• 제목/요약/키워드: chemical attack

검색결과 357건 처리시간 0.028초

Kinetics and Mechanism of Anilinolyses of Ethyl Methyl, Ethyl Propyl and Diisopropyl Chlorothiophosphates in Acetonitrile

  • Barai, Hasi Rani;Hoque, Md. Ehtesham Ul;Lee, Hai Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권12호
    • /
    • pp.3811-3816
    • /
    • 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.

부순모래를 사용한 시멘트 모르타르의 화학적 침해 저항 특성 (Chemical Attack Resistance Characteristics of Cement Mortars U sing in Crushed Sand)

  • 김강민;백동일;김명식;장희석
    • 한국콘크리트학회:학술대회논문집
    • /
    • 한국콘크리트학회 2005년도 추계 학술발표회 제17권2호
    • /
    • pp.519-522
    • /
    • 2005
  • As this study is to test effects of chemical attack on deterioration of cement mortars using in crushed sand. Besides tests have been carried out with cement mortars by river sand and crushed sand by fine sand, cement mortars mix various proportions of slica fume and fly ash(up to $15\%$ and $50\%$ by weight for cement) were prepared and immersed in pure water, sodium sulfate solution, magnesium sulfate solution, seawater for 28days. Test on the change in the weight and compressive strength of cement mortars according to the duration of immersion time and the content of slica fume and fly ash was performed.

  • PDF

Kinetics and Mechanism of the Pyridinolysis of Diisopropyl Thiophosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제32권12호
    • /
    • pp.4387-4391
    • /
    • 2011
  • The kinetic studies on the pyridinolysis of diisopropyl thiophosphinic chloride have been carried out in acetonitrile at $55.0^{\circ}C$. The free energy correlations for substituent X variations in the X-pyridines are biphasic concave upwards with a break point at X = 3-Ph. A concerted SN2 mechanism is proposed with a change of the attacking direction of the X-pyridine from a frontside attack for the strongly basic pyridines to a backside attack for the weakly basic pyridines. The factors to determine the rates and thio effects on the rates for the pyridinolyses of thiophophinic chloride, chlorothiophosphate, phosphinic chloride, phosphonochloridothioate, and chlorophosphate systems are briefly reviewed on the basis of the magnitude of the positive charge of the reaction center P atom and steric effects of the two ligands.

텡스텐 플러그 CVD 공정에서 SiH4 Soak의 영향 (SiH4 Soak Effects in the W plug CVD Process)

  • 이우선;서용진;김상용;박진성
    • 한국전기전자재료학회논문지
    • /
    • 제16권1호
    • /
    • pp.1-4
    • /
    • 2003
  • The SiH$_4$soak step is widely used to prevent the WF$_{6}$ attack to the underlayer metal using the chemical vapor deposition (CVD) method. Reduction or skipping of the SiH$_4$soak process time if lead to optimizing W-plug deposition process on via. The electrical characteristics including via resistance and the structure of W-film are affected by the time of SiH$_4$soak process. The possibility of elimination of SiH$_4$soak process is confirmed In the case of W- film grown on the stable Ti/TiN underlayer.

Kinetics and Mechanism of the Pyridinolysis of Dimethyl Isothiocyanophosphate in Acetonitrile

  • Adhikary, Keshab Kumar;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
    • /
    • 제33권7호
    • /
    • pp.2260-2264
    • /
    • 2012
  • The kinetics and mechanism of the pyridinolysis ($XC_5H_4N$) of dimethyl isothiocyanophosphate are investigated in acetonitrile at $55.0^{\circ}C$. The Hammett and Br$\ddot{o}$nsted plots for substituent X variations in the nucleophiles exhibit two discrete slopes with a break region between X = 3-Ac and 4-Ac. These are interpreted to indicate a mechanistic change at the break region from a concerted to a stepwise mechanism with a rate-limiting expulsion of the isothiocyanate leaving group from the intermediate. The relatively large ${\beta}x$ values imply much greater fraction of frontside nucleophilic attack TSf than that of backside attack TSb. The steric effects of the two ligands play an important role to determine the pyridinolysis rates of isothiocyanophosphates.

Metakaolin 혼합 고강도콘크리트의 내구특성 평가 (Estimation on the Durability of High-Strength Concrete using Metakaolin)

  • 문한영;염준환;문수동;이상호
    • 한국콘크리트학회:학술대회논문집
    • /
    • 한국콘크리트학회 2004년도 추계 학술발표회 제16권2호
    • /
    • pp.217-220
    • /
    • 2004
  • Metakaolin is a cementitious material for producing high-strength concrete. This material is now used as substitute for silica-fume. In this paper, we did the durability test such as chloride ion diffusion, chemical attack. repeated freezing and thawing, carbonation. In the chloride ion diffusion test, according to the increase of substitute of metakaolin & silica-fume for binder, the diffusion coefficient is more reduced. And in the chemical attack test, according to the increase of substitute, the resistance is more excellent. In the other durability test, the concrete using metakaolin is also compared with those of the portland cement concrete and silica fume concrete. According to these tests, we recognized that metakaolin is able to be used as a substitute for silica-fume.

  • PDF

Stereospecific C$_6$-Hydroxyethylation of the Penicillin Nucleus

  • Kim, Wan-Joo;Lee, Gwan-Sun;Shim, Sang-Chul
    • Bulletin of the Korean Chemical Society
    • /
    • 제5권5호
    • /
    • pp.191-193
    • /
    • 1984
  • 6, 6-Diiodopenicillanic acid was prepared from 6-aminopenicillanic acid using iodine-sodium iodide systems in good yield (60%). Enolates derived from 6-chloro-6-iodo-, 6,6-diiodo-penicillanate have been generated in situ by a metal-halogen exchange process at -$78^{\circ}C$ using methylmangnesium iodide and reacted with acetaldehyde to yield aldols. As the size of remaining halogen atom increases, the proportion of ${\beta}$-face attack was increased. In the case of 6,6-diiodopenicillanate, only ${\beta}$-face attack was observed yielding a single isomer (6S, 8R).

Mechanical Strength Evaluation of A53B Carbon Steel Subjected to High Temperature Hydrogen Attack

  • Kim, Maan-Won;Lee, Joon-Won;Yoon, Kee-Bong;Park, Jai-Hak
    • International Journal of Safety
    • /
    • 제6권2호
    • /
    • pp.1-7
    • /
    • 2007
  • In this study mechanical strength of A53B carbon steel was analyzed using several types of test specimens directly machined from oil recycling pipe experienced a failure due to hydrogen attack in chemical plants. High temperature hydrogen attack (HTHA) is the damage process of grain boundary facets due to a chemical reaction of carbides with hydrogen, thus forming cavities with high pressure methane gas. Driven by the methane gas pressure, the cavities grow on grain boundaries forming intergranular micro cracks. Microscopic optical examination, tensile test, Charpy impact test, hardness measurement, and small punch (SP) test were performed. Carbon content of the hydrogen attacked specimens was dramatically reduced compared with that of standard specification of A53B. Traces of decarburization and micro-cracks were observed by optical and scanning electron microscopy. Charpy impact energy in hydrogen attacked part of the pipe exhibited very low values due to the decarburization and micro fissure formation by HTHA, on the other hand, data tested from the sound part of the pipe showed high and scattered impact energy. Maximum reaction forces and ductility in SP test were decreased at hydrogen attacked part of the pipe compared with sound part of the pipe. Finite element analyses for SP test were performed to estimate tensile properties for untested part of the pipe in tensile test. And fracture toughness was calculated using an equivalent strain concept with SP test and finite element analysis results.

해안매립지에 위치한 콘크리트구조물의 염해조사 (Investigation of Salt Attack of Concrete Structures Exposed to Reclaimed Marine Land)

  • 김성수;정란;김영웅;김용철;박광필
    • 한국콘크리트학회:학술대회논문집
    • /
    • 한국콘크리트학회 2002년도 가을 학술발표회 논문집
    • /
    • pp.835-840
    • /
    • 2002
  • Chloride ions have a tendency to penetrate into concrete and proceed the corrosion by depassivating rebar surface. Thus tire deteriorated concrete is subject to experience severe degrading of durability under marine environment. In this study, concrete structures exposed to reclaimed marine land wet-e investigate to find out the salt attack along with analysis and review of it's cause. Under the reclaimed marine land, the main causes of deterioration of concrete structures is the steel corrosion due to the Penetration of chlorides and the deterioration of outer concrete itself by chemical attack.

  • PDF