• 제목/요약/키워드: Cyclic compound

검색결과 148건 처리시간 0.022초

Co(Ⅱ)$(dimethyl bipyridine)_3(ClO_4)_2$의 전기화학적 성질과 산소환원에 대한 전극 촉매 효과 (Electrocatalytic Effect on the Oxygen Reduction and Electrochemical Properties of Co(Ⅱ)-dimethyl Bipyridine Perchlorate)

  • 김일광;박종술;한완수;김윤근;전일철
    • 대한화학회지
    • /
    • 제41권8호
    • /
    • pp.385-391
    • /
    • 1997
  • Co$(dimethyl bipyridine)_3(ClO_4)_2$의 확산계수$(D_0)$와 전극반응속도상수$(K_0)$를 순환전압전류법과 대시간전류법으로 구하였다. 확산계수에 대한 용매, 농도, 주사속도 등의 영향과 반응속도상수에 대한 온도변화의 영향을 조사하였다. 25$^{\circ}C$에서 확산계수는 $5.54{\times}10^{-6 }cm^2/sec$이었고, 반응속도상수는 $2.39{\times}10^{-3 }/s$ 이었으며, 용매의 점도가 커질수록 봉우리전류값과 확산계수는 감소하였다. 반응속도상수에 대한 온도의 영향으로부터, ${\Delta}G^{\neq},\;{\Delta}H^{\neq},\;{\Delta}S$ 등의 열역학적 파라미터를 구하였다. 이 화합물은 $O_2$분자의 환원에서 봉우리전류를 크게 증가시키고, 환원전위를 양(+)전위방향으로 이동시키는 열역학적 전극촉매현상을 보였다.

  • PDF

Effect of Aluminum and Silicon on Atmospheric Corrosion of Low-alloying Steel under Containing NaHSO3 Wet/dry Environment

  • Chen Xinhua;Dong Junhua;Han Enhou;Ke Wei
    • Corrosion Science and Technology
    • /
    • 제7권6호
    • /
    • pp.315-318
    • /
    • 2008
  • The atmospheric corrosion performance of Al-alloying, Si-alloying and Al-Si-alloying steel were studied by wet/dry cyclic corrosion tests (CCT) at $30^{\circ}C$ and 60% relative humidity (RH). The corrosion electrolyte used for CCT was 0.052 wt% $NaHSO_{3}$ (pH~4) solution. The result of gravimetry demonstrated that Al-Si-bearing steels showed lower corrosion resistance than other rusted steels. But the rusted 0.7%Si-alloying steel showed a better corrosion resistance than rusted mild steel. Polarization curves demonstrated that Al-/Si-alloying and Al-Si-alloying improved the rest potential of steel at the initial stage; and accelerated the cathodic reduction and anodic dissolution after a rust layer formed on the surfaces of steels. XRD results showed that Al-Si-alloying decreased the volume fraction of $Fe_{3}O_{4}$ and $\alpha-FeOOH$. The recycle of acid accelerated the corrosion of steel at the initial stage. After the rust layer formed on the steel, the leak of rust destabilized the rust layer due to the dissolution of compound containing Al (such as $FeAl_{2}O_{4}$, $(Fe,\;Si)_{2}(Fe,\;Al)O_{4}$). Al-Si-alloying is hence not suitable for improving the anti-corrosion resistance of steel in industrial atmosphere.

A Kinetic Study on Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Polarizability and Steric Hindrance on Reactivity and Reaction Mechanism

  • Kim, Min-Young;Bae, Ae Ri;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
    • /
    • 제34권8호
    • /
    • pp.2325-2329
    • /
    • 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.

Reaction of Potassium 2-Thexyl-1,3,2-dioxaborinane Hydride with Selected Organic Compounds Containing Representative Functional Groups

  • Jin Soon Cha;Sung Eun Lee
    • Bulletin of the Korean Chemical Society
    • /
    • 제13권5호
    • /
    • pp.531-537
    • /
    • 1992
  • The approximate rates and stoichiometry of the reaction of excess potassium 2-thexyl-1,3,2-dioxaborinane hydride(KTDBNH) with 55 selected compounds containing representative functional groups under standardized conditions (tetrahydrofuran, TEX>$0^{\circ}C$, reagent : compound=4 : 1) was examined in order to define the characteristics of the reagent for selective reductions. Benzyl alcohol and phenol evolve hydrogen immediately. However, primary, secondary and tertiary alcohols evolve hydrogen slowly, and the rate of hydrogen evolution is in order of $1^{\circ}$> $2^{\circ}$> $3^{\circ}$. n-Hexylamine is inert toward the reagent, whereas the thiols examined evolve hydrogen rapidly. Aldehydes and ketones are reduced rapidly and quantitatively to give the corresponding alcohols. Cinnamaldehyde is rapidly reduced to cinnamyl alcohol, and further reduction is slow under these conditions. The reaction with p-benzoquinone dose not show a clean reduction, but anthraquinone is cleanly reduced to 9,10-dihydro-9,10-anthracenediol. Carboxylic acids liberate hydrogen immediately, further reduction is very slow. Cyclic anhydrides slowly consume 2 equiv of hydride, corresponding to reduction to the caboxylic acid and alcohol stages. Acid chlorides, esters, and lactones are rapidly and quantitatively reduced to the corresponding carbinols. Epoxides consume 1 equiv hydride slowly. Primary amides evolve 1 equiv of hydrogen readily, but further reduction is slow. Tertiary amides are also reduced slowly. Both aliphatic and aromatic nitriles consume 1 equiv of hydride rapidly, but further hydride uptake is slow. Analysis of the reaction mixture with 2,4-dinitrophenylhydrazine yields 64% of caproaldehyde and 87% of benzaldehyde, respectively. 1-Nitropropane utilizes 2 equiv of hydride, one for hydrogen evolution and the other for reduction. Other nitrogen compounds examined are also reduced slowly. Cyclohexanone oxime undergoes slow reduction to N-cyclohexylhydroxyamine. Pyridine ring is slowly attacked. Disulfides examined are reduced readily to the correponding thiols with rapid evolution of 1 equiv hydrogen. Dimethyl sulfoxide is reduced slowly to dimethyl sulfide, whereas the reduction of diphenyl sulfone is very slow. Sulfonic acids only liberate hydrogen quantitatively without any reduction. Finally, cyclohexyl tosylate is inert to this reagent. Consequently, potassium 2-thexyl-1,3,2-dioxaborinane hydride, a monoalkyldialkoxyborohydride, shows a unique reducing characteristics. The reducing power of this reagent exists somewhere between trialkylborohydrides and trialkoxyborohydride. Therefore, the reagent should find a useful application in organic synthesis, especially in the field of selective reduction.

유량 변화에 따른 exo-tetrahydrodicyclopentadiene의 열분해특성에 관한 연구 (A Study on Thermal Decomposition Characteristics of exo-tetrahydrodicyclopentadiene with Variation of Flow Rate)

  • 강샛별
    • Korean Chemical Engineering Research
    • /
    • 제57권6호
    • /
    • pp.763-767
    • /
    • 2019
  • 본 연구에서는 흐름형 반응기를 활용하여 단일 화합물로 구성된 연료인 exo-tetrahydrodicyclopentadiene (exo-THDCP)의 유량을 변화시킴에 따라 나타나는 열분해 특성에 대해 분석하였다. 실험은 $500^{\circ}C$, 50 bar의 온도와 압력 조건에서 수행하였으며, 각 유량 조건에서 반응을 통해 생성된 물질은 GC/MS를 사용하여 분석하였다. 그 결과, exo-THDCP는 열에 의해 주로 고리형 화합물로 분해됨과 동시에 일부는 이성질화 되는 것을 확인하였다. 또한, 유량이 증가할수록 분해 및 이성질화 반응을 통해 생성되는 화합물의 종류와 비율이 감소하였으며, 이에 따라 연료의 전환율과 분해 반응 시에 발생하는 흡열량도 함께 감소하였다. 열분해 반응 시에 비교적 빠르게 생성되는 화합물은 주로 1-cyclopentylcyclopentene (1-CPCP)의 radical 형태를 중간체로 하여 형성되는 것으로 분석되었는데, 이는 exo-THDCP로부터 생성될 수 있는 중간체 중에서도 특히 1-CPCP가 생성되는 데에 필요한 활성화 에너지가 약 42 kcal/mol로 가장 낮기 때문인 것으로 해석된다.

Electrochemical Behavior of Sm(III) on the Aluminium-Gallium Alloy Electrode in LiCl-KCl Eutectic

  • Ye, Chang-Mei;Jiang, Shi-Lin;Liu, Ya-Lan;Xu, Kai;Yang, Shao-Hua;Chang, Ke-Ke;Ren, Hao;Chai, Zhi-Fang;Shi, Wei-Qun
    • 방사성폐기물학회지
    • /
    • 제19권2호
    • /
    • pp.161-176
    • /
    • 2021
  • In this study, the electrochemical behavior of Sm on the binary liquid Al-Ga cathode in the LiCl-KCl molten salt system is investigated. First, the co-reduction process of Sm(III)-Al(III), Sm(III)-Ga(III), and Sm(III)-Ga(III)-Al(III) on the W electrode (inert) were studied using cyclic voltammetry (CV), square-wave voltammetry (SWV) and open circuit potential (OCP) methods, respectively. It was identified that Sm(III) can be co-reduced with Al(III) or Ga(III) to form AlzSmy or GaxSmy intermetallic compounds. Subsequently, the under-potential deposition of Sm(III) at the Al, Ga, and Al-Ga active cathode was performed to confirm the formation of Sm-based intermetallic compounds. The X-ray diffraction (XRD) and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analyses indicated that Ga3Sm and Ga6Sm intermetallic compounds were formed on the Mo grid electrode (inert) during the potentiostatic electrolysis in LiCl-KCl-SmCl3-AlCl3-GaCl3 melt, while only Ga6Sm intermetallic compound was generated on the Al-Ga alloy electrode during the galvanostatic electrolysis in LiCl-KCl-SmCl3 melt. The electrolysis results revealed that the interaction between Sm and Ga was predominant in the Al-Ga alloy electrode, with Al only acting as an additive to lower the melting point.

Influence of Annealing Temperature on Crystal Orientation of Electrodeposited Sb2Se3 Thin-Film Photovoltaic Absorbers

  • Kim, Seonghyun;Lee, Seunghun;Park, Jaehan;Kim, Shinho;Kim, Yangdo
    • 한국재료학회지
    • /
    • 제32권5호
    • /
    • pp.243-248
    • /
    • 2022
  • This study demonstrates a different approach method to fabricate antimony selenide (Sb2Se3) thin-films for the solar cell applications. As-deposited Sb2Se3 thin-films are fabricated via electrodeposition route and, subsequently, annealed in the temperature range of 230 ~ 310℃. Cyclic voltammetry is performed to investigate the electrochemical behavior of the Sb and Se ions. The deposition potential of the Sb2Se3 thin films is determined to be -0.6 V vs. Ag/AgCl (in 1 M KCl), where the stoichiometric composition of Sb2Se3 appeared. It is found that the crystal orientations of Sb2Se3 thin-films are largely dependent on the annealing temperature. At an annealing temperature of 250 ℃, the Sb2Se3 thin-film grew most along the c-axis [(211) and/or (221)] direction, which resulted in the smooth movement of carriers, thereby increasing the carrier collection probability. Therefore, the solar cell using Sb2Se3 thin-film annealed at 250 ℃ exhibited significant enhancement in JSC of 10.03 mA/cm2 and a highest conversion efficiency of 0.821 % because of the preferred orientation of the Sb2Se3 thin film.

Alkaline induced-cation crosslinking biopolymer soil treatment and field implementation for slope surface protection

  • Minhyeong Lee;Ilhan Chang;Seok-Jun Kang;Dong-Hyuk Lee;Gye-Chun Cho
    • Geomechanics and Engineering
    • /
    • 제33권1호
    • /
    • pp.29-40
    • /
    • 2023
  • Xanthan gum and starch compound biopolymer (XS), an environmentally friendly soil-binding material produced from natural resources, has been suggested as a slope protection material to enhance soil strength and erosion resistance. Insufficient wet strength and the consequent durability concerns remain, despite XS biopolymer-soil treatment showing high strength and erosion resistance in the dried state, even with a small dosage of soil mass. These concerns need to be solved to improve the field applicability and post-stability of this treatment. This study explored the utilization of an alkaline-based cation crosslinking method using calcium hydroxide and sodium hydroxide to induce non-thermal gelation, resulting in the enhancement of the wet strength and durability of biopolymer-treated soil. Laboratory experiments were conducted to assess the unconfined compressive strength and cyclic wetting-drying durability performance of the treated soil using a selected recipe based on a preliminary gel formation test. The results demonstrated that the uniformity of the gel structure and gelling time varied depending on the ratio of crosslinkers to biopolymer; consequently, the strength of the soil was affected. Subsequently, site soil treated with the recipe, which showed the best performance in indoor assessment, was implemented on the field slope at the bridge abutment via compaction and pressurized spraying methods to assess feasibility in field implementation. Moreover, the variation in surface soil hardness was monitored periodically for one year. Both slopes implemented by the two construction methods showed sufficient stability against detachment and scouring, with a higher soil hardness index than the natural slope for a year.

Bi2O3를 첨가한 8M KOH용액에서 다결정 Ag전극의 전기화학적 거동 (Electrochemical Behaviors of Polycrystalline Silver Electrodes in 8M KOH Solutions Containing Bi2O3)

  • 허태욱;공영경;정원섭
    • 전기화학회지
    • /
    • 제8권1호
    • /
    • pp.17-23
    • /
    • 2005
  • $Bi_2O_3$를 첨가한 8M KOH용액에서 다결정 Ag전극의 전기화학적인 거동과 생성된 산화물들의 미세조직 변화를 분석하였다. $Bi_2O_3$를 첨가한 8M KOH용액에서 Ag 산화물뿐만 아니라 새로운 Ag-Bi-O화합물들이 생성되는 것을 알 수 있었다. Ag(I) 산화물 생성 전위 영역에서는 $Ag_2O$ 이외에, Ag-Bi-O 화합물이 핵 생성과 3D성장 과정에 의해서 생성되고, Ag(II)산화물 생성 전위 영역에서는 AgO뿐만 아니라 새로운 Ag-Bi-O화합물들이 핵 생성과 3D성장 과정에 의해서 생성되었다. Ag(I) 산화물 생성 전위에서 두 가지 형상의 Ag(I) 산화물이 생성되는 것을 SEM 조직에 의해 관찰하였다.

차전초(Plantago asiatica)로부터 분리된 Plantamajoside의 단회와 14일 반복투여 독성시험 및 유전독성학적 안전성 평가 (Single & 14-Day Repeated Oral Toxicity Study and Genotoxicological Safety Estimate of Plantamajoside Isolated from Plantago asiatica)

  • 박병규;이현순;정성훈;구윤창;홍충의;이선주;이광원
    • Toxicological Research
    • /
    • 제23권1호
    • /
    • pp.79-86
    • /
    • 2007
  • The isolated plantamajoside from Plantago asiatica that is often used as a marker compound in chemotaxonomic studies has various bioactivites such as the inhibitions of cyclic AMP phosphodi-esterase and 5-lipoxygenase, microbial growth and inflammation, and currently demands the generation of toxicity data. The purpose of this study was to examine the toxicities of the single and 14 days repeated dose toxicity in Sprague-Dawley rats orally administrated with plantamajoside at dose levels of 0, 500, 1000, and 2000 mg of dried material/kg body weight/day. The results showed that there was no difference in body weight change, food intake, water consumption, or relative organ weight among different dose groups. Also we observed no death and abnormal clinical signs were observed during the experimental period. Between the groups orally administered Plantago asiatica and the control group, there was no statistical significance in hematological test or serum biochemical values. There were no gross findings at final sacrifice. There was no evidence of histopathological alteration mediated by 14 days treatment with Plantago asiatica. These results suggest that no observed adverse effect level (NOAEL) of the oral application was considered to be more than 2000 mg/kg in rats under the conditions employed in this study. Another observation was performed to investigate the safety of Plantago asiatica in respect of genotoxicity. This substance was examined that Salmonella typhimurium reversion assay (Ames test) in strain TA98, TA100, TA1535. In the reverse mutation test, Plantago asiatica did not induce mutagenicity in Samonella typhimurium with and without metabolic activation. These results indicated that Plantago asiatica had no genotoxicity.