• Title/Summary/Keyword: equilibria

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Tracer Study Using $H_2O^{18}$ on the Oxidation of Vanadium (III) by Molecular Oxygen (산소에 의한 바나듐 (III) 이온의 산화반응에 대한 $O^{18}$ 동위원소 연구)

  • Kim, Myeong Ja;Choe, Dong Sik
    • Journal of the Korean Chemical Society
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    • v.18 no.4
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    • pp.259-266
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    • 1974
  • Isotopic experiments using $H_2O^{18}$ on the oxidation of V(III) in acid perchlorate by molecular oxygen were performed in the range pH 1.0 to 3.0. At pH < 2, where a rate equation of the form TEX>$ -\frac{d[V(III)]}{dt}=k_1\frac{[O_2][V(III)]}{[H^+]}$ is adequate, the tracer study clearly indicated that all the product vanadyl ion's ($VO^{2+}$) oxygen originated from the molecular oxygen. At pH > ~2, where a different rate expression of the form $-\frac{d[V(III)]}{dt}=K_2\frac{[O_2][V(III)]^2}{[Ht]^2}$is required, the isotopic experiment showed that half the vanadyl oxygen originated from the molecular oxygen. Considering the results of the isotopic study, a mechanism for the V(Ⅲ)-O2 reaction at pH < ~2, may be suggested as follows: The tracer results at pH > ~2 imply that the rate determining step may be $$ V_2(OH)_2^{4+} + O_2 \rightarrow 2VO^{2+} + H_2O_2$$ followed by $$V_2(OH)_2^{4+} + H_2O_2 \rightarrow 2VO^{2+} + 2H_2O$$ after establishing the equilibria V^{3+} + H_2O \leftrightarrow VOH^{2+} + H^+, and 2VOH^{2+}\leftrightarrow V_2(OH)_2^{4+}$$

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Phase Equilibria and Processing of Pb_2Sr_2(Y_{1-x}Ca_x)Cu_3O_{8+\delta} Superconductors (x=0.4-0.6) (Pb_2Sr_2(Y_{1-x}Ca_x)Cu_3O_{8+\delta}초전도체 (x=0.4-0.6)의 제조방법 및 상평형)

  • Park, Young-il;Dongwoon Jung
    • Korean Journal of Materials Research
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    • v.5 no.6
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    • pp.723-731
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    • 1995
  • P $b_2$S $r_2$( $Y_{1-x}$ C $a_{x}$)C $u_3$ $O_{8+}$$\delta$/ samples were prepared with x=0.4~0.6 and small $\delta$. To minimize the extent of oxidative decomposition reaction which occurs during the preparation of this phase, two annealing steps were adopted : First, sintered samples of P $b_2$S $r_2$( $Y_{1-x}$ C $a_{x}$)C $u_3$ $O_{8+}$$\delta$/ are oxygenated under 100% $O_2$, which leads to a large $\delta$(e.g., $\delta$=1.8). Second, the resulting samples are deoxygenated under 0.1~1.0% $O_2$in $N_2$, lowering $\delta$ to desired values. This two-step annealing procedure minimized the extent of oxidative decomposition. However, even with the two-step annealing procedure, the oxidative decomposition of P $b_2$S $r_2$( $Y_{1-x}$ C $a_{x}$)C $u_3$ $O_{8+}$$\delta$/ cannot be completely suppressed if $\delta$ is to be reduced to maximize $T_{c}$. Electrical resistivity data show that $T_{c}$(onset) is a function of hole concentration in the Cu $O_2$layer, and the optimum hole concentration for the maximum $T_{c}$ is achieved when $Ca^{2+}$is substituted for $Y^{3+}$between 0.5 and 0.6 A $T_{c}$(onset)=80K has been observed for one such sample, and this is the highest $T_{c}$(onset) yet reported for this compound.ed for this compound.nd.

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A Game Theoretic Analysis of Social Commerce Ecosystem at the Crossroads (소셜커머스 생태계의 게임 분석)

  • Kim, Dohoon
    • Asia pacific journal of information systems
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    • v.23 no.2
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    • pp.67-86
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    • 2013
  • This study first provides a stylized model that captures the essential features of the SC (Social Commerce) business and the competition process. The model focuses on the relationship between key decision issues such as marketing inputs and market value. As more SCs join the industry, they are inevitably faced with fierce competition, which may lead to sharp increase in the total marketing and advertising expenditure. This type of competition may lead the industry away from its optimal development path, and at worst, toward a disruption of the entire industry ecosystem. Such being the case, another goal of this study is to examine the possibility that the ToC (Tragedy of the Commons) may occur in the SC industry. We build game models, each of which assumes homogeneity and heterogeneity of SC providers, respectively, and derive explicit equilibrium solutions from both models. Our basic analysis presents Nash equilibria in both models and shows that SC providers are inevitably faced with fierce competition, which may lead to sharp increase in the total marketing expenses. We also compare the game outcomes with one with a hypothetical social planner who determines the total marketing level that optimizes the entire market value. Then, ToC can be defined to describe the situation where the total marketing efforts exceed the socially optimal level of marketing efforts. In both models, we examine the possibility of the ecosystem disruption and specify the conditions under which ToC may occur. However, the chance of avoiding ToC is higher with heterogeneous players than with homogeneous players. To supplement our analytical results, we develop a simulation model which incorporates a market dynamics based on the gap between actual marketing efforts and socially optimal marketing level. Simulation experiments present some lessons and insights which also confirm out findings from equilibrium analysis. For example, heterogeneity in SC providers alleviates the severity of ToC and makes it faster for survivors to escape from the ToC trap. As a result, the degree of industrial concentration tends to increase, which also explains the 'rich-get-richer' phenomenon observed in some empirical studies on the SC industry. Lastly, based on our analytical and experimental results, we come up with some measures to avoid ToC and overcome the shortcomings intrinsic to the current business model. And further discussions provide strategic implications and policy directions to overcome the possible trap of ToC in this ecosystem, and eventually help the industry to sustainably develop itself toward the next level. To name a few examples of policy measures, regulations on the marketing activities so that the overall marketing expenses cannot go beyond the socially optimal level; institutional guidelines and rules to straightening up the distortions in the way that SC providers view the marketing costs (the current marketing costs are underestimated, thereby encouraging SC providers to increase marketing expenditure); and so on.

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Adsorption Characteristics of Nitrogen in Carbonaceous Micropore Structures with Local Molecular Orientation (국부분자배향의 탄소 미세기공 구조에 대한 질소의 흡착 특성)

  • Seo, Yang Gon
    • Clean Technology
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    • v.28 no.3
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    • pp.249-257
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    • 2022
  • The adsorption equilibria of nitrogen on a region of nanoporous carbonaceous adsorbent with local molecular orientation (LMO) were calculated by grand canonical Monte Carlo simulation at 77.16 K. Regions of LMO of identical size were arranged on a regular lattice with uniform spacing. Microporosity was predominately introduced to the model by removing successive out-of-plane domains from the regions of LMO and tilting pores were generated by tilting the basic structure units. This pore structure is a more realistic model than slit-shaped pores for studying adsorption in nanoporous carbon adsorbents. Their porosities, surface areas, and pore size distributions according to constrained nonlinear optimization were also reported. The adsorption in slit shaped pores was also reported for reference. In the slit shaped pores, a clear hysteresis loop was observed in pores of greater than 5 times the nitrogen molecule size, and in capillary condensation and reverse condensation, evaporation occurred immediately at one pressure. In the LMO pore model, three series of local condensations at the basal slip plane, armchair slip plane and interconnected channel were observed during adsorption at pore sizes greater than about 6 times the nitrogen molecular size. In the hysteresis loop, on the other hand, evaporation occurred at one or two pressures during desorption.

Performance Evaluation of Loss Functions and Composition Methods of Log-scale Train Data for Supervised Learning of Neural Network (신경 망의 지도 학습을 위한 로그 간격의 학습 자료 구성 방식과 손실 함수의 성능 평가)

  • Donggyu Song;Seheon Ko;Hyomin Lee
    • Korean Chemical Engineering Research
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    • v.61 no.3
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    • pp.388-393
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    • 2023
  • The analysis of engineering data using neural network based on supervised learning has been utilized in various engineering fields such as optimization of chemical engineering process, concentration prediction of particulate matter pollution, prediction of thermodynamic phase equilibria, and prediction of physical properties for transport phenomena system. The supervised learning requires training data, and the performance of the supervised learning is affected by the composition and the configurations of the given training data. Among the frequently observed engineering data, the data is given in log-scale such as length of DNA, concentration of analytes, etc. In this study, for widely distributed log-scaled training data of virtual 100×100 images, available loss functions were quantitatively evaluated in terms of (i) confusion matrix, (ii) maximum relative error and (iii) mean relative error. As a result, the loss functions of mean-absolute-percentage-error and mean-squared-logarithmic-error were the optimal functions for the log-scaled training data. Furthermore, we figured out that uniformly selected training data lead to the best prediction performance. The optimal loss functions and method for how to compose training data studied in this work would be applied to engineering problems such as evaluating DNA length, analyzing biomolecules, predicting concentration of colloidal suspension.

Game Theory Application in Wetland Conservation Across Various Hypothetical City Sizes (다양한 이론적 도시규모에서의 습지 보전을 위한 게임 이론 적용)

  • Ran-Young Im;Ji Yoon Kim;Yuno Do
    • Journal of Wetlands Research
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    • v.26 no.1
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    • pp.10-20
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    • 2024
  • The conservation and restoration of wetlands are essential tasks for the sustainable development of human society and the environment, providing vital benefits such as biodiversity maintenance, natural disaster mitigation, and climate change alleviation. This study aims to analyze the strategic interactions and interests among various stakeholders using game theory and to provide significant grounds for policy decisions related to wetland restoration and development. In this study, hypothetical scenarios were set up for three types of cities: large, medium, and small. Stakeholders such as governments, development companies, environmental groups, and local residents were identified. Strategic options for each stakeholder were developed, and a payoff matrix was established through discussions among wetland ecology experts. Subsequently, non-cooperative game theory was applied to analyze Nash equilibria and Pareto efficiency. In large cities, strategies of 'Wetland Conservation' and 'Eco-Friendly Development' were found beneficial for all stakeholders. In medium cities, various strategies were identified, while in small cities, 'Eco-Friendly Development' emerged as the optimal solution for all parties involved. The Pareto efficiency analysis revealed how the optimal solutions for wetland management could vary across different city types. The study highlighted the importance of wetland conservation, eco-friendly development, and wetland restoration projects for each city type. Accordingly, policymakers should establish regulations and incentives that harmonize environmental protection and urban development and consider programs that promote community participation. Understanding the roles and strategies of stakeholders and the advantages and disadvantages of each strategy is crucial for making more effective policy decisions.

Chemical Equilibria of Lanthanide {Ln(III)=Pr, Sm, Gd, Dy}-Macrocyclic Complexes with Auxiliary Ligands in $CH_3OH$(Part III); Study of the Coordination of Nitrogen-or Oxygen-Containing Bases ($CH_3OH$ 용매에서 란탄족 원소 {Ln(III)=Pr, Sm, Gd, Dy}-거대고리 착물과 보조리간드 간의 화학평형(제3보); 두자리 리간드(주게원자:N혹은 O)를 중심으로 고찰)

  • Byun, Jong-Chul;Park, Yu-Chul;Han, Chung-Hun
    • Journal of the Korean Chemical Society
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    • v.44 no.2
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    • pp.95-101
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    • 2000
  • Macroacyclic transition metal complexes such as $Cu(H_2L[A]).H_2O$, $Cu(H_2L[B]).H_2O$, CuFe(L[A]($NO_3$).$4H_2O$, CuFe(L[B])($NO_3$).$4H_2O$, [$CuGd(H_2L[A])(NO_3)_2](NO_3).2CH_3OH$, [CuGd($H_2L$[B])($NO_3)_2$]($NO_3).2CH_3OH were prepared from the corresponding hexadentate compartmental ligands, $H_4L[A]$ and $H_4L[B]$, which were obtained by the condensation of 2-hydroxy-3-hydroxymethy1-5-methyIbenzaldehyde(HHNNB) and ethylenediamine or l,3-diaminopropane. Ln-macrocyclic([20]DOTA) complexes,[Ln([20]DOTA)($NO_3)(H_2O)$]($NO_3$)2.$xH_2O${Ln(III)=Pr, Sm, Gd, Dy, which had been synthesized from 2,6-diformyl-p-cresol(DFPC), was placed in methanol for 2 days, and [Ln([20] DOTA)($NO_3)(CH_3OH)]^{2+}$ was formed The equilibrium constants (k) for the substitution of coordinated $CH_3OH$ in the Ln-[20]DOTA complexes by various bidentate auxiliary ligands, $L_a$(=o-phenylenediamine,1,10-phenanthroline, ethylenediamine,oxalicacid, malonic acid, acethylacetone) were determined by spectroscopic method at $25^{\circ}C$ and 0.1M $NaClO_4$.The pKa of auxiliary ligands is in the order of o-phenylenediamine < 1,10-phenanthroline < ethylene-diamine, oxalic acid < malonic acid < acethylacetone. However, the equilibrium constant(K) has shown thetrend of ethyleneiamine < 1,10-phenanthroline < o-phenylenediamine, acethylacetone < malonic acid < oxalic acid.

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Optical Absorption and Polarogram of Macrocyclic Nickel (II) Complexes in Polar Solvents (극성용매에서 거대고리 Ni (II) 착물의 광흡수와 폴라로그램)

  • Park Yuj-Chul;Jong-Chul Byun
    • Journal of the Korean Chemical Society
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    • v.31 no.2
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    • pp.168-177
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    • 1987
  • The equilibria of chemical reaction between $\alpha$-Ni(rac-[14]-decane)$^{2+}$ and polar solvents(L; ANT, MFA, DMSO, DMF, and DMA) have been investigated by the spectrophotometric method at $25^{\circ}C$. (The equilibrium constants($K_1$) of) the first step in ANT, MFA, DMSO, DMF, and DMA were 31.0, 27.5, 21.3 15.9, and 6.4, respectively. The smallness of equilibrium constants ($K_2$) of the second step compared with $K_1$, was observed. $\alpha$-Ni(rac-[14]-dacane)$^{2+}$ + L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}L]$^{2+}$ : $K_1$.[$\alpha$-Ni(rac-[14]-decane){\cdot}L)$^{2+}$+ L $\leftrightharpoons$ [$\alpha$-Ni(rac-[14]-decane){\cdot}$L_2$)$^{2+}$ :$K_2$. The relationship between d-d absorption energy and half-wave potential of complex ions at ACT was considered. Macrocyclic ligands increasing d-d transition energy caused half-wave potentials of Ni(II)-macrocycle to be shifted more positively. The half-wave potentials for Ni(rac-1[14]7-diene)$^{2+}$, Ni(meso-1[14]7-diene)$^{2+}$, Ni(1[14]4-diene)$^{2+}$, $\alpha$-Ni(rac-[14]-decane)$^{2+}$, ${\beta}-Ni(rac-[14]-decane)$^{2+}$, and Ni(meso-[14]-decane)$^{2+}$ reductions were -1.419, -1.431, -1.450, -1.473, and -1.480 (V vs. SCE), respectively. The d-d transition energies ($\nu_{max},\;cm^{-1}$) of the Ni(meso-[14]-decane)$^{2+}$ isomer were discussed with the dielectric constant (${\varepsilon}/{\varepsilon}_0$) of the various solvents, $\nu_{max}(cm^{-1})$ increased with increasing ${\varepsilon}/{\varepsilon}_0$.

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Limit Pricing by Noncooperative Oligopolists (과점산업(寡占産業)에서의 진입제한가격(進入制限價格))

  • Nam, Il-chong
    • KDI Journal of Economic Policy
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    • v.12 no.1
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    • pp.127-148
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    • 1990
  • A Milgrom-Roberts style signalling model of limit pricing is developed to analyze the possibility and the scope of limit pricing in general, noncooperative oligopolies. The model contains multiple incumbent firms facing a potential entrant and assumes an information asymmetry between incombents and the potential entrant about the market demand. There are two periods in the model. In period 1, n incumbent firms simultaneously and noncooperatively choose quantities. At the end of period 1, the potential entrant observes the market price and makes an entry decision. In period 2, depending on the entry decision of the entrant, n' or (n+1) firms choose quantities again before the game terminates. Since the choice of incumbent firms in period 1 depends on their information about demand, the market price in period 1 conveys information about the market demand. Thus, there is a systematic link between the market price and the profitability of entry. Using Bayes-Nash equilibrium as the solution concept, we find that there exist some demand conditions under which incumbent firms will limit price. In symmetric equilibria, incumbent firms each produce an output that is greater than the Cournot output and induce a price that is below the Cournot price. In doing so, each incumbent firm refrains from maximizing short-run profit and supplies a public good that is entry deterrence. The reason that entry is deterred by such a reduced price is that it conveys information about the demand of the industry that is unfavorable to the entrant. This establishes the possibility of limit pricing by noncooperative oligopolists in a setting that is fully rational, and also generalizes the result of Milgrom and Roberts to general oligopolies, confirming Bain's intuition. Limit pricing by incumbents explained above can be interpreted as a form of credible collusion in which each firm voluntarily deviates from myopic optimization in order to deter entry using their superior information. This type of implicit collusion differs from Folk-theorem type collusions in many ways and suggests that a collusion can be a credible one even in finite games as long as there is information asymmetry. Another important result is that as the number of incumbent firms approaches infinity, or as the industry approaches a competitive one, the probability that limit pricing occurs converges to zero and the probability of entry converges to that under complete information. This limit result confirms the intuition that as the number of agents sharing the same private information increases, the value of the private information decreases, and the probability that the information gets revealed increases. This limit result also supports the conventional belief that there is no entry problem in a competitive market. Considering the fact that limit pricing is generally believed to occur at an early stage of an industry and the fact that many industries in Korea are oligopolies in their infant stages, the theoretical results of this paper suggest that we should pay attention to the possibility of implicit collusion by incumbent firms aimed at deterring new entry using superior information. The long-term loss to the Korean economy from limit pricing can be very large if the industry in question is a part of the world market and the domestic potential entrant whose entry is deterred could .have developed into a competitor in the world market. In this case, the long-term loss to the Korean economy should include the lost opportunity in the world market in addition to the domestic long-run welfare loss.

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Studies on Polymerization of Metal Anion (III). The Temperature Effect on Polymolybdate Ions Equilibrium in 1 M $NaCIO_4$ Solution (Metal Anion Polymerization에 관한 연구 (제3보). The Temperature Effect on Polymolybdate Ions Equilibrium in 1 M $NaClO_4$Solution)

  • Sang Woon Ahn;Eui Suh Park
    • Journal of the Korean Chemical Society
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    • v.17 no.3
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    • pp.145-153
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    • 1973
  • The temperature effects on the equilibria between polymolybdatd anions in 1M sodium perchlorate solution has been investigated in the temperature range of 20~50$^{\circ}$C. The polymolybdate anions formed are heptamolybdate ($Mo_7O_{24}^{6-}$) ions and the protonized forms of heptamolybdate ions ($H_LMo_7O_{24}^{(6-L)-}$). The equilibrium constants for the formation of heptamolybdate ions calculated by Sillen's method are as follow;$8H^{+}+7MoO_4^{2-}=Mo_7O_{24}^{6-}+4H_2O$, $k_{7.8}=2.77{\times}10^{53}:20^{\circ}C= 9.29{\times}10^{51}:40^{\circ}C$,$k_{7.8}= 4.22{\times}10^{52}:30^{\circ}C = 9.29{\times}10^{51}:50^{\circ}C$ The enthalpy change for calculated for the above reaction is 31.51 kcal/mole. A method of calculation of the equilibrium constants for the formation of protonized heptamolybdate ions from heptamolybdate ions and hydrogen ions has been derived. The equilibrium constants calculated for the formation of protonized heptamolybdate ions are as follow; $ LH^++ Mo_7O_{24}^{-6} = H_LMo_7O_{24}^{(6-L)-} : L = 1\;or\;2$, $k_1 = 2.31{\times}10^4=2.53{\times}10^4=2.76{\times}10^4= 3.10{\times}10^4$, $k_2 = 6.19{\times}10^7\;20^{\circ}C = 7.80{\times}10^7\;30^{\circ}C = 1.22{\times}10^8\;40^{\circ}C = 2.03{\times}10^8\;50^{\circ}C$The enthalpy change for the following step reactions are as follow;$H^{+}+Mo_7O_{24}^{6-}= HMo_7O_{24}^{5-}\;{\Delta}H^{\circ}=1.90 kcal/mole$, $2H^{+}+Mo_7O_{24}^{6-}=H_2Mo_7O_{24}^{4-}\;{\Delta}H^{\circ}=7.50kcal/mole$

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