• Nuclear Engineering and Technology
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• v.31 no.2
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• pp.182-191
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• 1999

The sorption of UO$_{2}$$^{2+}$ onto goethite and kaolinite under various experimental conditions was successfully interpreted using surface complexation modeling (SCM). The SCM approach used in this work is the triple-layer model (TLM) in which weakly bonded ions are modeled as outer-sphere (ion-pair) complexes and strongly bonded ions as inner-sphere (surface coordination) complexes. The change of ionic strength did not affect the U(VI) sorption onto goethite, thus the formation of inner-sphere surface complexes, (FeO)$_2$UO$_2$ and (FeO)$_2$(UO$_2$)$_3$OH$_{5}$ was assumed to simulate the effects of ionic strength and goethite concentration. On the other hand, the U(VI) sorption onto kaolinite showed ionic strength dependence, thus the formation of AlO-UO$_{2}$$^{2+}$(outer-sphere complex) and SiO(UO$_2$)$_3$OH$_{5}$ (inner-sphere complex) was assumed to simulate the experimental data. In the presence of carbonates, the sorption of U(VI) onto kaolinite decreased in the weakly alkaline pH range. This was well simulated assuming the formation of a outer-sphere surface complex, A1OH$^{2+}$- (UO$_2$)$_2$CO$_3$OH$_3$. Since SCM approach uses thermodynamic data such as surface complexation constants, it is more predictive than empirical modeling approach in which conditional values such as partition coefficient are used. used.

• Journal of Integrative Natural Science
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• v.8 no.4
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• pp.235-243
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• 2015

Rhodium(I)-complex of $[Rh(CO)_2I_2{^-}]$ catalyzed carbonylation of anhydrous-trimethylamine in the presence of methyl iodide to give DMAC (N,N-dimethylacetamide) in no solvent. The catalyst had been reused 20 times, the analyses and distillation of collected products showed that the yields of DMAC, MAA (N-methylacetamide), and DMF (N,N-dimethylformamide) were 82.3%, 12.6%, and 4.4%. The conversion rate of trimethylamine was 99 % and the selectivity of DMAC was 82.3% with TON (Turnover Number) of 700. Stepwise procedure of inner-sphere reductive elimination for the formation of DMAC was suggested instead of acyl iodide intermediate.

• Bulletin of the Korean Chemical Society
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• v.19 no.3
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• pp.324-327
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• 1998

The mechanisms of Cu2+ adsorption onto goethite, hematite and kaolinite are different. Goethite and hematite showed a similar adsorption behavior (ionic-strength independent), but kaolinite gave somewhat different result (ionic-strength dependent). These experimenal results were successfully simulated using a surface complexation model, TLM, which defines the inner- or outer-sphere complex. The chemical nature of Cu2+ adsorption onto kaolinite was qualitatively identified by EPR spectroscopy.

• Nuclear Engineering and Technology
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• v.54 no.5
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• pp.1616-1622
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• 2022

Selenium has been identified as an element of interest for the safety assessment of a deep geological repository (DGR) for used nuclear fuel. In Canada, groundwaters at DGR depths in sedimentary rocks have been observed to have a high ionic strength. This paper examines the sorption behavior of Se(-II) onto illite, MX-80 bentonite, Queenston shale, and argillaceous limestone in Na-Ca-Cl solutions of varying ionic strength (0.1-6 mol/kgw (m)) and across a pH range of 4-9. Little ionic strength dependence for Se(-II) sorption onto all solids was observed except that sorption at high ionic strength (6 m) was generally slightly lower than sorption at low ionic strength (0.1 m). Illite and MX-80 exhibited the expected results for anion sorption, while shale and limestone exhibited more constant sorption across the pH range tested. A non-electrostatic surface complexation model successfully predicted sorption of Se(-II) onto illite and MX-80 using the formation of an inner-sphere surface complex and an outer-sphere surface complex. Optimized values for the formation reactions of these surface species were proposed.

• 한국전산유체공학회:학술대회논문집
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• 2008.03b
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• pp.220-223
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• 2008

A test facility to measure the performance of a KM(Kick Motor) is constructed, and prediction of blast wave propagation over the facility is performed to check if the safety of test personnel in MCC(Main Control Center) can be guaranteed even for the most severe explosion. Assuming that the initial explosion energy is contained in a sphere under the pressure of 500, 1000, 1500 psi, respectively, the radius of the sphere is determined for each pressure to set the mass of contained explosion gas to 35 kg. The material properties of explosion gas are set to be the ones of KM propellant combustion gas under normal condition. To reduce the effort and time required for a complex three-dimensional modeling, the flowfield is approximated to axismmetry. Calculations are performed for all three initial pressure conditions, and the analysis of the result is given for 1500 psi which is expected to be the worst case. The maximum pressure is 3.5 psig while the minimum pressure is -1.2 psig on the outer wall of MCC, and the maximum pressure difference between the inner and outer walls of protection wall amounts to 3.0 psi.

• Journal of the Korean Chemical Society
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• v.30 no.5
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• pp.475-482
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• 1986

Rates and equilibriurn of complex formation between $Ni^{2+}$ and D-penicillamine have been investigated in aqueous solutions. Kinetic study on the complex formation were performed in the pH range of 8∼9 by the use of pressure-jump technique. D-Penicillamine coordinates to the nickel(II) ion utilizing sulfur and nitrogen as donor atoms in the high pH condition (pH 9.2). However, in the pH range of 8.25∼9.07, the stepwise stability constant becomes drastically reduced and the undissociated mercapto group does not participate in bonding. The rate-determining step of the complexation reaction is found to be the release of a water molecule from the inner-coordination sphere of $Ni^{2+}$ ion.

• Journal of the Mineralogical Society of Korea
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• v.11 no.1
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• pp.20-31
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• 1998

Adsorption of metal elements onto illite and halloysite was investigated at $25^{\circ}C$ using pollutant water collected from the gold-bearing metal mine. Incipient solution of pH 3.19 was reacted with clay minerals as a function of time: 10 minute, 30 minute, 1 hour, 12 hour, 24 hour, 1 day, 2 day, 1 week, and 2 week. Twenty-seven cations and six anions from solutions were analyzed by AAs (atomic absorption spectrometer), ICP(induced-coupled plasma), and IC (ion chromatography). Speciation and saturation index of solutions were calculated by WATEQ4F and MINTEQA2 codes, indicating that most of metal ions exist as free ions and that there is little difference in chemical species and relative abundances between initial solution and reacted solutions. The adsorption results showed that the adsorption extent of elements varies depending on mineral types and reaction time. As for illite, adsorption after 1 hour-reaction occurs in the order of As>Pb>Ge>Li>Co, Pb, Cr, Ba>Cs for trace elements and Fe>K>Na>Mn>Al>Ca>Si for major elements, respectively. As for halloysite, adsorption after 1 hour-reaction occurs in the order of Cu>Pb>Li>Ge>Cr>Zn>As>Ba>Ti>Cd>Co for trace elements and Fe>K>Mn>Ca>Al>Na>Si for major elements, respectively. After 2 week-reaction, the adsorption occurs in the order of Cu>As>Zn>Li>Ge>Co>Ti>Ba>Ni>Pb>Cr>Cd>Se for trace elements and Fe>K>Mn>Al, Mg>Ca>Na, Si for major elements, respectively. No significant adsorption as well as selectivity was found for anions. Although halloysite has a 1:1 layer structure, its capacity of adsorption is greater than that of illite with 2:1 structure, probably due to its peculiar mineralogical characteristics. According to FTIR (Fourier transform infrared spectroscopy) results, there was no shift in the OH-stretching bond for illite, but the ν1 bond at 3695 cm-1 for halloysite was found to be stronger. In the viewpoint of adsorption, illite is characterized by an inner-sphere complex, whereas halloysite by an outer-sphere complex, respectively. Initial ion activity and dissociation constant of metal elements are regarded as the main factors that control the adsorption behaviors in a natural system containing multicomponents at the acidic condition.

• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.29-34
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• 1995

The rates for the oxidation reaction of l-ascorbic acid by Cu(Ⅱ)-polyamine complexes were measured by Onish's method at the pH 4.6. The oxidation process of l-ascorbic acid is proposed to occur by the inner-sphere mechanism that involves the formation of a Cu(Ⅱ)-ascorbic acid complex and electron transfer at the rate-determining step.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.303-306
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• 1990

Kinetic studies were carried out for the redox reaction of $[Co(NH_3)_4(C_2O_4)]^+$ with aqueous $[Fe(H_2O)_6]^{2+}$ solution in the present of $H^+$ by UV/VIS-spectrophotometric method. It was found that the order of $H^+$ for the reaction is first one in the higher $H^+$ concentration range of $1.67×10^{-1} M{\sim}1.00 M,$ while second order in the lower range of $6.30×10^{-2} M{\sim}1.67{\times}10^{-1} M.$ Reaction order of the substrates was found to be first order with respect to each of them. Accordingly overall reactions are third or fourth order. The results of calculation for the Extended Huckel Molecular Orbital theory contribute to estimate the preferred intermediates, bridging form of binuclear complex. On the basis of these results, we propose that this redox reaction proceed via inner-sphere reaction mechanism.

• Journal of the Korean Chemical Society
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• v.33 no.2
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• pp.225-231
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• 1989

The heterogeneous rate constants for the electrochemical reduction by $trans-[Co(en)_2X_2](ClO_4)_n$(where X is cyanide, nitrite, ammonia, and isothiocyanate) at mercury and glassy carbon electrode were investigated by cyclic voltammetry, DC polarography, and by using rotating disk electrode. The good linear relationship was obtained between the activation energy of reduction and absorption wave number of complexes on glassy carbon electrode. At mercury electrode, $NO_2^-$ ligated complex showed the large deviation from the linear relationship. The difference in the value of rate constants for $NO_2^-$ ligated complex between mercury and glassy carbon electrode was about three order of magnitude which was much larger than the other complexes. It was suggested that $NO_^-$ ligated complex was reduced by inner-sphere mechanism on mercury electrode from the larger value of activation energy and entropy on mercury than carbon electrode.