• 한국주조공학회지
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• 제34권2호
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• pp.54-59
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• 2014

In this study, the extruded Al-6.3Zn-2.4Mg alloys were selected among the 7000 series aluminum alloys sensitive to hydrogen environment in order to examine the effects of both the aging conditions and the length of hydrogen charging period on the mechanical properties of the alloy. The specimens were aged for 24hours at $100^{\circ}C$ (under aging (UA)), $120^{\circ}C$ (peak aging (PA)), and $160^{\circ}C$ (over aging (OA)), respectively. Charging tests were performed at RT for 12, 24, 36 hours under potentiostatic conditions (-2000 mV vs (Ag/AgCl)) for 12, 24 and 36 hours in 1M $H_2SO_4$ and 0.1%$NH_4SCN$ solution. The fracture surface was examined by scanning electron microscopy (SEM). X-ray diffraction (XRD) pattern in peak aged sample was obtained before and after hydrogen charging from extruded Al-6.3Zn-2.4Mg alloys. The decreasing rate of tensile strength and elongation is represented in order of over aging < under aging < peak aging, and it is believed that the hydrogen recharge is more sensitive to elongation than tensile strength. The formation of $AlH_3$ in hydrogen charged Al-6.3Zn-2.4Mg alloys has been confirmed by X-ray diffraction studies.

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1997-2002
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• 2011

The nucleophilic substitution reactions of dicyclohexyl phosphinic chloride [3; $cHex_2$P(=O)Cl] with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 60.0 $^{\circ}C$. The anilinolysis rate is too slow to be rationalized by the stereoelectronic effects. The rate is contrary to expectations for the electronic influence of the two ligands and exhibits exceptionally great negative deviation from the Taft's eq. The deuterium kinetic isotope effects (DKIEs) involving deuterated anilines invariably change from primary normal ($k_H/k_D$ > 1; max $k_H/k_D$ = 1.10 with X = 4-MeO) with the strongly basic anilines (X = 4-MeO, 4-Me, 3-Me) to secondary inverse ($k_H/k_D$ < 1; min $k_H/k_D$ = 0.673 with X = 3-Cl) with the weakly basic anilines (X = H, 4-F, 4-Cl, 3-Cl). A concerted $S_N2$ mechanism is proposed on the basis of both secondary inverse and primary normal DKIEs. The obtained DKIEs imply that the fraction of a frontside attack increases as the aniline becomes more basic. A hydrogen-bonded, four-center-type transition state is suggested for a frontside attack, while the trigonal bipyramidal pentacoordinate transition state is suggested for a backside attack.

• Bulletin of the Korean Chemical Society
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• 제32권8호
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• pp.2628-2632
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• 2011

The nucleophilic substitution reactions of Y-O-aryl phenyl phosphonochloridothioates with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are kinetically investigated in acetonitrile at $55.0^{\circ}C$. The deuterium kinetic isotope effects (DKIEs) invariably increase from an extremely large secondary inverse ($k_H/k_D$ = 0.439; min) to a primary normal ($k_H/k_D$ = 1.34; max) as both substituents of nucleophile (X) and substrate (Y) change from electron-donating to electron-withdrawing. These results are opposite to the DKIEs on Y-O-aryl methyl phosphonochloridothioates, and can be rationalized by the gradual transition state (TS) variation from backside to frontside attack. The trigonal bipyramidal pentacoordinate TS is proposed for a backside attack, while the hydrogen-bonded, four-center-type TS is proposed for a frontside attack. The negative values of the cross-interaction constants (${\rho}_{XY(H)}$ = -0.38 for $XC_6H_4NH_2$ and ${\rho}_{XY(D)}$ = -0.29 for $XC_6H_4ND_2$) indicate that the reactions proceed by a concerted $S_N2$ mechanism.

• Bulletin of the Korean Chemical Society
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• 제35권9호
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• pp.2797-2802
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• 2014

Nucleophilic substitution reactions of Y-aryl methyl (8) and Y-aryl propyl (10) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed for 8 based on the negative ${\rho}_{XY}$ (= -0.23) value, while a stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed for 10 based on the positive ${\rho}_{XY}$ (= +0.68) value. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are 0.89-1.28 and 0.62-1.20 with 8 and 10, respectively. Primary normal and secondary inverse DKIEs are rationalized by a frontside attack involving hydrogen bonded, four-center-type transition state and backside attack involving in-line-type transition state, respectively.

• Bulletin of the Korean Chemical Society
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• 제34권6호
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• pp.1829-1834
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• 2013

The nucleophilic substitution reactions of Y-aryl ethyl isothiocyanophosphates with substituted X-anilines and deuterated X-anilines were investigated kinetically in acetonitrile at $75.0^{\circ}C$. The free energy relationships with X in the nucleophiles exhibited biphasic concave downwards with a break point at X = H. A stepwise mechanism with rate-limiting bond formation for strongly basic anilines and with rate-limiting bond breaking for weakly basic anilines is proposed based on the negative and positive ${\rho}_{XY}$ values, respectively. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) changed gradually from primary normal with strongly basic anilines, via primary normal and secondary inverse with aniline, to secondary inverse with weakly basic anilines. The primary normal and secondary inverse DKIEs were rationalized by frontside attack involving hydrogen bonded, four-center-type TSf and backside attack involving in-line-type TSb, respectively.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3811-3816
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• 2013

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

• Bulletin of the Korean Chemical Society
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• 제11권1호
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• pp.60-64
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• 1990

The reactions of alkanesulfonyl chlorides with pyridines in the presence of various solvents have been studied by means of kinetic method. Alkanesulfonyl chlorides bearing ${\alpha}$-hydrogen with the normal attack of pyridine is found to be at the ${\alpha}$-hydrogen with elimination to form the sulfene intermediate evidently. From the mass spectra by the reaction of ethanesulfonyl chloride with 3-picoline in the presence of methanol-$d_1$, it has shown that the reaction has a witness favorable to the slulfene intermediate.

• 약학회지
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• 제26권1호
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• pp.25-27
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• 1982

We had reported that s-triazine can readily be converted into the corresponding 5-substituted pyrimide. In order to develop new synthetic method of 5-fluorouracil, we tried to replace eliminating fragment, 1, 3-dimethylurea, by fluoroacetamide, which was expected to undergo nucleophilic attack by proton extraction of both .alpha.-hydrogen and aminohydrogen by lithium diisopropylamide (LDA). We found that 5-fluorouracil could be transformed from s-triazine under strong base condition like LDA as well as other 5-substituted pyrimidines.

• 한국안전학회지
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• 제25권1호
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• pp.17-21
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• 2010

The chemistry and ignition delay of hydrogen/air/HFP premixed mixtures was investigated numerically with unsteady perfectly stirred reactor(PSR). The detailed chemistry of 93 species and 817 reaction mechanism was introduced for hydrogen/air/HFP mixtures. The results shows the temporal concentration variations of major or reactants such as hydrogen and oxygen during autoignition were similar to the spatial distribution of premixed flame while water vapor produced at the ignition temperature was decomposed later, which can be clarified with the relate species production rates that the the re-growth (or shoulder) of OH concentration is a result of F radicals attacking $H_20$ forming OH and HF. For the stoichiometric $H_2$/air mixture inhibited by 20% HFP, HFP thermal decomposition reaction prevails over the radical attack such as H at initial stage. Even though relatively large HFP addition contributes to delay the ignition, chemical effect on the ignition delay is not effective because of late thermal decomposition of HFP. The most small ignition delay was observed at a slightly fuel lean condition ($\phi$ = 0.9), and temperature dependency of ignition delay was clearly shown near 900 K.

• 한국가스학회지
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• 제15권2호
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• pp.1-8
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• 2011

본 연구에서는 강화되는 자동차 배기가스 규제를 만족시키기 위하여 압축천연가스자동차보다는 배기가스부분에서 유리하고, 아직 상용화되지 않은 수소연료전지자동차의 대안으로서 수소경제의 본격적인 도입을 위한 과도기적 대안연료로 주목받고 있는 수소와 천연가스를 혼합한 연료인 HCNG 충전소의 안전에 관한 동향 및 기술을 분석하였다. HCNG는 기존의 CNG 인프라의 활용, 점점 강화되는 배기가스 배출기준의 충족, 그리고 다가오는 수소시대를 대비하여 수소시대로 가기위한 기술적, 사회적 가교역할을 한다는 점에서 매우 중요한 기회이자 도전이다. 이를 위해 HCNG 상용화에 필수적으로 요구되는 수소-압축천연가스 혼합연료 사용에 대비한 각종 안전 고려사항 들에 대하여 검토하여 국내 사고 이력을 기초로 하여 사고발생시나리오, 안전거리 추가 필요성, 수소침식, 점화원, 화재감지 등의 안전 고려사항을 제시하였고, HCNG 충전소 기술 및 기준에 관한 최근동향을 분석하여 향후 HCNG 충전소 시범 운영을 위한 안전성평가 등 제도적 기반 구축을 제안하였다.