• Title/Summary/Keyword: Activation parameters

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A Study of Thermal Decomposition Characteristics and Toxicity of Product on PS/SAN/ABS (PS/SAN/ABS의 열분해특성과 생성물의 독성에 관한 연구)

  • Kang Yun Jin;Lee Nae Woo;Seul Soo Duk
    • Journal of the Korean Institute of Gas
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    • v.4 no.1 s.9
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    • pp.16-25
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    • 2000
  • To estimate the thermal characteristics and toxic parameters on styrene copolymers, We have investigated the activation energy, physical features and generation possibility of toxic material like narcotic gases. The activation energy was 25${\~}$50 Kcal/mol by the Kissinger's and DSC method at high temperature decomposition. It will be good information to estimate the possibility of fire occurrence. From calculations of FED, the values of $LC_{50}$ for PS, SAN and ABS were checked as 8,580, 265 and 308 $mg/m^3$ The mechanisms of thermal decomposition were mainly estimated by main chain scission, not by side group on FT-IR analysis.

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The Electronic Structure and Reactivity of Transition Metal Complexes (III). Effect of Pressure on the Aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ Ion (전이금속 착물의 전자구조 및 화학적 반응성 (제 3 보) $[Cr(NH_3)_5(DMF)]^{3+}$ 이온의 수화반응에 미치는 압력효과)

  • Jong-Jae Chung;Choi Jong-Ha;Eun-Ki Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.6
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    • pp.582-587
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    • 1989
  • Rates for aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. The volume of activation for the aquation is small negative and lies in the limited range -2.76 ∼ -3.65 $cm^3mol^{-1}$. The entropy and compressibility coefficient of activation are small negative values. From the results of thermodynamic activation parameters, it can be inferred that the aquation of $[Cr(NH_3)_5(DMF)]^{3+}$ ion proceeds through an associative interchange($I_a$) mechanism.

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Kinetics and Mechanism of the Pyridinolysis of 1,2-Phenylene Phosphorochloridate in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.270-274
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    • 2012
  • The nucleophilic substitution reactions of 1,2-phenylene phosphorochloridate (1c) with X-pyridines are investigated kinetically in acetonitrile at $-25.0^{\circ}C$. The free energy correlations for substituent X variations in the nucleophiles exhibit biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 1c with a cyclic five-membered ring is $2.70{\times}10^5$ times faster than its acyclic counterpart (1a: phenyl ethyl chlorophosphate) because of great positive value of the entropy of activation of 1c (${\Delta}S^{\neq}$ = +26 eu) compared to negative value of 1a (${\Delta}S^{\neq}$= -24 eu) over considerably unfavorable enthalpy of activation of 1c (${\Delta}H^{\neq}=20.5kcal\;mol^{-1}$) compared to 1a (${\Delta}H^{\neq}=12.7kcal\;mol^{-1}$). Great enthalpy and positive entropy of activation are ascribed to sterically congested transition state (TS) and solvent structure breaking in the TS. A concerted mechanism involving a change of nucleophilic attacking direction from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines is proposed on the basis of greater selectivity parameters (${\rho}_X$ = -1.99 and ${\beta}_X$ = 0.41) with the strongly basic pyridines compared to those (${\rho}_X$ = -0.42 and ${\beta}_X$ = 0.07) with the weakly basic pyridines.

Thermal Decomposition Kinetics of Copolymers Derived from p-dioxanone, L-lactide and Poly(ethylene glycol)

  • Bhattarai Narayan;Khil Myung Seob;Oh Seung Jin;Kim Hak Yong;Kim Kwan Woo
    • Fibers and Polymers
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    • v.5 no.4
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    • pp.289-296
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    • 2004
  • The kinetic parameters, including the activation energy E, the reaction order n, and the pre-exponential factor Z, of the degradation of the copolymers based on the poly(L-lactide) (PLLA) or poly(p-dioxanone-co-L-lactide) (PDO/PLLA) and diol-terminated poly(ethylene glycol) (PEG) segments have been evaluated by the single heating methods of Friedman and Freeman-Carroll. The experimental results showed that copolymers exhibited two degradation steps under nitrogen that can be ascribed to PLLA or PDO/PLLA and PEG segments, respectively. However, copolymers exhibited almost single degradation step in air. Although the values of initial decomposition temperature were scattered, copolymers showed the lower maximum weight loss rate and degradation-activation energy in air than in nitrogen whereas the higher value of temperature at the maximum rate of weight loss was observed in air.

Musculotendon Model to Represent Characteristics of Muscle Fatigue due to Functional Electrical Stimulation (기능적 전기자극에 의한 근육피로의 특성을 표현하는 근육 모델)

  • Lim, Jong-Kwang;Nam, Moon-Hyon
    • The Transactions of the Korean Institute of Electrical Engineers A
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    • v.48 no.8
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    • pp.1046-1053
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    • 1999
  • The musculotendon model is presented to show the declines in muscle force and shortening velocity during muscle fatigue due to the repeated functional electrical stimulation (FES). It consists of the nonlinear activation and contraction dynamics including physiological concepts of muscle fatigue. The activation dynamics represents $Ca^{2+}$ binding and unbinding mechanism with troponins of cross-bridges in sarcoplasm. It has the constant binding rate or activation time constant and two step nonlinear unbinding rate or inactivation time constant. The contraction dynamics is the modified Hill type model to represent muscle force - length and muscle force - velocity relations. A muscle fatigue profile as a function of the intracellular acidification, pH is applied into the contraction dynamics to represent the force decline. The computer simulation shows that muscle force and shortening velocity decline in stimulation time. And we validate the model. The model can predicts the proper muscle force without changing its parameters even when existing the estimation errors of the optimal fiber length. The change in the estimate of the optimal fiber length has an effect only on muscle time constant in transient period not on the tetanic force in the steady-state and relaxation periods.

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Electrocatalytic Effects for the Reduction of Thionyl Chloride in $Li/SOCl_2$ Cell Containing Schiff Base Metal(II) Complexes

  • Kim, Woo-Seong;Chung, Kwang-Il;Kim, Shin-Kook;Jeon, Seung-Won;Kim, Yeon-Hee;Sung, Yung-Eun;Choi, Yong-Kook
    • Bulletin of the Korean Chemical Society
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    • v.21 no.6
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    • pp.571-576
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    • 2000
  • Electrocatalytic effects for the reduction of thionyl chloride in $LiAICI_4/SOCl_2$ electrolyte solution containing Schiff base M(II) (M; Co and Fe) complexes are evaluated by determining kinetic parameters with cyclic voltammetry and chronoamperometry at a glassy carbon electrode. The charge transfer process during the reduction of thionyl chloride is affected by the concentration of the catalyst. The catalytic effects are demonstrated from both a shift of the reduction potential for the thionyl chloride toward a more positive direction and an increase in peak currents. Catalytic effects are larger in thionyl chloride solutions containing the binuclear [M(II) $_2$ (TSBP)] complex rather than mononuclear [M(II)(BSDT)] complexes. Significant improvements in the cell performance have been noted in terms of both thermodynamics and activation energy for the thionyl chloride reduction. The activation energy calculated from the Arrhenius plots is 4.5-5.9 kcal/mole at bare glassy carbon electrodes. The activation energy calculated for the catalyst containing solution is 3.3-4.9 kcalmole, depending on whether the temperature is lowered or rasied.

Simultaneous Motion Recognition Framework using Data Augmentation based on Muscle Activation Model (근육 활성화 모델 기반의 데이터 증강을 활용한 동시 동작 인식 프레임워크)

  • Sejin Kim;Wan Kyun Chung
    • The Journal of Korea Robotics Society
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    • v.19 no.2
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    • pp.203-212
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    • 2024
  • Simultaneous motion is essential in the activities of daily living (ADL). For motion intention recognition, surface electromyogram (sEMG) and corresponding motion label is necessary. However, this process is time-consuming and it may increase the burden of the user. Therefore, we propose a simultaneous motion recognition framework using data augmentation based on muscle activation model. The model consists of multiple point sources to be optimized while the number of point sources and their initial parameters are automatically determined. From the experimental results, it is shown that the framework has generated the data which are similar to the real one. This aspect is quantified with the following two metrics: structural similarity index measure (SSIM) and mean squared error (MSE). Furthermore, with k-nearest neighbor (k-NN) or support vector machine (SVM), the classification accuracy is also enhanced with the proposed framework. From these results, it can be concluded that the generalization property of the training data is enhanced and the classification accuracy is increased accordingly. We expect that this framework reduces the burden of the user from the excessive and time-consuming data acquisition.

Kinetic Study by Heating Rate Method (가열속도법에 의한 반응속도론 연구)

  • 박영수;양광규;김용태
    • Journal of the Korean Society of Tobacco Science
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    • v.4 no.2
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    • pp.57-61
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    • 1982
  • For evaluating kinetic parameters of various reactions and materials a straight- forward method has been studied by the variable heating rate method in DSC analysis. Based on the linear relationship between the logarithm of the heating rate and reciprocal Peak temperature, this method allows calculation of activation energy and the Arrhenius frequency factor by only one observation of the peak temperature versus the heating rate. According to tile D function, D=-In P(x)/dx, to x(=$\frac{E}{RT}$) we can calculate reasonably accurate activation energy, tile Arrhenius factor and the rate constant, and predict half-life times of various materials from the kinetic calculation.

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Temperature Profile Analysis of $Ti5_Si_3$ in Self-Propagating High Temperature Synthesis (SHS 법에 의한 $Ti5_Si_3$의 합성시 온도 Profile 분석)

  • 김도경;이형직;김익진;이형복
    • Journal of the Korean Ceramic Society
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    • v.32 no.3
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    • pp.341-348
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    • 1995
  • An analysis of the use of temperature profiles in the determination of the kinetic parameters of combustion synthesis of Ti5Si3 were investigated. From profile analysis, an apparent activation energy of 12KJ/mol was calculated. The Maximum heating rate achieved during 10wt% Ti5Si3 reaction by the product dilution method was approximately $1.5\times$104 K/s. Coupling this value with the measured wave velocity of 7.02 cm/s yields a maximum thermal gradient of 2.14$\times$103 K/cm. The value of tr (=t*) was calculated to be 1.2$\times$10-1 s and the value of td (=tx) was calculated to be 32.89 s. Using the definition of t* and the measured wave velocity, the effective thermal diffusivity, $\alpha$, was calculated to be 0.59$\times$10 $\textrm{cm}^2$/s. From these analysis, the power function, G, was also calculated.

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Creep Behaviours of Inconel 690 Alloy (인코넬 690 합금의 크리프거동)

  • 황경충;윤종호;최재하;김성청
    • Transactions of the Korean Society of Machine Tool Engineers
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    • v.11 no.4
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    • pp.54-61
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    • 2002
  • Inconel 690 alloy has widely been used in power plant and high temperature facilities because it has high thermal resistance and toughness. But we have little design data about the creep behaviors of the alloy. Therefore, in this study, an apparatus has been designed and built for conducting creep tests under constant load conditions. A series of creep tests on Inconel 690 alloy have been performed to get the basic design data and life prediction of inconel products and we have gotten the following results. First, the stress exponents decrease as the test temperatures increase. Secondly, the creep activation energy gradually decreases as the stresses become bigger. thirdly, the constant of Larson-Miller Parameters on this alloy is estimated about 10. And last the fractographs at the creep rupture show both the ductile and the brittle fracture according to the creep conditions.