conductometric and spectrophotometric methods at various pressure up to 2,000 bar in acetone-water mixture. The activation volumes (${\Delta}V^{\neq}) obtained from the pressure effect on rate constants were -0.2∼0.9 $cm^3mole^{-1}$ for en, -0.2∼0.6 $cm^3mole^{-1}$ for N-eten, -0.8∼6.0 $cm^3mole^{-1}$ for N-meen and 0.7∼7.0$cm^3mole^{-1}$ for tn. The rates of solvolysis of these complexes were analyzed by comparing with the results obtained from excess free energy ($G^E$) and free energy cycle. It was found that $S_N1$ character was increased with decreasing the pressure and increasing the content of acetone in the mixture solvent. In addition to that, the effect of charge separation on the mechanism of solvolysis was discussed.

물-메틸알코올, 물-아세톤, 물-이소프로필알코올, 물-에틸렌글리코올에서 클로로-코발트 (Ⅲ) 착이온의 가용매분해반응에 미치는 압력 및 촉매의 영향

박유철,배준웅,김상웅,Yu-Chul Park,Zun-Ung Bae,Sang-Woong Kim 대한화학회 1987 대한화학회지 Vol.31 No.1

몇가지 이성분 혼합용매(물-메틸알코올, 물-아세톤, 물-이소프로필알코올, 물-에틸렌글리코올)에서 $cis-[Co(en)_2Cl_2]^+$착이온의 가용매분해반응속도를 분광광도법을 이용하여 압력(1~1500bar)에 따라 측정하였다. 속도상수에 대한 압력의 영향으로부터 구한 활성화체적은 메틸알코올, 아세톤, 이소프로필알코올, 에틸렌글리코올에서 각각 1.13∼4.44, 1.13~3.59, 0.82~3.44, 1.13~2.68cm3mole-1이었다. 또한 메틸알코올에서는 촉매제로 Fe(Ⅱ)이온을 사용하여 가용매분해반응속도를 측정하였고, 활성화체적은 -0.56∼1.59cm3mole$^{-1}$이었다. 가용매분해반응성은 자유에너지변화사이클과 활성화체적을 이용하여 고찰하였다. The rates of solvolysis of $cis-[Co(en)_2Cl_2]^+$ complex have been investigated using spectrophotometric method at various pressures up to 1500 bar in several binary-aqueous mixtures(water-methyl alcohol, water-acetone, water-isopropyl alcohol and water-ethylene glycol). The activation volumes obtained from the pressure effect on rate constants were 1.13∼4.44 cm3mole-1 for methyl alcohol, 1.13∼3.59$cm^3mole^{-1}$ for acetone, 0.82∼3.44$cm^3mole^{-1}$ for isopropyl alcohol and 1.13∼2.68cm3mole-1 for ethylene glycol. In case of water-methyl alcohol, in addition to, the rates of solvolysis of this complex were determined in the presence of Fe(Ⅱ) ion and the activation volumes were -0.56∼1.59cm3mole$^{-1}$. The rates of solvolysis of this complex were analyzed by comparing with the results obtained from activation volumes and free energy cycle.

The Effects of Pressure, Temperature and Solvent Composition on Solvolysis of trans-[Co(N-eten)$_2Cl_2]^+$ in Water-t-butyl Alcohol Mixture

박유철,조영제,Park Yu Chul,Cho Young Je Korean Chemical Society 1988 Bulletin of the Korean Chemical Society Vol.9 No.1

Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${\Delta}V^{\neq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.