• Title/Summary/Keyword: metal-water interaction

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Spectral and Thermal Studies of Transition Metal PSSA Ionomers

  • Shim, Il-Wun;Risen, William M. Jr.
    • Bulletin of the Korean Chemical Society
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    • v.9 no.6
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    • pp.368-376
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    • 1988
  • Transition metal PSSA ionomers containing Co(II), Ni(II), Cr(III), Ru(III), and Rh(III) are investigated by IR, Far-IR, UV-Vis and DSC. Reliable IR Spectroscopic criteria are established for assessing the degree of ion-exchange of PSSA ionomers and the local structures around metal cations in them. In the hydrated transition metal PSSA ionomers, the ionic groups are solvated by water molecules and there is no significant interactions between sulfonate group and metal cations. The visible spectra indicated that metal cations are present as [M$(H_2O)_6$]$^{n+}$ with Oh symmetry. Their $T_g$ values increase as the extent of ionic site concentration increases, but there is no direct dependence of $T_g$ on the nature of metal cations or their oxidation states. Thus, the water content in PSSA ionomer is found to have dominant influence on $T_g$ of hydrated transition metal PSSA ionomers. Dehydration of the hydrated transition metal PSSA ionomers results in direct interaction between ionic groups and significant color changes of the ionomers due to the changes of the local structures around metal cations. On the base of spectral data, their local structures are discussed. In case of dehydrated 12.8 and 15.8 mol % transition metal PSSA ionomers, no glass transition is observed in 25-$250^{\circ}C$ region and this is believed to arise from the formation of highly crosslinked structures caused by direct coordination of sulfonate groups of metal cations. In the 6.9 mol % transition metal PSSA ionomers, the glass transition is always observed whether they are hydrated or dehydrated and this is though to be caused by the sufficient segmental mobility of the polymer backbone.

Metal Complexes of Enrofloxacin Part I: Preparation, Spectroscopic, Thermal Analyses Studies and Antimicrobial Evaluation

  • El-Shwiniy, Walaa H.;El-Attar, Mohamed S.;Sadeek, Sadeek A.
    • Journal of the Korean Chemical Society
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    • v.57 no.1
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    • pp.52-62
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    • 2013
  • The interaction of titanium (IV), yttrium (III), zirconium (IV), palladium (II) and cerium (IV) with deprotonated enrofloxacin leads to the formation of the neutral or cationic mononuclear complexes. The isolated solid complexes have been characterized with physicochemical and spectroscopic techniques and thermogravimeteric analyses. The spectroscopic data indicate that the enrofloxacin ligand is on the deprotonated mode acting as bidentate ligand coordinated to the metal ions through the ketone oxygen and a carboxylato oxygen and the metal ions completed the coordination number with water molecules. The thermal decomposition mechanisms proposed for enrofloxacin and their metal complexes were discussed. The activation energies, $E^*$, enthalpies, ${\Delta}H^*$, entropies, ${\Delta}S^*$ and Gibbs free energies, ${\Delta}G^*$, of the thermal decomposition reactions have been derived from thermogravimetric (TG) and differential thermogravimetric (DTG) curves, using Coats-Redfern (CR) and Horowitz-Metzeger (HM) methods. The antimicrobial activity has been evaluated against six different microorganisms.

A Review on Mineralogical and Geochemical Characteristics of Seafloor Massive Sulfide Deposits in Mid-Ocean Ridge and Volcanic Arc Settings: Water-Rock Interaction and Magmatic Contribution (중앙해령 및 섭입대 화산호 지역 해저열수광상의 광물·지구화학적 특성 고찰: 물-암석 상호작용 및 마그마 영향)

  • Choi, Sun Ki
    • Economic and Environmental Geology
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    • v.55 no.5
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    • pp.465-475
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    • 2022
  • The seafloor massive sulfide deposits are important mineral resources for base and precious metals, and their ore genesis and metal contents are mainly controlled by wall-rock leaching process and/or magmatic volatile input from the underlying magma chamber. However, the contribution of two different metal sources to the seafloor hydrothermal mineralization significantly varies in diverse geological settings and thus still remains controversial. In this review, mineralogical and geochemical characteristics of SMS deposits from mid-ocean ridges (MORs) and volcanic arcs were investigated to understand the contribution from different metal sources and to suggest future challenges that need to be addressed. As a result, the genetic occurrences of enargite and cubanite, galena and barite indicate the effects of magmatic input and water-rock interaction, respectively. Also, the distributional behaviors of Co, As, and Hg in pyrite and FeS content of sphalerite could be useful empirical indicators to discriminate the significant roles of different metal sources between MOR and Arc settings. To date, as most studies have focused on sulfide samples recovered from the seabed, further studies on magmatic sulfides and sulfate minerals are required to fully understand the genetic history of SMS deposits.

Fluid Effects on the Core Seismic Behavior of a Liquid Metal Reactor

  • Koo, Gyeong-Hoi;Lee, Jae-Han
    • Journal of Mechanical Science and Technology
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    • v.18 no.12
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    • pp.2125-2136
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    • 2004
  • In this paper, a numerical application algorithm for applying the CFAM (Consistent Fluid Added Mass) matrix for a core seismic analysis is developed and applied to the 7-ducts core system to investigate the fluid effects on the dynamic characteristics and the seismic time history responses. To this end, three cases such as the in-air condition, the in-water condition without the fluid coupling terms, and the in-water condition with the fluid coupling terms are considered in this paper. From modal analysis, the core duct assemblies revealed strongly coupled out-of-phase vibration modes unlike the other cases with the fluid coupling terms considered. From the results of the seismic time history analysis, it was also verified that the fluid coupling terms in the CFAM matrix can significantly affect the impact responses and the seismic displacement responses of the ducts.

Complexes of Polyvalent Metal Ions (Ⅶ). Complexes of Cadmium, Cobalt and Nickel with Hydroxycarboxylic Acids in Aqueous, Ethanol-Water and Acetone-Water Solutions$^*$

  • Park, Joon-W.;Mukherjee, C.
    • Bulletin of the Korean Chemical Society
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    • v.1 no.3
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    • pp.105-109
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    • 1980
  • A general spectroscopic method is described for studies on the complex formation between metal ions and ligands, and is applied to $Cu^{2+}$ and $Ca^{2+}$binding to glycosaminoglycans. The order of binding constants for both ions is heparin >dermatan sulfate >chondroitin sulfate. The electrostatic forces are shown to be the predominant factor in the interaction. The 2- to 3-fold higher affinity for $Cu^{2+}$ than for $Ca^{2+}$ is obtained for heparin and dermatan sulfate, but little difference for chondroitin sulfate. These results are explained as chelation of both carboxyl and sulfate groups to $Cu^{2+}$ in former cases. The difference of binding constants among glycosaminoglycans is related to proposed various biological functions of the biopolymers.

Template Synthesis, Crystal Structure, and Magnetic Properties of a Dinuclear Copper(II) Complex with Cooperative Hydrogen Bonding

  • Kang, Shin-Geol;Nam, Kwang-Hee;Min, Kil-Sik;Lee, Uk
    • Bulletin of the Korean Chemical Society
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    • v.32 no.3
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    • pp.1037-1040
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    • 2011
  • The dinuclear complex 1 with cooperative hydrogen bonds can be prepared by the metal-directed reaction of Eq. (2). This work shows that the coordinated hydroxyl group trans to the secondary amino group is deprotonated more readily than that trans to the tertiary amino group and acts as the hydrogen-bond accepter. The lattice water molecules in 1 act as bridges between the two mononuclear units through hydrogen bonds. The complex is quite stable as the dimeric form even in various polar solvents. The complex exhibits a weak antiferromagnetic interaction between the metal ions in spite of relatively long Cu$\cdots$Cu distance. This strongly supports the suggestion that the antiferromagnetic behavior is closely related to the cooperative hydrogen bonds.

The structures and catalytic activities of metallic nanoparticles on mixed oxide

  • Park, Jun-Beom
    • Proceedings of the Korean Vacuum Society Conference
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    • 2010.02a
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    • pp.339-339
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    • 2010
  • The metallic nanoparticles (Pt, Au, Ag. Cu, etc.) supported on ceria-titania mixed oxide exhibit a high catalytic activity for the water gas shift reaction ($H_2O\;+\;CO\;{\leftrightarrow}\;H_2\;+\;CO_2$) and the CO oxidation ($O_2\;+\;2CO\;{\leftrightarrow}\;2CO_2$). It has been speculated that the high catalytic activity is related to the easy exchange of the oxidation states of ceria ($Ce^{3+}$ and $Ce^{4+}$) on titania, but very little is known about the ceria titanium interaction, the growth mode of metal on ceria titania complex, and the reaction mechanism. In this work, the growth of $CeO_x$ and Au/$CeO_x$ on rutile $TiO_2$(110) have been investigated by Scanning Tunneling Microscopy (STM), Photoelectron Spectroscopy (PES), and DFT calculation. In the $CeO_x/TiO_2$(110) systems, the titania substrate imposes on the ceria nanoparticles non-typical coordination modes, favoring a $Ce^{3+}$ oxidation state and enhancing their chemical activity. The deposition of metal on a $CeO_x/TiO_2$(110) substrate generates much smaller nanoparticles with an extremely high activity. We proposed a mechanism that there is a strong coupling of the chemical properties of the admetal and the mixed-metal oxide: The adsorption and dissociation of water probably take place on the oxide, CO adsorbs on the admetal nanoparticles, and all subsequent reaction steps occur at the oxide-admetal interface.

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Measurement of metals in sediment of the Geum-River and their correlation (금강수계 퇴적물 중 금속류 분석 및 상관성 조사)

  • Lee, Jun-Bae;Hong, Seoun-Hwa;Kim, Dong-Ho;Huh, In-Ae;Huh, Yu-Jeong;Khan, Jong-Beom;Oh, Da-Yeon;Kim, Keon-Young;Lee, Young-Joon;Lee, Soo-Hyung;Shin, Ho-Sang
    • Analytical Science and Technology
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    • v.27 no.1
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    • pp.11-21
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    • 2014
  • An investigation of grain size, organic compounds and metal distribution in 23 sediment samples of the Geum-River basin (Korea) was conducted in two seasons of 2012 (dry season and rainy season). The samples of sediment were collected from the basin and investigated for concentrations of some metal and general indexes containing grain size. Concentrations of Pb, Zn, Cu, Cr, Ni, As, Cd, Hg, Al and Li have been determined by inductively coupled plasma spectrometer (ICP) and the sediments organic matter content was determined by the loss on ignition, and sediments were fractionated with three different nylon sieves. Correlation analysis was made for grain size, organic material and metal concentrations, and the Pearson correlation coefficients between their concentrations were determined. As a result, the higher metal concentrations were found in the period of the dry season than in another season. The metal concentrations showed high correlation with that of organic material (COD and TOC). Thereby, the high distribution of metal concentrations in sediment containing high organic compound is suggesting an interaction with organic matter.

Development of Separation and Trace Analysis Methods for Platinum Group Elements-Separation and Retention Behavior of Platinoid Metal Acetylacetonates in Reversed-Phase Liquid Chromatography (백금족 원소의 분리 및 미량분석법 개발에 관한 연구: 역상 액체 크로마토그래피에 의한 백금족 금속-아세틸아세톤 킬레이트들의 분리 및 머무름 거동)

  • Lee, Dai Woon;Kim, Kyung Soo;Park, Young Hun;Czea, Myoung Zoon;Chung, Koo Soon
    • Analytical Science and Technology
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    • v.6 no.1
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    • pp.107-119
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    • 1993
  • The purpose of this study is to investigated the elution behavior of platinoid metal acetylacetonates, which is the key to elucidate their retention mechanism and optimize their RPLC separation conditions. The retention data of four platinoid metal acetylacetonates have been measured on four different columns in methanol-water and acetonitrile-water systems. The retention of uncharged platinoid metal acetylacetonates is interpreted by solvophobic effect. The retention of platinoid metal acetylacetonates is also greatly influenced by the geometric structure of the complexes. The square planar chelates, $Pd(acac)_2$, $Pt(acac)_2$, are retained longer than the octahedral chelates, $Rh(acac)_3$, $Ir(acac)_3$. It is likely due to that square planar chelates show greater interaction with nonpolar stationary phase than octahedral chelates. The results of van't Hoff plots have shown that platinoid metal acetylacetonates is operated on the same retention mechanism in the temperature range of $25{\sim}45^{\circ}C$. The study of the retention mechanism by the enthalpy-entropy compensation phenomenon has indicated that the retention mechanism of octahedral chelates and square planar chelates do not vary with the composition change of methanol-water mobile phase, respectively. In acetonitrile-water mobile phase, however, the retention mechanism is observed to be more complicated. Optimum condition for the separation of four platinoid metal acetylacetonates is found to be 40% methanol, polymeric C18 column, and $45^{\circ}C$.

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Zundel- and Eigen-like Surface Hydrated Protons on Pt(111)

  • Kim, Youngsoon;Park, Youngwook;Shin, Sunghwan;Kang, Heon
    • Proceedings of the Korean Vacuum Society Conference
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    • 2016.02a
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    • pp.167.1-167.1
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    • 2016
  • The interaction between adsorbed water and hydrogen on metallic surfaces is important for fundamental understanding of heterogeneous catalysis and electrode surface reactions in acidic environment. Here, we explore a long-standing question of whether hydronium ion can exist or not on a Pt surface coadsorbed with atomic hydrogen and water. Studies based on mass spectrometry and infrared spectroscopy show clear evidence that hydrogen atoms are converted into hydrated protons on a Pt(111) surface. The preferential structures of hydrated protons are identified as multiply hydrated $H_5O_2{^+}$ and $H_7O_3{^+}$ species rather than as hydronium ions. The multiply hydrated protons may be regarded as two dimensional zundel ($H_5O_2{^+}$) and Eigen cation ($H_7O_3{^+}$) in water-metal interface. These surface-bound hydrated protons may be key surface intermediates of the electrochemical interconversion between adsorbed hydrogen atoms and solvated protons.

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