• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2260-2264
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• 2012

The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of dimethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for substituent X variations in the nucleophiles exhibit two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with a rate-limiting expulsion of the isothiocyanate leaving group from the intermediate. The relatively large ${\beta}x$ values imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb. The steric effects of the two ligands play an important role to determine the pyridinolysis rates of isothiocyanophosphates.

• Bulletin of the Korean Chemical Society
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• v.20 no.7
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• pp.805-808
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• 1999

Second-order-rate constants (kN) have been measured spectrophotometrically for the reactions of 4-nitrophenyl 2-furoate (1) with a series of secondary alicyclic amines in H2O containing 20 mole % DMSO at 25.0℃. 1 is about 5-8 times more reactive than 4-nitrophenyl benzoate (2), although 1 is expected to be less reactive than 2 based on MO calculations and 13 C NMR study. The Brфnsted-type plots for the aminolysis reactions of 1 and 2 are linear with βnuc values of 0.78 and 0.85, respectively. The replacement of the CH=CH group by an O atom in the acyl moiety (2->1) does not cause any mechanism change. The reaction of piperidine with a series of substituted phenyl 2-furoates gives a linear Hammett plot with a large ρ- value (ρ- = 2.88) when σ- constants are used. The linear Brфnsted and Hammett plots with a large ρ- value suggest that the aminolysis reaction of 1 proceeds via rate-determining break-down of the addition intermediate to the porducts.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 1994.05a
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• pp.108-110
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• 1994

Decomposition products by crosslinking reaction of PE using Dicumylperoxide(DCP) should influence on the electrical properties in XLPE. This paper studies on Behaviors of Decomposition products and Electrical Treeing ding to Drying condition. We used the Gas Chromatography for Decomposition Gases analysis FT-IR for investigating the behaviors of Decomposition products remained in XLPE Break Down Voltage Tester for Electrical Treeing measurement.

• Macromolecular Research
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• v.10 no.2
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• pp.108-114
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• 2002

Poly(butylene succinate) (PBS) prepolymers were prepared by the condensation polymerization of 1,4-butanediol (1,4-BD) and succinic atid (SCA) in the presence of titanium (VI) isoproxide(TPI) catalyst. The PBS prepolymers reacted with 1,4-BD or SCA to obtain hydroxyl or carboxylic acid group terminated PBS. High molecular weight linear or branched PBS was synthesized by a coupling reaction between hydroxyl and carboxylic acid group terminated PBS, or by a branching reaction between carboxylic acid group terminated PBS and glycerol as a branching agent. The weight average molecular weight of the prepared linear or branched PBS was in the range of 100,000-220,000. Both melting point and thermal stability of the high molecular weight linear and branched PBSs were somewhat higher than those of general PBS. From a tensile behavior by Instron test, modulus, tensile strength and elongation at break improved with increase in the molecular weight of the prepared PBS through the coupling or the branching reaction. In particular, the high molecular weight linear PBS had about 2.5 times higher value in modulus than the branched one.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1329-1332
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• 2014

The kinetic studies on the reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-pyridines have been carried out in dimethyl sulfoxide. The free energy correlations with X in the nucleophiles are biphasic concave upwards with a break point at X = H, while those for substituent Z variations in the leaving groups are linear. The negative sign of ${\rho}_{XZ}$ implies that the reaction proceeds through a concerted mechanism for both the strongly and weakly basic pyridines. The biphasic concave upward free energy relationships with X are rationalized by a change in the nucleophilic attacking direction from frontside with the strongly basic pyridines to backside with the weakly basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4387-4391
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• 2011

The kinetic studies on the pyridinolysis of diisopropyl thiophosphinic chloride have been carried out in acetonitrile at $55.0^{\circ}C$. The free energy correlations for substituent X variations in the X-pyridines are biphasic concave upwards with a break point at X = 3-Ph. A concerted SN2 mechanism is proposed with a change of the attacking direction of the X-pyridine from a frontside attack for the strongly basic pyridines to a backside attack for the weakly basic pyridines. The factors to determine the rates and thio effects on the rates for the pyridinolyses of thiophophinic chloride, chlorothiophosphate, phosphinic chloride, phosphonochloridothioate, and chlorophosphate systems are briefly reviewed on the basis of the magnitude of the positive charge of the reaction center P atom and steric effects of the two ligands.

• Journal of the Korean institute of surface engineering
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• v.32 no.3
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• pp.336-339
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• 1999

Photo-excited $TiO_2$ surface has a strong ability to induce various chemical reactions. Our study concentrates mainly on the utilisation of light energy to induce reactive radicals for environmental protection application. For instance, we have successfully used TiO$_2$ to break down foul smelling substances in air. In order to retain and separate the $TiO_2$ catalyst from the reactants and products, $TiO_2$ was immobilised by fixing onto various substrates. $TiO_2$ catalyst coated onto glass, wall paper and painted panel was found to show significant deodorising effect. The deodorising effect continues as long as$TiO_2$ is exposed to light irradiation.

• Journal of the Korean Society of Safety
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• v.9 no.1
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• pp.100-109
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• 1994

In this study, it is investigated that the possibility of the numerical simulation for the incineration of the hazardous material, crbon tetrachloride($CCl_4$). A 3-dimensional numerical technology is applied for turbulent reacting flows of the full-scale Dow Chemical incinerator. The calculations are made by a CRAY-2S, super computer. The major parameters considered in this study are kiln revolution rate (rpm), filling ratio of the solid waste(f), burner Injection velocity and angle, and turbulent air jets for swirl. And the employed turbulent reaction model is the eddy break-up model which is a kind of fast chemistry model assuming general equilibrium and used for a premixed flame. The calculated flow fields are presented and discussed. 1) The presence of turbulent air nozzles for swirl gives rise to visible increase of the convective motion over the region of the solid waste. This implies the possibility to enhance the mixing of the waste with the surrounding all and thereby to reduce thermal and species stratification, which were reported in a large rotary kiln operation. 2) Considering that the location of the recirculation region has a strong relation with the heating rate of the solid waste, the control of the recirculation region by the burner injection angle Is quite desirable in the sense of the flexible design of the rotary kiln incinerator for a carbon tetrachloride. 3) Finally, it is found that the eddy break-up model Is not suitable for carbon tetrachloride($CCl_4$) because this model is not incorporated the flame inhibition trend due to the presence $CCl_4$compound.

• The Journal of Korean Physical Therapy
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• v.30 no.5
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• pp.187-192
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• 2018

Purpose: This study compared the functional fitness and brake response of elderly and young drivers to confirm the correlation between the functional fitness and brake response. Methods: This study was a cross sectional observational design. Older drivers (>65age, n=21) and young adult drivers (20-40aged, n=20) were enrolled as subjects. The functional fitness of the subjects was measured using a senior fitness test consisting of a back scratch (BS), chair sit and reach (CSR), arm curl (AC), chair stand up (CSU), foot up and go (8-FUG), and 2-minute step (2-MS). The brake response used the virtual driving simulator to measure the brake reaction time (BRT) and braking distance (BD) according to the pedestrian protection and traffic signal compliance. Results: The older drivers had a lower BS (p<0.000), CSU (p=0.040), and 8-FUG (p=0.011) than the young adult drivers. BS and 8-FUG showed a significant positive correlation with the BRT and BD of pedestrian protection and traffic signal compliance. CSU showed a significant negative correlation with the BRT of pedestrian protection and traffic signal compliance. Conclusion: These findings suggest that the flexibility of the upper extremity, lower extremity strength, and agility are strongly correlated with the driving performance of elderly drivers.

• Bulletin of the Korean Chemical Society
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• v.35 no.5
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• pp.1460-1464
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• 2014

The substituent effects on the pyridinolysis (XC5H4N) of Y-aryl ethyl chlorophosphates are investigated in acetonitrile at $35.0^{\circ}C$. The two strong ${\pi}$-acceptor substituents, X = 4-Ac and 4-CN in the X-pyridines, exhibit large positive deviations from the Hammett plots but little positive deviations from the Br$\ddot{o}$nsted plots. The substituent Y effects on the rates are really significant and the Hammett plots for substituent Y variations in the substrates invariably change from biphasic concave downwards via isokinetic at X = H to biphasic concave upwards with a break point at Y = 3-Me as the pyridine becomes less basic. These are interpreted to indicate a mechanistic change at the break point from a stepwise mechanism with a rate-limiting bond formation (${\rho}_{XY}$ = -6.26) for Y = (4-MeO, 4-Me, 3-Me) to with a rate-limiting leaving group expulsion from the intermediate (${\rho}_{XY}$ = +5.47) for Y = (4-Me, H, 3-MeO). The exceptionally large magnitudes of ${\rho}_{XY}$ values imply frontside nucleophilic attack transition state.