• Bulletin of the Korean Chemical Society
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• v.28 no.2
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• pp.220-224
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• 2007

Second-order rate constants (kN) have been determined spectrophotometrically for reactions of 2,4-dintrophenyl 2-furoate (2) with a series of alicyclic secondary amines in 80 mol % H2O/20 mol % dimethyl sulfoxide (DMSO) at 25.0 oC. The furoate 2 is more reactive than 2,4-dintrophenyl benzoate (1) toward all the amines studied. The higher acidity of 2-furoic acid (pKa = 3.16) compared with benzoic acid (pKa = 4.20) has been suggested to be responsible for the reactivity order, at least in part. The Brønsted-type plots for the reactions of 1 and 2 are curved downwardly, indicating that the aminolyses of both 1 and 2 proceed through a zwitterionic tetrahedral intermediate (T±) with a change in the rate-determining step on changing the amine basicity. Dissection of the kN values into their microscopic rate constants has revealed that the pKao and k2/k-1 ratios for the reactions of 1 and 2 are identical, indicating that the nature of the nonleaving group (i.e., benzoyl and 2-furoyl) does not affect the reaction mechanism. The k1 values have been found to be larger for the reactions of 2 than for those of 1, which is fully responsible for the fact that the former is more reactive than the latter.

• Bulletin of the Korean Chemical Society
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• v.33 no.7
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• pp.2269-2273
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• 2012

Pseudo-first-order rate constants $k_{amine}$ have been measured spectrophotometrically for the reactions of benzyl 4-pyridyl carbonate 6 with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. The plots of $k_{amine}$ vs. [amine] curve upward, indicating that the reactions proceed through a stepwise mechanism with two intermediates, a zwitterionic tetrahedral intermediate $T^{\pm}$ and its deprotonated form $T^-$. This contrasts to the report that the corresponding reactions of benzyl 2-pyridyl carbonate 5 proceed through a forced concerted pathway. The $k_{amine}$ values for the reactions of 6 have been dissected into the second-order rate constant $Kk_2$ and the thirdorder rate constant $Kk_3$. The Br${\o}$nsted-type plots are linear with ${\beta}_{nuc}=0.94$ and 1.18 for $Kk_2$ and $Kk_3$, respectively. The $Kk_2$ for the reaction of 6 is smaller than the second-order rate constant $k_N$ for the corresponding reaction of 5, although 4-pyridyloxide in 6 is less basic and a better nucleofuge than 2-pyridyloxide in 5.

• Journal of the Korean Chemical Society
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• v.50 no.3
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• pp.247-255
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• 2006

The purpose of this study was to investigate the correlation between concepts on chemical reaction rates and concepts on chemical equilibrium in high school students. The subjects of the investigation consisted of 120 third grade students attending high school in K city of Kyunggi province. For this study, questionnaire relevant to the subject of chemical reaction rates and chemical equilibrium was developed and the answers were analyzed. As a result of the study, a large percentage of high school students answered questions on reaction rates correctly, but only a small percentage of the students could give explanations. Many high school students answered questions on the rates of forward reactions correctly, but not the questions on the rates of reverse reactions. For the concepts on chemical equilibrium, many high school students gave correct answers when faced with equilibrium questions that only required the understanding of one side of the reaction. But the students could not answer the questions requiring understanding of both forward and reverse reactions as well. Overall, there was a little high correlation between concepts on chemical reaction rates and concepts on chemical equilibrium in high school students. Especially, high school students with little understanding of reverse reaction rates did not understand that chemical equilibrium is a dynamic equilibrium. Also, high school students with little understanding of the collision mechanism regarding chemical reaction rates did not understand the effect of concentration and catalyst factors on chemical equilibrium. And the correlation between concepts on chemical reaction rates and concepts on chemical equilibrium related to concentration and catalyst factors was low. In conclusion, the formation of scientific concepts on chemical reactions rates can decrease misconceptions on chemical equilibrium. Also the teaching-learning method limited to one side of a reaction can cause difficulty in forming the concepts on chemical dynamic equilibrium. Therefore, the development of a teaching-learning method which covers both the forward and reverse reactions can be effective in helping students form the concepts on chemical equilibrium.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.589-596
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• 2012

In this paper, the reactive dynamics properties of the reactions Ba + $C_6H_5Br$ and Ba + m-$C_6H_4CH_3Br$ were studied by means of the quasi-classical trajectory method based on the London-Eyring-Polanyi-Sato potential energy surfaces. The vibrational distributions, reaction cross sections, rotational alignments of the products BaBr all were obtained. The peak values of the vibrational distributions are located at $\nu$ = 0 for the reactions Ba + $C_6H_5Br$ and Ba + m-$C_6H_4CH_3Br$ when the collision energies are 1.09 and 1.10 eV, respectively. The reaction cross sections increase with the increasing collision energy, which changes from 0.6 to 1.5 eV. The product rotational alignments deviate from -0.5 and firstly increase and then decrease while the collision energy is increasing, just like that of Heavy+Light-Light system.

• International Journal of Aeronautical and Space Sciences
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• v.17 no.4
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• pp.455-466
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• 2016

Chemical-kinetic parameters of the equilibrium constants to evaluate the reverse rate coefficients in the shock layer of a blunt body and the expanding flows are derived for the temperature range from 300 K to 20,000 K. The expanded equilibrium constants for the chemical reactions of the dissociation, ionization, associative ionization, and neutral and charge exchange reactions of the atmospheric species and carbon materials are proposed in the present work. In evaluating the equilibrium constants, the inter-nuclear potential energies of the molecular species are calculated by the analytical potential function of the Hulburt-Hirschfelder model, and the parameters of the analytical model are determined from the semi-classically calculated RKR potentials. The electronic states and energies of the atoms are calculated by the electronic energy grouping model, and the rovibrational states and energies of each electronic states of the molecules are evaluated by the WKB method. The expanded equilibrium constants for 31 types of the reactions are provided for the best curve-fit functions, and the recombination reaction rate coefficients evaluated from the present equilibrium constants are compared with existing measured values.

• Journal of Korean Society for Atmospheric Environment
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• v.21 no.E3
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• pp.75-85
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• 2005

A mathematical sensitivity analysis of the flow-through dynamic flux chamber technique, which has been utilized usually for various trace gas flux measurement from soil and water surface, was performed in an effort to provide physical and mathematical understandings of parameters essential for the NO flux calculation. The mass balance equation including chemical reactions was analytically solved for the soil NO flux under the steady state condition. The equilibrium concentration inside the chamber, $C_{eq}$, was found to be determined mainly by the balance between the soil flux and dilution of the gas concentration inside the chamber by introducing the ambient air. Surface deposition NO occurs inside the chamber when the $C_{eq}$ is greater than the ambient NO concentration ($C_{0}$) introducing to the chamber; NO emission from the soil occurs when the $C_{eq}$ is less than the ambient NO concentration. A sensitivity analysis of the significance of the chemical reactions of NO with the reactive species (i.e. $HO_{2},/CH_{3}O_{2},/O_{3}$) on the NO flux from soils was performed. The result of the analysis suggests that the NO flux calculated in the absence of chemical reactions and wall loss could be in error ranges from 40 to $85\%$ to the total flux.

• Korean Journal of Veterinary Pathology
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• v.1 no.1
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• pp.40-45
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• 1997

The phototoxic potentials of LB20304a a new quinolone compound being developed by LG Chemical Ltd, and reference compounds (Ciprofloxacin; CPFX, Enoxacin; ENX and Lomefloxacin; LFLX) were compared in a murine model. in addition photostability of these compunds was studied after irradiation with long-wave UV light(UVA, 0, 0.3 1 or 3 Joule/$Cm^2$) When hairless mice(9 to 11 weeks old 19-26g) were orally administered with different dose levels of test compunds and exposed to UVA(40J/$cm^2$) inflammatory reactions were observed in a dose dependent manner. Among the compounds tested, LB20304a demonstrated the least phototoxic effects and showed no inflammatroy lesions at a dose level of 100mg.kg (Low dose). ENX and LFLX demonstrated much greater phototoxic reactions while CPFX showed similar or slightly greater phototoxic reactions compared to LB20304a. Similar to the in-vivo results the solutions of LB20304a and CPFX irradiated with UVA demonstrated reduced spectral changes compared to those of ENX and LFLX. In conclusion these data suggest that phototoxic potencies of the quinolones tested were; LFLX > ENX > CPFX $\geq$ LB20304a. No phototoxic dose of LB20304a in mice was 100 mg/kg.

• The KSFM Journal of Fluid Machinery
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• v.14 no.6
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• pp.61-67
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• 2011

The study is to analyze the chemical and heat-flow reactions in the hydrogen generation unit(autothermal reformer), using computational numerical tools. Autothermal reformer(ATR) is involved in complex chemical reaction, mass and heat transfer due to exothermic and endothermic reactions. Therefore it is necessary to reveal the effects of various operation parameters and geometries on the ATR performance by using numerical analysis. Numerical analysis needs to dominant chemical reactions that includes Full Combustion(FC) reaction, Steam Reforming(SR) reaction, Water-Gas Shift(WGS) reaction and Direct Steam Reforming(DSR) reaction. The objective of the study is to improve theoretically the reformer design capability for the goal of high hydrogen production in the autothermal reformer using methane. Hydrogen production reached maximum in a certain value of Oxygen to Carbon Ratio(OCR) or Steam to Carbon Ratio(SCR). When the longitudinal distance to dimeter ratio(L/D) is increased, hydrogen production increases.

• Bulletin of the Korean Chemical Society
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• v.24 no.11
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• pp.1609-1612
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• 2003

The electrooxidation of 8-(3-acetylimino-6-methyl 2,4-dioxopyran)-1-aminonaphthaline (AMDAN) in aqueous and non aqueous media led to the formation of polymeric films, poly (AMDAN). The monomer, undergo anodic oxidation through the formation of a monocation radical irrespective of the nature of the medium. In aqueous medium, the monocation radical undergoes, through its resonance structures, dimerisation involving tail-to-tail, head-to-tail and even head-to-head coupling. The products formed, being more easily oxidisable than the parent substance, undergo further oxidation at the same potential so that the overall oxidation involves a one-step (i.e., a single wave), two-electron process. In non-aqueous medium, the monocation radical does not undergo dimerisation through coupling reactions. Retaining its identity, monomer oxidise in two steps involving one electron in each step. The fact that the cathodic peaks corresponding to these anodic peaks are rarely observed indicates fast consumption of the electrogenerated monocation radicals and dications by follow-up chemical reactions to produce polymeric products (poly AMDAN). The electrochemical behavior of the formed polymer films was investigated in both non aqueous and aqueous media. The films prepared in non aqueous medium were found to be more electroactive than that the films prepared in aqueous medium. This is confirmed with the results in litreature which illustrate that the film prepared in aqueous solution hold water in its structure via hydrogen bonding, which causes decomposition reactions.

• Proceedings of the Korean Vacuum Society Conference
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• 2013.08a
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• pp.143.2-143.2
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• 2013

Nanomechanical and electrical properties of vanadium dioxide (VO2) thin films across thermal-driven phase transition are investigated with ultra-high vacuum atomic force microscopy. VO2 thin films have been deposited on the n-type heavily doped silicon wafer by pulsed laser deposition. X-ray diffraction reveals that it is textured polycrystalline with preferential orientation of (100) and (120) planes in monoclinic phase. As the temperature increases, the friction decreased at the temperature below the transition temperature, and then the friction increased as increasing temperature above the transition temperature. We attribute this observation to the combined effect of the thermal lubricity and electronic contribution in friction. Furthermore, the dependence of nanoscale conductance on the local pressure was indicated at the various temperatures, and the result was discussed in the view of pressure-induced metal-insulator transition.