• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.24 no.11
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• pp.929-934
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• 2011

The adsorption kinetic study of ruthenium complex, N3, onto nanoporous titanium dioxide ($TiO_2$) photoanodes has been carried out by measuring dye uptake in-situ. Three simplified kinetic models including a pseudo first-order equation, pseudo second-order equation and intraparticle diffusion equation were chosen to follow the adsorption process. Kinetic parameters, rate constant, equilibrium adsorption capacities and related coefficient coefficients for each kinetic model were calculated and discussed. It was shown that the adsorption kinetics of N3 dye molecules onto porous $TiO_2$ obeys pseudo second-order kinetics with chemisorption being the rate determining step. Additionally the heterogeneous surface and the pore size distribution of porous $TiO_2$ adsorbents were also discussed.

• Bulletin of the Korean Chemical Society
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• v.26 no.3
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• pp.457-460
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• 2005

• Bulletin of the Korean Chemical Society
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• v.8 no.5
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• pp.408-414
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• 1987

The rate of bromine-exchange reaction between antimony tribromide and ${\alpha}-phenyl-n-butyl$ bromide in nitrobenzene has been determined, using antimony tribromide labelled with Br-82. The results indicate that the exchange reaction follows the first-order kinetics with respect to the organic bromide, and either the second- or first-order kinetics with respect to antimony tribromide depending on its concentration. The third-order rate constant obtained was 7.50 ${\times}10^{-2}l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. Similar study on the bromine-exchange reaction between antimony tribromide and ${\alpha}$-phenyl-i-butyl bromide has also been carried out. The results of the study show the same kinetic orders as the ones observed with $\alpha$-phenyl-n-butyl bromide. The third-order rate constant observed was 2.40 ${\times} 10^{-2} l^2mol^{-2}s^{-1}$ at 28$^{\circ}$C. The activation energy, the enthalpy of activation and the entropy of activation for the two exchange reactions mentioned above have been determined. The reaction mechanisms for the exchange reactions are discussed.

• Environmental Engineering Research
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• v.11 no.6
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• pp.318-324
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• 2006

The higher valence state of iron i.e., Fe(VI) was employed for the oxidation of one of an important toxic ion, cyanide in the aqueous medium. Cyanide was oxidized into cyanate, which is 1,000 times less toxic to cyanide and often accepted for its ultimate disposal. It was to be noted that Fe(VI) is a very powerful oxidizing agent and can oxidize most of the cyanide within few minutes i.e., ca 5 mins of contact. The data was obtained by the UV-Visible measurements for the Fe(VI) decomposition. The UV-Visible data was used to evaluate the overall rate constant for second order redox reaction between ferrate(VI) and cyanide. Also the pseudo first order rate constant was calculated as keeping the cyanide concentration in excess.

• Journal of the Korean Chemical Society
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• v.54 no.2
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• pp.208-214
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• 2010

In the presence of alcohol, phospholipase D (PLD) is known to perform transphosphatidylation activity, during which the overall reaction rate of PLD increased. To elucidate the reaction mechanism of transphosphatidylation further, we investigated rate constants of transphosphatidylation reaction of the purified ${\alpha}$-type PLD from cabbage in the presence of various alcohols. The second-oder rate constants of PLD transphosphatidylation showed a large increase with the primary alcohols examined as expected. In the case of butanol we observed the second-oder rate constant of $33.33{\pm}1.33M^{-1}sec^{-1}$. This second-order rate constant of transphosphatidylation was as 400 times greater as the second-order hydrolysis rate constant of $0.078M^{-1}sec^{-1}$ which was adjusted for the water concentration. A linear free energy relationship between the $pK_a$ of alcohol and transphosphatidylation rate gives a Br${\o}$nsted slope of ${\beta}_{nu}$ = 0.12 ${\pm}$ 0.03. This small ${\beta}_{nu}$ value implicates that the transition state of break down of phosphatidyl-enzyme intermediate (E-P) is likely dissociative. Finally, a reaction mechanism of cabbage PLD is suggested on the basis of our results presented here and the histidine residue known to be located in the active site of cabbage PLD.

• Korean Journal of Microbiology
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• v.28 no.1
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• pp.19-26
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• 1990

To examine the effects of sequence variations near the transcriptional start site on the rate of formation of the open complexes at bacteriophage $\lambda P_{R}$ promoter, two mutant promoters were created by site-specific mutagenesis using synthetic oligonucleotides. Mutant I coatains changes at positions -3 and -4 from TT to CC, thus having a 6-bp long G/C stretch between -10 region and transciptional start site (+1). Mutant II has changes at positions -5 and -6 from GG to AA, thereby having a 9-bp long A/T stretch between positions -11 and -3. Selective filter binding assays were performed to measure the rate of formation of the open complexes between the wild-type or two mutant $P_{R}$ promoters on 664 bp fragments and E. coli RNA polymerase at two temperatures. At 37.deg.C, the wild-type and two mutants showed similar rates for the formation of open complex. The second order rate constant $k_{a}$ and $\tau _{int}$, as determined from the .tau.-plot analysis, were $(6.0\pm0.4)\times10^{6}M^{-1}sec^{-1}$ and $11\pm5$sec, respectively. At 18.deg.C, however, the wild-type and two mutant promoters showed differences in the kinetic parameters. k for the wild-type promoter was (2.2$\pm$0.1)\times 10^{6}M^{-1}sec^{-1}$ and $\tau _{int}$ was 76$\pm$sec. Mutant I and II exhibited differences mainly in the rate of isomerization ($\tau_{int,I}=91\pm$10 sec, int,II=34$\pm$ sec), whereas the second order rate constant $k_{a}$ was similar to the wild type value. This result implies that at $18^{\circ}C$, the isomerization rate is determined by both protein conformational change and DNA melting, which are separable kinetically according to the 3-step mechanism of Roe et al.(1984,1985), and that the base changes affected mainly the rate of DNA melting as predicted.lting as predicted.

• Membrane and Water Treatment
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• v.8 no.1
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• pp.73-88
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• 2017

Adsorption kinetics of aqueous ferric ion ($Fe^{3+}$) onto bio-natural rice grains (BRG) have been studied in a batch system. The influence of contact time (0-180 minutes), the dosage of BRG adsorbent (10, 20, 40, and $60gL^{-1}$), and ambient temperature (27, 37, 47, and $57^{\circ}C$) for the adsorption system have been reported. The equilibrium time achieved after 20 minutes of adsorption contact time. The maximum removal of ferric ion is 99% by using $60gL^{-1}$ of BRG, $T=37^{\circ}C$, and $50mgL^{-1}$ ferric ion solution. Adsorption kinetic and diffusion models, such as pseudo-first order, pseudo-second order, and Weber-Morris intra-particle diffusion model, have been used to describe the adsorption rate and mechanism of the ferric ion onto BRG surface. The sorption data results are fitted by Lagergren pseudo-second order model ($R^2=1.0$). The kinetic parameters, rate constant, and sorption capacities have been calculated. The new information in this study suggests that BRG could adsorb ferric ion from water physiosorption during the first 5 minutes. Afterward, the electrostatic interaction between ferric ion and BGR-surface could take place as a very weak chemisorptions process. Thus, there is no significant change could be noticed in the FTIR spectra after adsorption. I recommend producing BGR as a bio-natural filtering material for removing the ferric ion from water.

• Carbon letters
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• v.9 no.3
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• pp.181-187
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• 2008

Batch sorption experiments were carried out for the removal of metylene blue from its aqueous solution using $H_3PO_4$ activated Acacia arabica carbon (AAC). The prepared activated carbon was characterized and was found as an effective adsorbent material. The operating variables studied were initial metylene blue concentration, AAC concentration and solution pH. AAC activated carbon posses a maximum sorption capacity for the range of initial dye concentrations studied (60~100 mg $L^{-1}$). The sorption kinetics were analyzed using reversible first order kinetics, second order, reversible first order, pseudo-first order, and pseudo-second order model. The sorption data tend to fit very well in pseudo-second order model for the entire sorption time. The average pseudo-second order rate constant, $K_{II}$ and regression coefficient value were determined to be 0.0174 mg $g^{-1}$ $min^{-1}$ and 0.9977. The biosorption process also fit well to reversible I order kinetics with a regression coefficient of 0.9878.

• Journal of the Korean Chemical Society
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• v.58 no.1
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• pp.17-24
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• 2014

The oxidative decarboxylation of phenylsulfinylacetic acid (PSAA) by Cr(VI) in 20% acetonitrile -80% water (v/v) medium follows overall second order kinetics, first order each with respect to [PSAA] and [Cr(VI)] at constant [$H^+$] and ionic strength. The reaction is acid catalysed, the order with respect to [$H^+$] is unity and the active oxidizing species is found to be $HCrO_3^+$. The reaction mechanism involves the rate determining nucleophilic attack of sulfur atom of PSAA on chromium of $HCrO_3^+$ forming a sulfonium ion intermediate. The intermediate then undergoes ${\alpha}$,${\beta}$-cleavage leading to the liberation of $CO_2$. The product of the reaction is found to be methyl phenyl sulfone. The operation of substituent effect shows that PSAA containing electron-releasing groups in the meta- and para-positions accelerate the reaction rate while electron withdrawing groups retard the rate. An excellent correlation is found to exist between log $k_2$ and Hammett ${\sigma}$ constants with a negative value of reaction constant. The ${\rho}$ value decreases with increase in temperature evidencing the high reactivity and low selectivity in the case of substituted PSAAs.

• Journal of the Korean Institute of Telematics and Electronics
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• v.26 no.6
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• pp.71-78
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• 1989

The imput-output relations for nonlinear systems can be explicitly represented by the Volterra series and they can be characterized by the Volterra kernels. This study is concerned with modeling an elastomer force-displacement relation due to step inputs by utilizing the truncated Volterra series. Since it is practically impossible to apply step inputs that have infinite slope at zero time, the loads due to constant penetration(displacement) rate followed by constant penetration inputs are measured as an alternative approach and estimated for step inputs and then utilized for the truncated Volterra series models. One second order and one third order truncated Volterra series models have been employed to model the force-displacement relation which is one of the prominent properties to characterize the viscoelastic material. The third order truncated Volterra series model has better results, compared with those of the second order truncated Volterra series model.