• Title/Summary/Keyword: rate constants

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Effect of Acetophenone on the Rate of Wool Dyeing (아세토페논이 양모의 염색속도에 미치는 영향)

  • Dho, Seong-Kook
    • Fashion & Textile Research Journal
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    • v.10 no.3
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    • pp.394-398
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    • 2008
  • One of barely water soluble ketones, acetophenone (AP) was dissolved in methanol and then was mixed with aqueous solution of C. I. Red Acid 114. In order to find out the role of AP in the dyeing process the rate constants and the activation parameters were calculated. The rate for the dyeing with AP was faster than that without it. Because of the reduced temperature dependence by AP the activation energy ($E_a$) for the dyeing with AP was smaller than that without it. With increasing temperature the activation enthalpy (${\Delta}H^*$), the activation entropy (${\Delta}S^*$), and the activation free energy ($G^*$) decreased, which was more noticeable in dyeing with AP. The rate constants and the activation parameters agreed well with the results from the previous reports that the ability of AP to increase disaggregation of dye molecules, loosening the wool fiber, and wickabilty of dyeing solution made it possible to dye wool fiber at low temperature.

A Kinetic Study on the Zinc-Nickel Plating on an Elstrolytic Sulface Bathe (황산용액 중에서 전해철표면상에 안연-니켈 합금도금에 관한 속도론적 연구)

  • 이응조;노재호
    • Journal of the Korean institute of surface engineering
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    • v.22 no.3
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    • pp.118-127
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    • 1989
  • The rate of electrodeposition Zinc-nickel alloy on to electrolytic ione in sulface solution both under an inter and air atmospherss has studied by use of a rotating disc geometry. The kinetics shows 1st order reaction, and the rate constants are proportional to the square root of rpm, however, they are less than the valuse suggested by Levich. The rate constants of zinc deposition approach the total mass transfer rate constants with increasing potential and deviate with increasing rotaing speed, but those of nickel deposition are constant. Below $40^{\circ}C$ the activation engrgies of zinc deposition and nikel deposition were 4.4Kcal/mol and 6.3Kcal/mol respectively. There results show that overall reaction rate of zinc-nickel plaeting is controlled by mixed reaction and zinc deposotion is more affected by mass transfer reaction than nickel. The current density for the zinc-nickel plating was less in an air atmosphere than in a nitrogen atmosphere. The cathode efficiency increased with decreasing cathode rotating speeds, potentials, and increasing temperatures. Zzinc-nickel platings are more improved in microhardnss than zinc platings.

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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.

Temperature Dependence of the Rate Constants of the VV Energy Exchange for N$_2$(v=1)+O$_2$(v=0)$\rightarrow$N$_2$(v=0)+O$_2$(v=1)

  • Ree, Jong-Baik;Chung, Keun-Ho;Kim, Hae-Jin
    • Bulletin of the Korean Chemical Society
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    • v.7 no.3
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    • pp.241-245
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    • 1986
  • The vibration-vibration energy exchange of $N_2(v=1)+O_2(v=0){\to}N_2(v=0)+O_2(v=1)$ has been investigated, in particular, at low temperatures. The energy exchange rate constants are calculated by use of the solution of the time-dependent Schrodinger equation with the interaction potential of the colliding molecule as a perturbation term. The predicted rate constants are significantly agree with a experimental values in the range of 295∼$90^{\circ}K$. The consideration of the VV-VT coupling decreases the predicted pure VV energy exchange value by a factor of ∼2. When the collision frequency correction is introduced, the VV-VT rate constant is consistent with the observed value in the liquid phase. The consideration of the population of the rotational energy level increases the VV-VT value significantly.

The Effects of Charge Transfer Complex on the Reaction of Aniline and Iodine (Aniline과 Iodine간의 반응에 있어서 전하이동 착물의 영향)

  • Oh-Yun Kwon;U-Hyon Paek;Eung-Ryul Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.174-179
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    • 1992
  • Reaction of aniline and iodine in$CHCl_3,\;CH_2Cl_2 : CHCl_3$(1 : 1), and $CH_2Cl_2$ has been studied kinetically by using conductivity method, Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[aniline]) are dependent on the aniline concentration. Second-order rate constants obtained were increased with increasing aniline concentration. We analysed these results on the basis of formation of charge transfer complex as reaction intermediate. From the construction of react ion scheme and derivation of rate equation, we calculated equilibrium constants and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants were decreased by an increase in the dielectric constant of the solvent and the value is 1.7-3.7$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity. ${\Delta}H^{\neq}$ is about 14.2kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -243J/mol K.

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Reaction Characteristics and Kinetics for Treatment of Wastewater Containing Phenol (Phenol 함유 폐수의 처리를 위한 반응 특성과 속도론)

  • Kang, Sun-Tae;Kim, Jeong-Mog
    • Journal of Korean Society of Water and Wastewater
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    • v.11 no.3
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    • pp.124-130
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    • 1997
  • Wastewater containing phenol was treated using Pseudomonas sp. B3 in continuous reactor, reaction characteristics and kinetics according to variation of volumetric loading rate in continuous reactor were studied. The removal efficiencies of phenol were more than 99% at the whole range of experiment, and those of COD were 97% at the volumetric loading rate, $0.96kg/m^3{\cdot}d$ and 88% at $3.0kg/m^3{\cdot}d$, respectively. Kinetics constants of $q_m$, $K_s$, Y and $K_d$ were obtained 0.901 l/d, 0.620mg/l, 0.659 and 0.219 l/d, respectively. As compared with to constants of standard activated sludge process, these constants were remarkably different because of toxicity and inhibition of phenol to microbes. And also, kinetics constants of oxygen utilization, a, and b, were shown 0.384 kg $O_2/kg$ phenol and 0.029 l/d.

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The Effect of Alkali Metal Ions on Nucleophilic Substitution Reactions of Alkali Metal Ethoxides with S-p-nitrophenyl 2-thiofuroate and 2-Thiophenethiocarboxylate in Absolute Ethanol

  • 엄익환;이윤정;남정현;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.18 no.7
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    • pp.749-754
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    • 1997
  • Rate constants have been measured spectrophotometrically for the reactions of alkali metal ethoxides (EtOM) with S-p-nitrophenyl 2-thiofuroate (1b) and 2-thiophenethiocarboxylate (2b) in absolute ethanol at 25.0±0.1 ℃. 1b is observed to be more reactive than 2b toward all the EtOM studied. The reactivity of EtOM is in the order EtOK > EtONa > EtO- > EtOLi for both substrates, indicating that K+ and Na+ behave as a catalyst while Li+ acts as an inhibitor in the present system. Equilibrium association constants of alkali metal ions with the transition state (KaTS) have been calculated from the known equilibrium association constants of alkali metal ion with ethoxide ion (Ka) and the rate constants for the reactions of EtOM with 1b and 2b. The catalytic effect (KaTS/Ka) is larger for the reaction of 1b than 2b, and decreases with decreasing the size of the alkali metal ions. Formation of 5-membered chelation at the transition state appears to be responsible for the catalytic effect.

Enzyme Kinetic Study for Degradation of Phytic acid by Phytase (Phytase에 의한 phytic acid의 분해 반응속도 연구)

  • Kim, Jae-Seok;Lee, Jae-Heung
    • KSBB Journal
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    • v.26 no.4
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    • pp.300-304
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    • 2011
  • Phytases are hydrolytic enzymes that catalyze the sequential hydrolysis of phytic acid (myo-inositol-1,2,3,4,5,6-hexakisphosphate) to myo-inositols with lower numbers of phosphate groups. Two types of phytases have been identified which initiate hydrolysis of the phytic acid at either the 3- or 6- position of the inositol ring. In the present investigation, a mathematical model was proposed and computed to estimate maximum enzyme reaction rate constants which fit the experimental data obtained by other authors. Although the data points were scattered to some extent, good agreement was found between the model and the experiment data. It appears that the maximum rate constants of removal of the first, second, and third phosphate groups were not equal. Also there was neither a steady trend upward or downward in the rate constants with the stepwise hydrolysis reactions.

Kinetic Study of the Lipase-Catalyzed Interesterification of Triolein and Stearic Acid in Nonpolar Media

  • Chi, Young-Min
    • BMB Reports
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    • v.30 no.1
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    • pp.7-12
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    • 1997
  • The kinetics of the interesterification of triolein and stearic acid catalyzed by immobilized Rhizopus delemar lipase were studied in a batch operation. In order to clarify the mechanisms of this reaction, three models are discussed under various conditions in terms of the ratio of triolein and stearic acid. The rate constants involved in the proposed model were determined by combining the numerical Gauss-elemination method, and the trial-and-error method so as to fit the calculated results with the experimental data. The accuracy of the obtained rate constants was confirmed after they were substituted for simultaneous differential equations and the equations simulated using an adaptive step-size Runge-Kutta method. Finally, the model which agrees with the calculated results and the experimental data was selected.

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Kinetic Study for the Reaction of Pyridine under High Pressure (고압하의 피리딘 반응에 대한 속도론적 연구)

  • 김명자
    • The Korean Journal of Food And Nutrition
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    • v.16 no.4
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    • pp.321-327
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    • 2003
  • The reaction rates of 4-ethyl pyridine with p-methyl benzylbromide have been measured by conductometry in acetonitrile, and the rate constants of these reactions are determined in accordance with various temperatures (20, 25, 30$^{\circ}C$) and pressures (1, 200, 500, 1000 bar). The rate constants increased with the higher pressure and temperature. The activation energies and activation parameter values of these reactions are calculated by determination of the rate constants the same. The activation volume, activation compressibility coefficient and the activation entropy are all negative. The result of kinetic studies for the pressure show that this reaction proceeds in typical bimolecular nucleophilic substitution reaction.