• Journal of the Korean Home Economics Association
• /
• v.36 no.8
• /
• pp.95-104
• /
• 1998

PET microfiber fabric dissociation reactions by ethylene glycol (EG) catalayzed by the corresponding EG anions were examined to provide an empirical basis for the improvement of a PET microfiber fabrics. The alkoxide ions, monosodium ethylene glycolate in ethylene glycol solution(MSEG-EG) are prepared by the reaction between NaH and the EG respectively. The dissociation reactions were carried out until the sample PET microfiber fabrics dissociate up to 80%. Temperature used ranged 100~$160^{\circ}C$. The kinetic behaviors of the dissociated PET microfiber fabrics were examined. The results are as follows : 1. In all cases, it was found that the PET-alkoxide dissociation rate constants increased exponentially with increasing temperature. The activation energies (Ea) of the reactions were 23.31kcal/mol in PET-EG system respectively. The calculated enthalpies of the activated [PET-EG] complexes from the corresponding Ea values were 22.53 ~ 22.61 kcal/mol, and the entropies were -19.03 ~ -19.24 kcal/mol/k respectively. 2. The kinetic behavior of the PET-alkoxide dissociation reactions examined was explained by the transition state theory. PET-alkoxide transition state is believed to be formed during the ester interchange mechanism between PET and MSEG-EG in the course of the PET dissociation reactions.

• Journal of the Korean Home Economics Association
• /
• v.50 no.5
• /
• pp.13-24
• /
• 2012

This study examined the effects of mothers' reactions toward children's negative emotion as well as mothers' emotional expressivity on children's social withdrawal. 206 children (103 boys, 103 girls; aged 4-5 years old) and their mothers participated in the study. Mothers reported their reactions to their child's negative emotion along with their expressivity. The teachers completed a rating scale to measure children's social withdrawal. The collected data was analyzed using descriptive statistics, Pearson's productive correlation coefficient, and hierarchical multiple regressions. The results showed a relation between mothers' distress reactions and punitive responses and children's social withdrawal. A mother's positive expressivity was negatively related to a child's social withdrawal. A hierarchical regression analysis indicated that the effects of mothers' punitive responses and minimization responses on children's withdrawal were moderated by a mother's positive expressivity. Mothers' punitive responses and minimization responses were positively associated with children's social withdrawal, especially for children who had the lowest level of mother's positive expressivity.

• Bulletin of the Korean Chemical Society
• /
• v.32 no.3
• /
• pp.964-972
• /
• 2011

This work investigated the difference between $Fe^{2+}$ autoxidation-induced and Fenton-type cleavage of pBR322 plasmid DNA. $^{\cdot}OH$ generation reactions in the absence and presence of $H_2O_2$ under various conditions were also investigated. Although both the $Fe^{2+}$ autoxidation and Fenton-type reactions showed DNA cleavage and $^{\cdot}OH$ generation, there were significant differences in their efficiencies and reaction rates. The rate and efficiency of the cleavage reaction were higher in the absence of 1.0 mM of $H_2O_2$ than in its presence in 20 mM phosphate buffer. In contrast, the $^{\cdot}OH$ generation reaction was more prominent in the presence of $H_2O_2$ and showed a pH-independent, fast initial reaction rate, but the rate was decreased in the absence of $H_2O_2$ at across the entire tested pH range. Studies using radical scavengers on DNA cleavage and $^{\cdot}OH$ generation reactions in both the absence and presence of $H_2O_2$ confirmed that both reactions spontaneously involved the active oxygen species $^{\cdot}OH$, ${O_2}^{\cdot-}$, $^1O_2$ and $H_2O_2$, indicating that a similar process may participate in both reactions. Based on the above observations, a new mechanism for the $Fe^{2+}$ autoxidation-induced DNA cleavage reaction is proposed.

• Journal of Electrochemical Science and Technology
• /
• v.7 no.4
• /
• pp.316-326
• /
• 2016

Development and discovery of efficient, cost-effective, and robust electrocatalysts are imperative for practical and widespread implementation of water electrolysis and fuel cell techniques in the anticipated hydrogen economy. The electrochemical reactions involved in water electrolysis, i.e., hydrogen and oxygen evolution reactions, are complex inner-sphere reactions with slow multi-electron transfer kinetics. To develop active electrocatalysts for water electrolysis, the physicochemical properties of the electrode surfaces in electrolyte solutions should be investigated and understood in detail. When electrocatalysis is conducted using nanoparticles with large surface areas and active surface states, analytical techniques with sub-nanometer resolution are required, along with material development. Scanning electrochemical microscopy (SECM) is an electrochemical technique for studying the surface reactions and properties of various types of electrodes using a very small tip electrode. Recently, the morphological and chemical characteristics of single nanoparticles and bio-enzymes for catalytic reactions were studied with nanometer resolution by combining SECM with atomic force microscopy (AFM). Herein, SECM techniques are briefly reviewed, including the AFM-SECM technique, to facilitate further development and discovery of highly active, cost-effective, and robust electrode materials for efficient electrolysis and photolysis.

• Bulletin of the Korean Chemical Society
• /
• v.25 no.10
• /
• pp.1538-1544
• /
• 2004

Fragmentations and proton transfer reactions of mono-, di-, and triethanolamines were studied using FTMS. It was found that the most abundant fragment ion was $[M-CH_2OH]^+$. The $[M-CH_2OH-H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. By increasing the ion trapping time in the ICR cell, the $[M+H]^+$ and $[M+H-H_2O]^+$ ions were notably increased for all the samples while the $[M+H-2H_2O]^+$ was observed in the mass spectra of diethanolamine and triethanolamine. The proton transfer reactions between the fragment ions and neutral molecules occurred predominantly by increasing the ion trapping time. The rate constants for the proton transfer reactions were calculated from experimental results. The proton transfer reaction of $CHO^+$ was the fastest one, which is consistent with the heats of reaction. The rate constants for proton transfer reactions of triethanolamine were much slower than those of ethanolamine and diethanolamine because of the steric hindered structure of triethanolamine. The plausible structures of observed ions and heats of reaction for proton transfer were calculated with AM1 semiempirical method.

• Proceedings of the Korean Society of Propulsion Engineers Conference
• /
• 2004.03a
• /
• pp.479-484
• /
• 2004

Reactions of NO$_{x}$, HO$_{x}$ and $O_3$ chemistry in a diffusion process of the exhaust plume under a stratospheric condition were investigated numerically. Expanding Box method was used to assess the effects of exhaust gases from a stratospheric flight system on $O_3$ depletions. Sensitivity analysis was also performed to identify prime reactions of $O_3$ depletions in an exhaust plume right after the nozzle. In addition, a calculation of reactive flows in stratospheric condition was performed to investigate the characteristics of reactions in a plume. As a result of this study, prime reactions of NO$_{x}$, HO$_{x}$ and $O_3$chemistry in an exhaust plume were identified, and fundamental behavior of chemical species were examined in a exhaust plume.t plume.

• Bulletin of the Korean Chemical Society
• /
• v.9 no.1
• /
• pp.55-59
• /
• 1988

The gaseous carbon dioxide has been irradiated with Co-60 gamma-radiation in the presence and absence of various alcohols, and the radiolysis products analyzed by gas chromatography. Experimental results indicate that no detectable amount of carbon monoxide is formed when pure carbon dioxide is irradiated. By adding small quantities of alcohols to carbon dioxide, however, considerable amount of carbon monoxide, ketones, alcohols and other organic products have been detected. By adding 0.1% of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-l-propanol, 2-butanol, and 2-methyl-2-propanol, G(CO) values obtained are 4.4, 4.5, 5.2, 4.4, 5.2, 5.0, 4.7 and 4.1, respectively. These high yields of carbon monoxide suggest that the oxidation reactions of carbon monoxide may be suppressed by scavenging oxygen atom with the alcohols. The main radiolytic decomposition reactions of the alcohols present in small quantity in carbon dioxide may be supposed to be the reactions with the oxygen atom produced by the radiolysis of carbon dioxide. The decomposition reactions seems to follow pseudo-first order kinetics with respect to the alcohols. The decomposition rate measured with 2-propanol is the fastest and that with 2-methyl-2-propanol the slowest. The mechanisms of the radiolytic decomposition reactions of the alcohols present in carbon dioxide are discussed on the basis of the experimental results of the present study.

• Bulletin of the Korean Chemical Society
• /
• v.18 no.8
• /
• pp.868-873
• /
• 1997

Nucleophilic substitution reactions of 1-phenylethyl chlorides (1-PEC; YC6H4CH(CH3)Cl) with phenoxides (XC6H4O-) and thiophenoxides (XC6H4S-) are investigated theoretically using the PM3 method. The Bronsted α and β values are greater for the phenoxides indicating a more advanced reaction in the transition state (TS) than for the thiophenoxides. This is supported by a greater magnitude of ρX (- 6.4 ∼ - 7.4) and ρXY (- 0.76) for the phenoxides than for the thiophenoxides (ρX = - 3.6 ∼ - 4.4 and ρXY = - 0.60). The percentage bond order changes, %Δn≠, suggest that the extents of bond making and breaking are similar for the phenoxides and hence the TS is symmetrical, but bond making is somewhat greater than bond cleavage for the thiophenoxides indicating an unsymmetrical TS. The reactions in the gas phase for both nucleophile series proceed by a SN2 mechanism with a tight TS and negative charge development on the reaction center carbon, Cα. The reactions in water investigated with model systems of benzyl and 1-phenylethyl chlorides using the Cramer-Truhlar solvation model (PM3-SM3) indicate that the reactions of 1-PEC are far more complex due to enhanced stabilization of the carbocation by the methyl substitution for a benzylic hydrogen.

• Bulletin of the Korean Chemical Society
• /
• v.22 no.7
• /
• pp.669-672
• /
• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the title reactions. The plot of kobs vs the concentration of alkali metal ethoxides is linear for the reactions performed in the presence of complexing age nt, 18-crown-6 ether, but curved upwardly for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions studied in this study behave as a catalyst. The catalytic effect was found to increase in the order Li+ << K+ ${\leq}$ Na+. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M+ ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M+/kEtO-) was found to be 2.3, 9.5 and 8.7 for the reaction of 8-(5-nitroquinolyl) 2-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, indicating that the catalytic effect is larger in the reaction of the former substrate than in that of the latter one. The larger catalytic effect was attributed to two possible complexing sites with alkali metal ions in the former substrate.

• Bulletin of the Korean Chemical Society
• /
• v.22 no.7
• /
• pp.673-677
• /
• 2001

Pseudo-first-order rate constants have been measured spectrophotometrically for the reactions of 8-(5-nitroquinolyl) 3-furoate with alkali metal ethoxides in anhydrous ethanol. The plot of kobs vs the concentration of alkali metal ethox ides is linear for the reactions performed in the presence of a complexing agent, 18-crown-6 ether, but exhibits upward curvatures for the corresponding reactions performed in the absence of the complexing agent, indicating that the alkali metal ions in this study behave as catalysts. Second-order rate constants were determined for the reactions with dissociated free ethoxide (kEtO-) and with ion paired alkali metal ethoxides (kEtO-M + ) from ion pairing treatments. The magnitude of catalytic effect (kEtO-M + /kEtO-) was found to be 1.7, 3.4 and 2.5 for the reaction of 8-(5-nitroquinolyl) 3-furoate, while 1.4, 3.6 and 4.2 for that of 4-nitrophenyl 2-furoate, 1.8, 3.7 and 2.4 for that of 8-(5-nitroquinolyl) benzoate, and 2.0, 9.8 and 9.3 for that of 8-(5-nitroquinolyl) 2-furoate with EtO- Li+ , EtO- Na+ and EtO- K+ , respectively. A 5-membered chelation at the leaving group is suggested to be responsible for the catalytic effect shown by alkali metal ions.