• Title/Summary/Keyword: Associative mechanism

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Bearing capacity at the pile tip embedded in rock depending on the shape factor and the flow

  • Ana S. Alencar;Ruben A. Galindo;Miguel A. Millan
    • Computers and Concrete
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    • v.31 no.5
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    • pp.443-455
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    • 2023
  • This is a research analyses on the bearing capacity at a pile tip embedded in rock. The aim is to propose a shape coefficient for an analytical solution and to investigate the influence of the plastic flow law on the problem. For this purpose, the finite difference method is used to analyze the bearing capacity of various types and states of rock masses, assuming the Hoek & Brown failure criterion, by considering both plane strain and an axisymmetric model. Different geometrical configurations were adopted for this analysis. First, the axisymmetric numerical results were compared with those obtained from the plane strain analytical solution. Then the pile shape influence on the bearing capacity was studied. A shape factor is now proposed. Furthermore, an evaluation was done on the influence of the plastic flow law on the pile tip bearing capacity. Associative flow and non-associative flow with null dilatancy were considered, resulting in a proposed correlation. A total of 324 cases were simulated, performing a sensitivity analysis on the results and using the graphic output of vertical displacement and maximum principal stress to understand how the failure mechanism occurs in the numerical model.

Kinetic Study on Nucleophilic Substitution of 1-Anthracenesulfonyl Chloride with Anilines (1-염화안트라센 술포닐의 치환아닐린과의 친핵성치환반응의 속도론적 연구)

  • Kim Hyong Tae;Yoh Soo Dong
    • Journal of the Korean Chemical Society
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    • v.29 no.2
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    • pp.88-97
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    • 1985
  • 1-Anthracenesulfonyl chloride used as a substrate has been prepared from anthra-quinone, and its melting point ($124^{circ}C$) was confirmed to be considerably different from the literature value ($90^{circ}C$). Rates of nucleophilic substitution reactions of this substrate with some p-substituted anilines in dry acetone were determined by electroconductometric method, and their mechanism has been discussed. As a result, it has been found that these reactions proceed in parallel catalyzed by anilines together with noncatalyzed process, and that their catalytic activities are electrophilic. Judging from $Br{\phi}nsted\;{\beta}$ (0.77), Hammett ${\rho}$(-3.2), and activation parameters which were determined from the temperature dependence of noncatalyzed second order rate constants, it appears most appropriate that their mechanism should be discussed in terms of an associative $S_N2$ involving sulfonylammonium intermediate.

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New Drowsy Cashing Method by Using Way-Line Prediction Unit for Low Power Cache (저전력 캐쉬를 위한 웨이-라인 예측 유닛을 이용한 새로운 드로시 캐싱 기법)

  • Lee, Jung-Hoon
    • Journal of The Institute of Information and Telecommunication Facilities Engineering
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    • v.10 no.2
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    • pp.74-79
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    • 2011
  • The goal of this research is to reduce dynamic and static power consumption for a low power cache system. The proposed cache can achieve a low power consumption by using a drowsy and a way prediction mechanism. For reducing the static power, the drowsy technique is used at 4-way set associative cache. And for reducing the dynamic energy, one among four ways is selectively accessed on the basis of information in the Way-Line Prediction Unit (WLPU). This prediction mechanism does not introduce any additional delay though prediction misses are occurred. The WLPU can effectively reduce the performance overhead of the conventional drowsy caching by waking only a drowsy cache line and one way in advance. Our results show that the proposed cache can reduce the power consumption by about 40% compared with the 4-way drowsy cache.

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Mechanism for the Reaction of Substututed Phenacyl Arenesulfonates with Substituted Pyridines under High Pressures

  • 박헌영;손기주;정덕영;여수동
    • Bulletin of the Korean Chemical Society
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    • v.18 no.11
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    • pp.1179-1182
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    • 1997
  • The rates for the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines in acetone were measured by an electrical conductivity method at 1-2000 bars and 45 ℃. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ, represent the degree of Nu-C bond formation and that of C-L bond breaking. The magnitude of correlation interaction term ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX, |ρY| and ρZ are increased, but correlation interaction coefficient, |ρXZ| and ρYZ, are decreased. The results indicate that the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines probably moves from an associative SN2 to late-type SN2 mechanism by increasing pressure.

Kinetics and Mechanism of the Aminolysis of Phenylacetyl Chlorides in Acetonitrile

  • 이해황;이지원;고한중;이익천
    • Bulletin of the Korean Chemical Society
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    • v.19 no.6
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    • pp.642-645
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    • 1998
  • The aminolysis reactions of phenylacetyl chlorides with anilines and N,N-dimethylanilines (DMAS) in acetonitrile at -15.0 ℃ are investigated. The magnitude of ρx (= -2.8 ∼ -2.9) and ρy (= 0.9 ∼ 1.3, after correcting for the fall-off), and the negative sign of ρxy (= -0.12) for the reactions with anilines suggest an associative SN2 mechanism. For the reactions with DMAs, the magnitude of these Hammett coefficients increases so that tighter bond making in the transition state (TS) is predicted. A nonlinear Hammett plots obtained for the DMAs with an electron acceptor substituent is interpreted to result from a more advanced degree of leaving group departure to assist closer approach of the bulky DMA in the TS. The normal secondary kinetic isotope effects $(k_H/k_D>1.0)$ involving deuterated anilines suggest partial deprotonation by hydrogen bonding to the departing chloride ion.

Exchange Reaction Mechanism of $Pb(II)-N_2O_m$ Macrocyclic Complexes by $^{207}Pb-NMR$ Spectroscopy ($^{207}Pb-NMR$ 분광법에 의한 $Pb(II)-N_2O_m$계 거대고리 리간드 착물형성 반응의 교환 메카니즘)

  • Kim, Jeong;Yun, Chang Ju;Yu, Han Jun;Kim, Geon;Kim, Si Jung
    • Journal of the Korean Chemical Society
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    • v.38 no.1
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    • pp.41-49
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    • 1994
  • Exchange reaction mechanisms of the Pb(II) ion for the complexes between Pb(II) ion and nitrogen oxygen donor macrocyclic ligands, such as 1,13-diaza-3,4 : $1011-dibenzo-59-dioxacyclohexa-decane(NtnOtnH_4)$, 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacycloheptadecane(NenOdienH_4)$, and 1,15-diaza-3,4 : $1213-dibenzo-5811-trioxacyclooctadecane(NtnOdienH_4)$, were studied by $^{207}Pb-NMR$ spectroscopy in N,N'-dimethylformamide(DMF) solutions. The associative-dissociative mechanism dominated in $NtnOtnH_4-Pb(II)$ and $NtnOdienH_4-Pb(II)$ system. For $NenOdienH_4-Pb(II)$ system, the bimolecular exchange mechanism prevailed below $-5^{\circ}C$, and both bimolecular exchange and associative-dissociative mechanism dominated above $+5^{\circ}C.$ The order of activation energies for dissociation was $NtnOdienH_4\;<\;NtnOtnH_4\;<\;NenOdienH_4$ which was reverse to the order of stabilities.

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Indexing and Retrieval Mechanism using Variation Patterns of Theme Melodies in Content-based Music Information Retrievals (내용 기반 음악 정보 검색에서 주제 선율의 변화 패턴을 이용한 색인 및 검색 기법)

  • 구경이;신창환;김유성
    • Journal of KIISE:Databases
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    • v.30 no.5
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    • pp.507-520
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    • 2003
  • In this paper, an automatic construction method of theme melody index for large music database and an associative content-based music retrieval mechanism in which the constructed theme melody index is mainly used to improve the users' response time are proposed. First, the system automatically extracted the theme melody from a music file by the graphical clustering algorithm based on the similarities between motifs of the music. To place an extracted theme melody into the metric space of M-tree, we chose the average length variation and the average pitch variation of the theme melody as the major features. Moreover, we added the pitch signature and length signature which summarize the pitch variation pattern and the length variation pattern of a theme melody, respectively, to increase the precision of retrieval results. We also proposed the associative content-based music retrieval mechanism in which the k-nearest neighborhood searching and the range searching algorithms of M-tree are used to select the similar melodies to user's query melody from the theme melody index. To improve the users' satisfaction, the proposed retrieval mechanism includes ranking and user's relevance feedback functions. Also, we implemented the proposed mechanisms as the essential components of content-based music retrieval systems to verify the usefulness.

Kinetic Study on the Alkaline Hydrolysis of the 4-Substituted Phenyl Ethyl Benzylphosphonates (4-치환 Phenyl Ethyl Benzylphosphonate의 알칼리 가수분해 반응에 대한 속도론적 연구)

  • Shon, Kyoung Hwa;Park, Kyung Kone;Lee, Bu Young;Shin, Bu Young
    • Journal of the Korean Chemical Society
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    • v.41 no.6
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    • pp.299-303
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    • 1997
  • The rate constants($k_{OH}$) for the alkaline hydrolysis of the 4-substituted phenyl ethyl benzylphosphonates were determined in various buffer solutions by UV(Vis spectrophotometer. The activation entropies of the title reactions show negative values and this result is not consistent with a dissociative mechanism (EA) for which a positive or slightly negative value of the entropy of activation should be expected. An associative mechanism(AE) is favorable because the negligible negative charge is generated on the leaving group in the rate determining step from a good Hammett relationship(ρ=1.89). By the results of a kinetic study, we conclude that a dissociative mechanism is not proceeded in the title reactions.

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Synthesis of TiO2 Fine Powder by Sol-Gel Process and Reaction Mechanism(II) : Hydrolysis of Titanium n-Propoxide (졸-겔법에 의한 TiO2미분말 합성과 반응메카니즘(II): Titanium n-propoxide의 가수분해)

  • Myung, Jung-Jae;Park, Jin-koo;Chung, Yong-Sun;Kyong, Jin-Bum;Kim, Ho-Kun
    • Applied Chemistry for Engineering
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    • v.8 no.5
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    • pp.777-783
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    • 1997
  • $TiO_2$ powders were synthesized via hydrolysis reaction of titanium n-propoxide in n-propanol solvent and the reaction rates were studied by use of UV-vis spectroscopic method. Concentration of water, reaction temperature, reaction time and acid-base effects of the solution were investigated to determine the optimum conditions for $TiO_2$ powder synthesis. The reaction were controlled to proceed to pseudo-first orders reaction in the presence of excess water in n-propanol solvent. The rate constants which varied with temperature and concentration of water were calculated by Guggenheim method. Reaction using $D_2O$ was also carried out to determine the catalytic character of water. $TiO_2$ powders were synthesized only in the neutral and basic solution and those were almost spheric forms having average particle size of $0.4-0.7{\mu}m$ diameter. Particle size decreased with increasing concentration of water and reaction temperature, however, increased with increasing reaction time. Associative $S_N2$ mechanism for the hydrolysis was proposed from the data of n-value in the transition state and thermodynamic parameter. $D_2O$ solvent isotope effect showed that $H_2O$ molecules reacted as nucleophilic catalysis.

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The Substitution Mechanism of $[CoCl(Hedta)]^-$ ion by Ethylenediamine in the Presence of $Hg^{2+}$ ion ($Hg^{2+}$이온의 존재하에서 $[CoCl(Hedta)]^-$ 이온에 대한 에틸렌디아민과의 치환반응기구에 관한 연구)

  • Sang-Mock Lee;Dong-Jin Lee;Myung-Ki Doh
    • Journal of the Korean Chemical Society
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    • v.31 no.6
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    • pp.534-541
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    • 1987
  • The study of reaction mechanism for the substitution of ethylenediamine (en) for Cl and Hedta from $[CoCl(Hedta)]^-$ in the presence of $Hg^{2+}$ ion was carried out by uv and CD spectra. From the kinetic data, we proposed that the first ethylenediamine be substituted through the associative reaction path by means of interaction of $Hg^{2+}$ ion with Co(III), and that the second and the third ethylenediamine be substituted stepwise. From the optical purities of $[Co(en)_3]^{3+}$ which was formed after reaction, we suggested the critical stereochemical step and new substitution reaction paths.

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