• Title/Summary/Keyword: secondary reaction

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Solvent Effects on the Nucleophilc Addition (I) Effect of Solvent Polarity on the Nucleophilic Addition of Amine to Phenylvinylketone (친핵성 첨가반응에 대한 용매효과 (I) Phenylvinylketone에 대한 아민의 첨가반응속도에 미치는 용매의 극성효과)

  • Gap-Cheol Shin;Tae-Rin Kim
    • Journal of the Korean Chemical Society
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    • v.36 no.2
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    • pp.287-292
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    • 1992
  • The rate constants of the nucleophilic addition reaction of amines (piperidine and diethylamine) to phenylvinylketone in various solvents have been determined by UV spectrophotometry at $25^{\circ}C$. On the basis of the high sensitivity of the rate to the polarity of the medium, it may be concluded that the reaction intermediate has zwitterionic character. The effect of the solvents on the rate of the bimolecular nucleophilic addition reaction is described well by the Kirkwood equation: The transition state of the reaction has a cyclic structure formed through an intramolecular hydrogen bond. The addition reaction of primary and secondary amines to phenylvinylketone in all solvents take place considerably faster than that of tertiary amine and this results also can be explained by the intermediate products in the reaction have a cyclic structure formed through an intramolecular hydrogen bond for the primary and secondary amines but not for the tertiary amine.

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Characteristic Analysis of a Linear Induction Motor for a Lightweight Train According to Various Secondary Schemes

  • Lee, Hyung-Woo;Lee, Sung-Gu;Park, Chan-Bae;Lee, Ju;Park, Hyun-June
    • International Journal of Railway
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    • v.1 no.1
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    • pp.6-11
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    • 2008
  • This paper presents a performance characteristic analysis methodology for a linear induction motor used for a lightweight train. In general, an analytical method cannot provide accurate results in a linear motor because of large airgap, end effect, transverse edge effect, 3-dimensional configurations, large leakage, and so on. Besides, a numerical method requires lots of memory and solving time for transient analysis. However, the suggested methodology which is a kind of hybrid solution with an analytical method and a numerical method is very fast and accurate. Based on the methodology, 3-D FEM analyses for various design schemes of the secondary reaction plate have been done and from the analysis results, the best configuration for an urban railway transit is chosen.

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Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.7
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    • pp.2306-2310
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    • 2011
  • The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

Study on the surface porosity of porous thin layer electrode for phosphoric acid fuel cell (인산형 연료전지용 다공성 박막의 표면 다공도에 관한 연구)

  • 김조웅;김영우;이주성
    • Journal of the Korean institute of surface engineering
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    • v.24 no.3
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    • pp.162-168
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    • 1991
  • Gas diffusion and electrolyte penetration in wetproofed gas diffusion electrodes were studied using layers of PTFE- bonded carbon. Minor variations in fabrication and testing procedures resulted in very large variations in catalyst layer wetting characteristics and permiability for reaction gas. By controlling the pore size of gas diffusion electrode carefully by varing the PTFE contents, baking temperature, baking time and ammonium bicarbonate as additive, the primary pore was decreased and the secondary pore was increased and so more reaction gas through the primary pore could be reacted at catalyst agglomertes in the secondary pore. And the cathode current density was increased to more than 400mA.$\textrm{cm}^2$ and Tafel slope value was decreased to lower than 110mA/decade.

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The Study on Secondary Pollutants of $PM_{10}$ in Pocheon (포천지역에서 측정한 $PM_{10}$중 2차 생성입자에 관한 연구)

  • Park Tae-Sool
    • Journal of environmental and Sanitary engineering
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    • v.20 no.4 s.58
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    • pp.9-20
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    • 2005
  • The purpose of the study was characteristics of secondary pollutants of $PM_{10}$ collected in pocheon between August 2002 and June 2003. The ambient concentrations of $PM_{10}$ mass, 9 water-soluble anions and cations, and 13 bulk composition trace elements were determined from filter samples collected by $PM_{10}$ high volume air sampler(UV-15H, Graseby-Anderson Co., USA). During this period average $PM_{10}$ mass concentration was $83.8{\mu}g/m^3(49.8{\mu}g/m^3\~111.6{\mu}g/m^3)$ in Pocheon. Mechanism for transformation of secondary pollutants by soluble ion components is divided into two categories; $NaNO_3$ type by the reaction of sea salt and $HNO_3$ in the atmosphere, and nitrate salt or phosphate salt type such as $(NH_4)_2SO_4,\;NH_4NaSO_4,\;and\;(NH_4)_2SO_4(2NH_4O_3)$.

Premature Stiffening of Cement Paste Caused by Secondary Gypsum and Syngenite Formation (False Set)

  • Chung, Chul-Woo;Lee, Jae-Yong
    • Architectural research
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    • v.13 no.1
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    • pp.25-32
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    • 2011
  • The purpose of this research is to investigate the effect of specific hydration reaction on the stiffening process of cement paste. The cement compositions are manipulated to cause specific hydration reactions (secondary gypsum and syngenite formation) responsible for false set, and the relationship between specific hydration reactions and the flow and stiffening behavior of cement paste were investigated using modified ASTM C 403 penetration resistance measurement and oscillatory shear rheology. X-ray powder diffraction (XRD) was used for the phase identification associated with premature stiffening of cement paste. Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) were used for verification of syngenite formation. From the results, both secondary gypsum and syngenite formation caused faster stiffening and set. The amount of syngenite produced during 1 hour hydration was approximately 1 % of total mass of the cement paste, but cement paste with syngenite formation showed significantly accelerated stiffening behavior compared to normal cement paste.

A New Method for Synthesizing Tetrazoles from Secondary Amines using Trichloroacetonitrile (이차 아민으로부터 트리클로로아세토니트릴을 사용한 테트라졸 유도체의 새로운 합성법)

  • Oh, Su-Jin
    • Journal of the Korea Institute of Military Science and Technology
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    • v.20 no.6
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    • pp.781-787
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    • 2017
  • A new method for synthesizing the tetrazole derivatives from secondary amines through cyanation/tetrazolation has been developed. Trichloroacetonitrile is used as the cyano source to synthesize N-nitrile instead of highly toxic and expensive cyanogen bromide. In this protocol, the reaction of secondary amines with various substituents proceed smoothly, and the desired tetrazole derivatives are obtained directly in fair to high yields without isolation of intermediate cyanamides.

Lipid Peroxidation and Its Nutritional Significance (지방질의 과산화와 영양)

  • 최홍식
    • Journal of the Korean Society of Food Science and Nutrition
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    • v.23 no.5
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    • pp.867-878
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    • 1994
  • A general overview of the lipid peroxidation and its nutritional significance are presented ,with emphasis on the reaction mechaisms, peroxidized products, further interaction and nutritional/biological deterioration in a series of oxidative process. Overall mechanism with various factors and elements for initiation , propagation and termination of free radical reaction is reviewed and the primary /secondary products of peroxidized lipids are defined. Since these products are potentially reactive substances that can cause deterioration of proteins /amino acids and vitamins (carotene, tocopherols and ascorbic acid etc), mechanism and actual damages of their deterioration in some foods and biological models are outlined. Especially , chemical changes caused by interaction of peroxidized products (related hydroperoxides, radicals and malonaldehye etc) and protein are emphasized here. And also, the detailed mechanisms on radical scavenging of the these vitamins which are the most prominent natural antioxidants are presented . Additionally , the possible roles of peroxidicaed lipids and their secondary products in the process of aging an carcinogenesis are briefly discussed . However, it is important to not that more detailed and integrated studies on the reaction kinetics, energetics of peroxidation, their decomposed products , biochemical interaction potential damaging/aging / carcinogenic effects, protection from their oxidative spoilage and novel antioxidants in food and heterogeneous biological systems will be essential in order to assessing the implication of lipid peroxidation to human nutrition and health.

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Kinetics and Mechanism of the Anilinolysis of Bis(N,N-dimethylamino) Phosphinic Chloride in Acetonitrile

  • Barai, Hasi Rani;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • v.32 no.12
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    • pp.4361-4365
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    • 2011
  • The nucleophilic substitution reactions of bis(N,N-dimethylamino) phosphinic chloride (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $65.0^{\circ}C$. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The magnitudes of ${\rho}_X$ (= -6.42) and ${\beta}_X$ (= 2.27) values are exceptionally great. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D$ = 0.69-0.96). A concerted $S_N2$ mechanism involving a backside attack is proposed on the basis of secondary inverse DKIEs and the variation trend of the $k_H/k_D$ values with X. The anilinolyses of six phosphinic chlorides in MeCN are briefly reviewed by means of DKIEs, steric effects of the two ligands, positive charge of the reaction center phosphorus atom, and selectivity parameters to obtain systematic information on phosphoryl transfer reaction mechanism.

Synthesis and Electrochemical Evaluation of La1-xSrxCoO3 Cathode Material for Zinc Air Secondary Batteries Application (아연공기이차전지용 La1-xSrxCoO3 양극촉매의 제조 및 이를 적용한 양극의 전기화학적 특성연구)

  • Eom, Seung-Wook;Sun, Yang-Kook
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.21 no.5
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    • pp.447-452
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    • 2008
  • We synthesized nano-sized $La_{1-x}Sr_xCoO_3$ ($x=0.1{\sim}0.4$) cathode catalyst for the zinc air secondary batteries by citrate method, And we measured the cathode's electrochemical characteristics according to content of strontium compose the cathode catalyst. We controlled the pH of precursor solution by 10 in the process of manufacturing the precursor, We heat treated the prepared precursor at various calcination temperature ($500{\sim}900^{\circ}C$), and examined the optimum calcinations temperature by XRD analysis and electrochemical evaluation. We examined the ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) performance of the prepared $La_{1-x}Sr_xCoO_3$ catalyst powder. When we consider ORR and OER performance simultaneously, $La_{0.7}Sr_{0.3}CoO_3$ catalyst has shown the best performance because of its lowest voltage deference between charge and discharge.