• Title/Summary/Keyword: kinetic effect

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Nucleophilic Substitution Reactions of 2-Chloro-2-Propen-1-yl Arenesulfonates with Anilines and N,N-Dimethylanilines in Acetonitrile

  • 오혁근;정은미;이익춘
    • Bulletin of the Korean Chemical Society
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    • v.19 no.12
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    • pp.1334-1336
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    • 1998
  • Kinetic studies are carried out on the reactions of 2-chloro-2-propen-1-yl arenesulfonates with anilines and N,N-dimethylanilines in acetonitrilile at 45.0 ℃. The 2-chloro substituent is found to deactive the allyl moiety with considerable decrease in the rates. The sign and magnitude of the cross-interaction constant (ρxz 0.3) and the inverse secondary kinetic isotope effect (kH/kD 0.92) support an SN2 mechanism with a relatively tight transition state. The possibility of an SN2' mechanism can be safely precluded based on the ρxz values observed.

Study of changes in the kinetic parameters of corrosion on the macrocell current induced by the repair of reinforced concrete structures - Results of numerical simulation

  • Mostafa Haghtalab;Vahed Ghiasi;Aliakbar Shirzadi Javid
    • Computers and Concrete
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    • v.32 no.3
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    • pp.287-302
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    • 2023
  • Corrosion of reinforcing bars in reinforced concrete structures due to chloride attack in environments containing chloride ions is one of the most important factors in the destruction of concrete structures. According to the abundant reports that the corrosion rate around the repair area has increased due to the macro-cell current known as the incipient anode, it is necessary to understand the effective parameters. The main objective of this paper is to investigate the effect of the kinetic parameters of corrosion including the cathodic Tafel slope, exchange current density, and equilibrium potential in repair materials on the total corrosion rate and maximum corrosion rate in the patch repair system. With the numerical simulation of the patch repair system and concerning the effect of parameters such as electromotive force (substrate concrete activity level), length of repair area, and resistivity of substrate and repair concrete, and with constant other parameters, the sensitivity of the macro-cell current caused by changes in the kinetic parameters of corrosion of the repairing materials has been investigated. The results show that the maximum effect on the macro-cell current values occurred with the change of cathodic Tafel slope, and the effect change of exchange current density and the equilibrium potential is almost the same. In the low repair extant and low resistivity of the repairing materials, with the increase in the electromotive force (degree of substrate concrete activity) of the patch repair system, the sensitivity of the total corrosion current reduces with the reduction in the cathode Tafel slope. The overall corrosion current will be very sensitive to changes in the kinetic parameters of corrosion. The change in the cathodic Tafel slope from 0.16 to 0.12 V/dec and in 300 mV the electromotive force will translate into an increase of 200% of the total corrosion current. While the percentage of this change in currency density and equilibrium potential is 53 and 43 percent, respectively. Moreover, by increasing the electro-motive force, the sensitivity of the total corrosion current decreases or becomes constant. The maximum corrosion does not change significantly based on the modification of the corrosion kinetic parameters and the modification will not affect the maximum corrosion in the repair system. Given that the macro-cell current in addition to the repair geometry is influenced by the sections of reactions of cathodic, anodic, and ohmic drop in repair and base concrete materials, in different parameters depending on the dominance of each section, the sensitivity of the total current and maximum corrosion in each scenario will be different.

The Effects of PNF Arm Patterns on Activation of Leg Muscles According to Open And Closed Kinemetic Chains (열린사슬과 닫힌사슬에 따른 PNF상지패턴이 하지 근활성도에 미치는 영향)

  • Park, Tae-Jun;Park, Hyung-Ki;Kim, Jong-Man
    • Journal of the Korean Society of Physical Medicine
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    • v.6 no.2
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    • pp.215-223
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    • 2011
  • Purpose: The purpose of this study was to determine the effect of leg muscle activation by applying proprioceptive neuromuscular facilitation (PNF) arm patterns to unilateral upper extremities under the condition of both open and closed kinetic chains in a seated position. Methods: Twenty-two healthy subjects participated in this study. Four PNF patterns were applied to each subject's unilateral upper extremity. EMG data were collected from the vastus medialis, biceps femoris, tibialis anterior and gastrocnemius. The measured EMG data were digitized and processed to root mean square (RMS) and expressed as percentage maximal voluntary isometric contraction (%MVIC). The data were analyzed using two-way analysis of variance (ANOVA) with repeated measures to determine the statistical significance. Results: The results of this study were summarized as follows: Firstly, in comparison to muscle activation of the biceps femoris, there was a significant increase in the D2 flexion pattern when it was compared with D2 extension pattern and when it was compared with D1 flexion pattern (p<.05). Secondly, there was a significant increase in the muscle activation of the vastus medialis and tibialis anterior with a closed kinetic chain rather than an open kinetic chain (p<.05). Conclusion: In conclusion, in order to increase muscle activation of the biceps femoris, the D2 flexion pattern can be applied, regardless of kinetic chain. In addition, in order to increase muscle activation of the vastus medialis and tibialis anterior, four arm patterns can be applied with a closed kinetic chain.

Determination of Kinetic Parameters for Texture Changes of Sweet Potatoes during Heating (고구마 조직의 가열변화에 대한 반응속도론적 상수 결정)

  • Lee, Jung-Ju;Rhim, Jong-Whan
    • Korean Journal of Food Science and Technology
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    • v.33 no.1
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    • pp.66-71
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    • 2001
  • Kinetic parameters for the texture degradation of three varieties of sweet potato during heating were determined using two alternative methods, the biphasic model and the fractional conversion method. The texture degradation of sweet potatoes during heating could be expressed by two simultaneous first order reactions using the biphasic method, whose activation energies were ranged $71.0{\sim}75.1\;kJ/mol\;and\;48.4{\sim}59.6\;kJ/mol$ for the initial fast texture degradation reaction and the slow texture degradation reaction at a prolonged heating period, respectively. However, the whole texture degradation phenomena of sweet potatoes during heating could also be explained by a single first order reaction using the fractional conversion method. The activation energies were $67.5{\sim}75.3\;kJ/mol$, which were comparable with those of the first phase reaction for the texture degradation determined by the biphasic model. A kinetic compensation effect shown between the kinetic parameters determined by both methods indicates that both methods can be conveniently used to determine kinetic parameters for the texture degradation of sweet potatoes by heating.

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Kinetic Studies of the Solvolyses of 2,2,2-Trichloro-1,1-Dimethylethyl Chloroformate

  • Koh, Han-Joong;Kang, Suk-Jin;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.31 no.4
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    • pp.835-839
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    • 2010
  • The rate constants of solvolyses of 2,2,2-trichloro-1,1-dimethylethyl chloroformate ($\underline{I}$) in 33 solvents can be well correlated using the extended Grunwald-Winstein equation, with incorporation of the $N_T$ solvent nucleophilicity scale and the $Y_{Cl}$ solvent ionizing scale, with sensitivities towards changes in the scale having values of $1.42\;{\pm}\;0.09$ for l and $0.39\;{\pm}\;0.05$ for m, respectively. The activation enthalpies are ${\Delta}H^{\neq}\;=\;12.3$ to $14.5\;kcal{\cdot}mol^{-1}$ and the activation entropies are -28.2 to $-35.5\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$, consistent with the proposed bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.14 in MeOH/MeOD is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

Kinetics and Mechanism of the Anilinolysis of Dipropyl Chlorophosphate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.1879-1884
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    • 2012
  • The kinetic studies on the reactions of dipropyl chlorophosphate (3O) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) have been carried out in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are primary normal ($k_H/k_D$ = 1.09-1.01) with the strongly basic anilines while secondary inverse ($k_H/k_D$ = 0.74-0.82) with the weakly basic anilines. The steric effects of the two ligands on the rates are extensively discussed for the anilinolyses of the ($R_1O$)($R_2O$)P(=O or S)Cl-type chlorophosphates and chlorothiophosphates. A concerted mechanism is proposed with a frontside nucleophilic attack involving a hydrogen-bonded four-center-type transition state for the strongly basic anilines and with a backside attack transition state for the weakly basic anilines on the basis of the DKIEs, primary normal and secondary inverse with the strongly and weakly basic anilines, respectively.

Adsorption and electro-Fenton processes over FeZSM-5 nano-zeolite for tetracycline removal from wastewater

  • Niaei, Hadi Adel;Rostamizadeh, Mohammad
    • Advances in nano research
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    • v.9 no.3
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    • pp.173-181
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    • 2020
  • Adsorption and heterogeneous electro-Fenton process using iron-loaded ZSM-5 nano-zeolite were investigated for the removal of Tetracycline (TC) from wastewater. The nano-zeolite was synthesized hydrothermally and modified through impregnation. The zeolite was characterized by XRD, FT-IR, FE-SEM, N2 adsorption-desorption, and NH3-TPD techniques. The equilibrium data were best represented by the Freundlich isotherm. The pseudo-second-order kinetic model was the most accurate model for the adsorption of TC on the modified nano-zeolite. The effect of parameters such as pH of solution and current density were investigated for the heterogeneous electro-Fenton process. The results showed that the current density of 150 mA and pH of 3 led to the highest TC removal (90.35%) at 50 min. The nano-zeolite showed the appropriate reusability. Furthermore, the developed kinetic model was in good agreement with the removal data of TC through the electro-Fenton process.

Effect of Partial Pressure of the Reactant Gas on the Kinetic Model and Mechanical Properties of the Chemical Vapor Deposited Silicon Carbide (화학증착된 실리콘 카바이드 박막의 속도론적 모델 및 기계적 성질에 미치는 반응가스 분압의 영향)

  • 어경훈;소명기
    • Journal of the Korean Ceramic Society
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    • v.28 no.6
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    • pp.429-436
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    • 1991
  • Silicon carbide has been grown by a chemical vapor deposition (CVD) technique using CH3SiCl3 and H2 gaseous mixture onto a graphite substrate. Based on the thermodynamic equilibrium studies and the suggestion that the deposition rate of SiC is controlled by surface reaction theoretical kinetic equation for CVD of silicon carbide has been proposed. The proposed theoretical kinetic equation for CVD of silicon carbide agreed well with the experimental results for the variation of the deposition rate as a function of the partial pressure of reactant gases. The Vikers microhardness of the SiC layer was about 3000∼3400 kg/$\textrm{mm}^2$ at room temperature.

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The Influence of $C_2HCl_3$ on the $CH_4/Air$ Counterflow Nonpremixed Flames (메탄/공기 대향류 비예혼합화염에서 $C_2HCl_3$의 영향)

  • Lee, Ki-Yong
    • Journal of the Korean Society of Combustion
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    • v.3 no.2
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    • pp.41-50
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    • 1998
  • Numerical simulations of nonpremixed $CH_4/C_2HCl_3$(Trichloroethylene, TCE)/Air flames are conducted at atmospheric pressure in order to understand the effect of hydrocabon bound chlorine on methane/air flames. A chemical kinetic mechanism is employed, the adopted scheme involving 48 gas-phase species and 445 elementray reaction steps containing 223 backward reactions. The calculated temperature, velocity, and critical strain rate are compared with the experiments for the flame (16.1% TCE by Vol.) estabilished at a strain rate of $175s^{-1}$. Whereas there is overall good agreement between predictions and the measurements, it appears that the critical strain rate is higher than measured, and some areas of further refinement in the kinetic mechanism are required.

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