• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3587-3591
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• 2011

The reactions of O,O-diethyl Z-S-aryl phosphorothioates with X-benzylamines are kinetically investigated in dimethyl sulfoxide at $85.0^{\circ}C$. The Hammett (log $k_2$ vs ${\sigma}x$) and Br$\ddot{o}$nsted [log $k_2$ vs $pK_a$(X)] plots are biphasic concave downwards for substituent X variations in the nucleophiles with a break point at X = H. The signs of the cross-interaction constants (${\rho}xz$) are positive for both the strongly and weakly basic nucleophiles. Considerably great magnitude of ${\rho}xz$ (= 6.56) value is observed with the weakly basic nucleophiles, while ${\rho}xz$ = 0.91 with the strongly basic nucleophiles. Proposed reaction mechanism is a stepwise process with a rate-limiting leaving group expulsion from the intermediate involving a backside nucleophilic attack with the strongly basic nucleophiles and a frontside attack with the weakly basic nucleophiles. The kinetic results are compared with those of the benzylaminolysis of O,O-diphenyl Z-S-aryl phosphorothioates.

• Bulletin of the Korean Chemical Society
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• v.18 no.5
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• pp.523-527
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• 1997

Apparent second-order rate constants (kapp) have been measured spectrophotometrically for the reaction of 2,4-dinitrophenyl benzoate (DNPB) with 6 secondary cyclic amines in H2O containing 20 mole% DMSO at 25.0±0.1 ℃. The Bronsted-type plot (log kapp vs. pKa) shows a break at pKa near 9.1, e.g. two straight lines with βapp values of 0.67 and 0.44 for the low basic (pKa < 9.1) and the highly basic (pKa > 9.1) amines, respectively. Using an estimated k2 value of 3×109 sec-1, all the other microconstants (k1, k-1 and K) involved in the present aminolysis have been calculated. The k value decreases with increasing the basicity of amines while k1 and K values increase with increasing the amine basicity, as expected. Good linear Bronsted-type plots have been obtained for these microconstants of the present aminolysis of DNPB. The magnitudes of the slope of the Bronsted-type plots, k1 and k-1 have been calculated to be 0.43 and - 0.24, respectively, indicating the k-1 step is about two folds less sensitive than the k1 step to the amine basicity. The K value has been calculated to be 0.66, which appears to be much smaller than the one for other aminolyses showing general base catalysis. The small K value has been attributed to the absence of general base catalysis in the present aminolysis of DNPB.

• Environmental Engineering Research
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• v.24 no.2
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• pp.202-210
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• 2019

In order to maximize the utilization of sewage sludge, a waste from wastewater treatment facility, the residual sewage sludge generated after lipid and carbohydrate extraction for biodiesel and bioethanol production was used to produce bio-oil by pyrolysis. Thermogravimetric analysis showed that sludge pyrolysis mainly occurred between 200 and $550^{\circ}C$ (with peaks formed around 337.0 and $379.3^{\circ}C$) with the decomposition of the main components (carbohydrate, lipid, and protein). Bio-oil was produced using a micro-tubing reactor, and its yield (wt%, g-bio-oil/g-residual sewage sludge) increased with an increase in the reaction temperature and time. The maximum bio-oil yield of 33.3% was obtained after pyrolysis at $390^{\circ}C$ for 5 min, where the largest amount of energy was introduced into the reactor to break the bonds of organic compounds in the sludge. The main components of bio-oil were found to be trans-2-pentenoic acid and 2-methyl-2-pentenoic acid with the highest selectivity of 28.4% and 12.3%, respectively. The kinetic rate constants indicated that the predominant reaction pathway was sewage sludge to bio-oil ($0.1054min^{-1}$), and subsequently to gas ($0.0541min^{-1}$), rather than the direct conversion of sewage sludge to gas ($0.0318min^{-1}$).

• Transactions of the Korean hydrogen and new energy society
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• v.6 no.2
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• pp.85-90
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• 1995

Activation behavior, hydriding rate and disintegration were tested for hydrogen storage alloy particles fixed in an adhesive after treating with inorganic solution. Commertial adhesive as a binder was used. Chemical-treated particles showed the best characteristics for activation and a little effect of prevention the break down of the powders themselves after several repeated operations. Furthermore activation characteristics were found to show a similar trend to chemical-treated powders even in the fixed one with an adhesive, except for a slight decrease in reaction velocity.

• Bulletin of the Korean Chemical Society
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• v.33 no.10
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• pp.3203-3207
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• 2012

The nucleophilic substitution reactions of diisopropyl chlorothiophosphate (5) with X-pyridines have been kinetically studied in MeCN at $35.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for the substituent X variations in the nucleophiles show biphasic concave upwards with a break point at X = 3-Ph. The pyridinolysis rate of 5 exhibits great negative deviation from the Taft plot. A concerted $S_N2$ mechanism is proposed involving a change of the attacking direction of the X-pyridines from a frontside attack with the strongly basic pyridines to a backside attack with the weakly basic pyridines.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1829-1834
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• 2013

The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at $75.0^{\circ}C$. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ${\rho}_{XY}$ values, respectively. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.

• Proceedings of the KIEE Conference
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• 1988.11a
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• pp.179-182
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• 1988

This study is to investigate the adhesive strength of composite material's interface on the experimental methode of tree growth in the material. The results are as fellows 1) The irradiations of ultrasonic energy cause the mechanical vibration in the polymer composite materials of fluid state, so then bring about physical dispersion and heat form inorganic materials, being supposed to produce chemical crosslinking reaction, decreasing of voids between filler and matrix. 2) The characterics of the breakdown are increased by using coupling agent in the composite material. 3) As the intensity of ultrasonic energy and its irradiated time are larger, the tree inception and break-down voltages increase and the tree growing is slower. so we obtain that the interface adhesive force tan be strengthened by the irradiation of ultrasonic energy.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1754-1758
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• 2014

The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at $35.0^{\circ}C$. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ${\rho}_{XY}$) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

• Fibers and Polymers
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• v.5 no.1
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• pp.59-67
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• 2004

The development of high tenacity, high modulus monofilaments from Polypropylene/Clay nanocomposite has been investigated. Pure sodium montmorillonite nanoclay was modified using hexadecyl trimethyl ammonium bromide (HTAB) via an ion exchange reaction. Pure and modified clay were characterized through X-ray diffraction, FTIR and TGA. The modified clay was melt blended with polypropylene (PP) in presence of a swelling agent. Composite filaments from PP/Clay nanocomposite were prepared at different weight percentages of nanoclay and the spinning and drawing conditions were optimized. The filaments were characterized for their mechanical, morphological and thermal properties. The composite PP filaments with modified clay showed improved tensile strength, modulus and reduced elongation at break. The composite filaments with unmodified clay did not show any improvement in tensile strength but the modulus improved. The sharp and narrow X-ray diffraction peaks of PP/nanoclay composite filaments indicate increase in crystallinity in presence of modified clay at small loadings (0.5 %). The improved thermal stability was observed in filaments with modified as well as unmodified clays.

• Transactions of the Korean Society of Mechanical Engineers
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• v.7 no.3
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• pp.328-334
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• 1983

The turbulent hydrogen-air diffussion flame was studied experimentally and theoretically. Laser Doppler anemometer was used to measure the velocity field in the flame. Two mathematical models for the combustion reaction term, which are infinite rate model and finite rate to be derived eddy break-up model, were tested by comparing predictions with experimental data for coaxial turbulent diffusion flame. The agreement between the predictions and the data is, on the whole, very good in the case of employing the finite rate model rather than the infinite rate model. But, it was shown that the finite rate model was practically applicable to the predictions of the turbulent diffussion flame structure.