• Journal of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.512-519
• /
• 1991

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.

• Journal of Food Hygiene and Safety
• /
• v.14 no.2
• /
• pp.146-152
• /
• 1999

The present study was performed to investigate the bioconcentration of BPMC, chlorothalonil, dichlorvos and methidathion. The BCFs(bioconcentration factors) and depuration rate constants for four pesticides in zebrafish(brachydanio rerio) were measured under semi-static conditions(OECD guideline 305-B) in a concentration of one-hundredth of the 96 hours LC50 of each pesticide at the equilibrium condition. The results obtained are summarized as follows : The BCFs of BPMC, chlorothalonil, dichlorvos and methidathion were 1.44$\pm$0.09, 2.223$\pm$0.063, 0.81$\pm$0.08 and 5.53$\pm$0.13, respectively. Depuration rate constants of BPMC, chlorothalonil, dichlorvos and methidathion were 0.028, 0.015, 0.220 and 0.152, respectively. The concentrations of BPMC, dichlorovs and methidathion in zebrafish reached an equilibrium in 3 days, and the equilibrium of chlorothalonil was reached after 14 days. Depuration rate of dichlorvos was the fastest followed by methidathion, BPMC and chlorothalonil. The lower BCF of BPMC was due to its relatively high KOW, slow KDEP, and low SW and VP, compared to chlorothalonil and methidathion. The BCF of chlorothalonil was much lower than that excepted on the basis of high KOW, slow KDEP, SW and VP. The reason is that the experimental concentration for chlorothalonil is 1/100~1/1000 lower than that of BPMC, dichlorvos and methidathion. The BCF of dichlorvos was lower than that of other pesticides due to its very rapid KDEP, very high VP and SW, and very low KOW. The BCF of methidathion was higher than that of other pesticides due to its very low VP and SW. Therefore, these data suggest that physicochemical properties of pesticides may be important in the bioconcentration.

• Journal of The Korean Society of Agricultural Engineers
• /
• v.57 no.1
• /
• pp.79-87
• /
• 2015

A thermochemical equilibrium model was constructed for predicting composition of synthesis gas in biomass gasification. The model included estimation of equilibrium constants using Gibbs free energy. After constructing the model, the results were compared with the experimental values and predictions from a previous model. Gas compositions were reasonably well agreed with them and showed effects of operational and fuel condition. When the reaction temperature increased, the lower heating values decreased due to the decrease in CH4 concentrations. The methane concentrations were lower than those observed in experimental results. The model was used to predict the gas composition and heating values for the cases of mixed fuel of charcoal and un-dry woodchips. Although downdraft gasifiers require fuels less than 15% of moisture contents, the model results indicated that the mixed fuel with charcoal and woodchips which had over 25% of moisture contents could be used in the downdraft gasifiers. It might be explained by increase in energy density resulting from mixing charcoal. The results imply that the efforts and costs for drying biomass fuels could be reduced by mixing charcoal or fuels with higher calorific values.

• Journal of Korean Association for Spatial Structures
• /
• v.18 no.3
• /
• pp.83-91
• /
• 2018

In this study, we investigated the dynamic stability of the system and the semi-analytical solution of the shallow arch. The governing equation for the primary symmetric mode of the arch under external load was derived and expressed simply by using parameters. The semi-analytical solution of the equation was obtained using the Taylor series and the stability of the system for the constant load was analyzed. As a result, we can classify equilibrium points by root of equilibrium equation, and classified stable, asymptotical stable and unstable resigns of equilibrium path. We observed stable points and attractors that appeared differently depending on the shape parameter h, and we can see the points where dynamic buckling occurs. Dynamic buckling of arches with initial condition did not occur in low shape parameter, and sensitive range of critical boundary was observed in low damping constants.

• Textile Coloration and Finishing
• /
• v.5 no.3
• /
• pp.216-220
• /
• 1993

Dissociation constants and heat of dissociation of dimers of 3, 3'-diethyl-thiacarbocyanine dye(Dye 2) have been studied. At $10~40^{\circ}C$, absorption spectra of 2 vol% aqueous ethanol solutions of Dye 2 showed monomer and dimer bands. From the temperature dependence of monomer absorbance, dissociation constants K and ${\Delta}H$ were estimated to be $6.2(10^{\circ}C)-10.6(40^{\circ}C)mon/\ell$ and 3kcal/mol, respectively. These K valus are about one half of those for 3,3'-diethyl-2,2'-cyanine dye with one methine carbon, indication a higher dimer stability than that of 3,3-diethyl-2,2'-cyanine dye.

• Journal of the korean Society of Automotive Engineers
• /
• v.10 no.4
• /
• pp.39-56
• /
• 1988

In this study, the computer program was developed to predict the engine performances and exhaust emissions of a 4-cylinder 4-stroke cycle ignition engine including intake and exhaust system. The simulation models applied to each process were as follows. For the combustion process, two zone model which requires only one empirical constant was applied, and for the gas exchange process, the method of characteristics that allows the calculations of the time variation and spatial variation of properties along the pipes was used. Constant pressure perfect mixing model was applied to take into account of the interaction at manifold branches. To predict exhaust emissions, twelve chemical species were considered to be present in combustion products. These species were calculated through equilibrium thermodynamics and kinetic theory. The empirical constants reduced to least number as possible were determined through the comparison with the experimental indicator diagram of one particular operating condition and these constants were applied to other operating conditions. The predicted performances and emissions were compared with the experimental results over the wide range of operating conditions.

• Analytical Science and Technology
• /
• v.8 no.4
• /
• pp.691-698
• /
• 1995

The complexation of platinum and palladium with synthetic polyelectrolytes was studied. The successive and overall stability constants of Pd(II) with PEI and 2PVP were obtained by potentiometric titration. Because of the slow equilibrium time, the potentiometric titrations were performed using the home-made automatic titrator in order to analyze the complexations according to the modified Bjerrum method. The complex formation constant of Pt(IV) with 2PVP, measured by differential pulse polarography, was calculated from the peak currents that were obtained in non-complexing media and in solution containing 2PVP.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.4
• /
• pp.850-858
• /
• 2010

The electronic absorption spectra of five Schiff bases derived from 2-hydroxy-1-naphthaldehyde with glycine, alanine, leucine, valine and phenylalanine have been measured in various solvents. The observed bands were assigned to the proper electronic transitions and compared with the predicted transitions at the semiempirical level of theory. The calculated equilibrium constants are in agreement with the experimental results, predicting the existence of all studied compounds predominantly or completely in keto-imine tautomerism. On the other hand, a correlation between $\nu\;(cm^{-1})$ (main frequency of each compound) and the well known solvent parameters $E_T$ (30), $\varepsilon_T$, $\pi^*$ been made. Furthermore, the acid dissociation constants, $pK_a$, were determined by using three different spectrophotometric methods.

• Bulletin of the Korean Chemical Society
• /
• v.1 no.3
• /
• pp.109-112
• /
• 1980

Ultraviolet spectrophotometric investigations were carried out on monoalkylbenzene-iodine systems in carbon tetrachloride. The results reveal the formation of one-to-one molecular complexes. On the basis of the equilibrium constants for these complexes of representative monosubstituted benzenes, the following order of increasing stability is obtained: i-propyl- ${\Delta}$H, ${\Delta}$G and ${\Delta}$S for the interaction of a number of monoalkyl substituted benzenes with iodine have been determined. In general, it can be said that as ${\Delta}$H becomes increasingly negative, corresponding decreases in the ${\Delta}$G and the ${\Delta}$S values are observed, and these variations are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes. Thus, analysis of these findings is discussed.

• Bulletin of the Korean Chemical Society
• /
• v.1 no.2
• /
• pp.62-68
• /
• 1980

Ultraviolet spectrophotometric investigations have been carried out the systems of monoalkylbenzene with iodine in carbon tetrachloride. The results reveal the formation of one to one molecular complexes. The equilibrium constants for these complexes of representative monosubstituted benzene reveal the following order of increasing stability: benzene < methyl- < ethyl- < n-propyl-benzene. The value of ${\Delta}H$, ${\Delta}G$, and ${\Delta}S$ for interaction of a number of monoalkyl substituted benzene with iodine has been determinated. In general, as ΛH becomes increasingly negative, corresponding decreases in ${\Delta}G$ and ${\Delta}S$ values are observed, and these variation are linear. The thermodynamic constants become increasingly negative with increasing monoalkyl substitution of the aromatic donor nucleus. The complex bond is therefore weak, and its formation is accompanied by relatively small entropy changes.