• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2306-2310
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• 2011

The nucleophilic substitution reactions of diethyl thiophosphinic chloride 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 values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

• 한국초전도학회:학술대회논문집
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• v.10
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• pp.70-75
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• 2000

We report results of a comparative study of the normal-state and superconducting properties in the GdBa$_2$(Cu$_{2.9}$Al$_{0.1}$)O$_z$ system with substitutions by Pr for the Gd and Ba sites. It is observed that, fur both Pr-doped systems, the superconducting transition temperature(T$_c$) decreases almost linearly with the Pr-content, but Pr at Ba sites results in a faster T$_c$ drop than that of Pr at Gd sites. The thermoelectric power measurements indicate that there is a strong correlation between the T$_c$ and the room temperature value of thermoelectric power. The experimental results are discussed in connection with existing models.

• Journal of the Korean Chemical Society
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• v.24 no.5
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• pp.337-341
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• 1980

Radical formation reaction of phenolic antioxidants were examined MO theoretically. Results show that substitution of electron-donating alkyl groups in phenol increases the rate of phenoxy radical formation when attacked by an electrophilic radical by stabilization of cationic transition state.

• Journal of the Korean Ceramic Society
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• v.37 no.1
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• pp.63-69
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• 2000

Electrically-induced strain(S) and polarization(P) for Pb(Sc1/2Nb1/2)O3-PbTiO3(1-x)PSN-xPT) crystalline solutions were studied. From the compositional dependence of S and P we could observe two maximum values at x=0.10 and x=0.425. It is considered that PSNT10(x=0.10) composition is the structural phase boundary to indicate the variable order-disorder[VOD] region. PSNT(x=0.425) composition is the morphotropic phase boundary[MPB] to indicate the rhombohedral to tetragonal phase transition. Higher S (0.437%) and P (0.3974$\mu$C/$\textrm{cm}^2$) values were attained by the La substitution (5 wt%) at Pb site in the MPB composition of 57.5PSN-42.5PT.

• Proceeding of EDISON Challenge
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• 2016.03a
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• pp.336-338
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• 2016

Recent multifunctional two-dimensional material research has triggered huge interests in various modifications for substitution of atoms. Instead of novel metals used as the most popular catalysts, nonprecious transition metals are promising candidates for efficient oxidation-reduction transfers. The recent discovery of $Co@C_2N$ has an alternate possiblity as catalysts for the ORR(Oxygen Reduction Reaction) in DSSc(Dye Sensitized Solar Cell) and OER(Oxygen evolution cobalt oxides). Here we report spin-polarized DFT calculations of the structure doped Iron that is one of ferromagnetism atoms like Co to provide a basic desciption of the ferromagnetism of the elemental metals. The spin-density-funtional results present the most stable state energetically is when having pairwise up/down spin.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1997.11a
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• pp.52-55
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• 1997

In this study, PLZT stock solutions were prepared by sol-gel processing to fabricate PLZT thin films. The stock solutions were spin-coated on ITO-glass and the film were annealed by rapid thermal annealing(RTA). The variation of tile crystallographic structure of the thin films and the phase transition with respect to it were observed using Raman spectra. Raman result showed that the band of spectra are broad as the amount of Zr substitution increased and specially, abrupt change occurs in the raman spectra upon crossing the tetragonal-rhombohedral phase boundry at 2/55/45 PLZT thin film. So, the fact that the crystallographic structure was transitted from tetragonal to rhombohedral structure was certified.

• Bulletin of the Korean Chemical Society
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• v.16 no.1
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• pp.53-58
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• 1995

Heats of solution of aniline (AN), benzylamine (BA), ethyl-(EBS) and 2-phenylethyl benzenesulfonates (PEB) are calorimetrically measured in acetonitrile-methanol mixtures at 25.0 $^{\circ}C$. The activation parameters, ${\Delta}H^{\neq}$, ${\Delta}S^{\neq}$ and ${\Delta}G^{\neq}$, are determined for the reactions of EBS and PEB with AN and BA using the kinetic data at three temperatures. Calorimetric transfer enthalpies of initial state, ${\delta}H_t^{0{\rightarrow}x})$(IS), and kinetically derived activation enthalpies, ${\delta}\;{\Delta}H^{\neq}$, in the MeCN-MeOH mixtures are combined to determine the transfer enthalpies of transition state, ${\delta}H_t^{0{\rightarrow}x})$(TS); ${\delta}H_t^{0{\rightarrow}x})$(IS) = ${\delta}{\Delta}H^{\neq}\;+\;{\delta}H_t^{0{\rightarrow}x}$(IS) The preferential solvation of anionic charge in the TS predicts a loose TS with a greater degree of bond cleavage for the reactions of PEB than for EBS, and also for the reactions with BA compared to the reactions with AN.

• Bulletin of the Korean Chemical Society
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• v.17 no.9
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• pp.840-845
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• 1996

Rate constants have been measured spectrophotometrically for the reactions of p-and m-nitrophenyl 2-thiophenecarboxylate (5a and 5b, respectively) with alkali metal ethoxides (EtO-M+) in absolute ethanol at 25.0±0.1 ℃. The reactivity of EtO-M+ exhibits dependence on the size of alkali metal ions, i.e. the reactivity of EtO-M+ toward 5a decreases in the order EtO-K+ ≥ EtO-Na+ > EtO-Li+ > EtO-, while the one toward 5b does in the order EtO-Na+ ≥ EtO-K+ > EtO-Li+ > EtO-. This result indicates that ion paired EtO-M+ is more reactive than dissociated EtO-, and alkali metal ions form complexes with the substrate more strongly at the transition state than at the ground state. The catalytic effect shown by alkali metal ions appears to be less significant in the reaction of 5 than in the corresponding reaction of 4, indicating that complexation of alkali metal ions with 5 is not as strong as the one with 4.

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1010-1013
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• 1997

Nucleophilic substitution reactions of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines were investigated in acetonitrile at 60 ℃ under respective pressures. The magnitudes of the Hammett reaction constants, ρX, ρY and ρZ indicate that a stronger nucleophile leads to a greater degree of bond formation of C-N and a better leaving group is accompanied by a less degree of bond breaking. The magnitude of correlation interaction term, ρij can be used to determine the structure of the transition state (TS) for the SN reaction. As the pressure is increased, the Hammett reaction constants, ρX and |ρY|, are decreased, but correlation interaction coefficient, ρXZ and |ρYZ|, are increased. The results indicate that the reaction of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines probably moves from a dissociative SN2 to early-type concerted SN2 mechanism by increasing pressure. This result shows that the correlation interaction term ρij can be useful tool to determine the structure of TS, and also the sign of the product ρXZ·ρYZ can be predict the movement of the TS.

• Bulletin of the Korean Chemical Society
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• v.22 no.4
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• pp.383-387
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• 2001

The kinetics and mechanism of the reactions of thiophenyl dimethylacetates (TDA) and trimethylacetates (TTA) with benzylamines in acetonitrile are studied. The reactions are first order in both the amine and the substrate. Relatively large values of ${\beta}X(\betanuc$ = 1.1-1.5; TDA and 1.1-1.5; TTA) and ${\beta}Z({\beta}lg$ = -1.8~-2.0; DTA and -1.3~-1.6; TTA) for benzylamines, significantly large kH/kD values (=1.2-1.5; DTA and 1.2-1.5; TTA) involving deuterated benzylamines, and large ${\rho}XZ$ (=0.82; TDA and 1.05; TTA) values are interpreted to indicate stepwise acyl transfer mechanism, but with the hydrogen bonded four center type transition state for benzylamine. The relatively greater magnitudes of ${\rho}XZ$ and the secondary kinetic isotope effects involving deuterated nucleophiles are in line with the proposed mechanism.