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Mechanisms for Aquation of trans-$[CoETECl_2]^+\;and\;cis-{\beta}-[CoTETCl_2]^+\;and\;Isomerization\;of\;trans-[CoETEClOH_2]_2^+$ (trans-[CoETECl_2]+와 cis-${\beta}$-[CoTETCl_2]+ 착이온의 수화반응 및 $trans-[CoETEClOH_2]_2^+$ 착이온의 이성질화반응의 메카니즘)

  • Jeong, Jong Jae;Baek, Seong O
    • Journal of the Korean Chemical Society
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    • v.34 no.2
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    • pp.117-122
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    • 1990
  • The rate constants for the aquation of $trans-[CoETECl_2]^+ \;and \;cis-{\beta}-[CoTETCl_2]^+$ and the isomerization of $trans-[CoETEClOH_2]^{2+}$ were measured by spectrophotometric method under various temperature and pressure conditions. For the aquations of $trans-[CoETECl_2]^+ \;and\; cis-{\beta}-[CoTETCl_2]^+$, the activation entropies are 4.0 eu and 5.3 eu respectively and the activation volumes are $-5.8 cm^3mol-1\; and\; -6.6 cm^3mol^{-1}$ at 40$^{\circ}C$, respectively. From these data the dissociative mechanism involving trigonal bipyramid-type intermediate is proposed for the acquation reaction. For the isomerization of $trans-[CoETEClOH_2]^{2+}\; to\; cis-{\beta}-[CoETEClOH_2]^{2+}$ the activation entropy is 9.5 eu and the activation volume is $8.4 cm^3mol^{-1}(30^{\circ}C$. The mechanism of isomerization may be considered as the dissociative mechanism with $H_2O$-dissociation.

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Kinetics and Mechanism for Substitution of cis-[Co$(NH_3)_4$Cl($H_2O$)]$^{2+}$ and GlyOR (R = $C_2H_5$, $CH_3$, H) in Acidic Solution (Ⅰ) (산성용액내에서 cis-[Co$(NH_3)_4$Cl($H_2O$)]$^{2+}$ 와 GlyOR (R = $C_2H_5$, $CH_3$, H)과의 치환반응에 대한 속도론적 연구(Ⅰ))

  • Lee, Il Bong;Mun, Jin Hui;Park, Byeong Gak
    • Journal of the Korean Chemical Society
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    • v.38 no.10
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    • pp.719-725
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    • 1994
  • Kinetic studies were carried out for substitution reaction of $cis-[Co(NH_3)_4Cl(OH_2)]^{2+}(\mu$ = 0.75) with GlyOR (R = $C_2H_5$, $CH_3$, H) in pH 5 buffer solution at $20^{\circ}C$ by UV/Vis-spectrophotometry. We obtained cis-[Co$(NH_3)_4$Cl(glyOR)]$^{2+}$ as product. The reaction turns out to be first order for Co(III) and GlyOR, respectively. The rate constants are obtained as 9.21, 11.66 and 15.33 l${\cdot}\;mol^{-1}{\cdot}sec^{-1}$ for GlyOEt, GlyOMt and GlyOH, respectively. The activation parameters $E_a,\;{\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$ for GlyOEt were obtained as 65.77, 63.35 kJ/mol and -53.51(e.u.), respectively and were obtained as 70.91, 68.50 kJ/mol and -38.42(e.u.) for GlyOMt. In case of GlyOH, respectable values of 79.72, 77.30 kJ/mol and -26.59(e.u.) were obtained. On the basis of kinetic data and the observed activation parameters, we propose that the proper mechanism involves $S_N$2 step.

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Kinetic Study of Macrocyclic Ligand-Metal Ion Complexes (거대고리 리간드와 금속이온과의 착물에 관한 반응속도론적 연구)

  • Moon-Hwan Cho;Jin-Ho Kim;Hyu-Bum Park;Si-Joon Kim
    • Journal of the Korean Chemical Society
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    • v.33 no.4
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    • pp.366-370
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    • 1989
  • A new macrocyclic ligand 1,15,18-triaza-3,4;12,13-dibenzo-5,8,11-cycloeicosane (NdienOdien$H_4$ = $N_3O_3$) has been synthesized and identified by element analysis, NMR and IR spectrophotometry. Stepwise protonation constants of ligand are determined by potentiometry in 95% methanol solution(I = 0.1 mol $dm^{-3}$, $Me_4$NCl). log $K_1$;log $K_2$;log $K_3$ = 9.1;8.1;3.6.The kinetics of the acid-promoted dissociation reactions of complex cations of nickel(II) and copper(III) with NdienOdien and NdienOen macrocyclic ligands having, respectively, 17 and 20 ring members, have been studied spectrophotometrically in HCl$O_4$ NaCl$O_4$ aqueous solutions. From the temperature effect on kinetic constant ($k_{obs}$), the parameters of activation(${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$) of dissociation reaction for $ML^{2+}$ with $H^+$ ion have been determined. We have proposed the possible mechanism of the reaction from the data obtained.

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Design and Analysis of Code Sequence Generating Algorithms using Almost Perfect Nonlinear Functions (APN 함수를 이용한 부호계열 발생 알고리즘 설계 빛 분석)

  • Lee, Jeong-Jae
    • Journal of the Institute of Convergence Signal Processing
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    • v.11 no.1
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    • pp.47-52
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    • 2010
  • For cryptographic systems, nonlinearity is crucial since most linear systems are easily decipherable. C.Bracken, Z.Zhaetc., propose the APN(Almost Perfect Nonlinear) functions with the properties similar to those of the bent functions with perfect nonlinearity. We design two kinds of new code sequence generating algorithms using the above APN functions. And we find that the out of phase ${\tau}\;{\neq}\;0$, autocorrelation functions, $R_{ii}(\tau)$ and the crosscorrelation functions, $R_{ik}(\tau)$ of the binary code sequences generated by two new algorithms over GF(2), have three values of {-1, $-1-2^{n/2}$, $-1+2^{n/2}$}. We also find that the out of phase ${\tau}\;{\neq}\;0$, autocorrelation functions, $R_{p,ii}(\tau)$ and the crosscorrelation functions, $R_{p,ik}(\tau)$ of the nonbinary code sequences generated by the modified algorithms over GF(p), $p\;{\geq}\;3$, have also three values of {$-1+p^{n-1}$, $-1-p^{(n-1)/2}+p^{n-1}$, $-1+p^{(n-1)/2}p^{n-1}$}. We show that these code sequences have the characteristics of the correlation functions similar to those of Gold code sequences.

Kinetics of the Reaction of Phenacyl Bromide with Anilines in Methanol and Dimethylformamide (Phenacyl Bromide와 置換아닐린類와의 反應에 關한 反應速度論的 硏究)

  • Soo-Dong Yoh;Doo-Jung Kim
    • Journal of the Korean Chemical Society
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    • v.25 no.6
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    • pp.376-382
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    • 1981
  • The rates and the activation parameters for the reaction of phenacyl bromide with substituted anilines in methanol and dimethylformamide were measured. The effects of substituted anilines were discussed. The rate of the reaction was increased with the electron donating power of substituent and showed larger value in DMF than in MeOH. The isokinetic relationship was shown between ${\delta}H^{\neq}$ and ${\delta}S^{\neq}$, isokinetic temperature was 539 and $400^{\circ}C$ in MeOH and DMF respectively, but p-nitro aniline was deviated from linearity in both solvents caused by solvent effects. The excellent linear relationship between log k and p$K_a$ of substituted anilines was observed by following equation. log k = 0.57p$K_a$-1.28 (r = 0.996) in MeOH at $45^{\circ}C$, log k = 0.65p$K_a$-0.88 (r = 0.970) in DMF at $45^{\circ}C$. From the Hammett plot, this reaction was a nucleophilic displacement of aniline to phenacyl bromide and the following equation was obtained at $45^{\circ}C$. log k/$k_0$ = -2.00${\sigma}$ + 0.06 (r = 0.985) in MeOH; log k/$k_0$ = -2.22${\sigma}$ + 0.08 (r = 0.995) in DMF. Large deviation of p-nitro aniline in DMF is resulted from solvent effects too. From above results, the substituent effect of this reaction can be described as $S_N2$ mechanism and bond formation more proceeds in DMF relative to MeOH.

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The Effects of Charge Transfer Complex on the Reaction of N,N-dimethylaniline and Iodine (N,N-Dimethylaniline과 Iodine간의 반응에 있어서 Charge Transfer Complex의 영향)

  • Oh-Yun Kwon;U-Hyon Paek;Eung-Ryul Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.191-196
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    • 1992
  • Reaction of N,N-dimethylaniline(N,N-DMA) and iodine in $CHCl_3,\;CH_2Cl_2 : CHCl_3$(1:1), $CH_2Cl_2$(1:1), and CH2Cl2 has been studied kinetically by using conductivity method. Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[N,N-DMA]) are dependent on the N,N-DMA concentration. Second-order rate constants obtained were decreased with increasing N,N-DMA concentration. We analysed these results on the basis of formation of charge transfer complex as a reaction intermediate. From the construction of reaction scheme and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants decreased when the dielectric constant of solvent was increased, and the value is 1.9${\sim}$4.2$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity.${\Delta}H^{\neq}$ is 6.3-12.6kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -234J/mol K.

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Kinetics and Hydrolysis Mechanism of Herbicidal N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide Derivatives (제초성, N-(2,6-dimethoxypyrimidin-2-yl)aminocarbonyl-2-치환(Z)-6-(1-hyd roxy-2-fluoroethyl)benzenesulfonamide 유도체의 가수분해 반응 메카니즘)

  • Lee, Chan-Bog;Ryu, Jae-Wook;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.38 no.5
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    • pp.455-462
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    • 1995
  • The new six herbicidal N-[(pyrimidin-2-yl)aminocarbonyl]-2-substituted-6-(1-hydroxy-2-fluoroethyl)benzenesulfonamide derivatives(S) were synthesized and rate constants for the hydrolysis of thier in the range of pH $1.0{\sim}10.0$ have been studied in 15%(v/v) aqueous acetonitrile solution at $45^{\circ}C$. From the basis of the results, pH-effect, solvent effect, ortho-substituent effect, thermodynamic parameters(${\Delta}H^{\neq}$ & ${\Delta}S^{\neq}$), pKa constant(4.80), rate equation, analysis of hydrolysis products(2-(1-hydroxy-2-fluoroethyl)benzenesulfonamide & 4,6-dimethoxyaminopyrimidine), it may be concluded that the general acid catalyzed hydrolysis through $A-S_E2$ mechanism and specific acid catalyzed hydrolysis through A-2 type(or $A_{AC}2$) mechanism proceeds via conjugate acid($SH^+$) and tetrahedral intermediate(I) below pH 8.0, whereas, above pH 9.0, the general base catalyzed hydrolysis by water molecules(B) through $(E_1)_{anion}$ mechanism proceeds via conjugate base(CB). In the range between $pH\;7.0{\sim}pH\;9.0$, these two reactions occur competitively.

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Kinetics for the Transformation of Outer Charge Transfer Complex to Inner Complex (Outer Charge Transfer Complex가 Inner Complex로의 변환에 따른 속도론적 연구)

  • Kwon Oh-Yun;Paek U-Hyon;Kim Eung-Ryul
    • Journal of the Korean Chemical Society
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    • v.35 no.4
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    • pp.343-349
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    • 1991
  • Formation of charge transfer complex between iodine and substituted aniline [aniline, N,N-dimethylaniline(N,N-DMA), 2,6-dimethylaniline(2,6-DMA), 2,4,6-trimethylaniline(2,4,6-TMA)] in CHCl$_3$, CH$_2$Cl$_2$ : CHCl$_3$ (1 : 1), and CH$_2$Cl$_2$ have been studied kinetically by using conductivity method. In the transformation of initially formed outer charge transfer complex to inner complex, the effects of substituted aniline as electron donor and polar medium on the reaction were investigated. The rate of transformation depend on the dielectric contribution of medium and pK$_a$ value of substituted aniline. The order of rate increasing is 2,4,6-TMA, 2,6-DMA, aniline, and N,N-DMA. The activation enthalpy ${\Delta}H^{\neq}$ for 2.5 M-substituted aniline in CHCl$_3$ at 25$^{\circ}C$ is respectively N,N-DMA, 3.47 kcal/mol; aniline, 4.25 kcal/mol; 2,6-DMA, 7.79 kcal/mol and 2,4,6-TMA, 7.96 kcal/mol; and activation entropy ${\Delta}S^{\neq}$ is large and negative value of -41 ~ -55 cal/mol${\cdot}$K.

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A Development of 3-D Numeric Model for the Confined Flow and Discharge under Sea Ground (해저 지중 피압유체의 흐름과 양수량 산출에 관한 3차원 수치모형의 개발)

  • Kim, Sang-Jun
    • Journal of Korean Society of Coastal and Ocean Engineers
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    • v.22 no.6
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    • pp.387-396
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    • 2010
  • A 3-D numeric model for the confined transient flow under sea ground have been developed. This is FDM model using Gauss-Seidel SOR (successive over-relaxation). This model shows the similar head distribution pattern to Theis analytic solution and MODFLOW simulation. The input flowrate to the aquifer and discharge of well have been compared. And it have been found that mass balance is influenced by the weight factor ${\alpha}$, i.e. fullyimplicit method (${\alpha}$=1) shows 5% error, but when ${\alpha}$ becomes to 0.5(Crank and Nicolson method) the mass balance becomes worse and the model result diverges. And the convergency of the model is not much different when $\lambda$ (over-relaxation factor)=0.8~1.5, but when $\lambda$>1.5, the model result diverges. The test-run shows that the well discharge becomes smaller when another well is near. This model can cover the isotropy$(Kx{\neq}Ky{\neq}Kz)$ and inhomogeneity, and can be used for the selection of well site, discharge calculation, and head prediction in case of the artificial recharge etc.

The Historical Trauma of Korean and The Challenges of Korean Unification (코리언의 역사적 트라우마와 통일의 과제)

  • Park, Young-kyun
    • Journal of Korean Philosophical Society
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    • v.143
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    • pp.119-140
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    • 2017
  • After the collapse of the Cold War, there was a shift in perception at two points in discussions on Korean unification. The real core issue of unification is first, that it is a shift in perception that the real problem of unification is not the integration of systems, but the integration of people. Second, there is a shift in perception that there are many Koreans in the four major powers related to the Korean division and their distribution is associated with the tragic history of the Korean Peninsula. The historical trauma of Korean people resulted from the oppression of the collective libido of Koreans, stemming from the pain of modern history of the Korean Peninsula. In addition, the trauma of colonization, diaspora, and division all share the structure of suppression as the '$nation{\neq}states$'. Thus, unification aims to overcome the notion that '$nation{\neq}state$' can not be separated from the process of healing the historical trauma of Koreans. First of all, this article argues that in order to achieve unification on the Korean peninsula, it requires the process of healing the traumas of colonization, diaspora, and division. Second, this paper claims that Korean unification is not only a matter of two countries, but also of making peace by healing historical trauma in Northeast Asia. Third, this paper argues that the healing of Korean's historical trauma should begin with 'sympathy' for pain and proceed to the production of a 'national commonality' through 'communication of difference', which will create a unified peninsula.