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$Hg^{2+}$-promoted Aquation and Chelation of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = Amines) Complexes ($Hg^{2+}$에 의한 cis-[Co(en)$_2$(L)Cl]$^{2+}$ (L = 아민류) 착물의 아쿠아화 및 킬레이트화 반응)

  • Chang Eon Oh;Doo Cheon Yoon;Bok Jo Kim;Myung Ki Doh
    • Journal of the Korean Chemical Society
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    • v.36 no.4
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    • pp.565-578
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    • 1992
  • It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

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EN 1991-1-2 Annex A를 활용한 구획화재의 화재성상 예측에 대한 연구

  • Lee, Jong-Hwa;Ji, Seung-Uk;Kim, Si-Guk
    • Proceedings of the Korea Institute of Fire Science and Engineering Conference
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    • 2013.11a
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    • pp.174-175
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    • 2013
  • 본 연구에서는 구획화재의 화재성상을 온도곡선으로 나타내어 시간 경과에 따른 단계별 화재성장을 예측하고자 EN 1991-1-2 Annex A의 이론식을 프로그램화 하였다. 그리고 이를 검증하기 위하여 선행연구 조사 후 선행연구에 사용된 입력 값을 프로그램화 된 이론식에 입력하여 도출된 결과와 선행연구에서 제시하고 있는 결과와 비교 분석하였다.

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Application of Two Centre Huckel Method for Basicity of the Polydentate Amine Ligands (여러자리 아민리간드의 염기도에 대한 이중심 Huckel 법의 응용)

  • Kim, Ja Hong;Lee Kae Soo
    • Journal of the Korean Chemical Society
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    • v.22 no.5
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    • pp.317-319
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    • 1978
  • The change of the electron densities of polydentate amine ligands in the reaction of protonation are discussed on the basis of the calculation by Two Center Huckel method. From results, such as ${\Delta}E_{\sigma}$, $q_N,\;q_H$ , and observed pKb, it is concluded that the stabilities of polydentate amine ligands are in the order of trien > en > gly > dien.

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Pressure Effect on the Aquation of trans-[Cr(tn)$_2Cl_2]^+$ and trans-[Cr(en)(tn)Cl$_2]^+$ Complex Ions (trans-[Cr(tn)$_2Cl_2]^+$ 및 trans-[Cr(en)(tn)Cl$_2]^+$ 착이온의 수화반응에 미치는 압력효과)

  • Jong-Jae Chung;Jong-Ha Choi;Deog-Jin Kim
    • Journal of the Korean Chemical Society
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    • v.31 no.5
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    • pp.375-381
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    • 1987
  • Rates for the aquation of trans-[Cr(tn)$_2Cl_2]^+$ and trans-[Cr(en)(tn)Cl$_2$]^+$ ions in aqueous acidic solution have been measured by spectrophotometric method at various temperatures and pressures. Activation volumes are negative and lie in the limited range -1.7 ∼ -2.9cm$^3$mol$^{-1}$ or the complex ions. Activation entropies and activation compressibility coefficients are small negative values. From the results of thermodynamic parameters, it can be inferred that the aquation of the complex ions proceed through an associative interchange(Ia) mechanism. Furthermore, the information on possible transition state structure and reaction paths can be obtained by considering total stabilization energy of the hypothetical intermediates within the framework of angular overlap model. It is found that the theoretically predicted mechanism is consistent with the experimentally observed results.

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Solvent Effects on the Solvolysis of cis-$[Co(en)_2ClNO_2]^+$ Ion and Its Mechanism (cis-$[Co(en)_2ClNO_2]^+$ 착이온의 가용매 분해반응에 미치는 용매의 영향과 그 반응 메카니즘)

  • Jong-Jae Chung;Young-Ho Park
    • Journal of the Korean Chemical Society
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    • v.30 no.1
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    • pp.3-8
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    • 1986
  • The investigation of the effect of solvent structure on the first-order solvolysis of cis-$[Co(en)_2ClNO_2]^+$ion has been extended to water + co-solvent mixtures where the co-solvents are glycerol, ethylene glycol, isopropyl alcohol and t-butyl alcohol. Rates of solvolysis have been evaluated by spectrophotometric method at temperature 25∼30$^{\circ}$C. The polarity of solvent has influence on the variation of rate constant. The non-linear plot of the rate constant in log scale versus $\frac{D-1}{2D+1}$ implies that change in solvent structure with composition plays an important role in determining the variation of rate constant. The linearity of the plot of the rate constant in log scale versus the Grundwald-Winstein Y factor confirms that the solvolysis is an Id-type process with considerable extension of the metal chloride bond in the transition state. In the Kivinen equation the slope of the plot of log k versus $log(H_2O)$ suggests that the solvolysis is also an Id-type process. The application of free energy cycle shows that the effect of solvent structure is greater in the transition state than in the initial state.

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Structure-activity relationships on the herbicidal activity of the 2,3-dihydro-2,2,4,6,7-pentamethylbenzofuran-5-yl substituents in 5-benzofuryl-2-[1-(alkoxyimino)alkyl]-3-hydroxycyclohex-2-en-1-one derivatives (5-Benzofuryl-2-[1-(alkoxyimino)alkyl]-3-hyoxycyclohex-2-en-1-one 유도체 중 2,3-dihydro-2,2,4,6,7-pentamethylbenzofuran-5-yl 치환체들의 제초활성에 관한 구조-활성관계)

  • Sung, Nack-Do;Song, Jong-Hwan;Kim, Hyoung-Rae
    • The Korean Journal of Pesticide Science
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    • v.4 no.3
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    • pp.47-51
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    • 2000
  • A some of synthesized 2,3-dihydro-2,2,4,6,7-pentamethylbenzofuran-5-yl substituents in 5-benzofuryl-2-[1-(alkoxyimino)alkyl]-3-hydroxycyclohex-2-en-1-one derivatives as substrates were found to show herbicidal activity against rice plant (Oryza sativa L.) and barnyard grass (Echinochloa crus-galli) with post emergence under submerged conditions. The substrate with $R_{1}$=methyl substituents, $1{\sim}5$ showed the higher herbicidal activity to the seed, 3 leaf stage of rice plant and barnyard grass. The structure activity relationships (SARs) on the herbicidal activity of $R_{1}$ and $R_{2}$ on the azomethine bond in substrate were analysized. In the condition of $R_{1}$ groups are same, the herbicidal activity against 3 leaf stage of rice plant were governed by the optimal hydrophobicity $(logP)_{opt.}=4.57$. Whereas, in the case of barnyard grass, the herbicidal activities were largely dependent upon the steric effect, $B_{2}$ constant than hydrophobicity. In order to take the selective herbicidal activity between rice plant and barnyard grass, it is assumed that the (S) should be a round shape with higher hydrophobicity (logP>4.57) than optimal value. Also, the $R_{1}$ groups must be small and the $R_{2}$ groups are advisable to be unsaturate.

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Evaluation of accuracy for measurement of Dioxins (PCDDs/PCDFs) by using certified reference material (CRM) (인증표준물질(Certified reference materials, CRM)을 이용한 이옥신류(PCDDs/PCDFs) 측정의 정확도 평가)

  • Youn, Yeu Young;Park, Deok Hie;Lim, Young Hee;Cho, Hye Sung
    • Analytical Science and Technology
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    • v.22 no.5
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    • pp.376-385
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    • 2009
  • In our study, the accuracy for measurement of seventeen 2,3,7,8-substituted PCDDs/PCDFs in certified reference material (CRM) which is the sample of homogeneous sediment matrix taken from an area known to have significant chemical contamination, particularly PCBs (polychlorinated biphenyls), was evaluated. Though the methodology in this study followed the official method of unintentionally produced persistent organic pollutants (UPOPs) announced by the Ministry of Environment of the Republic of Korea in 2007, there were slight changes using additional purification step by activated carbon column because the interferences of sample were not sufficiently removed when only multi-silica column and alumina column have been used for purification. The |En| number proposed by the Korea Research Institute of Standards and Science was used for a valuation basis of the accuracy. The |En| numbers of seventeen 2,3,7,8-substituted PCDDs/PCDFs have been indicated as 1 and below, they were decided "Pass" in this test, when DB-5MS column and SP-2331 column were used together. Because 1,2,3,7,8-PeCDD and #169-HxCB were not separated on DB-5MS column, the ions of 1,2,3,7,8-PeCDD were selected at M/M+2 instead of M+2/M+4 suggested by EPA 1613. It is possible to distinguish them in HRGC/HRMS analysis.

Verifying the Suitability or Unsuitability of the Opening Force Criteria Applied to Air Pressurized Access Door to a Smoke Control Zone (급기 가압 제연구역 출입문에 적용되는 개방력 기준의 적합성 여부에 관한 연구)

  • Lee, Jae-Ou;Choi, Chung-Seog
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.15 no.9
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    • pp.5820-5825
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    • 2014
  • The aim of this study was to verify the suitability or unsuitability of Korean body types by measuring the opening force criteria of an air pressurized access door to a smoke control zone. The opening force criteria were verified by comparing the NFSC 501A, NFPA 92A and BS-EN 12101-6 based on the body standards information from the Korean Agency for Technology and Standards. When measuring the opening forces, the posture of the body should be standing upright and pushing an access door with the right hand, which is a criterion for designing doors. As a result of analyzing the actual measurement results, the pushing force of men and women in their 30's was the maximum value and the forces in those in their 60's was the minimum value. In addition, the deviations in the pushing forces varied considerably. As a result of comparing the NFSC 501A, the men showed lower values than the criteria in every gender and age variable except for the 20's, 30's and 50's variable. A comparison of the criteria of NFPA 92A showed that the mean of the measured values from every gender and age was also lower than the criteria. In addition, when comparing the criteria of BS-EN 12101-6, it was found that the men in every age variable were higher than the criteria. On the other hand, the women in every age variable were lower than the criteria. Therefore, considering the Korean body type against the Western body type, it was decided that the opening force of an access door to a smoke control area to make a downward adjustment should be 110 N in the local criteria. Furthermore, the criteria should consider the characteristics of buildings and users because an optional application of the international standard is not necessarily suitable for local situations.

Pressure Effects on the Ionic Dissociation of $[Co(en)]_3Cl_3\;and\;[Co(NH_3)_6Cl_3$ in Aqueous Solutions (수용액에서 $[Co(en)_3]Cl_3$$[Co(NH_3)_6]Cl_3$착물의 이온 해리에 미치는 압력의 영향)

  • Jong Jae Chung;Rho Byung Gill
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.335-450
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    • 1986
  • The thermodynamic dissociation constants of $[Co(en)]_3Cl_3\;and\;[Co(NH_3)_6Cl_3$ in aqueous solutions at $25{\circ}$ and at the pressure from 1 bar to 2000 bars were measured by conductometric method. The dissociation constants were increased with pressure elevation because of volume decreasing by the formation of charged ions during dissociation reaction. That is, the $pK^T$ values of $[Co(en)]_3Cl_3$ were 2.16 for I bar, 2.08 for 500 bars, 2,08 for 1000 bars, 2.05 for 1500 bars and 2.03 for 2000 bars, respectively and those of $[Co(NH_3)_6Cl_3$ were 2.02 for 1 bar 1.96 for 500 bars, 1.90 for 1000 bars, 1. 88 for 1500 bars and 1. 87 for 2000 bars, respectively. Comparing and analyzing the values of Stokes' radii and $K^T$, the formation of ion pair compound was affected by not only the electrostatic interaction, but also the Interal Conjugate Base(ICB), which was increased by the elevation of the pressure.

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Micellar Effect of the Aquation and the Base Hydrolysis of cis-[Co(en)2NH3Cl]2+ Ion (cis-[Co(en)2NH3Cl]2+ 이온의 수화반응과 염기성 가수분해반응에 미치는 미셀의 효과)

  • Jeong, Jong Jae;Baek, Seong O;Lee, Jeong A
    • Journal of the Korean Chemical Society
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    • v.38 no.4
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    • pp.265-270
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    • 1994
  • The aquation and base hydrolysis of [Co(en)$_2$NH$_3$Cl]$^{2+}$ were studied by UV spectroscopic method in various SDS aqueous solution. The base hydrolysis of [Co(en)$_2$NH$_3$Cl]$^{2+}$ with the addition of 0, 0.05, 0.1 mol dm$^{-3}$ sodium chloride was studied. For the aquation of the complex, the rate constant in the micellar phase(kH$^M$) was a little larger than that in the aqueous phase(kH$^W$). With the increase of SDS concentration, the second order rate constant(kOH) for the base hydrolysis unchanged below the CMC and sharply decreased down to a limiting value after the CMC was reached. The effect of added NaCl on the rate behavior of the complexes in the micellar solution were investigated by using an ion-exchanged model.

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