• Bulletin of the Korean Chemical Society
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• v.12 no.3
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• pp.350-352
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• 1991

• Nuclear Engineering and Technology
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• v.54 no.8
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• pp.3106-3116
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• 2022

The present work presents analysis results of the core design optimizations for an annular, prismatic High Temperature Gas-cooled Reactor (HTGR) with passive decay-heat removal features. Its thermal power is 100 MW_t and the operating temperature is 850 ℃ (1123 K). The neutronic calculations are done for the core with heterogeneous distribution of fuel and burnable poison particles (BPPs) to flatten the reactivity swing and power peaking factor (PPF) during the reactor operation as well as for control rod (CR) insertion into the core to restrain a small excess reactivity less than 1$. The next step of the study is done for evaluation of core reactivity coefficient of temperature.

• Transactions of the Korean hydrogen and new energy society
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• v.28 no.5
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• pp.554-560
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• 2017

Reduction reactivity of new oxygen carriers for chemical looping combustion system were investigated using $CH_4$ as a reduction gas in a bubbling fluidized bed reactor and compared with that of former SDN70 oxygen carrier. New oxygen carriers showed good reduction reactivity at different $CH_4$ concentration. N018-R2 particle represented better reactivity than SDN70 at high $CH_4$ concentration. N018-R2 particle showed higher fuel conversion and $CO_2$ selectivity than those of SDN70 particle within the temperature range of $750-900^{\circ}C$. Moreover, attrition loss of N018-R2 particle was almost same with that of SDN70 particle. Consequently, we could select N018-R2 particle as the best oxygen carrier.

• Journal of the Korean Chemical Society
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• v.63 no.3
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• pp.216-219
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• 2019

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2410-2414
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• 2014

A kinetic study is reported on nucleophilic substitution reactions of Y-substituted-phenyl picolinates (7a-7h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Comparison of the kinetic results with those reported previously for the corresponding reactions of Y-substituted-phenyl benzoates (1a-1f) reveals that 7a-7h are significantly more reactive than 1a-1f. The Br${\o}$nsted-type plot for the aminolysis of 4-nitrophenyl picolinate (7a) is linear with ${\beta}_{nuc}=0.78$, which is typical for reactions proceeding through a stepwise mechanism with expulsion of the leaving group being the rate-determining step. The Br${\o}$nsted-type plots for the piperidinolysis of 7a-7h and 1a-1f are also linear with ${\beta}_{lg}=-1.04$ and -1.39, respectively, indicating that the more reactive 7a-7h are less selective than the less reactive 1a-1f to the leaving-group basicity. One might suggest that the enhanced reactivity of 7a-7h is due to the inductive effect exerted by the electronegative N atom in the picolinyl moiety, while the decreased selectivity of the more reactive substrates is in accord with the reactivity-selectivity principle. However, the nature of intermediate (e.g., a stabilized cyclic intermediate through the intramolecular H-bonding interaction for the reactions of 7a-7h, which is structurally not possible for the reactions of 1a-1f) is also responsible for the enhanced reactivity with a decreased selectivity.

• Bulletin of the Korean Chemical Society
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• v.34 no.4
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• pp.1115-1119
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• 2013

A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

• Bulletin of the Korean Chemical Society
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• v.34 no.8
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• pp.2325-2329
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• 2013

Second-order rate constants $k_N$ have been measured for reactions of benzyl 2-pyridyl thionocarbonate (4b) and t-butyl 2-pyridyl thionocarbonate (5b) with a series of cyclic secondary amines in MeCN at $25.0{\pm}0.1^{\circ}C$. The $k_N$ values for the reactions of 4b and 5b have been compared with those reported previously for the corresponding reactions of benzyl 2-pyridyl carbonate (4a) and t-butyl 2-pyridyl carbonate (5a) to investigate the effect of changing the electrophilic center from C=O to C=S on reactivity and reaction mechanism. The thiono compound 4b is more reactive than its oxygen analogue 4a. The Br${\o}$nsted-type plots for the reactions of 4a and 4b are linear with ${\beta}_{nuc}=0.57$ and 0.37, respectively. The reactions of 4a were previously reported to proceed through a concerted mechanism, while those of 4b in this study have been concluded to proceed through a stepwise mechanism with formation of an intermediate being the rate-determining step on the basis of the ${\beta}_{nuc}$ value of 0.37. Enhanced polarizability upon changing the C=O in 4a by C=S has been suggested to be responsible for the reactivity order and the contrasting reaction mechanisms. In contrast, the reactivity of 5a and 5b is similar, but they are much less reactive than 4a and 4b. Furthermore, the reactions of 5a and 5b have been concluded to proceed through the same mechanism (i.e., a concerted mechanism) on the basis of linear Bronsted-type plots with ${\beta}_{nuc}=0.45$ or 0.47. It has been concluded that the strong steric hindrance exerted by the t-Bu in 5a and 5b causes a decrease in their reactivity and forces the reactions to proceed through a concerted mechanism.

• Bulletin of the Korean Chemical Society
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• v.15 no.6
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• pp.453-455
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• 1994

Semiempirical MO calculations are applied to estimate the substituent effects on acylations of the nonfused N-vinyl-2-amino $\beta-lactams$ having frameworks analogous to 3-cephems. The stabilization energy for the reaction intermediate of the nucleophilic attack by the hydroxide ion is selected as the reactivity index and calculated by AM1 and PM3 methods for the model $\beta-lactams$ with substituents at the C1 and N-vinyl terminal positions. The reactivities are larger for -SH connected to the C1 and strong $\pi-acceptors$ at the N-vinyl terminal implying the large reactivity for known active cephalosporins. Quantum chemical calculation of stabilization energy could be useful in correlating antibiotic activities of many compounds obtained as derivatives of a lead compound.

• Journal of the Korean Ceramic Society
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• v.11 no.1
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• pp.10-18
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• 1974

The hydration at $23^{\circ}C$ between $Ca(OH)_2$ and siliceous materials with various compositions of silica gel and quartz were studied in paste state, and also diatomite was empolyed as another form of silica. The effect of the structural state of silica on the pozzolanic reactivity was investigated by X-ray, DTA, electron microscopy, and chemical analysis. The results obtained were as follows. (1) The molar ratio of $Ca(OH)_2$ to silica gel(C/Sg) being changed in 0.49, 0.81 and 1.22, the free $Ca(OH)_2$ was disappeared within six hours, three days and two weeks respectively and ill-crystallized CSH(I) was formed. However, in the case fo molar ratio of C/Sg=2.45, almost lime was remained uncombinedly after twenty four weeks yet. (2) Though the molar ratio C/Sg of diatomite was 0.71, the hydration was stabilized at three weeks and the result exhibited very peculiar characteristics from silica gel. (3) Pozzolanic reactivity of quartz was negligible, but $\alpha$-cristobalite in diatomite showed appreciable reactivity. (4) The thermal curves showed the exothermic peaks in the range 830 to $930^{\circ}C$ and lower broad peaks at high temperature in the initial steps of hydration, transfered to lower temperature with sharp peaks by proceeding of hydration. (5) The samples containing more silica gel exhibited higher pozzolanic reactivity and martar strength, but the diatomite gave remarkable result for them and they were matched to the strength development rate.

• Korean Chemical Engineering Research
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• v.49 no.3
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• pp.372-380
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• 2011

Char gasification is affected by operating conditions such as reaction temperature, reactants gas partial pressure, total system pressure and particle size in addition to chemical composition and physical structure of char. The aim of the present work was to characterize the effect of coal particle size on $CO_{2}$ gasification of chars prepared from two different types of bituminous coals at different reaction temperatures(1,000-$1,400{^{\circ}C}$). Lab scale experiments were carried out at atmospheric pressure in a fixed reactor where heat was supplied into a sample of char particles. When a flow of $CO_{2}$(40 vol%) was delivered into the reactor, the char reacted with $CO_{2}$ and was transformed into CO. Carbon conversion of the char was measured using a real time gas analyzer having NDIR CO/$CO_{2}$ sensor. The results showed that the gasification reactivity increased as the particle size decreased for a given temperature. The sensitivity of the reactivity to particle size became higher as the temperature increases. The size effects became remarkably prominent at higher temperatures and became a little prominent for lower reactivity coal. The particle size and coal type also affected reaction models. The shrinking core model described better for lower reactivity coal, whereas the volume reaction model described better for higher reactivity coal.