• Title/Summary/Keyword: Chemical reactivities

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Chemical Looping Combustion Characteristics of Coal and Char in a Batch Type Fluidized Bed Reactor (회분식 유동층 반응기에서 석탄과 촤의 매체순환연소 특성)

  • Ryu, Ho-Jung;Hyun, Ju-Soo;Kim, Young-Joo;Park, Yeong-Seong;Park, Moon-Hee
    • Transactions of the Korean hydrogen and new energy society
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    • v.22 no.6
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    • pp.884-894
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    • 2011
  • Effects of temperature, volatile content, particle diameter and solid input weight were investigated in the batch fluidized bed reactor using OCN703-1100 particle as oxygen carrier and Roto coal and char as fuels. Two solid fuels represented the best reactivity at different temperature, $900^{\circ}C$ for Roto coal and $950^{\circ}C$ for char, respectively. However, we selected $900^{\circ}C$ as the best operating temperature because the improvement of reactivity of char at $950^{\circ}C$ was negligible. Char represented better reactivity than Roto coal because char contains low volatile than Roto coal. For both solid fuels, reactivities were improved with increasing of the particle diameter. These results were explained by solid mixing tests in a transparent fluidized bed using two char particles having different particle size ranges and OCN703-1100 particle. The bigger particle showed better solid mixing with OCN703-1100 particle, and therefore, represented better reactivity. For both solid fuels, reactivities were improved with increasing of the solid input weight within the experimental conditions of this study because the weight of coarse particles increased with the solid input weight increased, and therefore, these coarse particles can mix well with the oxygen carrier.

Determination of Reactivities by Molecular Orbital Theory (VI). Sigma MO Treatment on $C_6H_5YCH_2Cl$ (화학반응성의 분자궤도론적 연구 (제 6 보). $C_6H_5YCH_2Cl$ 형 화합물의 시그마분자궤도론적 고찰)

  • Lee, Ikc-Hoon;Lee, Bon-Su;Lee, Jae-Eui
    • Journal of the Korean Chemical Society
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    • v.18 no.2
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    • pp.85-96
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    • 1974
  • Extended H ckel Theory and CNDO/2 MO calculation methods have been applied to $C_6H_5YCH_2Cl$(Y = None, -$CH_2$-, -O-, -S-, -CO-, -$SO_2$-). It has been shown that charge distributions in molecules are mainly controlled by the migration of valence inactive electron, giving the order of ${\sigma}$-acceptor and ${\pi}$-donor effects -O- > -S- > -$CH_2$- > -$SO_2$-. The -CO- group exceptionally acts as ${\sigma}$-donor and ${\pi}$-acceptor. It was also predicted that, $S_N2$ reactivities of C$C_6H_5YCH_2Cl$ would be in the order of -O-${\thickapprox}$-CO- >>-S-${\thickapprox}$None > -$CH_2$-, neglecting solvent effect. From the results of our studies, we conclude that the structural factors influencing 의 $S_N$ reactivities will be: (1) positive charge developments on reaction center carbon atom (2) energy level of ${\sigma}$-antibonding unoccupied MO with respect to C-Cl bond. (3) ${\sigma}$-antibonding strength of C-Cl bond at that level.

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Application of HMO for Reactives of the Benzologous Pyridine Ligands (Ⅰ) (Benzologous Pyridine계 리간드의 반응성에 대한 HMO의 응용 (제1보))

  • Kim Ja-Hong;Lee Gae-Soo
    • Journal of the Korean Chemical Society
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    • v.23 no.2
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    • pp.75-79
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    • 1979
  • The frontier orbital energy, superdelocalizability and charge density of a series of benzologous pyridine ligands have been calculated by using HMO. According to ${\Delta}E_{\pi}$ of ligands on the basis of the above results, it is concluded that the stabilities are in the order of 1,10-Phen > 4,5-Phen > 1,5-Phen > 8-Hox > Hox-azoquinolinato. And also, the reactivities of electrophilic, nucleophilic and radical reaction, and bond strength have been respectively studied by superdelocalizabilities and charge densities.

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Kinetics and Mechanism of the Anilinolysis of Dibutyl Chlorothiophosphate in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.33 no.3
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    • pp.843-847
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    • 2012
  • The nucleophilic substitution reactions of dibutyl chlorothiophosphate (4S) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs;$k_H/k_D$) are primary normal ($k_H/k_D$ = 1.10-1.35). A concerted mechanism involving predominant frontside nucleophilic attack is proposed on the basis of the primary normal DKIEs and selectivity parameters. Hydrogen bonded, four-center-type transition state is proposed. The steric effects of the two ligands on the anilinolysis rates of the chlorothiophosphates are discussed. The anilinolyses of P=S systems are compared with those of their P=O counterparts on the basis of the reactivities, thio effects, selectivity parameters, and DKIEs.

Kinetic Studies on Nucleophilic Substitution Reactions of Alkane Sulfonylchlorides with Anilines in MeOH-MeCN Mixtures (메탄올-아세토니트릴 혼합용매에서 염화알칸술포닐과 아닐린의 친핵 치환반응에 대한 속도론적 연구)

  • Ikchoon Lee;Han Keun Kang;Hai Whang Lee
    • Journal of the Korean Chemical Society
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    • v.29 no.5
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    • pp.478-481
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    • 1985
  • Nucleophilic substitution reactions between Alkanesulfonylchlorides and p-substituted anilines in methanol-acetonitrile mixture have been studied kinetically. Reactivities of substrates, substituent effects of nucleophile and solvent effects indicate that the studied reaction proceeds via $S_N2$. The kinetic results show that transition state of the reaction between i-PSC and anilines becomes looser as the composition of methanol increases.

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Application of HMO for Reactivity of the Benzologous Pyridine Ligands (Ⅱ) (Benzologous Pyridine 계 리간드의 반응성에 대한 HMO 의 응용(제 2보))

  • Ja Hong Kim;Gae Soo Lee
    • Journal of the Korean Chemical Society
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    • v.24 no.1
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    • pp.20-24
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    • 1980
  • The frontier electron densities and pK values for benzologous pyridine ligands are calculated using the HMO. Linear regression formula for pK in protonation of ligands is derived from the electron densities and observed pK values. The calculated pK values are in agreement with those of experimental values and a parallelism is shown between pK and qN. The reactivities for electrophilic, nucleophilic and radical reactions have also been calculated respectively by frontier electron densities.

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The Effect of Pressure on the Rate of Solvolysis (Ⅲ) Kinetics on the Nucleophilic Substitution Reactions of Acyl- and Alkyl groups in Binary Solvents (가용매분해반응속도에 대한 압력의 영향(Ⅲ) 이성분용매내 Acyl류와 Alkyl류의 친핵성 치환반응의 속도론적 연구)

  • Kyong, Jin Burm;Park, Byoung Chun;Kwun, Oh Cheun
    • Journal of the Korean Chemical Society
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    • v.41 no.9
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    • pp.443-448
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    • 1997
  • Kinetics for the solvolyses of acyl chlorides and alkyl chlorides in hydroxylic solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters (${\Delta}V^{\neq},\; {\Delta}H^{\neq},\; {\Delta}S^{\neq}$) were estimated from the rate constants. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies.

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미끄럼운동을 하는 면에 윤활 조건에 따라 발생하는 보호막의 형성과 파괴에 관한 연구

  • 이영재
    • Proceedings of the Korean Society of Tribologists and Lubrication Engineers Conference
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    • 1990.11a
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    • pp.16-35
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    • 1990
  • The mechanism of failure of lubricated surfaces at high sliding speeds was Investigated. Experiments were performed with the ball-on-flat and cylinder-on-flat geometries, using lubricants of four different chemical reactivities. Surface failure was found to not be predictable using the ratlo, $\lambda$, of fluid film thickness to composite surface roughness except when chemically inert lubricants are used. Even then the influence of temperature rise on fluid film thickness does not adequately explain the low load carrying capacity of lubricants at high sliding speeds. which causes surface failure. The protective layers on sliding surfaces that form by chemical reaction with the lubricant were found to reduce the surface roughentrig and Increase the load carrying capacity of surfaces to values of $\lambda$ as low as 0.03. Neither the surface toughening nor the formation of the protective layers have been incorporated Into failure models for lubricated systems.

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A Study on the Formation and the Loss of the Protective Layer the Sliding Surface According to the Lubricating Conditions (미끄럼운동을 하는 면에 윤활 조건에 따라 발생하는 보호막의 형성과 파괴에 관한 연구)

  • 이영제
    • Tribology and Lubricants
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    • v.7 no.1
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    • pp.16-27
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    • 1991
  • The mechanism of failure of lubricated surfaces at high sliding speeds was investigated. Experiments were performed with the ball-on-flat and cylinder-on-flat geometries, using lubricants of four different chemical reactivities. Surface failure was found to not be predictable using the ratio, $\lambda$, of fluid film thickness to composite surface roughness except when chemically inert lubricants are used. Even then the influence of temperature rise on fluid film thickness does not adequately explain the low load carrying capacity of lubricants at high sliding speeds, which causes surface failure. The protective layers on sliding surfaces that form by chemical reaction with the lubricant were found to reduce the surface roughening and increase the load carrying capacity of surfaces to values of $\lambda$ as low as 0.03. Neither the surface roughening nor the formation of the protective layers have been incorporated into failure models for lubricated systems.

Solution Viscosity and Relative Reactivity of Branched and Linear Polycarbonates

  • Kim, Sang-Pil;Lee, Bong-Hee;Kim, Sang-Hern;Kim, Whan-Gi
    • Journal of the Korean Applied Science and Technology
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    • v.17 no.2
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    • pp.76-82
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    • 2000
  • The relative reactivities of branched and linear polycarbonates were investigated by measuring unreacted chloroformate concentration. It was found that the polymerization for the branched polymer proceeded ca. 10 times faster than that for the linear polymers. The effect of catalyst on a condensation step was studied by changing the amount of TEA (triethylamine) at $t_{0}$ and $t_{60}$ with keeping constant amount of TEA. The viscosity average molecular weight for the obtained branched polycarbonates were measured and compared with those of linear polycarbonates. It was found that the viscosity molecular weights of the obtained polymers decreased nonlinearly as wt % of added oligomer increased. The solution viscosities in methylenechloride for linear and branched polycarbonate increased nonlinearly as the content of polymer increased.