• Title/Summary/Keyword: activation rate constant

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Kinetics and Mechanism for aquation of [Co(en)2(CO3)]+ in [H+] aqueous solution (산 수용액내에서 [Co(en)2(CO3)]+의 아쿠아 반응속도와 반응메커니즘)

  • Lee, Chul-Je;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.8 no.3
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    • pp.155-160
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    • 2005
  • Kinetic studies were carried out for aquation of carbonatobis(ethylenediamine)cobalt(III) complexes in [H+] aqueous solution by UV/VIS-spectrophotometry. The rate law that in deduced from rate data is $rate=k_H{^+}[H^+]^{1.4}$ {$[Co(en)_2(CO_3)]^+$}1.0 where $k_H{^+}$ is the rate constant considering acidic catalyst, $H^+$ ion whose value is $0.241l{\cdot}mol^{-1}{\cdot}sec^{-1}$. The values of activation parameters Ea, ${\Delta}H^{\ast}$ and ${\Delta}S^{\ast}$ were $15.33Kcal{\cdot}mol^{-1}$, $14.52Kcal{\cdot}mol^{-1}$ and -57.49 e.u. respectively. On the basis of kinetic data and the observed activation parameters, we have proposed the mechanism that proceeds with two step protonations. The rate equation derived from the proposed mechanism has been in agreement with the observed rate equation. It has been seen that our modified mechanism for Harris's proton freequilibrium one prefer to the his concerted mechanism, and more the last product substitute $H_2O$ for $OH^-$ the Harris's mechanism in the acidity range 2 < pH < 5.

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High Temperature Deformation Behavior of L12 Modified Titanium Trialuminides Doped with Chromium and Copper (크롬 및 구리로 치환한 L12 Titanium Trialuminides합금의 고온변형거동)

  • Han, Chang-Suk;Jin, Sung-Yooun;Bang, Hyo-In
    • Korean Journal of Materials Research
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    • v.28 no.6
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    • pp.317-323
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    • 2018
  • Crystal structure of the $L1_2$ type $(Al,X)_3Ti$ alloy (X = Cr,Cu) is analyzed by X-ray diffractometry and the nonuniform strain behavior at high temperature is investigated. The lattice constants for the $L1_2$ type $(Al,X)_3Ti$ alloys decrease in the order of the atomic number of the substituted atom X, and the hardness tends to increase. In a compressive test at around 473K for $Al_{67.5}Ti_{25}Cr_{7.5}$, $Al_{65}Ti_{25}Cr_{10}$ and $Al_{62.5}Ti_{25}Cu_{12.5}$ alloys, it is found that the stress-strain curves showed serration, and deformation rate dependence appeared. It is assumed that the generation of serration is due to dynamic strain aging caused by the diffusion of solute atoms. As a result, activation energy of 60-95 kJ/mol is obtained. This process does not require direct involvement. In order to investigate the generation of serrations in detail, compression tests are carried out under various conditions. As a result, in the strain rate range of this experiment, serration is found to occur after 470K at a certain critical strain. The critical strain increases as the strain rate increases at constant temperature, and the critical strain tends to decrease as temperature rises under constant strain rate. This tendency is common to all alloys produced. In the case of this alloy system, the serration at around 473K corresponds to the case in which the dislocation velocity is faster than the diffusion rate of interstitial solute atoms at low temperature.

The Solvolysis of Benzoyl Chloride in Water-Acetone Mixtures Under High Pressure

  • Jee, Jong-Gi;Ree, Taik-Yue
    • Bulletin of the Korean Chemical Society
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    • v.8 no.1
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    • pp.31-39
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    • 1987
  • By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

Comparison of Cooking Rates of Olchal and Hangangchalbyeo Waxy Rices (올찰 및 한강찰벼 찹쌀의 취반속도의 비교)

  • Jang, Myung-Sook;Kim, Sung-Kon
    • Korean Journal of Food Science and Technology
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    • v.22 no.2
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    • pp.227-228
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    • 1990
  • The cooking properties of waxy rice, Olchal (Japonica type) and Hangang-chalbyeo $(J{\times}\;Indica\;type)$, were studied. The values of cooking rate constant of Hanganchalbyeo were higher than those of Olchal. However, the activation energies were essentially the same. The activation energy for cooking at $80-100^{\circ}C$ was about 1.6 times greater than at $100-120^{\circ}C$. The Z-value and $Q_{10}$ calculated from the terminal point of cooking were also similar between waxy rices.

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New Tridentate Ligands with Mixed Donor Atoms for Cu-Based Atom Transfer Radical Polymerization

  • Cho, Hong-Youl;Han, Byung-Hui;Kim, Il;Paik, Hyun-Jong
    • Macromolecular Research
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    • v.14 no.5
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    • pp.539-544
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    • 2006
  • 2-Furancarboxaldehyde-2-pyridinylhydrazone (FPH) and 5-methyl-2-furancarboxaldehyde-2-pyridinylhydrazone (MFPH) were synthesized and used as tridentate ligands of copper (I) bromide for the atom transfer radical polymerization of methyl methacrylate (MMA) and styrene. The polymerization of methyl methacrylate achieved high conversion and yielded polymers with a good control of molecular weight and low polydispersity (PDI=1.33). Higher PDI were observed in the polymerization of styrene. Using 1-phenyl ethylbromide (PEBr) and ethyl 2-bromoisobutyrate (EBiB) as model compounds for the polymeric chain ends, the activation rate constants of the new catalytic systems were measured. These results were correlated with the polymerization results and compared with another catalytic system previously reported.

Interconversion of Electronic Spin State of p-Substituted Arylketocarbene Reactions

  • Sung, Dae-Dong;Jeong, Jin-Hee;Ryu, Zoon-Ha;Chin, Won-Bae;Lee, Ik-Choon
    • Bulletin of the Korean Chemical Society
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    • v.25 no.8
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    • pp.1231-1237
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    • 2004
  • Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ -values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.

Propylene Hydrogenation over Cubic Pt Nanoparticles Deposited on Alumina

  • Yoo, Jung-Whan;Lee, Sung-Min;Kim, Hyung-Tae;El-Sayed, M.A.
    • Bulletin of the Korean Chemical Society
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    • v.25 no.6
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    • pp.843-846
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    • 2004
  • Pt nanoparticles loaded on alumina through an impregnation at room temperature was prepared using $K_2PtCl_4$ and acrylic acid as capping material. Transmission electron microscopy showed that the deposited Pt particles indicate ca. 80% cubic shapes with a narrow distribution of 8-10 nm in size. Propylene hydrogenation over the catalyst has been carried out to evaluate their catalytic performance by the values of activation energy. It is determined from the initial rate, reaction order, and rate constant and is found to be $9.7{\pm}0.5$ kcal/mol. This value has been discussed by comparing to those of encapsulated- and truncated octahedral Pt nanoparticles deposited on alumina, respectively, to study influence of the particle size and shape, and capping material used on the activation energy.

Cerebral Activation Area Following Oxygen Administration using a 3 Tesla Functional MR Imaging (고 자장 기능적 MR 영상을 이용한 뇌 운동 영역에서 산소 주입에 따른 활성화 영역에 관한 연구)

  • Goo, Eun-Hoe;Kweon, Dae-Cheol
    • Journal of the Ergonomics Society of Korea
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    • v.24 no.4
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    • pp.47-53
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    • 2005
  • This study aim to investigate the effects of supply of oxygen enhances cerebral activation through increased activation in the brain and using a 3 Tesla fMRI system. Five volunteers (right handed, average age of 21.3) were selected as subjects for this study. Oxygen supply equipment that provides 30% oxygen at a constant rate of 15L/min was given using face mask. A 3 Tesla fMRI system using the EPI BOLD technique, and three-pulse sequence technique get of the true axial planes scanned brain images. The author can get the perfusion images of the brain by oxygen inhalation with susceptibility contrast EPI sequence at the volunteers. Complex movement consisted of a finger task in which subjects flexed and extended all fingers repeatedly in union, without the fingers touching each other. Both task consisted of 96 phases including 6 activations and rests contents. Post-processing was done on MRDx software program by using cross-correlation method. The result shows that there was an improvement in performance and also increased activation in several areas in the oxygen method. These finding demonstrates that while performing cognitive tasks, oxygen administration was due to increase of cerebral activation.

The Effects of Cure System on Vulcanization Reaction Constant and Physical Properties of Rubber Compounds (가황시스템 변화가 배합고무의 가황반응속도 및 물리적 특성에 미치는 영향)

  • Lee, Seag;Park, Nam Cook
    • Applied Chemistry for Engineering
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    • v.10 no.3
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    • pp.419-426
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    • 1999
  • In this study, the reaction rate constant, activation energy, total crosslinking density, elastic constant, cure properties ($t_5,\;t_{90}$), modulus, and abrasion resistance of rubber compounds were investigated as a function of cure temperatures, cure systems and reinforcing filler loadings. Reaction rate constants showed strong dependence on thc carbon black loading, cure temperature and cure system, and increased sharply with increasing the reaction temperatures. The lowest activation energy was obtained in the efficient cure (EC) system which corresponds to the high level of sulfur to accelerator ratio, and the activation energy was decreased with decreasing the carbon black loadings. The change of carbon black loadings directly affects the modulus and abrasion resistance, but the change of cure system showed various effects on the rubber compounds. Increased carbon black loadings showed the high modulus, improved abrasion resistance and short scorch time but decrease in crosslinking density and elastic constant. Higher crosslinking density and elastic constant were shown in the EC cure system regardless of carbon black loadings, but scorch timc ($t_5$) was not affected by the change of the ratio of sulfur to accelerator. Rapid optimum cure time ($t_{90}$) were showen in the EC cure system. Also, the equivalent cure curve coefficient of rubber compound was 0.96 for conventional cure (CC) system, and 0.94 for semi-efficient cure (SEC) and EC system regardless carbon black loadings. As regarding the abrasion resistance, wear volume showed the logarithmic increase for the loaded weight.

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Flip-Flop of Phospholipids in DMPC/POPC Mixed Vesicles

  • Kim, Min Ki;Kim, Chul
    • Journal of the Korean Chemical Society
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    • v.64 no.3
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    • pp.145-152
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    • 2020
  • Flip-flop rate constants were measured by dithionite assay of NBD-PE fluorescence in DMPC/POPC vesicles made of various DMPC/POPC ratios. The activation energy, enthalpy, entropy, and free energy were determined based on the transition state theory. We found that the activation energy, enthalpy, and entropy increased as the amount of POPC increased, but the activation free energy was almost constant. These experimental results and other similar studies allow us to propose that the POPC molecules included in DMPC vesicles affect the flip-flop motion of NBD-PE in DMPC/POPC vesicles via increasing the packing order of the ground state of the bilayer of the vesicles. The increase in the packing order in the ground state seems to be a result of the effect of the overall molecular shape of POPC with a monounsaturated tail group, rather than the effect of the longer tail group.