• Bulletin of the Korean Chemical Society
• /
• v.11 no.4
• /
• pp.309-313
• /
• 1990

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

• Proceedings of the Korean Society for Technology of Plasticity Conference
• /
• 2007.05a
• /
• pp.421-424
• /
• 2007

Dry sliding wear behavior of ultra-fine grained (UFG) plain low carbon dual phase steel, of which microstructure consists of hard martensite in a ductile ferrite matrix, has been investigated. The wear characteristics of the UFG dual phase steel was compared with that of a coarse grained dual phase steel under various applied load conditions. Dry sliding wear test were carried out using a pin-on-disk type tester at various loads of 1N to 100N under a constant sliding speed condition of 0.20m/s against an AISI 52100 bearing steel ball at room temperature. The sliding distance was fixed as 1000m for all wear tests. The wear rate was calculated by dividing the weight loss, measured to the accuracy of 10-5g by the specific gravity and sliding distance. The worn surfaces and wear debris were analyzed by SEM, EDS and profilometer. Micro-vickers hardness of the cross section of worn surfaces were conducted to analyze strain hardening underneath the contact surfaces. The wear mechanism of the UFG dual phase steel was investigated with emphasis on the unstable nature of the grain boundaries of the UFG microstructure.

• Journal of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.10-18
• /
• 1990

Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, $N_{BS}$, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured $ν_{max}$. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and ${\beta},{\rho}_s$, values.

• Journal of the Korean Chemical Society
• /
• v.35 no.6
• /
• pp.673-679
• /
• 1991

The electrochemical reduction of N-tert-butylbenzothiazole-2-sulfenamide (TBBS; vulcanization accelerator) was investigated by direct current, differential pulse polarography, cyclic voltammetry and controlled potential coulometry. The electrode reduction of TBBS proceeded E-C-E-C reaction mechanism by four electrons transfer at irreversible one wave (-2.31 volts vs. Ag/0.1M AgN$O_3$ in AN). As the results of controlled potential electrolysis, mercaptobenzothiazole (MBT), benzothiazole disulfide (MBT dimer) and extricated sulfur were products which followed by cleavage of the sulfenamide (-S-N=) bond. Upon the basis of products analysis and polarogram interpretation with pH variable, electrochemical reaction mechanism was suggested.

• Bulletin of the Korean Chemical Society
• /
• v.10 no.1
• /
• pp.47-50
• /
• 1989

The methanolysis reactions of phenylacetyl chlorides have been investigated in methanol-acetonitrile mixtures at temperatures ranging - $15.0-0.0^{\circ}C.$ Substituent and solvent effects on the rate supported an associative $S_N2$ mechanism for the solvolysis. Activation parameters indicated that the reaction is entropy controlled, while the a/s ratios of the Taft's solvactochromic correlation proved to be remarkably constant with a typical value of 0.50 that is consistent for the reactions proceeding by a typical $S_N2$ path.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.1
• /
• pp.91-94
• /
• 2003

Kinetic studies of the reaction of O-methyl-S-phenylthiocarbonates with benzylamines in methanol at 45.0 ℃ have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, $T^{\pm}$, with a hydrogen-bonded four-center type transition state (TS). These mechanistic conclusions are drawn based on (ⅰ) the large magnitude of ${\rho}_X\;and\;{\rho}_Z$, (ⅱ) the normal kinetic isotope effects $(k_H/k_D\;>\;1.0)$ involving deuterated benzylamine nucleophiles, (ⅲ) the positive sign of ${\rho}_{XZ}$ and the larger magnitude of ${\rho}_{XZ}$ than that for normal $S_N2$ processes, and lastly (ⅳ) adherence to the reactivity-selectivity principle (RSP) in all cases.

• Archives of Pharmacal Research
• /
• v.26 no.9
• /
• pp.667-678
• /
• 2003

We examined the effect of p-substituents in p-substituted cinnamyl methyl ethers and 1-(p-substituted phenyl)allyl methyl ethers with CSI, and confirmed that the CSI reaction of allyl ethers (p-substituted ethers) is a competitive reaction of $S_Ni{\;}and{\;}S_N1$ mechanism according to the stability of the carbocation. And, the only terminal allylic amine was obtained through the migration reaction in thermodynamic reaction condition.

• Speech Sciences
• /
• v.13 no.2
• /
• pp.19-33
• /
• 2006

The purpose of this paper was to examine acoustical characteristics of phonatory offset-onset mechanism in the connected speech of female adults with stuttering and normal nonfluency. The phonatory offset-onset mechanism refers to the laryngeal articulatory gestures. Those gestures are required to mark word boundaries in phonetic contexts of the connected speech. This mechanism included 7 patterns based on the speech spectrogram. This study showed the acoustic features in the connected speech in the production of female adults with stuttering (n=1) and normal nonfluency (n=3). Speech tokens in V_V, V_H, and V_S contexts were selected for the analysis. Speech samples were recorded by Sound Forge, and the spectrographic analysis was conducted using Praat. Results revealed a stuttering (with a type of block) female exhibited more laryngealization gestures in the V_V context. Laryngealization gesture was more characterized by a complete glottal stop or glottal fry both in V_H and in V_S contexts. The results were discussed from theoretical and clinical perspectives.

• KSTLE International Journal
• /
• v.3 no.1
• /
• pp.43-48
• /
• 2002

Dry sliding wear and friction test of CrN coaling on two types of aluminum alloy substrates,6061 Al and 7075 Al deposited by arc ion plating, was peformed with a ball-on-disk tribometer. The effects of normal Bead and the mechanical properties of substrate on the friction coefficient and wear-resistance of CrN coating were investigated. The worn surfaces were observed by SEM. The results show that surface micro-hardness of CrN- coated 7075 Al is higher than that of CrN-coated 6061 Al. With an increase in normal lead, wear volume increases, while the friction coefficient decreases. The friction coefficient of CrN-coated 6061 Al is higher than that of CrN-coated 7075 Al, while the wear-resistance of CrN-coated 6061 Al is lower than the CrN-coated 7075 Al's, which indicates that the substrate mechanical properties have strong inf1uences on the friction coefficient and wear of CrN coating. The main wear mechanism was fragments of CrN coating, which were caused by apparent plastic deformation of substrate during wear test.

• Bulletin of the Korean Chemical Society
• /
• v.31 no.7
• /
• pp.1915-1919
• /
• 2010

Second-order rate constants $(k_N)$ have been measured for reactions of 2,4-dinitrophenyl phenyl carbonate (2) with a series of pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$ and compared with the $k_N$ values reported for the corresponding reactions of 2,4-dinitrophenyl benzoate (1) to investigate the effect of nonleaving group on reactivity and mechanism. The reactions of 2 result in larger $k_N$ values than those of 1. The Br${\o}$nsted-type plot for the reactions of 2 exhibits a downward curvature (i.e., ${\beta}2$ = 0.84 and ${\beta}1$ = 0.16), which is typical for reactions reported to proceed through a stepwise mechanism with a change in rate-determining step. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a{^{\circ}}$, has been found to be 8.5 and 9.5 for the reactions of 2 and 1, respectively. Dissection of $k_N$ into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1}$ ratio) has revealed that the reactions of 2 result in larger k1 values than those of 1, indicating that PhO behaves as a stronger electron-withdrawing group than Ph. However, the $k_2/k_{-1}$ ratio has been found to be independent of the electronic nature of Ph and PhO.