• Journal of Environmental Science International
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• v.6 no.4
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• pp.399-407
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• 1997

The pyrolysis reactions of atomic hydrogen with chloroform were studied In a 4 cm 1.6. tubular flow reactor with low flow velocity 1518 cm/sec and a 2.6 cm 1.4. tubular flow reactor with high flow velocity (1227 cm/sec). The hydrogen atom concentration was measured by chemiluminescence titration with nitrogen dioxide, and the chloroform concentrations were determined using a gas chromatography. The chloroform conversion efficiency depended on both the chloroform flow rate and linear flow velocity, but 416 not depend on the flow rate of hydrogen atom. A computer model was employed to estimate a rate constant for the initial reaction of atomic hydrogen with chloroform. The model consisted of a scheme for chloroform-hydrogen atom reaction, Runge-Kutta 4th-order method for Integration of first-order differential equations describing the time dependence of the concentrations of various chemical species, and Rosenbrock method for optimization to match model and experimental results. The scheme for chloroform-hydrogen atom reaction Included 22 elementary reactions. The rate constant estimated using the data obtained from the 2.6 cm 1.4. reactor was to be 8.1 $\times$ $10^{-14}$ $cm^3$/molecule-sec and 3.8 $\times$ $10^{-15}$ cms/molecule-sec, and the deviations of computer model from experimental results were 9% and 12% , for the each reaction time of 0.028 sec and 0.072 sec, respectively.

• Bulletin of the Korean Chemical Society
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• v.13 no.5
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• pp.531-537
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• 1992

The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

• 유체기계공업학회:학술대회논문집
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• 2005.12a
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• pp.759-764
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• 2005

In this paper, numerical analysis of hydrogen recycle system has been conducted in order to enhance the efficiency of automotive fuel cell. Generally, the excess hydrogen is provided in the automotive fuel cell. Since the non-reaction hydrogen reduces automotive fuel cell efficiency, reuse of the non-reaction hydrogen can be helpful to improve the fuel cell performance. In case of PEM FC, the water vapor is provided to hydrogen from the cathode so that the mixture experiences phase change depending on the changes of pressure and temperature. The internal flow of the mixture in the hydrogen recirculation system of fuel cell was investigated for real flow conditions. The variation of performance, properties and mass fractions of mixture, hydrogen and water-vapor were investigated. This study was performed based on 80KW level automotive fuel cell's recycling system.

• Transactions of the Korean hydrogen and new energy society
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• v.8 no.1
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• pp.31-41
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• 1997

In order to investigate the mechanism of electrochemical hydrogenation reaction on Zr-based Laves phase hydrogen storage alloy electrodes, electrochemical charge/discharge characteristics, potentiostatic/dynamic polarizations and electrocehmical impedance spectroscopy(EIS) of Zr-Ti-Mn-Ni and Zr-Ti-Mn-Ni-M(M=Fe, Co, Al) alloys were examined. Electrochemical discharge capacities of the alloys were quite different with gas charge capacities. Therefore, it was considered that discharge capacities of the alloys depend on electrochemical kinetic factors rather then thermodynamic ones. Discharge efficiencies were increased linearly with exchange current densities. The results of potentiostatic/dynamic polarization measurements showed that electrochemical charge and discharge reaction of Zr-based Laves phase hydrogen storage alloys is controlled by charge transfer process at the electrode surface. The EIS measurements also confirmed this result.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.5
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• pp.453-458
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• 2017

A study on the modeling of the methane Chemical Looping Reforming system was carried out. It is aimed to predict the temperature and concentration behavior of the product through modeling of oxygen carrier fixed bed reactors composed of multiple stacks. In order to design the reaction system, first of all, the flow rate of the hydrogen to be produced was calculated. The flow rate ratio of the oxidation/reduction reactor was calculated considering the heat of reaction between adjacent reactors. Finally, in this paper, kinetic model including empirical coefficients was suggested.

• Journal of Environmental Health Sciences
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• v.14 no.1
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• pp.11-22
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• 1988

Calcium oxide, lithium oxide and titanium oxide were investigated as additives of zinc oxide for the removal of hydrogen sulfide at high temperature. This experiment was performed in the range of 1.0-2.0 vol.% H$_2$S concentration at 623-873 K reaction temperature, using a thermogravimetric analyzer. A pore blocking model was found to fit the reaction rate and the kinetics data were sucessfully expressed by this model. The reactions between additive sorbents and hydrogen sulfide were first order with respect to hydrogen sulfide concentration in a gaseous mixture with nitrogen. Among the used sorbents, ZnO-CaO 0.5 at.% and ZnO-TiO$_2$ 2.0 at.% sorbents had the best additive effects on the sulfidation reaction between additive sorbents and hydrogen sulfide, whereas the ZnO-Li$_2$O sorbents were ineffective.

• Transactions of the Korean Society of Mechanical Engineers B
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• v.29 no.9 s.240
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• pp.979-987
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• 2005

Numerical simulations were performed at atmospheric pressure in order to understand the effect of additives on flame speed, flame temperature, radical concentrations, $NO_x$ formation, and heat flux in freely propagating $CH_4-Air$ flames. The additives were both carbon dioxide and hydrogen chloride which had a combination of physical and chemical behavior on hydrocarbon flame. In the flame established with the same mole of methane and additive, hydrogen chloride significantly contributed toward the reduction of flame speed, flame temperature, $NO_x$ formation and heat flux by the chemical effect, whereas carbon dioxide mainly did so by the physical effect. The impact of hydrogen chloride on the decrease of the radical concentration was about $1.4\~3.0$ times as large as that of carbon dioxide. Hydrogen chloride had higher effect on the reduction of $EI_{NO}$ than carbon dioxide because of the chemical effect of hydrogen chloride. The reaction, $OH+HCl{\rightarrow}Cl+H_2O$, played an important role in the heat flux from flames added by hydrogen chloride instead of the reaction, $OH+H_2{\rightarrow}H+H_2O$ which was an important reaction in hydrocarbon flames.

• Transactions of the Korean hydrogen and new energy society
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• v.21 no.3
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• pp.158-166
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• 2010

The purification of two liquid phases ($H_2SO_4$ phase and HIx phase) formed from a Bunsen reaction in Sulfur-Iodine (SI) hydrogen production process was investigated in order to operate SI process efficiently. The each synthetic solution for two liquid phases contained impurities was prepared on the basis of a proper composition obtained from Bunsen reaction. The purification of each solution was performed by counter-current flow using a packed column at different temperatures and $N_2$ flow rates. As the results of purification, impurities existed in each phase were decreased with increasing the temperature and the $N_2$ flow rate. In particular, the increase of the $N_2$ flow rate at the lower temperatures was effective to remove impurities by a reverse Bunsen reaction without side reactions. On the whole, it may be concluded that the purification of each phase is accomplished by mixing effects of the stripping, the evaporation, and the reverse Bunsen reaction.

• Journal of Advanced Marine Engineering and Technology
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• v.23 no.1
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• pp.88-95
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• 1999

This study investigates the effects of different kind fuels on the flame structure by using the numerical simulation in triple flame made by a co-flowing fuels-air stream based on the elementary chemical reaction mechanism. Methane and Hydrogen were used as fuel for this study. In order to interpret the result of the study on numerical simulation Skeletal chemistry is employe as the elementary chemical reaction mechanism for methane Gutheil's as an offset ele-mentary chemical reaction mechanism for hydrogen. The result of this study is as follows. In com-parison between the apparent burning velocity change of triple flame and the one-dimensional pre-mixed flame hydrogen fuel flame is higher than methane fuel flame. The flame thrusts out for-ward in the down stream of the boundary between air-fuel mixture and air stream and a part of the flow is bent and forks out in this protruding flame so that a triple flame is originated.

• Transactions of the Korean hydrogen and new energy society
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• v.19 no.2
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• pp.111-117
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• 2008

A Bunsen reaction section is a primary stage of Sulfur-iodine thermochemical hydrogen production cycle. This section is important, because it decides the efficiency of next stages. In order to produce hydrogen very efficiently, the characteristics of Bunsen reaction were investigated via two experimental methods. The one is a phase separation of $H_2SO_4-HI-H_2O-I_2$ mixture system, and the other is a direct Bunsen reaction. The characteristics of each method were investigated and compared. As the result of this study, the amount of HI and $I_2$ in $H_2SO_4$ phase via Bunsen reaction was more decreased than that via $H_2SO_4-HI-H_2O-I_2$ mixture system with increasing $I_2$ concentration. However, the amount of $H_2SO_4$ in $HI_x$ phase via Bunsen reaction was remarkably increased with increasing $I_2$ concentration, while that via $H_2SO_4-HI-H_2O-I_2$ mixture system was decreased. On the other hand, the range of initial composition which is able to separate into two liquid phases without $I_2$ solidification was almost alike.