• The Journal of the Acoustical Society of Korea
• /
• v.31 no.2
• /
• pp.100-106
• /
• 2012

The aim of this work was to reveal the effect of butanoic acid in its dissociated form and undissociated form as a guest molecule on the kinetic parameters in an inclusion reaction with ${\beta}$-cyclodextrin (${\beta}$-CD). Ultrasonic absorption measurements in the frequency range from 0.2 to 45 MHz were carried out for ${\beta}$-CD solutions with butanoic acid at $25^{\circ}C$ by ultrasonic relaxation method. The rate and the equilibrium constants were obtained from the guest concentration dependence of the relaxation frequency, and the standard volume change of the complexation reaction were obtained from the maximum absorption per wavelength. A single relaxational absorption was observed, and the cause of the relaxation was attributed to a perturbation of the chemical equilibrium associated with a complexation reaction between ${\beta}$-CD and butanoic acid. These results were compared with those in solutions containing both ${\beta}$-CD and different guest molecules. It was found that the hydrophobicity of guest molecules played an important role in the formation of the inclusion complex and also that the charge on the carboxylic group had a considerable effect on the kinetic characteristics of the complexation reaction.

• Applied Chemistry
• /
• v.16 no.1
• /
• pp.25-28
• /
• 2012

A determination method of cyanide ion (CN^-) using nickel complexation reaction by continuous monitoring system. The mechanical parameters and chemical conditions of the complexation reaction were investigated prior to application of continuous monitoring system for determination of cyanide. On the optimized conditions, the calibration curve was linear over the range from 5.0×10^-6 to 1.0×10^-4 M. In this range, 2.40% of the reproducibility (RSD, n=3) was obtained. The limit of detection (3σ/s) was calculated to be 1.8×10^-6 M.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.3 no.2
• /
• pp.146-155
• /
• 2002

Surface complexation models employ mass law equations to describe the reaction of surface functional groups with ions in the solution and also Gouy-Chapman theory to consider the electrostatic effects in the surface reactions. In current surface complexation models, however, the coulombic factors used are not wholly consistent with the Gouy-Chapman model of the surface. This study was to provide the derivation of the coulombic term usually employed and then a revised coulombic term completely consistent with Gouy-Chapman Theory. The electrical potential energy. zF${\psi}$, in current surface complexation models is not consistent with the Gouy-Chapman theory with the potential gradient close to the charged surface but with the Donnan model with the uniform potential. Even though the new coulombic factor yielded lower surface potential, it provided worse fits for acid-base titration data of the goethite suspensions.

• Journal of Environmental Science International
• /
• v.21 no.5
• /
• pp.555-562
• /
• 2012

The experimental determination of equilibrium constants is required to estimate concentrations of reagents and/or products in environmental chemical reactions. For an example, the choice of copper (Cu) complexation reactions was motivated by their fast kinetics and the ease of measurement of Cu by an ion-sensitive electrode. Each individual titrant of sulfate ($SO{_4}^{2-}$) and oxalate ($C_2O{_4}^{2-}$) was expected to have its own unique characteristics, depending on the bonding in Culigands connected to the aqueous species. The complexation reaction of Cu with $SO{_4}^{2-}$ somewhat fast reached equilibrium status compared with $C_2O{_4}^{2-}$. The experimental equilibrium constants ($K_{eq}$) of copper sulfate ($CuSO_4$) and copper oxalate ($CuC_2O_4$) were determined $10^{2.2}$ and $10^{3{\sim}4.3}$, respectively.

• Bulletin of the Korean Chemical Society
• /
• v.14 no.4
• /
• pp.444-449
• /
• 1993

Anaerobic oxidation of D-penicillamine by Fe(III) in acidic solution has been studied kinetically by the use of stopped-flow system. The reaction is biphasic with a rapid complexation of 1: 1 complex, $Fepen^+$ (pen= D-penicillamine dianion) which is then internally reduced to Fe(II) and disulfide. Rates of both the complexation and the redox process are pH dependent and also are affected by the presence of chloride ion. Different from the reaction of Cu(II) with D-penicillamine, partially oxidized mixed-valence complex is not formed even transiently in this reaction.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.11
• /
• pp.3313-3318
• /
• 2014

The reaction mechanism of Lead ions catalyzing complexation reactions between TIPP and metal ions was investigated by researching the kinetics of the formation of metalloporphyrins by UV/Vis-spectra, and verified by exploring the formation of metalloporphyrins catalyzed by acetic acid. Kinetics studies suggested that the fluctuations of reaction rate indicated the formation of metalloporphyrin was step-wise, including the pre-equilibrium step (the coordination of the pyrrolenine nitrogens to $Mn^+$) and the rate-controlling step (the deprotonation of the pyrrole proton). In the pre-equalization step, a sitting-atop (SAT) structure formed first with the complexation between larger radius of $Pb^{2+}$ and TIPP, changed the activation, then $Pb^{2+}$ left with the smaller radius of metal ions attacking from the back of the porphyrin ring center. In the rate-controlling step, two pyrrole protons dissociated to restore a stable structure. This was verified by adding acetic acid at different reaction times.

• Journal of the Mineralogical Society of Korea
• /
• v.11 no.2
• /
• pp.106-116
• /
• 1998

The adsorption of Cs-137 and Sr-90 onto kaolinite in prescence of major groundwater cations (Ca2+, K+, Na+) with different concentrations was simulated by using triple-layer surface complexation model (TL-SCM). The site density (8.73 sites/nm2) of kaolinite used for TL-SCM was calculated from it's CEC and specific surface area. TL-SCM modeling results indicate that concentrations dependence on 137Cs and 90Sr adsorption onto kaolinite as a function of pH is best modeled as an outer-sphere surface reaction. This suggests that Cs+ and Sr2+ are adsorbed at the $\beta$-layer in kaolinite-water interface where the electrolytes, Nacl, KCl and CaCl2, bind. However, TL-SCM results on Sr adsorption show a discrepancy between batch data and fitting data in alkaline condition. This may be due to precipitation of SrCO3 and complexation such as SrOH+. Intrinsic reaction constants of ions obtained from model fit are as follows: Kintcs=10-2.10, KintSr=10-2.30, KintK=10-2.80, KintCa=10-3.10 and KintNa=10-3.32. The results are in the agreement with competition order among groundwater ions (K+>Ca2+>Na+) and sorption reference of nuclides (Cs-137>Sr-90) at kaolinite-water interface showed in batch test.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.21 no.4
• /
• pp.427-438
• /
• 2023

Thermodynamic sorption modeling can enhance confidence in assessing and demonstrating the radionuclide sorption phenomena onto various mineral adsorbents. In this work, Ca-montmorillonite was successfully purified from Bentonil-WRK bentonite by performing the sequential physical and chemical treatments, and its geochemical properties were characterized using X-ray diffraction, Brunauer-Emmett-Teller analysis, cesium-saturation method, and controlled continuous acid-base titration. Further, batch experiments were conducted to evaluate the adsorption properties of Cs(I) and Sr(II) onto the homoionic Ca-montmorillonite under ambient conditions, and the diffuse double layer model-based inverse analysis of sorption data was performed to establish the relevant surface reaction models and obtain corresponding thermodynamic constants. Two types of surface reactions were identified as responsible for the sorption of Cs(I) and Sr(II) onto Ca-montmorillonite: cation exchange at interlayer site and complexation with edge silanol functionality. The thermodynamic sorption modeling provides acceptable representations of the experimental data, and the species distributions calculated using the resulting reaction constants accounts for the predominance of cation exchange mechanism of Cs(I) and Sr(II) under the ambient aqueous conditions. The surface complexation of cationic fission products with silanol group slightly facilitates their sorption at pH > 8.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.9
• /
• pp.1014-1017
• /
• 1997

1,3-Dipropyloxycalix[4]arene dibenzocrown ethers were synthesized in the fixed 1,3-alternate conformation by the reaction of 1,3-dipropyloxycalix[4]arenes with a dibenzo dimesylates. Complexation toward alkali metal ions using ISEs showed a high cesium selectivity. Conformational flexibility of the corresponding 1,3-alternate calixcrown ether (4) with respect to the NMR time scale is found to depend on the temperature and polarity of the NMR solvent.

• Journal of Microbiology and Biotechnology
• /
• v.32 no.4
• /
• pp.514-521
• /
• 2022

We report the effect of pH on the supramolecular complexation of two biothiols, viz., homocysteine (Hcy) and cysteine (Cys), with cucurbit[7]uril (CB[7]). Under basic pH conditions, Cys did not complex with CB[7], whereas Hcy efficiently complexed with CB[7], as confirmed by ¹H NMR spectroscopy and Ellman's reagent (5,5'-dithio-bis(2-nitrobenzoic acid), DTNB) assay. ¹H NMR and Raman spectroscopic studies revealed that, in the absence of CB[7], Hcy auto-oxidized slowly (~36 h) to homocystine (HSSH) under basic pH conditions. However, the rate of Hcy oxidation increased by up to 150 fold in the presence of CB[7], as suggested by the DTNB assay. Thus, supramolecular complexation under basic pH conditions led to the formation of a HSSH-CB[7] complex, and not Hcy-CB[7]. The results indicate that Hcy is rapidly oxidized to HSSH under the catalysis of CB[7], which acts as a reaction chamber, in basic pH conditions. Our studies suggest that Hcy concentration, a risk factor for cardiovascular disease, can be selectively and more easily quantified by supramolecular complexation with CB [7].