• Title/Summary/Keyword: Complexation reaction

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Microemulsions in Supercritical Carbon Dioxide Utilizing Nonionic Surfactants (초임계 이산화탄소내 비이온성 계면활성제를 이용한 마이크로에멀젼 형성연구)

  • Koh, Moonsung;Yoo, Jaeryong;Park, Kwangheon;Kim, Hongdoo;Kim, Hakwon
    • Clean Technology
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    • v.10 no.4
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    • pp.221-228
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    • 2004
  • Ethoxylated Nonyl Phenol Series (NP-series), nonionic surfactants, were applied for forming microemulsions in supercritical $CO_2$. Measurement results of the solubility in supercritical $CO_2$ are in the following; NP-series were high soluble in carbon dioxide in spite of the fact that those were not $CO_2$-philic surfactants traditionally well known. Water in $CO_2$ microemulsions were also formed stably. A complexation of hydrophilic lengths for $CO_2$-philic parts of NP-Series surfactants was optimized by NP-4 surfactant(N=4) for forming the microemulsions through the experiments. Formation of microemulsions was confirmed by measuring the UV-Visible spectrum through a spectroscopic method and existence of water in the microemulsions was confirmed as well. In order to apply it for a metal surface treatment or electroplating, an experiment for forming acid(organic, inorganic) solution in $CO_2$ microemulsions was carried out. Ionic surfactant in the reaction to an acid solution became unstable to form microemulsions, however, nonionic surfactant was formed stably in the reaction. Results of the study will be utilized for expanding the application scope of supercritical $CO_2$ which is an environmental-friendly solvent.

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Interaction Experiment on Chloride Ion Adsorption Behavior of C-S-H Phases (C-S-H 상의 염소이온 흡착 메커니즘 규명을 위한 반응 작용 실험)

  • Yoon, In-Seok
    • Journal of the Korea Concrete Institute
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    • v.29 no.1
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    • pp.65-75
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    • 2017
  • C-S-H phase is the most abundant reaction product, occupying about 50~60% of cement paste volume. The phase is also responsible for most of engineering properties of cement paste. This is not because it is intrinsically strong or stable, but because it forms a continuous layer that binds together the original cement particles into a cohesive whole. The binding ability of C-S-H phase arises from its nanometer-level structure. In terms of chloride penetration in concrete, C-S-H phase is known to adsorb chloride ions, however, its mechanism is very complicated and still not clear. The purpose of this study is to examine the interaction between chloride ions and C-S-H phase with various Ca/Si ratios and identify the adsorption mechanism. C-S-H phase can absorb chloride ions with 3 steps. In the C-S-H phase with low Ca/Si ratios, momentary physical adsorption could not be expected. Physical adsorption is strongly dependent on electro-kinetic interaction between surface area of C-S-H phase and chloride ions. For C-S-H phase with high Ca/Si ratio, electrical kinetic interaction was strongly activated and the amount of surface complexation increased. However, chemical adsorption could not be activated for C-S-H phase with high Ca/Si ratio. The reason can be explained in such a speculation that chloride ions cannot be penetrated and adsorbed chemically. Thus, the maximum chloride adsorption capacity was obtained from the C-S-H phase with a 1.50 Ca/Si ratio.

Sorption of Arsenite Using Nanosized Mackinawite (FeS)-Coated Silica Sand (나노 크기 매킨나와이트로 코팅된 규사를 이용한 아비산염의 흡착)

  • Lee, Seungyeol;Kang, Jung Chun;Park, Minji;Yang, Kyounghee;Jeong, Hoon Young
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.185-195
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    • 2012
  • Due to the high reduction and sorption capacity as well as the large specific surface area, nanosized mackinawite (FeS) is useful in reductively transforming chlorinated organic pollutants and sequestering toxic metals and metalloids. Due to the dynamic nature in its colloid stability, however, nanosized FeS may be washed out with the groundwater flow or result in aquifer clogging via particle aggregation. Thus, these nanoparticles should be modified such as to be built into permeable reactive barriers. This study employed coating methods in efforts to facilitate the installation of permeable reactive barriers of nanosized mackinawite. In applying the methods, nanosized mackinawite was coated on non-treated silica sand (NTS) and chemically treated silica sand (CTS). For both silica sands, the maximum coating of mackinawite occurred around pH 5.4, the condition of which was governed by (1) the solubility of mackinawite and (2) the surface charge of both silica and mackinawite. Under this pH condition, the maximum coating by NTS and CTS were found to be 0.101 mmol FeS/g and 0.043 mmol FeS/g respectively, with such elevated coatings by NTS likely linked with impurities (e.g., iron oxides) on its surface. Arsenite sorption experiments were performed under anoxic conditions using uncoated silica sands and those coated with mackinawite at the optimal pH to compare their reactivity. At pH 7, the relative sorption efficiency between uncoated NTS and coated NTS changed with the initial concentration of arsenite. At the lower initial concentration, uncoated NTS showed the higher sorption efficiency, whereas at the higher concentration, coated NTS exhibited the higher sorption efficiency. This could be attributed to different sorption mechanisms as a function of arsenite concentration: the surface complexation of arsenite with the iron oxide impurity on silica sand at the low concentration and the precipitation as arsenic sulfides by reaction with mackinawite coating at the high concentration. Compared to coated NTS, coated CTS showed the lower arsenite removal at pH 7 due to its relatively lower mackinawite coating. Taken together, our results indicate that NTS is a more effective material than CTS for the coating of nanosized mackinawite.

Preparation of Cationic Liposomes Modified by Polyethylenimine and Their Application as Gene Carrier (폴리에틸렌이민으로 수식된 양이온 리포좀의 제조 및 유전자 전달체로서의 응용)

  • Seo, Dong-Hoan;Shin, Byung-Cheol;Kim, Moon-Suk
    • Polymer(Korea)
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    • v.29 no.3
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    • pp.277-281
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    • 2005
  • Recently, various curriers prepared by the modification both cationic polymers and liposomes have been examined. In this work, we prepared the lipid with polyethylenimine (PEI) to investigate the possibility as effective DNA carrier. Cationic lipid (PEI-DSPE) was synthesized by the reaction of PEI and 1,2-diacyl-sn-glycero-3-phosphoetha-nolamine (DSPE). The liposomes were prepared by the concenoation changes of PEI-DSPE for a mixture of 1,2-disteanyl-sn-glycero-3-phosphocholine (DSPC), L-$\alpha$-phosphatidylcholine, hydrogenated (HSPC) and cholesterol (CHOL). Particle size decreased as PEI-DSPE concentration increased. In addition, the charge of liposome surface increased to positive value according to increasing the relative of PEI-DSPE concentration. The complexation of DNA was confirmed by gel retardation assay and fluorescence measurement. The surface charge of liposome/DNA complexes increased as the liposome concentration or surface charge of liposome increased. In conclusion, we confirmed that the prepared liposomes have the possibility as a DNA carrier.

Characterization of Poly(methyl methacrylate)-tin (IV) Chloride Blend by TG-DTG-DTA, IR and Pyrolysis-GC-MS Techniques

  • Arshad, Muhammad;Masud, Khalid;Arif, Muhammad;Rehman, Saeed-Ur;Saeed, Aamer;Zaidi, Jamshed Hussain
    • Bulletin of the Korean Chemical Society
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    • v.32 no.9
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    • pp.3295-3305
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    • 2011
  • Thermal behavior of poly (methyl methacrylate) was analyzed in the presence of tin (IV) chloride. Five different proportions - polymer to additive - were selected for casting films from common solvent. TG, DTG and DTA were employed to monitor thermal degradation of the systems. IR and py-GC-MS helped identify the decomposition products. The blends start degrading at a temperature lower than that of the neat polymer and higher than that of the pure additive. Complex formation between tin of additive and carbonyl oxygen (pendent groups of MMA units) was noticed in the films soon after the mixing of the components in the blends. The samples were also heated at three different temperatures to determine the composition of residues left after the expulsion of volatiles. The polymer, blends and additive exhibited a one step, two-step and three-step degradation, respectively. $T_0$ is highest for the polymer, lowest for the additive and is either $60^{\circ}C$ or $70^{\circ}C$ for the blends. The amount of residue increases down the series [moving from blend-1 (minimum additive concentration) to blend-5 (maximum additive concentration)]. For blend-1, it is 7% of the original mass whereas it is 16% for blend-5. $T_{max}$ also goes up as the concentration of additive in the blends is elevated. The complexation appears to be the cause of observed stabilization. Some new products of degradation were noted apart from those reported earlier. These included methanol, isobutyric acid, acid chloride, etc. Molecular-level mixing of the constituents and "positioning effect" of the additive may have brought about the formation of new compounds. Routes are proposed for the appearance of these substances. Horizontal burning tests were also conducted on polymer and blends and the results are discussed. Activation energies and reaction orders were calculated. Activation energy is highest for the polymer, i.e., 138.9 Kcal/mol while the range for blends is from 51 to 39 Kcal/mol. Stability zones are highlighted for the blends. The interaction between the blended parts seems to be chemical in nature.

X-ray and Spectroscopy Studies of Mercury (II) and Silver (I) Complexes of α-Ketostabilized Phosphorus Ylides (α-케토안정화된 일리드화 인의 수은(II) 및 은(I) 착물에 대한 X-선 및 분광학적 연구)

  • Karami, K.;Buyukgungor, O.;Dalvand, H.
    • Journal of the Korean Chemical Society
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    • v.55 no.1
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    • pp.38-45
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    • 2011
  • The complexation behavior of the $\alpha$-ketostabilized phosphorus ylides $Ph_3P$=CHC(O) $C_6H_4-X$ (X=Br, Ph) towards the transition metal ions mercury (II) and Silver (I) was investigated. The mercury(II) complex {$HgX_2$ [Y]} 2 ($Y_1$=4-bromo benzoyl methylene triphenyl phosphorane; X=Cl(1), Br(2), I(3), $Y_2$=4-phenyl benzoyl methylene triphenyl phosphorane; X=Cl(4), Br(5), I(6)) have been prepared from the reaction of $Y_1$ and $Y_2$ with $HgX_2$ (X=Cl, Br, I) respectively. Silver complexes [$Ag(Y_2)_2]$ X(X=$BF_4$(7), OTf(8)) of the $\alpha$-keto-stabilized phosphorus ylides ($Y_2$) were obtained by reacting this ylide with AgX (X=$BF_4$, OTf) in $Me_2CO$. The crystal structure of complexes (1) and (4) was discussed. These reactions led to binuclear complexes C-coordination of ylide and trans-like structure of complexes $[Y_1HgCl_2]_2$. $CHCl_3$ (1) and $[Y_2HgCl_2]_2$ (4) is demonstrated by single crystal X-ray analyses. Not only all of complexes have been studied by IR, $^1H$ and $^{31}P$ NMR spectroscopy, but also complexes 1-3 have been characterized by $^{13}$CNMR.

Reduction and Equilibrium of Vanadium-Diethylenetriamine Pentaacetates at Mercury Electrode in Aqueous Solution (수용액중의 수은전극에서 바나듐-디에틸렌트리아민 펜타아세트산염의 환원 및 평형연구)

  • Ki-Suk Jung;Se Chul Sohn;Young Kyung Ha;Tae Yoon Eom;Sock Sung Yun
    • Journal of the Korean Chemical Society
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    • v.33 no.1
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    • pp.55-64
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    • 1989
  • Reduction and equilibrium of vanadium-DTPA (DTPA = diethylenetriaminepentaacetic acid, $H_5A$) complexes at mercury electrodes are studied in 0.5M $NaClO_4$ aqueous solution at 3.2 < pH < 10.5 and 25$^{\circ}$C. At 3.2 < pH < 5.9, the reduction reaction is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}HA^{2-}$, while at 5.9 < pH < 10.5 it is $V{\cdot}A^{2-}+H^-+e^-=V{\cdot}A^{3-}$. The stability constants of $V{\cdot}HA^{2-}$ and $V{\cdot}A^{3-}$ are found to be $6.46{\times}10^{9}$ and $3.09{\times}10^{14}$, respectively. V(IV)-DTPA undergoes stepwise complexation as $VO^{2+}+H_2A^{3-}=VO{\cdot}HA^{2+}H^{+}$ and $VO{\cdot}HA^{2-}=VO{\cdot}A^{3+}+H$, where acidity constant of $VO{\cdot}HA^{2-}$- is pKa = 7.15. Stability constants of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $1.41{\times}10^{14}$ and $3.80{\times}10^{17}$, respectively. It is detected that $VO^{2+}-DATA$ is reduced irreversibly to $VO^{2-}$ with the transfer coefficient of $\alpha$ = 0.43. At more cathodic overpotential, the reduction is stepwise as V(IV)${\to}$V(III)${\to}$V(II). The first one corresponds to $VO{\cdot}HA^{2-}+e^{-}{\to}VO{\cdot}HA{3+}$ at 3.2 < pH < 7.2 and $VO{\cdot}A^{3-}+e^{-}{\to}VO{\cdot}A^{4-}$ at 7.2 < pH < 10.5. The second is identical to that of V(III). Diffusion coefficients of $VO{\cdot}HA^{2-}$ and $VO{\cdot}A^{3-}$ are found to be $(9.0{\pm}0.3){\times}10^{-6}cm^2/s$ and $(5.9{\pm}0.4){\times}10^{-6}cm^2/ses$, respectively.

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