• Journal of the Korean Chemical Society
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• v.65 no.1
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• pp.9-14
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• 2021

In this study, the DFT calculation was performed using the B3LYP/6-31G(d,p) basis sets for the reaction process in which phenanthrene decomposes due to the chain reaction of two OH radicals on phenanthrene in the gaseous state of 298 K at 1 atm. As a result of the calculation, even when two OH radicals act on phenanthrene in a chain, the reaction for producing phenanthren-9-ol is predicted to be more advantageous than the reaction for producing phenanthren-1-ol. On the other hand, it was predicted that the OH addition process at room temperature would be advantageous for the priority of the OH addition and H abstraction process.

• Korean Chemical Engineering Research
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• v.53 no.1
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• pp.83-90
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• 2015

In this study, we investigated optimum conditions for the introduction of a lot of free radical polymerizable methacrylate groups on the multi-walled carbon nanotube (MWCNT) surface. Carboxyl groups were introduced first on MWCNT surfaces by treating with a mixture of sulfuric acid and nitric acid with ultrasonic bath for 2 hours, and oxidized MWCNTs were reacted further with thionyl chloride followed by triethylenetetramine (TETA) to introduce amino groups on the oxidized MWCNT surface, to make MWCNT-$NH_2$. To introduce free radical polymerizable methacrylate groups on the MWCNT-$NH_2$, MWCNT-$NH_2$ was reacted with 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) by Michael addition reaction. We investigated progress of modification reactions for MWCNT by fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and elemental analysis (EA). We found maximum degree of Michael addition reactions between AHM and TETA grafted on MWCNT-$NH_2$ for 10:1 mol ratio and 8 hour reaction time in our reaction conditions.

• Bulletin of the Korean Chemical Society
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• v.23 no.9
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• pp.1263-1307
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• 2002

Pseudo-first-order rate constants (kobs) have been determined for the nucleophilic substitution reactions of p-nitrophenyl diphenyl phosphinate (PNPDPP) with substituted phenoxides (XC6H4O - ) and butane-2,3-dione monoximate (Ox- ) in 0.1 M borate buffer (pH = 10.0) at 25.0 ${\pm}0.1^{\circ}C$. The kobs value increases sharply upon addition of cethyltrimethylammonium bromide (CTAB) to the reaction medium up to near 7 ${\times}$ 10-4 M CTAB and then decreases smoothly upon further addition of CTAB. The rate enhancement upon the addition of CTAB is most significant for the reaction with -O2CC6H4O- and least significant for the one with C6H5O- , indicating that the reactivity of these aryloxides in the presence of CTAB cannot be determined by the basicity alone. The strength of the interaction of these anionic aryloxides with the positively charged micellar aggregates has been suggested to be an important factor to determine the reactivity in the presence of CTAB. The kobs value for the reaction with Ox- increases also upon the addition of CTAB. However, the increase in the kobs value is much more significant for the reaction with Ox- than for the one with ClC6H4O- , indicating that Ox- is less strongly solvated than ClC6H4O- in H2O. The ${\alpha}-effect$ shown by Ox- in H2O has been attributed to the ground-state solvation difference between Ox- and ClC6H4O- .

• Textile Coloration and Finishing
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• v.24 no.1
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• pp.39-44
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• 2012

To improve flame retardation of poly(ethylene terephthalate) (PET) against burning, resorcinol bis(diphenyl phosphate) (RDP), phosphorous containing flame retardant, was incorporated into PET backbone by radical reaction pathway. Radical endcapping of PET with RDP was confirmed by spectroscopic and thermal analysis. From 400 MHz $^{31}P$ solid state FT-NMR spectrum of PET with RDP (PET-RDP), phosphorus spectra peak in RDP was found at ca. -10 ppm. Furthermore, P-C bond stretching vibration peaks were found ca. $530cm^{-1}$ in FT-IR spectrums of PET-RDP. These results indicated that RDP can be chemically bound at the ends of PET by radical addition method. Thermal characteristics of pure PET (pPET) and PET-RDP were measured and evaluated by TGA thermal analysis. There was not significant changes in thermal characteristics of PET-RDP compared to that of pPET.

• Bulletin of the Korean Chemical Society
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• v.19 no.7
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• pp.776-779
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• 1998

Second-order rate constants have been measured spectrophotometrically for the addition reaction of a series of alicyclic amines to 3-butyn-2-one to yield their respective enamines at 25.0 'C. The reactivity of the amines increases with increasing the basicity of the amines. However, the Bronsted-type plot obtained exhibits a downward curvature as the basicity of the amines increases, i.e. βnuc decreases from 0.3 for low basic amines (pKa < 9) and to 0.1 for highly basic amines (pKa > 9). Such a curvature in the Bronsted-type plot is clearly indicative of a change in the reaction mechanism or transition state structure. From the corresponding reactions run in D2O, the magnitude of kinetic isotope effect (KIE) has been calculated to be about 0.8 for highly basic amines and 1.21 for weakly basic amines. The difference in the magnitude of KIE also supports a change in the reaction mechanism or transition state structure upon changing the basicity of the amines. Furthermore, the small KIE clearly suggests that H+ transfer is not involved in the rate-determining step, i.e. the addition reaction is considered to proceed via a stepwise mechanism in which the attack of the amines to the acetylene is the rate-determining step. The curvature in the Bronsted-type plot has been attributed to a change in the degree of bond formation between the amine and the acetylene.

• Journal of Life Science
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• v.5 no.4
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• pp.155-161
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• 1995

The effects of substrate concentration, enzyme concentration, reaction temperature, and water content were investigated in intramolecular esterification. This study used cyclohexane as organic solvent, power lipase as enzyme, and benzyl alcohol and octanoic acid as substrate. The initial reaction rate was found to be proportional to enzyme concentration; followed Michaelis-Menten equation for octanoic acid; and was inhibited by benzyl alcohol . The observed initial reaction rate first increased, then decreased with increasing reaction temperature, giving rise to the maximum rate at 20$\circ$. The drop in the reaction rate at higher temperature was to partition equilibrium change of substrate between organic solvent and hydration layer of enzyme molecule in addition to the deactivation by enzyme denaturation. Water layer surrounding enzyme molecule seemed to activate in organic solvent and the realistic reaction was done in the water layer. In the enzymatic reaction in organic solvent, the initial reaction rate was influenced by partition quilibrium of substrate, so the optimum condition of substrate concentration, enzyme concentration, reaction temperature, and water content would give a good design tool.

• Bulletin of the Korean Chemical Society
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• v.18 no.4
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• pp.374-379
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• 1997

The rate constants for the nucleophilic addition of thiophenol derivatives (p-OCH3, H, p-CH3, m-CH3, p-Br and p-NO2) to 4'-[N-(9-acridinyl)]-1'-(N-methanesulfonyl)-3'-methoxyquinonediimide (AMQD) were determined by ultraviolet spectrophotometer in water at 5 ℃, and rate equations which can be applied over a wide pH range were obtained. On the basis of pH-rate profile, Bronsted plot, adduct analysis, general base catalysis and substituent effect, a plausible mechanism of this addition reaction was proposed: Below pH 2.5, the reaction proceeded by the addition of thiophenol molecule to 6'-position of quinonoid after protonation at the acridinyl nitrogen. Above pH 6.2, the addition of sulfide anion to 6'-position of quinonoid was rate controlling. However, in the range of pH 3.0-6.0, these two reactions occured competively.

• Journal of the Korean Wood Science and Technology
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• v.40 no.2
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• pp.110-122
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• 2012

This study investigated the effects of layered clay on the thermal curing behavior and tensile properties of resole phenol-formaldehyde (PF) resin/clay/cellulose nanocomposites. The thermal curing behavior of the nanocomposite was characterized using conventional differential scanning calorimetry (DSC) and temperature modulated (TMDSC). The addition of clay was found to accelerate resin curing, as measured by peak temperature ($T_p$) and heat of reaction (${\Delta}H$) of the nanocomposite’ curing reaction increasing clay addition decreased $T_p$ with a minimum at 3~5% clay. However, the reversing heat flow and heat capacity showed that the clay addition up to 3% delayed the vitrification process of the resole PF resin in the nanocomposite, indicating an inhibition effect of the clay on curing in the later stages of the reaction. Three different methods were employed to determineactivation energies for the curing reaction of the nanocomposite. Both the Ozawa and Kissinger methods showed the lowest activation energy (E) at 3% clay content. Using the isoconversional method, the activation energy ($E_{\alpha}$) as a function of the degree of conversion was measured and showed that as the degree of cure increased, the $E_{\alpha}$ showed a gradual decrease, and gave the lowest value at 3% nanoclay. The addition of clay improved the tensile strengths of the nanocomposites, although a slight decrease in the elongation at break was observed as the clay content increased. These results demonstrated that the addition of clay to resole PF resins accelerate the curing behavior of the nanocomposites with an optimum level of 3% clay based on the balance between the cure kinetics and tensile properties.

• Journal of the Korean Chemical Society
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• v.33 no.1
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• pp.127-134
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• 1989

The rate constants of the nucleophilic addition reaction of 3-mercaptopropionic acid to the ${\beta},\;{\beta}$-diethoxycarbonylstryene derivatives (H, p-OCH$_3$, 3,4,5-(OCH$_3)_3$, 3,4-methylenedioxy) were determined by ultraviolet spectrophotometry, and rate equation which could be applied over a wide pH range was obtained. On the basis of pH-rate profile and the presence of general base catalysis, a plausible mechanism of this addition reaction was propound:Below pH 6.0 the reaction was initiated by the addition of neutral 3-mercaptopropionic acid molecule, and in the range of pH 6.0∼8.0, a neutral 3-mercaptopropionic acid molecule and a sulfide anion competitively attacked to the double bond. Above pH 8.0, the reaction proceeded through the addition of a sulfide anion.

• Transactions of the Korean hydrogen and new energy society
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• v.30 no.6
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• pp.593-600
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• 2019

The combustion characteristics of methane/hydrogen pre-mixed flame have been investigated with swirl stabilized flame in a laboratory-scale pre-mixed combustor with constant heat load of 5.81 kW. Hydrogen/methane fuel and air were mixed in a pre-mixer and introduced to the combustor through a burner nozzle with different degrees of swirl angle. The effects of hydrogen addition and swirl intensity on the combustion characteristics of pre-mixed methane flames were examined using particle image velocimetry (PIV), micro-thermocouples, various optical interference filters and gas analyzers to provide information about flow velocity, temperature distributions, and species concentrations of the reaction field. The results show that higher swirl intensity creates more recirculation flow, which reduces the temperature of the reaction zone and, consequently, reduces the thermal NO production. The distributions of flame radicals (OH, CH, C₂) are dependent more on the swirl intensity than the percentage of hydrogen added to methane fuel. The NO concentration at the upper part of the reaction zone is increased with an increase in hydrogen content in the fuel mixture because higher combustibility of hydrogen assists to promote faster chemical reaction, enabling more expansion of the gases at the upper part of the reaction zone, which reduces the recirculation flow. The CO concentration in the reaction zone is reduced with an increase in hydrogen content because the amount of C content is relatively decreased.