• Title/Summary/Keyword: delta-v

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Pressure Effect on the Solvolysis of o-Methylbenzyl Chloride in Ethanol-Water Mixtures (o-메틸염화벤질의 가용매분해반응에 대한 압력의 영향)

  • Oh Cheun Kwun;Jin Burm Kyong;Yong Kyun Shin
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.40-46
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    • 1986
  • Rate constants for the solvolysis of o-methylbenzyl chloride were determined at 30$^{\circ}$ and 40$^{\circ}$C in aqueous ethanol mixtures under various pressures up to 1600 bar. From the rate constants, the activation parameters ${\Delta}V^{\neq}$, ${\Delta}{\beta}^{\neq}$, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and${\Delta}G^{\neq}$ were evaluated. The values exhibit the extremum behavior at about 0.30 mole fraction of ethanol. This behavior is discussed in terms of electrostriction. To examine the reaction mechanism by Laidler and Eyring equation, we compared the rate constants with the dielectric constants of aqueous ethanol and the number of water molecule participated in the transition state. It was concluded that solvolytic reaction proceeds via $S_N$1 mechanism.

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Kinetics for the Reaction of Benzyl Benzenesulfonate with Pyridine in Acetone Under High Pressure (Benzyl Benzenesulfonate와 피리딘과의 고압반응에 대한 반응속도론적 연구)

  • Jung-Ui Hwang;Soo-Dong Yoh;Jong-Gi Jee
    • Journal of the Korean Chemical Society
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    • v.24 no.2
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    • pp.150-154
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    • 1980
  • Kinetic studies of the reaction of benzyl benzenesulfonate with pyridine in acetone were carried out by the electric conductivity method under 1 to 2000 bars and at 20 to $40^{\circ}C$. The rate increases with increasing pressure and temperature. The activation enthalpy $({\Delta}H^{\neq}),\;entropy\;({\Delta}S^{\neq})$ and activation volume $({\Delta}V^{\neq})$ of the reaction are obtained by the above experiment. The isokinetic relationship between $({\Delta}H^{\neq})\;and\;({\Delta}S^{\neq})$ for pressure change in the reaction was shown, and its isokinetic temperature was $342^{\circ}K$. From all of the above results it was found that this reaction precedes on the $S_N2$ reaction mechanism in which the rate of the reaction was determined by $C{\cdots}N$ bond formation at transition state.

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The Effect of Pressure on the Electrophilic Substitution Reaction of Tetramethyltin with Iodine (Tetramethyltin과 Iodine의 친전자 치환반응에 대한 압력의 영향)

  • Kwun Oh Cheun;Lee Young Hoon
    • Journal of the Korean Chemical Society
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    • v.37 no.6
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    • pp.555-561
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    • 1993
  • Ultraviolet spectrophotometric investigation has been carried out on the system of iododestannylation iodine and tetramethyltin in methanol. The transient CT absorption spectrum can be observed and the subsequent disappearance of CT absorption spectrum was accompained by the cleavage of tetramethyltin with iodine. From there, the rate constants for the iododestannylation were determined at 10, 25 and 35$^{\circ}C$ up to 1600 bar and the reaction rates were increased with increasing temperature and pressure. From these rate constants, the values of the activation parameters (${\Delta}V^\neq,\;{\Delta}{\beta}^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S^{\neq}\;and\;{\Delta}G^{\neq}$) were obtained. The activation volumes and activation compressibility coefficients were both negativity. The activation enthalpies were positive and activation entropies had large negative values. From these values discussed in terms of solvent structure variation of transition state and mechanism. From these results, it was found that the reaction is followed with $S_E2$ mechaenism and weakened $S_E2$ mechanism nature by increasing pressure.

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Thermo-Mechanical Fatigue Crack Propagation Behaviors of 1.5Cr-0.67Mo-0.33V Alloy (1.5Cr-0.67Mo-0.33V강의 열피로 크랙전파 거동)

  • 송삼홍;강명수
    • Transactions of the Korean Society of Mechanical Engineers
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    • v.19 no.9
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    • pp.2133-2141
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    • 1995
  • The thermo-mechanical fatigue tests were performed on the specimens extracted from 1.5Cr-0. 67Mo-0.33V alloy. The characteristics of thermo-mechanical fatigue crack propagation were examined and reviewed in view of fracture mechanics. The results obtained from the present study are summarized as follows : (1) The propagation characteristics of isothermal low-cycle fatigue crack are dominated by .DELTA.J$_{f}$ in case of PP waveform, and .DELTA.J$_{c}$ in case of CP waveform. (II)The propagation characteristics of thermo-mechanical fatigue crack are dominated by .DELTA.J$_{c}$ for in-phase case, and by .DELTA.J$_{c}$ for out-of-phase. The present results were in good agreement with the equation of propagation law for isothermal low-cycle fatigue crack in case of thermo-mechanical fatigue.tigue.e.

A Study on the Fatigue Crack Propagation Behavior of Cr-Mo-V Alloy with Micro Defects at High Temperature. (미소 원공결함을 갖는 Cr-Mo-V강의 고온피로 크랙전파거동)

  • Song, Samhong;Kang, Myungsoo
    • Journal of the Korean Society for Precision Engineering
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    • v.13 no.12
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    • pp.70-77
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    • 1996
  • Fatigue tests were carried out at high temperature on a Cr-Mo-V steel in order to assess the fatigue life of components used in power plants. The characteristics of high temperature fatigue were divided in terms of cycle-dependent fatigue and time-dependent fatigue, each crack propagation rate was examined with respect to fatigue J-integral range, .DELTA. J$_{f}$and creep J-integral range, .DELTA. J$_{c}$. The fatigue life was evaluated by analysis of J-integral value at the crack tip with a dimensional finite element method. The results obtained from the present study are summarized as follows : The propagation characteristics of high temperature fatigue cracks are determined by .DELTA. J$_{f}$for the PP(tensile plasticity-compressive plasticity deformation) and PC(tensile plasticity - compressive creep deformation) stress waveform types, and by .DELTA. J$_{c}$for the CP(tensile creep- compressive plasticity deformation) stress waveform type. The crack propagation law of high temperature fatigue is obtained by analysis of J-integral value at the crack tip using the finite element method and applied to examine crack propagation behavior. The fatigue life is evaluated using the results of analysis by the finite element method. The predicted life and the actual life are close, within a factor of 2.f 2.f 2.

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Major, Trace and Rare Earth Element Geochemistry, and Oxygen-Isotope Systematics of Illite/smectite in the Reindeer D-27 Well, Beaufort-Mackenzie Basin, Arctic Canada (카나다 보포트-맥켄지 분지의 일라이트/스멕타이트의 원소 지화학 및 산소동위원소 연구)

  • Ko, J.;Hesse, R.;Longstaffe, F.J.
    • Economic and Environmental Geology
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    • v.28 no.4
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    • pp.351-367
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    • 1995
  • The elemental geochemistry and oxygen isotopes of illite/smectite (I/S) have been studied in relationship to the mineralogical trend in the Reindeer D-27 well, Beaufort-Mackenzie Basin. The increase in concentrations of $K_2O$, Rb and rare earth elements (REE), the decrease in concentrations of tetrahedral elements such as Mg, Ti, Sc, Zn and Zr, and the increase in concentrations of tetrahedral elements such as Be and V can be related to I/S compositions that vary systematically with depth. Layer formulae of S- and I-layers are estimated as $[Al_{1.57}Fe_{.19}Mg_{.31}Ti_{.07}][Si_{3.84}Al_{.16}]O_{10}(OH)_2$ and $[Al_{1.84}Mg_{.16}][Si_{3.33}Al_{.67}]O_{10}(OH)_2$, respectively. The mobilization of REE appears to occur during illitization. The increase in concentrations of REE, especially La and Ce, with depth is probably linked to incorporation of ions with high valency (e.g. $V^{5+}$) in tetrahedral sites. The excess valency due to V is partly counter-balanced by ions with low valency (e.g. $Be^{2+}$) and, in turn, the local valency deficiency caused by $Be^{2+}$ could be compensated by high-charge interlayer cations such as REE (+3). ${\delta}^{18}O$ values of I/S range from 2.91 to 15.72‰ (SMOW), and increase with depth, contrasting to trends observed in the Gulf Coast and elsewhere. The increase in ${\delta}^{18}O$ of I/S results from the rapid increase in ${\delta}^{18}O$ of pore water that overcomes the decrease in temperature-dependent fractionation values with increasing burial depth (${\delta}^{18}O_{pore\;water}>-d{\Delta}/_{I/S-water};\;d{\delta}^{18}O_{I/S}>0$). Calculated ${\delta}^{18}O$ values of pore water in equilibrium with I/S suggest that the original water was probably meteoric water. The stratification of pore water is postulated from the presence of an isotopically light interval, about 450m thick. The depth range of the isotopically light zone overlaps, but does not coincide with the interval of lowered I-content and $K_2O$ concentrations, suggesting that oxygens may have been exchanged independently of mineralogical and geochemical reactions.

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EXISTENCE OF SOLUTIONS FOR FRACTIONAL p&q-KIRCHHOFF SYSTEM IN UNBOUNDED DOMAIN

  • Bao, Jinfeng;Chen, Caisheng
    • Bulletin of the Korean Mathematical Society
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    • v.55 no.5
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    • pp.1441-1462
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    • 2018
  • In this paper, we investigate the fractional p&q-Kirchhoff type system $$\{M_1([u]^p_{s,p})(-{\Delta})^s_pu+V_1(x){\mid}u{\mid}^{p-2}u\\{\hfill{10}}={\ell}k^{-1}F_u(x,\;u,\;v)+{\lambda}{\alpha}(x){\mid}u{\mid}^{m-2}u,\;x{\in}{\Omega}\\M_2([u]^q_{s,q})(-{\Delta})^s_qv+V_2(x){\mid}v{\mid}^{q-2}v\\{\hfill{10}}={\ell}k^{-1}F_v(x,u,v)+{\mu}{\alpha}(x){\mid}v{\mid}^{m-2}v,\;x{\in}{\Omega},\\u=v=0,\;x{\in}{\partial}{\Omega},$$ where ${\Omega}{\subset}{\mathbb{R}}^N$ is an unbounded domain with smooth boundary ${\partial}{\Omega}$, and $0<s<1<p{\leq}q$ and sq < N, ${\lambda},{\mu}>0$, $1<m{\leq}k<p^*_s$, ${\ell}{\in}R$, while $[u]^t_{s,t}$ denotes the Gagliardo semi-norm given in (1.2) below. $V_1(x)$, $V_2(x)$, $a(x):{\mathbb{R}}^N{\rightarrow}(0,\;{\infty})$ are three positive weights, $M_1$, $M_2$ are continuous and positive functions in ${\mathbb{R}}^+$. Using variational methods, we prove existence of infinitely many high-energy solutions for the above system.

Theoretical Calculation of Activity Coefficients of Liquid Mixtures (액체혼합물의 활동도계수의 이론적 계산)

  • Moon Dae-Won;Jhon Mu Shik;Lee Taikyue
    • Journal of the Korean Chemical Society
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    • v.21 no.6
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    • pp.395-403
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    • 1977
  • Significant structure theory was applied to some liquid mixture systems ranging from simple monatomic molecule systems to polyatomic molecule systems, and the activity coefficients ${\gamma}$ of the liquid mixture systems were calculated over whole mole fractions using the following thermodynamic relation $RTln_{{\gamma}i} = (\frac{{\partial A}^E}{{\partial N}_i})_{T,V,N_i} $ where $A^E$ represents the excess Helmholtz free energy, and $N_i$ is the number of molecules of component i. The activity coefficients of the solutions such as monatomic molecule systems (Ar-Kr, Kr-Xe) and diatomic molecule systems $(Ar-O_2,\;N_2-CO)$ and $CH_4-Kr$ systems whose components have similar shapes for intermolecular potential curves were calculated successfully only with the ${\delta}E_s$, correction parameter for energy $E_s$, for mixture systems. For other systems such as $Ar-N_2,\;O_2-N_2\;and\;CH_4-C_3H_8$ whose components have dissimilar intermolecular potential curve shapes an additional correction parameters ${\delta}$V and even one more parameter ${\delta}$n were necessary [see Eqs.(10)∼(12)].

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Analysis of Browning Factors During Fermentation of Kochujang (고추장 발효 중 갈변 요인에 대한 분석)

  • Kim, Moon-Sook;Ahn, Yong-Seon;Shin, Dong-Hwa
    • Korean Journal of Food Science and Technology
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    • v.32 no.5
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    • pp.1149-1157
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    • 2000
  • To confirm the factors concerning color changes of traditional kochujang, heating, U.V. and $N_2$ gas substitution treatment were conducted on duk(rice cake) kochujang and shikhae(malt digested syrup) kochujang. The value of L, a and b value by Hunter of each kochujang were gradually decreased during fermentation and ${\delta}E$ increased. The ${\delta}E$ value of duk kochujang treated by U.V. was higher than those of the other treatments and non heated shikhae kochujang showed higher ${\delta}E$ value. The main cause of color change by factor analysis on various factors of duk kochujang and shikhae kochujang were light, and light and heat respectively. The acetone and water extracted pigments had maximum absorbance at 450-470 nm and 200-205 nm respectively.

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