• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.281-286
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• 1990

The kinetics and mechanism of reduction of Cu(II) with an excess D-penicillamine have been examined at pH = 6.2 and 0.60M in ionic strength. The reaction at the initial stage is biphasic with a rapid complexation process to give "red" transient complex of $[Cu(II)(pen)_2]^2$- that is partially reduced to another transient "brown" intermediate. The "brown" intermediate is finally reduced to diamagnetic "yellow" complex, $[Cu(I)(Hpen)]_n$. The final reduction process is pseudo-first order in ["brown" transient] disappearance $with {\kappa} = {{\kappa}_{3a} + {\kappa}_{3b}[pen]^{2-}},$ where ${\kappa}_{3a} = (5.0{\pm}0.8){\times}10^{-3}sec^{-1}$ and ${\kappa} = (0.14{\pm}0.02) M^{-1}sec^{-1}$ at $25^{\circ}C$. The activation parameters for the $[H_2pen]$-independent and $[H_2pen]$-dependent paths are ${\Delta}H^{\neq} = (52{\pm}5)kJmol^{-1},$ and ${\Delta}S^{\neq} = ( - 27{\pm}3)JK^{-1}mo^{l-1},$ and ${\Delta}H^{\neq} = (56{\pm}2)kJmol^{-1}$ and ${\Delta} S^{\neq} = ( - 18{\pm}0.7)JK^{-1}mol^{-1}$ respectively. The nature of "brown" intermediate is not clearly identified, but this intermediate seems to be in the mixed-valence state, judging from the kinetic and spectroscopic informations.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.318-323
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• 1990

The bis(malonato)diaquochromate(III) ion, $Cr(C_3H_2O_4)_2^-$ in acidic solution hydrolyzes to give $Cr(C_3H_2O_4)^{+}.$ This reaction is catalyzed by ferric ion and the rate law for this cation catalyzed-aquation in a $HClO_4/NaClO_4$ medium, $I = 1.00 M, is-d[Cr(C_3H_2O_4)_2^-]/dt = ({\kappa}_1[Fe^{3+}] + {\kappa}_2[H^+])[Cr(C_3H_2O_4)_2^-]$ where ${\kappa}_1(25^{\circ}C) = 4.72×10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 22.5 Kcal/mol, {\Delta}S^{\neq} = - 2.58 eu) and {\kappa}_2(25^{\circ}C) = 4.75{\times}10^{-5} M^{-1}sec^{-1} ({\Delta}H^{\neq} = 21.2 Kcal/mol, {\Delta}S^{\neq} = - 7.13 eu).$ Rapid preequilibrium association of basic Cr-bound oxygen with $Fe^{3+},$ followed by rate-determining ring opening, is proposed to account for the ${\kappa}_1,$ hydrolysis pathway.

• Journal of the Korean Chemical Society
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• v.35 no.1
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• pp.64-69
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• 1991

Kinetics of the reaction of p-methylphenacyl arenesulfonates with pyridine in acetonitrile were investigated by an electric conductivity method at 1∼2000 bars and 35∼55$^{\circ}C$. The rates of these reactions were increased with raising pressures and temperatures. The activation enthalpy(${\Delta}H^{\neq}$), entropy(${\Delta}S^{\neq}$) and activation volume(${\Delta}V^{\neq}$) of the reaction were obtained with the rate constants. Activation volume and entropy were both negative valued, and activation enthalpy was positive. The acteivation parameters (${\Delta}V^{\neq}$ and ${\Delta}S^{\neq}$) were decreased with increasing pressure. From all of the above results, it was found that this reaction proceeds on the S$_N$2 in which C${\cdots}$O bond breaking is more advanced as pressure increases.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.549-554
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• 1993

The CO substitution reactions in the complex, $Cp^*(C_5H_7)$CrCO with $PR_3(PR_3=PMePh_2,\;P(OCH_3)_3,\;PMe_2Ph)$ were investigated spectrophotometrically at various temperatures. For the reaction rates, it was suggested that the CO substitution reaction took place by first-order (dissociative) pathway. Activation parameters in decaline are ${\Delta}H^{\neq}= 21.99{\pm}2.4$ kcal/mol, ${\Delta}S^{\neq}= 8.9{\pm}7.1$ cal/mol·k. Unusually low value of ${\Delta}S^{\neq}$, suggested an ${\eta}^5-S{\to}\;{\eta}^5$-U conversion of the pentadienyl ligand. At various temperature, the rates of reaction for the Cp(pdl)CrCO complexes increase in the order $Cp^*(C_5H_7)$-CrCO < Cp$(C_5H_7)$CrCO < Cp(2,4-$C_5H_{11}$)CrCO, which can be attributed to the usual steric acceration or electronic influence for the ligand substitution of metal complexes. This suggestion was confirmed by the extended-Huckel molecular orbital (EHMO) calculations, which revealed that the energy of $[Cp^*(U-C_5H_7)Cr]^{\neq}$ transition state is about 4.93 kcal/mol lower than that of [Cp(S-$C_5H_7)Cr]^{\neq}$ transition state, and the arrangement of the overlap populations between Cr and the carbon of CO is $Cp^*(C_5H_7)$CrCO > Cp($C_5H_7$)CrCO > Cp(2,4-$C_7H_{11}$)CrCO.

• Proceedings of the Korean Society for Noise and Vibration Engineering Conference
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• 1993.04a
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• pp.23-29
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• 1993

내부공진 (.omega.$_{3}$ = .omega.$_{1}$ + 2.omega.$_{2}$)을 가진 원판 의 조합공진(.OMEGA. = 2.omega.$_{1}$ + .omega.$_{2}$)응답의 안정성 을 해석한 결과 다음과 같은 결론을 얻었다. 1) 모든 진폭이 0(.alpha.$_{1}$=.alpha.$_{2}$=.alpha.$_{3}$=0)인 공진응답 은 매개변수의 값에 관계없이 안정하다. 2) 모든 진폭이 0이 아닌 (.alpha.$_{1}$.neq.0, .alpha.$_{2}$.neq.0, .alpha.$_{3}$.neq.0) 공진응답은 쌍으로 존재하는데 진폭이 큰 응답(upper branch)은 안정하나 진폭이 작은 응답(lower branch)은 불안정하다. 3) 진폭이 0이 아닌 공진응답이 존재하지 않는 경우에는 선형계와 마찬가지 로 모든 진폭이 0이 공진응답(결과적으로 비공진 응답)이 계의 응답을 지배 하지만 모든 진폭이 0이 아닌 공진응답이 존재하는 경우에는 안정한 공진응 답이 2개이므로 초기조건이 실제의 응답을 결정하게 된다.

• 전기의세계
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• v.28 no.7
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• pp.60-66
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• 1979

In this paper we deal with a hardware redundency, using the replications of an original module to enhance the reliability of the system in view of static and dynamic redundancy. As results of the study the following facts have been proved that (1) if the mission time is small (T .neq. 0.5), the effect of spare modules cannot be expected significantly, (2) for the small mission time (0.1 .neq. T .neq. 0.3) the SPR system is more reliable than the other redundant systems. In addition to above facts, it is also proved that for the large mission time (T=1), the dynamic redundant system is more reliable than the static redundant system, and that the SR system is more reliable than the HR system in the dynamic redundant system.

• The Pure and Applied Mathematics
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• v.10 no.3
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• pp.185-192
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• 2003

It is shown that every almost linear mapping $h{\;}:{\;}X{\;}{\rightarrow}{\;}Y$ of a complex normed space X to a complex normed space Y is a linen. mapping when h(rx) = rh(x) (r > 0,$r\;{\neq}\;1$$x{\;}{\in}{\;}X$, that every almost quadratic mapping $h{\;}:{\;}X{\;}{\rightarrow}{\;}Y$ of a complex normed space X to a complex normed space Y is a quadratic mapping when $h(rx){\;}={\;}r^2h(x){\;}(r{\;}>{\;}0,r\;{\neq}\;1)$ holds for all $x{\;}{\in}{\;}X$, and that every almost cubic mapping $h{\;}:{\;}X{\;}{\rightarrow}{\;}Y$ of a complex normed space X to a complex normed space Y is a cubic mapping when $h(rx){\;}={\;}r^3h(x){\;}(r{\;}>{\;}0,r\;{\neq}\;1)$ holds for all $x{\;}{\in}{\;}X$.

• Bulletin of the Korean Chemical Society
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• v.22 no.7
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• pp.732-738
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• 2001

The cross second-derivative of the activation energy,${\theta}$G${\neq}$ , with respect to the two component thermodynamic barriers, ${\theta}$G˚X and ${\theta}$G$^{\circ}C$Y, can be given in terms of a cross-interaction constant (CIC), $\betaXY(\rhoXY)$, and also in terms of the intrinsic barrier,${\theta}$G${\neq}$ , with a simple relationship between the two: $\betaXY$ = $-1}(6${\theta}$G${\neq}$).$ This equation shows that the distance between the two reactants in the adduct (TS, intermediate, or product) is inversely related to the intrinsic barrier. An important corollary is that the Ritchie N+ equation holds (for which $\betaXY$ = 0) for the reactions with high intrinsic barrier. Various experimental and theoretical examples are presented to show the validity of the relationship, and the mechanistic implications are discussed.

• Bulletin of the Korean Chemical Society
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• v.13 no.3
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• pp.334-336
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• 1992

Through two different techniques TGA and DSC the thermal decomposition processes of salicyaldehyde G-P complexes having the general formula: $$[MCl_2(L)_2]^{2+}$2Cl^-$; where L = salicyaldehyde carbohydrazone pyridinum cation, and M= Fe(III), Co(II), Cu(II) and Zn(II), have been studied. From the obtained thermogravimetric curves the following parameters n, $E_{\alpha}$, A, ${\Delta}S^{\neq}$, ${\Delta}H^{\neq}$ and ${\Delta}G^{\neq}$ were evaluated. The effect of the nature of the metal ions present in the complexes studied upon the calculated thermodynamic parameters was reported. A suitable mechanism for the thermal decomposition process was suggested.

• The Pure and Applied Mathematics
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• v.29 no.2
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• pp.179-188
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• 2022

In this paper we investigate the Hyers-Ulam stability of the s-variable additive and l-variable quadratic functional equations of the form $$f\(\sum\limits_{i=1}^{s}x_i\)+\sum\limits_{j=1}^{s}f\(-sx_j+\sum\limits_{i=1,i{\neq}j}^{s}x_i\)=0$$ and $$f\(\sum\limits_{i=1}^{l}x_i\)+\sum\limits_{j=1}^{l}f\(-lx_j+\sum\limits_{i=1,i{\neq}j}^{l}x_i\)=(l+1)$$$\sum\limits_{i=1,i{\neq}j}^{l}f(x_i-x_j)+(l+1)\sum\limits_{i=1}^{l}f(x_i)$ (s, l ∈ N, s, l ≥ 3) in quasi-Banach spaces.