• Journal of the Korean Chemical Society
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• v.24 no.1
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• pp.44-52
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• 1980

Ionic dissociation rates of $\alpha$-chlorobenzyl ethyl ether in each solvent of toluene-$d_8$ and carbon tetrachloride were measured by the method of dynamic NMR spectroscopy. The spin system of these 1H NMR spectra was $AB_3$. The theoretical spectrum was calculated by computer simulation of dynamic NMR spectra, which agreed very well with observed spectra. From this computer simulation, the ionic dissociation rate constant k was obtained, and by Eyring plot with it, slope and intercept length was gained, from which kinetic parameters were calculated.The easiness of ionic dissociation depended upon solvent polarity. Activation enthalpy was 4.7 kcal/mole in toluene-$d_8$, 10.7 kcal/mole in carbon tetrachloride, and activation entropy was -35. 8 e.u. in toluene-$d_8$, -14.4 e.u. in carbon tetrachloride. It was understood that though the ${\Delta}H^{neq}$ value was small, this ionic dissociation had an easier procession in nonpolar solvents with increasing temperatures. Considering that the ionic dissociation could be thought as the first step of $S_N1$ mechanism, attention might be paid to the results that the value of ${\Delta}S^{neq}$ had a large negative value in comparison with a small ${\Delta}H^{neq}$.

• Journal of the Korean Chemical Society
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• v.23 no.4
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• pp.217-236
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• 1979

The author's theory for plastic deformation was applied to superplastic alloys (Zn-Al eutectoid, Al-Cu, Pb-Sn, Sn-Bi, Mg-Al eutectics). The plastic deformation of the superplastic alloys could be described by two Maxwell models connected in parallel which represent two grain boundary flow units. The flow units are characterized by the two parameters $X_{gj}/{\alpha}_{gj}\;and\;{\beta}_{gj}$ (j=l or 2, g signifies the grain boundary) the values of which were obtained by applying our flow equation [Eq. (5)] to experiment. We confirmed that our flow equation describes the superplasticity very well. The curve of strain rate sensitivity m (=${\partial}\;In\;f/{\partial}\;In\;\dot{s})\;vs.\;-In\dot{s}$, where f and s are stress and strain rate, respectively, showed two peaks corresponding to flow unit gl and g2, the separation of the two peaks is determined by the difference between ${\beta}_{g1}\;and\;{\beta}_{g2}$. The condition of superplasticity is also determined by ${\beta}_{gj}$, which satisfies $\dot{s}_{mj}{\leqslant}1.53}{\beta}_{gj}$ [Eq.(13)], where $\dot{s}_{mj}$ is the s of the jth unit at the peak. The grain size dependence of ${\beta}_{gj}$ is described by $ln({\beta}_{gj})^{-1}$=alnx+b [Eq. (16)], where x is the grain size, and a and b are constants. The activation enthalpy for each flow unit, ${\Delta}H_{gj}^{\neq}$ was also determined from the temperature dependence of ${\beta}_{gj}$ which is proportional to the relaxation time of the j th unit. Since the superplasticity is determined by Eq. (13), and since ${\beta}_{gj}$ and ${\Delta}H_{gj}^{\neq}$ are related, we obtained the conclusion that superplasticity occurs in the system having small ${\Delta}H_{gj}^{\neq}$ values. The Aej values were equal to the activation enthalpies of grain boundary self-diffusion of the component atoms of the alloys, this accords with our proposed flow mechanism. The ${\Delta}H_{gj}^{\neq}$ value increases with grain size as expected from Eq. (16).

• Journal of the Korean Chemical Society
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• v.33 no.4
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• pp.371-378
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• 1989

Kinetics of the substitution reaction of [pt[dien]X]$^+$(X = $Cl^-$, $Br^-$, $I^-$) with NO2- in aqueous solution were investigated by a spectrophotometric method at $20-35^{\circ}C$ and 1-1500 bars. The rates of these reactions were increased with raising temperature and pressure. The relative reactivities of replaceable ligands in [pt[dien]X]$^+$ follow the order ($Cl^-$ > $Br^-$ > $I^-$). Activation volumes (${\mid}{\Delta}V^{\neq}{\mid}$) were large negative values and decreased with raising temperature. First ($k_1$) and second($k_2$) order rate constants of these reactions were determined at $25^{\circ}C$ and both $k_1$ and $k_2$ were increased with raising pressure and activation volumes (${\Delta}{V_1}^{\neq}$, ${\Delta}{V_2}^{\neq}$) for the $k_1$ and $k_2$ path were large negative values respectively. The $k_1$ and $k_2$ of these reactions were determined at 1 bar and these values were increased with raising temperature. Activation parameters of $k_1$ and $k_2$ path were determined, therefore it can be inferred frp, these results that the substitution reactions of [pt[dien]X]$^+$ with ${NO_2}^-$ proceed through on associative (A) mechanism independent of a leaving groups and reaction paths.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.540-545
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• 1992

Kinetics and mechanism on the solvent extraction of nickel(Ⅱ) with 8-hydroxyquinoline (HOx) was studied spectrophotometrically. Absorbance variation was measured by changing the 8-hydroxyquinoline concentration in the chloroform organic phase and the pH values in the aquous phase. By analyzing absorbance data the reaction rate was found to be the first order for 8-hydroxyquinoline concentration and the inverse first one for [H$^+$]. Therefore the rate determining step of the extraction reaction is the formation of the one-to-one metal chelate NiOx$^+$ and the rate equation is as follows; -d[Ni$^{2+}$]/dt = k[Ni$^{2+}$][Ox$^-$] = k'[Ni$^{2+}$][HOx]$_0$/[H$^+$]. The value of k' was evaluated from the slope of plot of log [Ni$^{2+}$]$_0$/[Ni$^{2+}$]$_t$ versus time and the rate constant k was calculated according to the equation k' = k ${\times}$ K$_{HOx}$ / K$_{D,HOx}$. From the temperature dependence of the extraction rate, the activation energy E$_a$ = 6.26 kcal/mol is calculated, and activation parameters, ${\Delta}$G$^{\neq}_{298}$ = 6.59 kcal/mol, ${\Delta}$H$^{\neq}_{298}$ = 5.68 kcal/mol, ${\Delta}$S$^{\neq}_{298}$ = -3.09 eu/mol are estimated.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.629-636
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• 1990

Dephosphorylation of p-nitrophenyldiphenylphosphate(p-NPDPP) mediated by anions of sodium 2-alkylbenzimidazole-5-sulfonate(R-BI-SO$_3$Na) in CTABr micellar solutions are obviously slower than that by anion of sodium benzimidazole-5-sulfonate(BI-SO$_3$Na), and the reation rates were decreased with increase of lengths of alkyl groups. This presents a striking contrast to the reactions in aqueous solutions without added CTABr, of which the reaction rates are on approximately same levels. It seems due to steric effect of alkyl groups of R-BI$^-$SO$_3$Na in the Stern layer of micelle, and it is supported by measured activation parameters(△H$^\neq$/TEX>, △G$^\neq$/TEX> and △S$^\neq$/TEX>) of the reactions in aqueous and micellar solutions. In addition to nucleophilic ability of benzimidazole moiety of R-BI$^-$SO$_3$Na on the reactions, these compounds with long alkyl groups(nonyl to pentadecyl) are micellized for themseleves, and increase the reaction rates due to their micellar catalyses in aqueous solutions, not including CTABr.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.203-210
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• 1988

Mono-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_3(Phen)_2(NCS)_4]$ produces di-oxo-bridged binuclear molybdenum(V) complex, $[Mo_2O_4(Phen)_2(NCS)_2]$ in water + co-solvent, where the co-solvent are acetone, acetonitrile and N,N-dimethylformamide. The rate of conversion of $[Mo_2O_3(Phen)_2(NCS)_4]\;into\;[Mo_2O_4(Phen)_2(NCS)_2]$ has been measured by spectrophotometric method. Temperature was $10^{\circ}C$ to $40^{\circ}C$ and pressure was varied up to 1500 bar. The rate constants are increased with increasing water mole fraction and decreased with increasing concentration of hydrogen ion. The order of oxygen ring formation reaction rate in various cosolvent is as follows, ACT > AN > DMF which is agreed with solvent dielectric constants. The observed negative activation entropy ($[\Delta}S^{\neq}$), activation volume($[\Delta}V^{\neq}$) and activation compressibility coefficient(${\Delta}{\beta}^{\neq}$) values show that the solvent water molecule is strongly attracted to the complex at transition state. From these results, the oxygen ring formation reaction of $[Mo_2O_3(Phen)_2(NCS)_4]$ is believed association mechanism.

• Journal of the Korean Statistical Society
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• v.17 no.2
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• pp.81-92
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• 1988

We observe independent random variable $Y_i \sim N(\theta_i,1), i=1,2,\cdots,k$, and we are interested in detecting the treatment with the largest $\theta_i$. We consider a procedure which infers $\theta_{(k)} \geq max\theta_i (i\neq(k))$ whenever $Y_{(k)} \geq maxY_i+C (i\neq(k))$. The maximum probability of a false inference is found, and it is shown that the inference can be made with the two-sample one-sided critical value for the usual error levels. The result also holds in the case of common unknown variance.

• Communications of the Korean Mathematical Society
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• v.10 no.4
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• pp.823-829
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• 1995

In this paper, we prove that $x^{1+\frac{q-1}{5}} + ax (a \neq 0)$ is not a permutation polynomial over $F_{q^r} (r \geq 2)$ and we show some properties of $x^{1+\frac{q-1}{m}} + ax (a \neq 0)$ over $F_{q^r} (r \geq 2)$.

• Bulletin of the Korean Mathematical Society
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• v.45 no.4
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• pp.709-715
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• 2008

We construct certain ring class fields over an imaginary quadratic field by making use of Shimura's canonical models and extend the result of Chen-Yui ([1] Theorem 3.7.5(2)) to the case where (a, b, N) $\neq$ N or (a/N, N) $\neq$ 1 for a positive integer N > 1.

• Communications for Statistical Applications and Methods
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• v.4 no.1
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• pp.281-292
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• 1997

In this paper we are concered with the counting processes with intersity function $g_n(t)$, where $g_n(t)$ not only depends on t but n. It is shown that under certain conditions the number of events in [0, t] follows a generalizes Poisson distribution. A counting process is also provided such that $g_i(t)$$\neq$$g_i(t)$ for i$\neq$j and the number of events in [0, t] has a transformed geometric distribution.