• Bulletin of the Korean Chemical Society
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• 제34권4호
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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.

• 한국식품영양과학회지
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• 제40권2호
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• pp.205-213
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• 2011

본 연구에서는 F-C시약을 이용한 페놀성 물질의 정량방법에서 다양한 종류의 페놀성 성분들의 반응특성 및 반응영향요인들을 분석하였다. 정량방법 중 $Na_2CO_3$를 선처리는 F-C시약을 먼저 처리하는 방법에 비해 대부분 페놀성 물질들의 발색반응도 감소를 야기하였으며, 특히 -OH 밀도가 높은 galloyl group을 가진 gallic acid 및 EGCG 등의 성분이 두드러진 감소를 나타내었다. F-C시약과 $Na_2CO_3$를 동시에 처리하는 경우 F-C시약을 선처리 하는 경우에 비해 각 페놀성 물질의 반응성이 약간 감소되는 경향을 나타내었다. 그 원인은 페놀성 물질들이 산성인 F-C시약에서보다 $Na_2CO_3$ 용액의 알칼리 환경에서 화학적으로 불안정하기 때문이며, pH 7.4 및 9의 환경에서 페놀성 물질로부터 생성된 산화물들은 F-C시약과의 반응성이 약화됨을 확인하였다. 이 과정중에 같이 형성된 $H_2O_2$는 F-C와의 반응에 직접적인 영향을 미치지 않았다. FeA와 SiA와 같은 monophenol류는 방법의 차이에 따라 큰 반응성의 변화를 나타내지 않았으며, 발색도는 느리지만 꾸준히 증가하는 kinetics 패턴을 보였다. 실제 시료에의 적용을 위해 연잎 추출물을 제조하고 각 정량방법에 대한 반응도 차이를 조사한 결과, 역시 $Na_2CO_3$ 처리환경에서 현저한 발색반응도 저하를 나타내었다. 보다 정확한 페놀성 물질의 정량을 위해 적절한 표준물질의 선택 및 정량 방법 등에 대한 표준화가 필요할 것으로 사료된다.

• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1263-1307
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• 2002

Pseudo-first-order rate constants (kobs) have been determined for the nucleophilic substitution reactions of p-nitrophenyl diphenyl phosphinate (PNPDPP) with substituted phenoxides (XC6H4O - ) and butane-2,3-dione monoximate (Ox- ) in 0.1 M borate buffer (pH = 10.0) at 25.0 ${\pm}0.1^{\circ}C$. The kobs value increases sharply upon addition of cethyltrimethylammonium bromide (CTAB) to the reaction medium up to near 7 ${\times}$ 10-4 M CTAB and then decreases smoothly upon further addition of CTAB. The rate enhancement upon the addition of CTAB is most significant for the reaction with -O2CC6H4O- and least significant for the one with C6H5O- , indicating that the reactivity of these aryloxides in the presence of CTAB cannot be determined by the basicity alone. The strength of the interaction of these anionic aryloxides with the positively charged micellar aggregates has been suggested to be an important factor to determine the reactivity in the presence of CTAB. The kobs value for the reaction with Ox- increases also upon the addition of CTAB. However, the increase in the kobs value is much more significant for the reaction with Ox- than for the one with ClC6H4O- , indicating that Ox- is less strongly solvated than ClC6H4O- in H2O. The ${\alpha}-effect$ shown by Ox- in H2O has been attributed to the ground-state solvation difference between Ox- and ClC6H4O- .

• Nuclear Engineering and Technology
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• 제52권7호
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• pp.1367-1379
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• 2020

The small modular sodium-cooled fast reactor (SMSFR) is an important component of Generation-IV reactors. The objective of this work is to improve the reactivity control in SMSFR by using innovative systems, including burnable poisons and optimized control rods. SMSFR with MOX fuel usually exhibits high burnup reactivity loss that leads to high excess reactivity and potential fuel melting in control rod withdrawal (CRW) accidents, which becomes an important constraint on the safety and economic efficiency of SMSFR. This work applies two types of burnable poisons in a SMSFR to reduce the excess reactivity. The first one homogenously loads minor actinides in the fuel. The second one combines absorber and moderators in specific assemblies. The influence of burnable poisons on the core characteristics is discussed and integrated into the analysis of CRW accidents. The results show that burnable poisons improve the safety performance of the core in a significant way. Burnable poisons also lessen the demand for the number, absorption ability, and insertion depth of control rods. Two optimized control rod designs with rare earth oxides (Eu₂O₃ and Gd₂O₃) and moderators are compared to the conventional design with natural boron carbide (B₄C). The optimized designs show improved neutronic and safety performance.

• 한국세라믹학회지
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• 제31권10호
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• pp.1231-1239
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• 1994

In this study, gel powder which had relatively high hydration reactivity in CaO and P2O5 rich composition of CaO-P2O5-SiO2-H2O system was prepared by sol-gel process and its hydrated specimen was manufactured. The it was investigated to appropriate calcination temperature in sol-gel process which hydrated specimen of gel powder have proven to strength and the effect of factors influenced strength in hydration process. The major product of before and after hydration reaction was hydroxyapatite, and crystalline phase of C-S-H was already formed during gelation process. After hydration reaction of pressed specimen, crystalline phase of C-S-P-H was formed. It was hydrated product of silicocarnotite (5CaO.P2O5.SiO2). Gel phases of C-S-H and C-S-P-H occured as a result of partial substitution of amorphous silica by P2O5 was formed. The strength of hydrated hardened body is developed by strong bonding and bridging between the gel phases of C-S-H or C-S-P-H and the crystalline products such as hydroxyapatite, Ca(OH)2 C-S-H and C-S-P-H. In addition, the ultrafine gel powder have an great effect on increase of hydration reaction.

• Nuclear Engineering and Technology
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• 제9권1호
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• pp.33-38
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• 1977

p-Substituted phenyl-$\beta$-chloroethylsulfones, R-(equation omitted)-$SO_2CH_2CH_2Cl$,에서 R이 $CH_3O\;,CH_3$, Cl, H인 화합물들의 반응기구와 반응성을 EHT 방법으로 계산하고 실험값과 비교 검토 하였다.

• 한국세라믹학회지
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• 제28권6호
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• pp.465-470
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• 1991

AlN powder was synthesized by carbothermal reduction and nitridation of aluminum hydroxides precipitated in 5∼11 pH range from Al2(SO4)3$.$18H2O aqueous solution. Nitridation reactivity of hydroxide, which depends on precipitation pH, reaction temperature and time, was examined by XRD analysis at 1200∼1350$^{\circ}C$ and compared with that of commercial ${\alpha}$-Al2O3. Hydroxides obtained at higher pH could be more easily nitridated and, considering DTA/TG and BET results, the reason seems to be specific surface area difference of reactants depending on the content of decomposed structural water and the transition rate from transition-Al2O3 to ${\alpha}$-Al2O3.

• Advances in concrete construction
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• 제13권1호
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• pp.71-81
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• 2022

Aluminosilicate materials as precursors are heterogenous in nature, consisting of inert and partially reactive portion, and have varying proportions depending upon source materials. It is essential to assess the reactivity of precursor prior to synthesize geopolymers. Moreover, reactivity may act as decisive factor for setting molar concentration of NaOH, curing temperature and setting proportion of different precursors. In this experimental work, the reactivities of two precursors, low calcium (fly ash (FA)) and high calcium (ground granulated blast furnace slag (GGBS)), were assessed through the dissolution of aluminosilicate at (i) three molar concentrations (8, 12, and 16 M) of NaOH solution, (ii) 6 to 24 h dissolution time, and (iii) 20-100℃. Based on paratermeters influencing the reactivity, different proportions of ternary binders (two precursors and ordinary cement) were activated by the combined NaOH and Na2SiO3 solutions with two alkaline activators to precursor ratios, to synthesize the geopolymer. Reactivity results revealed that GGBS was 20-30% more reactive than FA at 20℃, at all three molar concentrations, but its reactivity decreased by 32-46% with increasing temperature due to the high calcium content. Setting time of geopolymer paste was reduced by adding GGBS due to its fast reactivity. Both GGBS and cement promoted the formation of all types of gels (i.e., C-S-H, C-A-S-H, and N-A-S-H). As a result, it was found that a specified mixing proportion could be used to improve the compressive strength over 30 MPa at both the ambient and hot curing conditions.

• 한국결정학회:학술대회논문집
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• 한국결정학회 2004년도 학술대회지
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• pp.14-14
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• 2004

• 에너지공학
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• 제11권2호
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• pp.136-141
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• 2002

석탄가스화 복합발전용 고온건식 탈황제의 반응성을 개선하기 위하여 $Al_2$O$_3$를 지지체로사용한 ZnO/Al$_2$O$_3$ 탈황제를 제조하고 반응특성을 조사하였다. ZnO/Al$_2$O$_3$의 성분함량 및 소성온도에 따른 물리화학적 구조변화를 XRD로 관찰하였고 ZnO의 소결 및 열화로 인한 활성저하를 $Al_2$O$_3$의 함량과 소성온도를 변화시켜 개선할 수 있음을 탈황 및 재생반응실험을 통하여 확인하였다. 마지막으로 첨가제를 함유한 ZnO/Al$_2$O$_3$ 탈황제의 내구성실험에 의한 고온건식 탈황제로의 사용가능성을 실험적으로 확인하였다.