• Title/Summary/Keyword: equilibria

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Ionization and Divalent Cation Complexation of Quinolone Antibiotics in Aqueous Solution

  • Park, Hyeong Ryun;Jeong, Gwang Yeong;Lee, Hyeong Cheol;Lee, Jin Gi;Baek, Gi Min
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.849-854
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    • 2000
  • The protonation and divalent cation complexation equilibria of several quinolone antibiotics such as nalidixic acid (NAL),flumequine (FLU), oxolinic acid (OXO), ofloxacin (OFL), norfloxacin (NOR) and enoxacin (ENO) have been examined by potentiome tric titration and spectrophotometric method. The antibacterial activity of these drugs depends upon the pH and the concentration of metal cations such as Mg2+ , Ca2+ in solu-tion. The apparent ionization constants of NAL, FLU, OXO, OFL, NOR and ENO in aqueous solution were found to be 6.33, 6.51, 6.72, 7.18, 7.26, and 7.53, respectively. In aqueous solution, NAL, FLU and OXO were found to be present mainly as two chemical species : molecularand anionic; but OFL, NOR and ENO were present mainly as three chemical species : anionic, neutral zwitterionic and cationic form, in equilibrium. The pKa1 and pKa2are found to be 6.10 and 8.28 for OFL; 6.23 and 8.55 for NOR; 6.32 and8.62 for ENO, respec-tively. The complex formation constants between OFL, NOR or FLU and some divalent cations are measured at pH 7.5. The 1 : 1 complexes are formed mainly by ion-dipole interaction. FLU has somewhat larger Kf values than OFL and NOR because its molecular size is small and the FLU is present asanionic form at pH 7.5.

Studies on Equilibria and Analytical Applications of Synergistic Solvent Extraction(II). Determination of Trace Lithium in Sea Water using TTA and TOPO

  • Kim, Yeong Sang;Choe, Jong Mun;Lee, Chi U
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.855-859
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    • 2000
  • An application of synergistic solvent extraction for the etermination of trace lithium in sea water has been studied by forming an adduct complex of thenoyltrifluoroacetone (TTA) and trioctylphosphine oxide (TOPO) in a solvent. The interference by major constituents in sea water was eliminated by phosphate precipitation. Ex-perimental conditions such as solution pH, concentrations of TTA and TOPO etc. were optimized in synthetic sea water with similar compositionto its natural counterpart. To eliminate the interference, 1.38g of ammoni-um dihydrogen phosphate and 2.5 mL of ammonia water were added into 100 mL of thediluted solution at $60^{\circ}C$ to form the phosphate precipitates of Ca2+ and Mg2+ ions. After the pH of this filtrate was adjusted to 8.0, 10.0 mL of m-xylene containing 0.1 M TTA and 0.05 M TOPO was added to the solution in a separatory funnel, and the solution was shaken vigorously for 20 minutes. The solvent was separated from the aqueous solution, and 20 uL of m-xylene solution was injected into a gaphite tube to measure the absorbance by GF-AAS. The detection limit was 0.42 ng/mL. Lithium was determined within the range of 146 to 221 ng/mLin Korean coast-al sea waters, and the recoveries in the spiked samples were 94 to 106%.

Transmission Substituent Effects through Five-Membered Heteroaromatic Rigns, Ⅱ. Deprotonation Equilibra of Phenol Analogues

  • Son, Chang Guk;Im, Seon Hui;Ri, Sun Gi;Kim, Chang Gon;Kim, Chan Gyeong;Lee, Ik Hun
    • Bulletin of the Korean Chemical Society
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    • v.21 no.9
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    • pp.891-895
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    • 2000
  • Transmission of substituent effects through 5-membered heteroaromaticrings isinvestigated theoretically at the RHF/6-31+G* and B3LYP/6-31+G* levelsusing the deprotonation equilibria of phenol analogues with heteroatoms Y = NH, O, PHand S. The incr ease in the resonance delocalization of the $\pilone-pair$ on the phe-nolic oxygen atom, $n\pi(O)$, accompanied with the deprotonation depends on the heteroatom Y,in the order NH < O < PH < S. This represents the $\pielectron$ accepting ability, or conversely reverse order of the $\pielectron$ donating ability of the $\pilone-pair$ on Y, $n\pi(Y).$ The transmission efficiency of substituenteffects is, however,in the reverse order NH > O > S, which represents the order of delocalizability of $n\pi(Y).$ A better correlation is obtained with ${\sigma}p$ - than with ${\sigma}p$ for the Hammett type plots with the positive slope, $\rho-$ > 0, of the magnitude in the same order as that for the delocalizability of $n\pi(Y).$ Thedeprotonation energy, ΔG = [G(PA) + G(H+)] -G(P), decreases with the increasein the extence delocalization in the order NH > O > PH > S.

Polymer Adsorption at the Oil-Water Interface

  • Lee, Woong-Ki;Pak, Hyung-Suk
    • Bulletin of the Korean Chemical Society
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    • v.8 no.5
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    • pp.398-403
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    • 1987
  • A general theory of polymer adsorption at a semi-permeable oil-water interface of the biphasic solution is presented. The configurational factor of the solution in the presence of the semi-open boundary at the interface is evaluated by the quasicrystalline lattice model. The present theory gives the feature of the bulk concentration equilibria between oil-water subsystems and the surface excesses of ${\Gamma}^{\alpha}$ and ${\Gamma}^\{beta}$ of the polymer segments as a function of the degree of polymerization $\gamma$, the Flory-Huggins parameter in $\beta$-phase $x_{\rho}^{{\beta}_{\rho}}$, the differential adsorption energy parameter in $\beta$-phase $x_{\sigma}^{{\beta}_{\rho}}$, the differential interaction energy parameter ${\Delta}x_{\rho}$ and the bulk concentration of the polymer in ${\beta}-phase ${\varphi}_2^{{\beta(*)}_2}$. From our numerical results, the characteristics of ${\Gamma}^{\alpha}$ are shown to be significantly different from those of ${\Gamma}^{\beta}$ in the case of high polymers, and this would be the most apparent feature of the adsorption behavior of the polymer at a semi-permeable oil-water interface, which is sensitively dependent on ${\Delta}x_{\rho}$ and r.

Liquid-Liquid Equilibrium and Physical Properties of Aqueous Mixtures of Poly (Ethylene Glycol) 3000 with Tri-Potassium Citrate at Different pH: Experiment, Correlation and Thermodynamic Modeling

  • Ketabi, Mahnam;Pirdashti, Mohsen;Mobalegholeslam, Poorya
    • Journal of the Korean Chemical Society
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    • v.63 no.1
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    • pp.12-23
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    • 2019
  • The new experimental data of liquid-liquid equilibrium (LLE) of aqueous two-phase system (ATPS) consisting of poly(ethylene glycol) 3000 + tri-potassium citrate at different pH were presented. It was found that an increase in pH resulted in the expansion of the two-phase region. The TLL and STL increased with increasing the pH values. The Merchuk equation can be appropriately employed to correlate the binodal curves and also the tie-line compositions were adjusted to both the Othmer-Tobias and Bancroft equations. In order to calculate the compositions of the phase and the ends of the tie-lines, density and refractive indices as two physical properties were used. Finally, the extended UNIQUAC, UNIFAC, Virial-(Mobalegholeslam & Bakhshi) and modified UNIQUAC-FV were used to measure the phase equilibria at different pH. The results of the models suggested that it can be used quite well to correlate the LLE in an aqueous solution of polymer-salt.

The Free Energy of Mixing for a Binary Lattice Solution Consisting of Two Identical Interpenetrating Sublattices (두개의 동등한 상호침투 부격자로 구성된 이성분 격자 용액의 혼합자유에너지)

  • Jung, Hae-Young
    • Journal of the Korean Chemical Society
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    • v.66 no.4
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    • pp.278-283
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    • 2022
  • Using the Kirkwood's method, the free energy of a binary lattice solution consisting of two identical interpenetrating sublattices, such as a simple cubic lattice or a body-centered cubic lattice, was calculated up to the tenth order of the reciprocal of absolute temperature. Using this, liquid-liquid coexistence curves and critical solution temperatures for the binary lattice solutions were calculated to quantitatively investigate the effect of non-random mixing of molecules. And it was shown that the coexistence curve of the simple cubic lattice solution was in good agreement with the Monte-Carlo computer simulation result.

Single and Binary Competitive Sorption of Phenanthrene and Pyrene in Natural and Synthetic Sorbents

  • Masud, Md Abdullah Al;Shin, Won Sik
    • Journal of Soil and Groundwater Environment
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    • v.27 no.6
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    • pp.11-21
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    • 2022
  • Sorption of phenanthrene (PHE) and pyrene (PYR) in several sorbents, i.e., natural soil, BionSoil®, Pahokee peat, vermicompost and Devonian Ohio Shale and a surfactant (hexadecyltrimethyl ammonium chloride)-modified montmorillonite (HDTMA-M) were investigated. Pyrene exhibited higher sorption tendency than phenanthrene, as predicted by its higher octanol to water partition coefficient (Kow). Several sorption models: linear, Freundlich, solubility-normalized Freundlich model, and Polanyi-Manes model (PMM) were used to analyze sorption isotherms. Linear isotherms were observed for natural soil, BionSoil®, Pahokee peat, vermicompost, while nonlinear Freundlich isotherms fitted for Ohio shale and HDTMA-M. The relationship between sorption model parameters, organic carbon content (foc), and elemental C/N ratio was studied. In the binary competitive sorption of phenanthrene and pyrene in natural soil, competition between the solutes caused reduction in the sorption of each solute compared with that in the single-solute system. The ideal adsorbed solution theory (IAST) coupled with the single-solute Freundlich model was not successful in describing the binary competitive sorption equilibria. This was due to the inherent nature of linear sorption of phenanthrene and pyrene in natural soil. The result indicates that the applicability of IAST for the prediction of binary competitive sorption is limited when the sorption isotherms are inherently linear.

The Effect of Inaccurate Quality Signaling under Information Asymmetry

  • Seung Huh
    • Asia-Pacific Journal of Business
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    • v.14 no.1
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    • pp.231-246
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    • 2023
  • Purpose - This study attempts to provide a new theoretical perspective on the quality signaling and its impact on a market under information asymmetry, focusing on how the accuracy and the cost of quality signaling affect sellers' and buyers' profit, suggesting appropriate designs of quality signaling methods which mitigates information asymmetry. Design/methodology/approach - In order to examine the effect of quality signaling on strategic interactions within the market, we establish an analytic model where market outcomes are determined by seller's quality claim and price, and buyers are risk-neutral. By investigating this analytic model through relevant game trees, we find the subgame perfect Nash equilibria of the market and predict related market outcomes based on sellers' quality signaling strategy. Findings - Our analytic model shows counterintuitive results that seller profit will be the lowest with inaccurate quality signaling and the highest with no quality signaling, mostly due to the certification cost. Consequently, sellers should proceed with caution if the quality signaling is less than accurate, as it may backfire. We believe that this is due to the fact that the inaccuracy of quality signaling causes some confusion and uncertainty in both sellers and buyers' decision to maximize profit, making it hard for sellers to predict buyers' behavior. Research implications or Originality - Although the sources and types of quality signaling errors have been investigated in the literature, there has not been satisfactory understanding regarding how inaccuracy of quality certification affects specific market outcomes. We expect that our theoretical model would provide important implications on how to utilize quality signaling to solve adverse selection issues in markets under information asymmetry.

Critical Ratios of Ca/Al and Mg/Al in Nutrent Solution Limiting Growth of Pinus thunbergii (해송의 생육을 저해하는 Ca/Al 및 Mg/Al의 한계 비율)

  • Lee, Wi-Young;Yang, Jae E.;Park, Chang-Jin;Zhang, Yong-Seon;Ok, Yong-Sik
    • Korean Journal of Soil Science and Fertilizer
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    • v.37 no.5
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    • pp.329-335
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    • 2004
  • Acid deposition in forest adjacent to the industrial complexes causes soil acidification resulting in the leaching of cations, decreases of buffering capacity and increases of toxic metal concentrations such as Al, Fe, Mn and Cu in soil solution. Changes of nutrient availability equilibria by acid deposition have been known to retard the growth of pine trees. Objective of this research was to assess the critical ratios of Ca/Al and Mg/Al limiting the growth of Pinus thunbergii in the hydroponic culture. The Ca concentration and Ca/Al ratio in stalks of pine tree were increased as increasing Ca/Al molar ratio in the nutrient solution, but were not changed when the Ca/Al molar ratio was adjusted to greater than 1. Growth of Pinus thunbergii was inhibited at the Ca/Al molar ratio lower than l due to the Ca deficiency. The molar ratios of Ca/Al in the needles of Pinus thunbergii showed the similar tendency with the stalks. This indicated that Ca/Al molar ratio of 1 in the growth media was the critical level limiting the growth of Pinus thunbergii. Concentration of Mg and Mg/Al molar ratios in the stalks of pine tree were increased as increasing Mg/Al molar ratio in nutrient solution. Molar ratios of Mg/Al in the needles were increased as increasing Mg/Al ratios in nutrient solution up to 0.83, which was the critical level limiting the growth of Pinus thunbergii.

Relationship Between Chemical Properties of Forest soil Solutions and Element concentrations in Needles of Pinus thunbergii in Industral Complexes (공단 인접지역 해송 잎의 무기성분 함량과 산림 토양용액의 화학적 특성간의 관계)

  • Lee, Wi-Young;Yang, Jae E.;Park, Chang-Jin;Zhang, Yong-Seon;Ok, Yong-Sik
    • Korean Journal of Soil Science and Fertilizer
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    • v.37 no.5
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    • pp.322-328
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    • 2004
  • Available nutrients in soil solution play key roles on the growth of plants, but the equilibria in soil solution can be disturbed by acid precipitation. In this study, we investigated the relationships between element concentrations in the needles of Pinus thunbergii and chemical properties of forest soil solutions in the industrial complexes as an effort to find the possible limiting factor(s) causing the forest decline. The Ca/Al molar ratios in needles of Pinus thunbergii collected from the control sites were 18. However, at Onsan and Ulsan industrial complexes, those were decreased to the ranges from 10 to 11 for the one-year old needles and from 9 to 10 for the two-year old needles. The Mg/Al molar ratios showed similar tendencies with the Ca/Al molar ratios of the needles of Pinus thunbergii. In the A horizon, there existed a significant correlation between Mg concentrations in the needles of Pinus thunbergii and Ca/Al molar ratio of forest soil solution. Calcium concentrations in the needles of Pinus thunbergii in the B horizon were also significantly correlated with Ca/Al molar ratios of forest soil solutions. The uptakes of Ca and Mg by Pinus thunbergii were mainly limited by Al in the soil solutions of the A horizon and by Mn and Al in the soil solutions of the B horizon.