• Nuclear Engineering and Technology
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• v.51 no.8
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• pp.1957-1963
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• 2019

A UVC photo-Fenton advanced oxidation process (AOP) was studied to develop a process for the decomposition of oxalic acid waste generated in the chemical decontamination of nuclear power plants. The oxalate decomposition behavior was investigated by using a UVC photo-Fenton reactor system with a recirculation tank. The effects of the three operational variables-UVC irradiation, H₂O₂ and Fenton reagent-on the oxalate decomposition behavior were experimentally studied, and the behavior of the decomposition product, CO₂, was observed. UVC irradiation of oxalate resulted in vigorous CO₂ bubbling, and the irradiation dose was thought to be a rate-determining variable. Based on the above results, the oxalate decomposition kinetics were investigated from the viewpoint of radical formation, propagation, and termination reactions. The proposed UVC irradiation density model, expressed by the first-order reaction of oxalate with the same amount of H₂O₂ consumption, satisfactorily predicted the oxalate decomposition behavior, irrespective of the circulate rate in the reactor system within the experimental range.

• Bulletin of the Korean Chemical Society
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• v.35 no.2
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• pp.587-596
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• 2014

A new ${\pi}$-stacked donor-acceptor (D-A) system, [Ru(1-([2,2'-bipyridine]-6-yl-methyl)-3-(2-cyclohexa-2',5'-diene-1,4-dionyl)-1H-imidazole)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (ImQ_T), has been synthesized and characterized. Similar to its precedent, [Ru(6-(2-cyclohexa-2',5'-diene-1,4-dione)-2,2':6',2"-terpyridine)(2,2':6',2"-terpyridine)]$[PF_6]_2$ (TQ_T), this system has a cofacial alignment of terpyridine (tpy) ligand and quinonyl (Q) group, which facilitates an electron transfer through ${\pi}$-stacked manifold. Despite the presence of lowest-energy charge transfer transition from the Ru-based-HOMO-to-Q-based-LUMO (MQCT) predicted by theoretical calculations by using time-dependent density functional theory (TD-DFT), the experimental steady-state absorption spectrum does not exhibit such a band. The selective excitation to the Ru-based occupied orbitals-to-tpy-based virtual orbital MLCT state was thus possible, from which charge separation (CS) reaction occurred. The photo-induced CS and thermal charge recombination (CR) reactions were probed by using ultrafast visible-pump/mid-IR-probe (TrIR) spectroscopic method. Analysis of decay kinetics of Q and $Q^-$ state CO stretching modes as well as aromatic C=C stretching mode of tpy ligand gave time constants of <1 ps for CS, 1-3 ps for CR, and 10-20 ps for vibrational cooling processes. The electron transfer pathway was revealed to be Ru-tpy-Q rather than Ru-bpy-imidazol-Q.

• Journal of the Korean Chemical Society
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• v.37 no.1
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• pp.3-9
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• 1993

Specific rates of solvolysis of 1-adamantyl fluoroformate in hydroxylic solvents have been measured by an electric conductivity method under various pressures. The activation parameters (${\Delta}V^{\neq}{_o},\;{\Delta}{\beta}^{\neq},\;{Delta}H^{\neq},\;{Delta}S^{\neq}$,/TEX>) and average pressure within the solvation-shell of activated complex (charge development) have been estimated from the rates. Also, the selectivities for the formation of solvolysis products in aqueous ethanol have been determined by response-calibrated GC. The values of ${\Delta}V^{\neq}{_o},\;and\;{\Delta}{\beta}^{\neq}$ are both negative, but ${Delta}H^{\neq}$ is positive and ${Delta}S^{\neq}$, is large negative. This behavior is discussed in terms of electrostriction of solvation. From these results, it could be postulated that the solvolysis of 1-adamantyl fluoroformate have two major reaction pathway.

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• Journal of the Korean Chemical Society
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• v.28 no.5
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• pp.328-334
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• 1984

A series of phenyl N-benzenesulfonylchloroformimidate derivatives (p-H, p-Cl, p-CH3 & p-OCH3) were prepared and the hydrolysis of these compounds were studied kinetically at various pH by UV spectrophotometry in 1 ; 4 dioxane-water at $25^{\circ}C$. Hammett ${\rho}$ values measured at pH 5.0 (${\rho}$ = -0.45) and pH 10.0 (${\rho}$ = 0.40) indicate that the reaction proceeds via an azocarbonium ion intermediate in the acidic medium, whereas, it involves direct attack by hydroxide ion on the azomethine carbon atom occurs under the basic medium. The formation of stabilized azocarbonium ion species at pH 5.0 is also consistent with the large solvent effect(m = 1.3-1.5 & n = 5.0-5.5). On the basis of these findings, we may concluded that the hydrolysis of phenyl N-benzenesulfonylchloroformimidate derivatives proceeds by $SN_1$ below pH 8.0, however, above pH 10.0, the hydrolysis proceeds through $SN_2$ and in the range of pH 8.0-10.0, these two reactions occur competitively.

• Journal of the Korean Institute of Gas
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• v.20 no.6
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• pp.95-101
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• 2016

For a natural gas steam reforming, comparative studies of the performance in a conventional packed-bed reactor and a membrane reactor, a new conceptual reactor consisting of a reactor with series of hydrogen separation membranes, have been performed. Based on experimental kinetics reported by Xu and Froment, a process simulation model was developed with Aspen $HYSYS^{(R)}$, a commercial process simulator, and effects of various operating conditions like temperature, $H_2$ permeance, and Ar sweep gas flow rate on the performance in a membrane reactor were investigated in terms of reactant conversion and $H_2$ yield enhancement showing improved $H_2$ yield and methane conversion in a membrane reactor. In addition, a preliminary cost estimation focusing on natural gas consumption to supply heat required for the system was carried out and feasibility of possible cost savings in a membrane reactor was assessed with a cost saving of 10.94% in a membrane reactor.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.11 no.3
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• pp.1027-1034
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• 2010

Effects of inorganic nano-powders on the polymerization and thermal degradation kinetics as well as the mechanical properties of polyurethane nano-composites were studied by both the measurement of polymerization temperature as a function of time and non-isothermal thermogravimetric analysis (TGA) as well as the Instron test. As the results from polymerization studies, the reaction rates of MMT-filled PU composites were faster than those of Ce500-filled ones, and moreover, the activation energies using Kissinger method for the thermal degradation of composites were calculated as 139.34 kJ/mol for the Ce500-filled PU composites and 91.12 kJ/mol for MMT-filled one, respectivel, exhibiting that MMT nano-powder seemed to be acting as the catalyst for both polymerization and degradation of PU composites. UTM result, however, showed that tensile strength at break of MMT-filled composites was much higher than that of Ce500-filled ones above the concentrations range of 5 phr in the composites.

• Bulletin of the Korean Chemical Society
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• v.18 no.11
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• pp.1166-1172
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• 1997

[FeⅢ(BLPA)DBC]BPh4, a new functional model for the catechol dioxygenases, has been synthesized, where BLPA is bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine and DBC is 3,5-di-tert-butylcatecholate dianion. The BLPA complex has a structural feature that iron center has a six-coordinate geometry with N4O2 donor set. It exhibits EPR signals at g=5.5 and 8.0 which are typical values for the high-spin FeⅢ (S=5/2) complex with axial symmetry. The BLPA complex reacts with O2 within a few hours to afford intradiol cleavage (75%) and extradiol cleavage (15%) products which is very unique result of all [Fe(L)DBC] complexes studied. The iron-catecholate interaction of BLPA complex is significantly stronger, resulting in the enhanced covalency of the metal-catecholate bonds and low energy catecholate to FeⅢ charge transfer bands at 583 and 962 nm in CH3CN. The enhanced covalency is also reflected by the isotropic shifts exhibited by the DBC protons, which indicate increased semiquinone character. The greater semiquinone character in the BLPA complex correlates well with its high reactivity towards O2. Kinetic studies of the reaction of the BLPA complex with 1 atm O2 in CH3OH and CH2Cl2 under pseudo-first order conditions show that the BLPA complex reacts with O2 much slower than the TPA complex, where TPA is tris(2-pyridylmethyl)amine. It is presumably due to the steric effect of the methyl substituent on the pyridine ring. Nevertheless, both the high specificity and the fast kinetics can be rationalized on the basis of its low energy catecholate to FeⅢ charge transfer bands and large isotropic NMR shifts for the BLPA protons. These results provide insight into the nature of the oxygenation mechanism of the catechol dioxygenases.

• Korean Chemical Engineering Research
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• v.48 no.2
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• pp.259-267
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• 2010

The catalytic wet oxidations of the wastewater containing azo dye Reactive Black 5(RB5) with heterogeneous catalyst of CuO have been carried out to investigate the effects of temperature($190{\sim}230^{\circ}C$) and catalyst concentration(0.00~0.20 g/l) on the removals of colour and total organic carbon TOC. The wastewater colour was measured with spectrophotometer, and the oxidation rate was estimated with TOC. About 90% of colour was removed during 120 min in thermal degradation of the RB5 wastewater at $230^{\circ}C$, while TOC was not removed at all. As increasing reaction temperature and catalyst concentration, the removal rates of colour and TOC increased in the catalytic wet oxidations of RB5 wastewater. The effects of catalyst were already considerable even at 0.01 g CuO/l, while the removal rates of colour and TOC increased negligibly with increasing the catalyst concentration above 0.05 g CuO/l. The initial destruction rates of the wastewater colour have shown the first-order kinetics with respect to the wastewater colour. TOC changes during catalytic wet oxidations have been well described with the global model, in which the easily degradable TOC was distinguished from non-degradable TOC of the wastewater. The impacts of reaction temperature on the destruction rate of the wastewater colour and TOC could be described with Arrhenius relationship. Activation energies of the colour removal reaction in thermal degradation, wet oxidation, and catalytic wet oxidation(0.20 g CuO/l) of the RB5 wastewater were 108.4, 78.3 and 74.1 kJ/mol, respectively. The selectivity of wastewater TOC into the non-degradable intermediates relative to the end products in the catalytic wet oxidations of RB5 wastewater was higher compared to that in phenol wet oxidations.

• Clean Technology
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• v.20 no.4
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• pp.425-432
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• 2014

The effect of two important parameters of a catalytic membrane reactor (CMR), hydrogen selectivity and hydrogen permeance, coupled with an Ar sweep flow and an operating pressure on the performance of a water gas shift reaction in a CMR has been extensively studied using a one-dimensional reactor model and reaction kinetics. As an alternative pre-combustion $CO_2$ capture method, the feasibility of capturing a pressurized and concentrated $CO_2$ in a retentate (a shell side of a CMR) and separating a purified $H_2$ in a permeate (a tube side of a CMR) simultaneously in a CMR was examined and a guideline for a hydrogen permeance, a hydrogen selectivity, an Ar sweep flow rate, and an operating pressure to achieve a simultaneous capture of a concentrate $CO_2$ in a retentate and production of a purified $H_2$ in a permeate is presented. For example, with an operating pressure of 8 atm and Ar sweep gas for rate of $6.7{\times}10^{-4}mols^{-1}$, a concentrated $CO_2$ in a retentate (~90%) and a purified $H_2$ in a permeate (~100%) was simultaneously obtained in a CMR fitted with a membrane with hydrogen permeance of $1{\times}10^{-8}molm^{-2}s^{-1}Pa^{-1}$ and a hydrogen selectivity of 10000.