• 제어로봇시스템학회:학술대회논문집
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• 1991.10a
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• pp.1085-1090
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• 1991

Chemical heat pump is a system to upgrade the low level energy such as industrial waste heat and solar energy by using coupled endothermic and exothermic chemical reactions. Dehydrogenation of 2-propanol can absorb heat near 80.deg. C and is transformed into acetone and hydrogen. Hydrogenation of acetone can liberate heat near 200.deg. C. Dehydrogenation of 2-propanol is difficult around 80.deg. C because .DELTA.G has positive value, but dehydrogenation reaction in liquid phase can overcome this problem because vaporized acetone and hydrogen can be rapidly eliminated. In this work, dehydrogenation of 2-propanol was investigated in liquid phase with Raney nickel catalyst. The energy efficiency of the chemical heat pump was estimated by computer simulation.

• Bulletin of the Korean Chemical Society
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• v.23 no.11
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• pp.1553-1559
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• 2002

Calculations are presented for the molecule HC2N and its geometrical isomers. The structures, harmonic frequencies and dipole moments are reported. The potential energy surface of the [H,C,C,N] system is investigated in detail, and the transition states, intermediate complexes, and the energies of barrier for the isomerization and dissociation reactions are computed in order to determine the reaction paths and to estimate the stability of the isomers. The barriers of isomerization among HCCN, HCNC and HNCC are computed to be rather large and dissociations of these molecules are highly endothermic, indicating that these molecules are kinetically stable. The association reactions HC + CN→HCCN, HC + NC→HCNC, and HN + CC →HNCC are barrierless and very exothermic, suggesting that they may be considered as efficient means of producing the HCCN and the isomers in the laboratory and in interstellar space.

• Transactions of the Korean hydrogen and new energy society
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• v.6 no.1
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• pp.11-16
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• 1995

Chemical heat pump is one of the energy conversion technologies, which enables to use waste heat as a source of high grade heat. In 2-propanol/acetone system, the dehydrogenation of 2-propanol is an endothermic(heat absorption) reaction, and can be used to generate hydrogen because 2-propanol can be converted to acetone and hydrogen at low temperature(about $8^{\circ}C$) using catalyst. For the dehydrogenation of 2-propanol 5% Ru catalyst based on activated carbon is the best one at the reaction temparature of $83^{\circ}C$.

• Journal of Aerospace System Engineering
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• v.14 no.4
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• pp.32-39
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• 2020

A technological review and analysis were performed on thermal cracking of aviation hydrocarbon fuels that circulate as coolants in regenerative cooling systems of hypersonic flights. Liquid hydrocarbons decompose into low-carbon-number hydrocarbons when they absorb a considerable amount of energy at extremely high temperatures, and these thermal cracking behaviors are represented by heat sink capacity, conversion ratio, reaction products, and coking propensity. These parameters are closely interrelated, and thus, they must be considered for optimum performance in terms of the overall heat absorption in the regenerative cooling system and supersonic combustion in the scramjet engine.

• Bulletin of the Korean Chemical Society
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• v.16 no.9
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• pp.827-831
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• 1995

Kinetic studies on the reactions of five secondary acylic alkyl arenesulfonates with anilines are carried out in acetonitrile at 65.0 ℃. The magnitude of ρXZ determined (ρXZ=0.12-0.13) is slightly greater than that for the alicyclic series (ρXZ=0.11) under the same experimental condition. Ab initio MO results are found to support the slightly tighter transition state expected from the greater magnitude of ρXZ for the acyclic series. Despite the small variations, the magnitude of ρXZ and the theoretical transition state tightness remain relatively constant for the secondary carbon centers. Secondary kinetic isotope effects involving deuterated aniline nucleophiles show a successively smaller kH/kD(<1.0) value for a more sterically crowded reaction center carbon. This is in accord with the later transition state for bond-making predicted by the Bell-Evans-Polanyi principle for the more endothermic nucleophilic substitution reaction. Further support is provided by the results of the AM1 MO calculations on the reactions of secondary alkyl benzenesulfonates with chloride nucleophile.

• Bulletin of the Korean Chemical Society
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• v.19 no.10
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• pp.1084-1090
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• 1998

The oxidation of triphenylphosphine by [(tpy)(phen)RuⅣ(O)]2+ and [(bpy)(p-tert-butylpy)RuⅣ(0)]2+ (tpy is 2,2': 6',2"-terpyridine, phen is 1,10-phenanthroline, bpy is 2,2'-bipyridine, and p-tert-butylpy is para-tertbutylpyridine) in CH3CN has been studied. Experiments using 18O-labeled complex show the oxyl group transfer from [RuⅣ=O]2+ to triphenylphosphine occured quantitatively within experimental error. Kinetic data were fit to a second-order for [RuⅣ=O]2+ and [PPh3]. The initial product, [RuⅡ-OPPh3]2+, was formed as an observable intermediate and then underwent slow solvolysis. The reaction proceeded as endothermic in activation enthalpy and a decrease in activation entropy. The oxidative reactivity of four representative ruthenium mono-oxo oxidants against triphenylphosphine was compared. These systems have been utilized as electrochemical oxidative catalysts.

• Journal of The Korean Society of Agricultural Engineers
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• v.64 no.5
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• pp.1-8
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• 2022

Hydrogen can be produced by gasification of biomass and other combustible fuels. Depending on oxydant agents, syngas or producer gas compositions become quite different. Since biomass has limited amount of hydrogen including moisture in it, the hydrogen concentration in the syngas is about 15% when air is supplied for oxidant agent. Experiments were conducted to investigate the channges in hydrogen concentrations in syngas with different oxidant agent conditions, fuel conditions, and external heat supply. Allothermal reaction resulted in higher concentrations of hydrogen with the supply of steam over air, reaching over 60%. Hydrogen is produced by water-gas and water-gas shift reactions. These reactions are endothermic and require enough heat. Autothermal reaction occurred in the downdraft gasifier used in the experiment did not provide enough heat in the reactions for hydrogen production. Steam seems a more desirable oxidant agent in producing the syngas with higher concentrations of hydrogen from biomass gasifications since nitrogen is included in syngas when air is used.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.2051-2056
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• 2009

The rate constants of alkaline fading of malachite green ($MG^+$) was measured in the presence of nonionic (TX-100), cationic (DTAB) and anionic (SDS) surfactants. This reaction was studied under pseudo-first-order conditions at 283∼303 K. The rate of fading reaction showed noticeable dependence on the electrical charge of the used surfactants. It was observed that the reaction rate constants were increased in the presence of TX-100 and DTAB and decreased in the presence of SDS. According to Hughs-Ingold rules for nucleophilic substitution reactions, the electric charge of MG/surfactant compound along with decrease in dielectric constant of $MG^+$ micro-environment in this compound varies the rate of fading reaction. Binding constants of surfactant molecules to $MG^+$ were calculated using cooperativity, pseudo-phase ion exchange and classical models and the related thermodynamic parameters were obtained by classical model. The results show that the binding of $MG^+$ to TX-100 is exothermic and binding of $MG^+$ to DTAB and SDS in some concentration ranges of the used surfactants is endothermic and in the other ones is exothermic.

• Journal of Korean Society on Water Environment
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• v.23 no.2
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• pp.222-227
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• 2007

The adsorption features of fluoride ion on the oyster shell have been investigated for the purpose of the employment of waste oyster shell as an adsorbent for the treatment of fluoride ion-containing wastewater. The major component of oyster shell was examined to be Ca with minor components of Na, Si, Mg, Al, and Fe. As the initial concentration of fluoride ion was raised, its absorbed amount was enhanced at equilibrium, however, the adsorption ratio of fluoride ion compared with its initial concentration was shown to be decreased. Also, adsorption of fluoride ion onto the oyster shell resulted in the formation of $CaF_2$ in the morphological structure of adsorbent. Kinetic analysis showed that the adsorption reaction of fluoride ion generally followed a second order reaction with decreasing rate constant with the initial concentration of adsorbate. Freundlich model agreed well with the adsorption behavior of fluoride ion at equilibrium and the adsorption reaction of fluoride ion was examined to be endothermic. Several thermodynamic parameters for the adsorption reaction were calculated based on thermodynamic equations and the activation energy for the adsorption of fluoride ion onto oyster shell was estimated to be ca. 13.589 kJ/mole.

• Bulletin of the Korean Chemical Society
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• v.10 no.1
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• pp.50-57
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• 1989

A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.