• Title/Summary/Keyword: Ionic dissociation

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The Kinetics of Complexation of Nickel(II) and Cobalt(II) Mandelates in Aqueous Solution

  • Choi, Ki-Young;Yun, Sock-Sung;Kim, Mal-Jin
    • Bulletin of the Korean Chemical Society
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    • v.12 no.6
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    • pp.629-632
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    • 1991
  • The rate constants for the formation and dissociation of nickel(II) and cobalt(II) complexes with mandelate have been determined by the pressure-jump relaxation study. The forward and reverse rate constants for the mandelate complex formation reactions were obtained to be $k_f=3.60{\times}10^4\;M^{-1}s^{-1}$ and $k_r=1.73{\times}10^2\;s^{-1}$ for the nickel(II), and $k_f=1.75{\times}10^5\;M^{-1}s{-1}$ and $2.33{\times}10^3\;s^{-1}$ for the cobalt(II) in aqueous solution of zero ionic strength ($(\mu{\to}0)\;at\;25^{\circ}C$. The results were interpreted by the use of the multistep complex formation mechanism. The rate constants evaluated for each individual steps in the multistep mechanism draw a conclusion that the rate of the reaction would be controlled by the chelate ring closure step in concert with the solvent exchange step in the nickel(II) complexation, while solely by the chelate ring closure step for the cobalt(II) complex.

The Kinetics of Complexation of Manganese(Ⅱ), Cobalt(Ⅱ) and Nickel(Ⅱ) Ions with Some Dicarboxylates in Aqueous Solution

  • Yun Sock Sung;Doh Jae-Bum;Choi Ki Young
    • Bulletin of the Korean Chemical Society
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    • v.13 no.6
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    • pp.659-662
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    • 1992
  • The pressure-jump relaxation method has been used to determine the rate constants for the formation and dissociation of maganese(Ⅱ), cobalt(Ⅱ), and nickel(Ⅱ) with some dicarboxylates in aqueous solution at zero ionic strength. The carboxylate ligands used are 3-nitrophthalate, 4-nitrophthalate, and phenylmalonate. The activation parameters have alse been obtained from the temperature dependence of the rate constants. A dissociative interchange mechanism with a chelate ring closure step as rate determining is employed to interpret the kinetic data of manganese(Ⅱ) and cobalt(Ⅱ) complexes. The rates of formation of nickel(Ⅱ) complexes are controlled by both the solvent exchange step and the chelate ring closure step.

Interactions between Water-Soluble Polyparacyclophanes and Drugs (III) -Complex Formation of Water-Soluble Polyparacyclophanes with Fluorescent Hydrophobic Naphthalene Derivatives in Aqueous Solution- (수용성 폴리파라시클로판류와 약물과의 상호작용(제 3보)-수용액 중 수용성 폴리파라시클로판류와 형광 소수 나프탈렌 유도체류와의 복합체 형성-)

  • Chun, In-Koo;Lee, Min-Hwa
    • Journal of Pharmaceutical Investigation
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    • v.19 no.2
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    • pp.71-79
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    • 1989
  • Complex formation of water-soluble polyparacyclophanes bearing two diphenylmethane or two diphenyl ether skeletons with l-anilinonaphthalene-8-sulfonate (ANS) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated quantitatively to develop useful host compounds comparing with ${\alpha}\;-\;and\;{\beta}-cyc1odextrins$$({\alpha}-\;and\;{\beta}-CyDs$) in aqueous solution. Benesi-Hildebrand type analysis of the fluorescent intensity showed that the dissociation constants (Kd) of paracyclophane-ANS complexes were $1.55\;{\times}\;10^{-4}M$ for 1,6,20,25-tetraaza[6.1.6.1]paracyclophane(CPM 44) and $1.23\;{\times}\;10^{-4}M$ for 1,7,21,27-tetraaza[7.1.7.1]paracyclophane (CPM 55), and those of paracyclophane-TNS complexes were $6.99\;{\times}\;10^{-6}M$ for CPM 44 and $6.23\;{\times}\;10^{-5}M$ for CPM 55, in 1:1 molar ratio. On the other hand, the Kd values of 1,7,21,27-tetraaza-14,34-dioxa[7.1.7.1]paracyclophane (CPE 55)-ANS, 1,8,22,29-tetraaza-15,36-dioxa[8.1.8.1]paracyclophane (CPE 66)-ANS, CPE 55-TNS, CPE 66-TNS complexes were $1.75\;{\times}\;10^{-3}M$, $3.07\;{\times}\;10^{-3}M$, $3.75\;{\times}\;10^{-3}M$ and $2.15\;{\times}\;10^{-3}M$, respectively. On the contrary, the Kd values of ${\alpha}-CyD-ANS$, ${\beta}-CyD-ANS$, ${\alpha}-CyD-TNS$ and ${\beta}-CyD-TNS$ complexes were found to be $3.98\;{\times}\;10^{-2}M$, $1.05\;{\times}\;10^{-2}M$, $1.38\;{\times}\;10^{-2}M$ and $3.52\;{\times}\;10^{-4}M$, respectively. These results mean that the complexation of CPMs with ANS or TNS is by 5.6-1,975 fold stronger than that for ${\alpha}-or\;{\beta}-CyDs$, and the complex formation of CPEs with ANS or TNS is nearly same as or somewhat stronger than that for ${\alpha}-or\;{\beta}-CyDs$. From the Kd values determined at different temperatures, thermodynamic parameters were calculated and the complexation was found to be a spontaneous exothermic reaction. The effects of pH on Kd values of CPM 44-ANS, and CPM 55-ANS complexes were negligible in the range of pH 1.2-1.8. However, the Kd values of these complexes increased significantly with increasing ionic strength.

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Calculations of radical and ion densities in a $CF_4$ plasma using global model (글로벌 모델에 의한 $CF_4$플라즈마에서의 라디칼 및 이온 밀도 계산)

  • 이호준;태흥식;이정희;이용현;황기웅
    • Journal of the Korean Vacuum Society
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    • v.7 no.4
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    • pp.374-380
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    • 1998
  • Radical and ion densities in a $CF_4$plasma have been calculated as a function of input power density, gas pressure and feed gas flow rate using simple 0 dimensional global model. Fluorine atom is found to be the most abundant neutral particle. Highly fragmented species such as CF and $CF^+$ become dominant neutral and ionic radical at the high power condition. As the pressure increase, ion density increases but ionization rate decreases due to the decrease in electron temperature. The fractional dissociation of $CF_4$feed gas decreases with pressure after increasing at the low pressure range. Electron density and temperature are almost independent of flow rate within calculation conditions studied. The fractional dissociation of $CF_4$monotonically decreases with flow rate, which results in increase in $CF_3$and decrease in CF density. The calculation results show that the $SiO_2$etch selectivity improvement correlates to the increase in the relative density of fluorocarbon ion and neutral radicals which has high C/F ratio.

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Relationship between Dielectric Constant and Increament of Si-O bond in SiOC Film (SiOC 박막에서 Si-O 결합의 증가와 유전상수의 관계)

  • Oh, Teresa
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.11 no.11
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    • pp.4468-4472
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    • 2010
  • SiOC films made by the inductively coupled plasma chemical vapor deposition were researched the relationship between the dielectric constant and the chemical shift. SiOC film obtained by plasma method had the main Si-O-C bond with the molecule vibration mode in the range of $930{\sim}1230\;cm^{-1}$ which consists of C-O and Si-O bonds related to the cross link formation according to the dissociation and recombination. The C-O bond originated from the elongation effect by the neighboring highly electron negative oxygen atoms at terminal C-H bond in Si-$CH_3$ of $1270cm^{-1}$. However, the Si-O bond was formed from the second ionic sites recombined after the dissociation of Si-$CH_3$ of $1270cm^{-1}$. The increase of the Si-O bond induced the redshift as the shift of peak in FTIR spectra because of the increase of right shoulder in main bond. These results mean that SiOC films become more stable and stronger than SiOC film with dominant C-O bond. So it was researched that the roughness was also decreased due to the high degree of amorphous structure at SiOC film with the redshift after annealing.

Oligo(EDOT)/PVdF Blend Electrolyte for All Solid Polymer Battery (전 고체 고분자 전지용 Oligo(EDOT)/PVdF 블렌드 전해질)

  • Kim, Min Su;Gwon, Hyeon-Ju;Jo, Nam-Ju
    • Applied Chemistry for Engineering
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    • v.33 no.3
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    • pp.289-295
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    • 2022
  • In this study, we intend to fabricate an all solid polymer battery with a reduced interfacial resistance between the solid electrolyte and the electrode by applying thiophene based polymers as both electrode and electrolyte materials. In order to minimize the interfacial resistance with the poly(3,4-ethylenedioxy thiophene) (PEDOT) based electrode, 3,4-ethylenedioxy thiophene (EDOT) oligomer was introduced into the solid electrolyte. Also, to improve the lithium salt dissociation ability of the EDOT oligomer [oligo(EDOT)] electrolyte, it was blended with poly(vinylidene fluoride) (PVdF). As a result, the ionic conductivity of the solid polymer electrolyte increased by introducing PVdF into the oligo (EDOT). From the result of evaluating the electrochemical properties of an all solid polymer battery, the interfacial resistance significantly decreased by introducing a thiophene based polymer to the electrode and electrolyte.

Synthesis of Naphthol-Containing Polyamines and Determination of Stability Constants of Their Metal Complexes by Potentiometric Titration (나프톨을 포함하는 폴리아민의 합성 및 전위차 적정에 의한 금속착물의 안정도상수 결정)

  • Kim, Sun-Deuk;Kim, Jun-Kwang
    • Analytical Science and Technology
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    • v.10 no.4
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    • pp.256-263
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    • 1997
  • The new naphthol-containing hexadentate ligands, 1,12-bis (2-naphthol)- 2,5,8,11-tetraazadodecane 4HCl (nptr) and 1,14-bis(2-naphthol)- 2,6,9,13- tetraazatetradodecane .4HCl (npptr) were synthesized and characterized by elemental analysis, IR, NMR, and mass spectrometry. Acid dissociation constants and stability constants of Co(II), Ni(II). Cu(II), and Zn(II) complexes were determined at $25.0^{\circ}C$ and ionic strength ($\mu$)=0.10M($KNO_3$) by potentiometry. The relationship between basicity and stability constants of ligands containing aliphatic amines and 2-naphthol were studied.

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A Study on the Complexation of Nickel(II) Ion with 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris) in Aqueous Solution (수용액 중에서 Ni(II) 이온과 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris)과의 착물형성에 대한 연구)

  • Hong, Kyung-Hee;Shim, Seung-Bo;Oh, Seong-Geun;Chun, Yong-Jin
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.11 no.12
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    • pp.5221-5231
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    • 2010
  • The complex formation from Ni(II) ion and 2-(2-Hydroxyethylamino)-2-(hydroxymethyl)-1,3-propanediol(Monotris) in aqueous solution at $25^{\circ}C$ and at ionic strength of 0.10M has been studied potentiometrically. In the Monotris(L) comlex $NiL^{2+}$, hydroxyl oxygen atom as well as the amine nitrogen of the ligand are coordinated to the Ni(II) ion.. The complex $NiL^{2+}$ undergoes further dissociation as the pH is increased forming triply deprotonated dinuclear complex $Ni_2L_2H_{-3}^+$.

The Physicochemical Properties of $\alpha$-Amylase Inhibitors from Black Bean and Naked Barey in Korea (한국산 검정콩 및 쌀보리 $\alpha$-Amylase 저해물질의 이화학적 특성)

  • 심기환;문주석;배영일
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.27 no.3
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    • pp.367-375
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    • 1998
  • The physicochemical properties of the $\alpha$-amylase inhibitors from black bean and naked barley is Korea were investigated. Preincubation time for maximum inhibition was 30min and no activity change was seen after that time. Optimum pH of the $\alpha$-amylase inhibitors from the black bean and naked barley was pH 7.0 and the inhibitory activities were stable in the range of pH 6.0~8.0 in both phosphate and Tris-HCI buffer solutions. Both inhibitors maintained more than 50% of activity after incubation for 17 min at 7$0^{\circ}C$. The inhibitors from the black bean and naked barley maintained more than 50% of activities after treatment for 40 min and 30 min with pepsin, and 30 min and 50 min with trypsin, respectively. Both inhibitors functioned via a noncompetitive mechanism and were active against porcine pancreatic and human salivary $\alpha$-amylases. The activities of both inhibitors were linear for the ionic stength ranging from 0 to 0.9. The addition of 70 mM maltose to the reaction mixture caused a maximum increase in the relative activities of both inhibitors, but it did not affect the dissociation of the EI complex. The activities of both inhibitors were significantly enhanced by adding 1mM of K+ or Mg2+.

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Polymer Electrolyte Membranes for Flexible Electrochromic Device (플렉시블 전기변색 소자를 위한 고분자 전해질 멤브레인)

  • Lee, Ji-Hyeon;Kang, Moon-Sung
    • Membrane Journal
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    • v.30 no.5
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    • pp.333-341
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    • 2020
  • In this study, the optimum design conditions of a polymer electrolyte membrane for application to a flexible electrochromic device (ECD) were tried to be derived. Polyvinyl butyral (PVB) with excellent adhesive property and transparency was selected as the base polymer for the preparation of the electrolyte membrane, and adipate-based polymer was used as the plasticizer. As a result, it was confirmed that the most influential factors on the ECD performance were the ionic conductivity and permeability of the electrolyte membrane. In addition, it was found that the factor has a close relationship with the dissociation property of the lithium salt. Overall, the optimal ECD performance was achieved when LiTFSI salt having a large anion size among various lithium salts was dissolved in a content of about 25 wt.%.