• Title/Summary/Keyword: Binary Mixtures

검색결과 336건 처리시간 0.025초

Nucleophilic Substitution Reaction of α-Methoxy-α-(trifluoromethyl)phenylacetyl Chloride in Alcohol-Water Mixtures

  • 구인선;이성인;안선경;양기열;이익춘
    • Bulletin of the Korean Chemical Society
    • /
    • 제20권12호
    • /
    • pp.1451-1456
    • /
    • 1999
  • Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

Transition-State Variation in the Solvolyses of Phenyl Chlorothionoformate in Alcohol-Water Mixtures

  • 구인선;양기열;강대호;박혜진;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
    • /
    • 제20권5호
    • /
    • pp.577-580
    • /
    • 1999
  • Solvolyses of phenyl chlorothionoformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of firstorder rate constants for phenyl chlorothionoformate with Ycl (based on 2-adamantyl chloride) show a dispersion phenomenon, and also the extended Grunwald-Winstein plots show a poor correlation for the solvolyses of phenyl chlorothionoformate. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original and extended Grunwald-Winstein correlations. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by the conjugation between the reaction center and the aromatic ring in the vicinity of the reaction center. This study has shown that the magnitude of l and m values associated with a change of solvent composition leads to predict the SN2 transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed SN2 mechanism.

Phase Behavior Study of Poly(ethylene-co-octene) in normal-Hydrocarbons

  • Kwon, Hyuk-Sung;Lee, Sang-Ho
    • Elastomers and Composites
    • /
    • 제38권1호
    • /
    • pp.51-56
    • /
    • 2003
  • Cloud-point and bubble-point data to $170^{\circ}C$ and 50 bar are presented for four different solvents, normal pentane. n-hexane, n-heptane, and n-octane with poly(ethylene-co-42 wt% octene) ($PEO_{42}$) copolymer. The pressure-concentration isotherms measured for $PEO_{42}$ - normal pentane have maximums at around 5 wt% of the copolymer concentrations in the solution. $PEO_{42}$- normal pentane system exhibits LCST-type phase behavior at temperatures greater than $130^{\circ}C$. Below $120^{\circ}C$, bubble-point type transitions are observed. However, the binary mixtures for $PEO_{42}$ in n-hexane, n-heptane, and n-octane have only bubble-point type transitions at the pressure-temperature region investigated in this study. The single-phase region of PEO - alkane mixtures increases with the molecular size of alkane solvent due to the increasing dispersion interactions between PEO and the alkane.

Measurement of the excited Xe atoms density of matastable state$(1S_5)$ under various binary gas mixtures(Ne-Xe) by Laser Absorption Spectroscopy.

  • Lee, Jun-Ho;OH, P.Y.;Moon, M.W.;Ko, B.D.;Jeong, J.M.;Lee, H.J.;Choi, E.H.
    • 한국정보디스플레이학회:학술대회논문집
    • /
    • 한국정보디스플레이학회 2005년도 International Meeting on Information Displayvol.II
    • /
    • pp.1218-1220
    • /
    • 2005
  • We have developed laser absorption spectroscopy system for the measurement of excited Xe atoms in micro-discharged AC-PDP plasma. In this study, we have measured the absorption signals for the $1S_5$ xenon metastable state in the PDP cell with the various gas mixtures of Ne-Xe(1%), Ne-Xe(4%) and Ne-Xe(10%) under fixed gas pressure of 350 Torr and the eletrode gap distance of 50um. It is found that the maximum excited xenon densities are $1.2^{\ast}10^{12}\;cm^{-3}$, $1.8^{\ast}10^{12}\;cm^{-3}$ and $2.7^{\ast}10^{12}cm^{-3}$ for gas mixtures of Ne-Xe(1%), Ne-Xe(4%) and Ne-Xe(10%) respectively, in this experiment.

  • PDF

Poly(dimethyl siloxane)막에 의한 삼성분 알코올수용액의 투과증발 (Pervaporation of Ternary Aqueous Alcohol Solutions through Poly(dimethyl siloxane) Membrane)

  • 김상집;김진환
    • 공업화학
    • /
    • 제7권6호
    • /
    • pp.1087-1095
    • /
    • 1996
  • Poly(dimethyl siloxane)막을 이용하여 $45^{\circ}C$에서 에탄올/이소프로판올/물의 삼성분 혼합물에 대한 투과증발실험을 행하고, 에탄올과 이소프로판올의 존재가 상호의 투과특성에 미치는 영향을 연구하였다. 에탄올과 이소프로판올은 각각 상호의 투과속도를 감소시키는 경향을 나타내었으며, 이소프로판올이 에탄올의 투과에 미치는 영향보다는 에탄올이 이소프로판올의 투과에 미치는 영향이 더 현저하였다. 투과속도의 감소는 고분자막에 대한 에탄올이나 이소프로판올의 가소화 영향보다는 투과성분 사이의 상호작용에 의한 영향이 더 크기 때문으로 생각되었다. 삼성분 혼합물에서 투과성분 사이의 강한 상호작용은 에탄올과 이소프로판올의 투과에 대한 추진력을 감소시키는 결과를 나타내었다.

  • PDF

Correlation of Rates of Solvolysis of Phenyl Chlorodithioformate

  • An, Sun-Kyoung;Yang, Jin-Soon;Cho, Jun-Mi;Yang, Ki-yull;Lee, Jong-Pal;Bentley, T.W.;Lee, Ik-choon;Koo, In-Sun
    • Bulletin of the Korean Chemical Society
    • /
    • 제23권10호
    • /
    • pp.1445-1450
    • /
    • 2002
  • Solvolytic rate constants at 25 $^{\circ}C$ are reported for solvolysis of chlorodithioformate (1) in binary mixtures of water with acetone, ethanol, methanol, methanol-d, 50%methanol-d/50%D2O, and 2,2,2-trifluroethanol (TFE), and also in TFE-ethanol mixtures. The Grunwald-Winstein plot shows that the three aqueous mixtures exhibit dispersions into separate line. The correlation is improved only slightly by additional parameters NT for solvent nucleophilicity and/or I for aromatic ring parameter. Rate ratios in solvents of the same $Y_cl$ value, having different nucleophilicity provide measures of the minimum extent of nucleophilic solvent assistance, and the value of 3.35 for $[$k_{40EW}$/$k_97TFE$]_Y$ (EW = ethanol-water), is consistent with an essentially SN1 reaction mechanism. This study has shown that the magnitude of l, m and h values associated with a change of solvent composition is able to predict the SN1 reaction mechanism. log(k/$k_o$) = mY + lN + hI

Fuzzy inference systems based prediction of engineering properties of two-stage concrete

  • Najjar, Manal F.;Nehdi, Moncef L.;Azabi, Tareq M.;Soliman, Ahmed M.
    • Computers and Concrete
    • /
    • 제19권2호
    • /
    • pp.133-142
    • /
    • 2017
  • Two-stage concrete (TSC), also known as pre-placed aggregate concrete, is characterized by its unique placement technique, whereby the coarse aggregate is first placed in the formwork, then injected with a special grout. Despite its superior sustainability and technical features, TSC has remained a basic concrete technology without much use of modern chemical admixtures, new binders, fiber reinforcement or other emerging additions. In the present study, an experimental database for TSC was built. Different types of cementitious binders (single, binary, and ternary) comprising ordinary portland cement, fly ash, silica fume, and metakaolin were used to produce the various TSC mixtures. Different dosages of steel fibres having different lengths were also incorporated to enhance the mechanical properties of TSC. The database thus created was used to develop fuzzy logic models as predictive tools for the grout flowability and mechanical properties of TSC mixtures. The performance of the developed models was evaluated using statistical parameters and error analyses. The results indicate that the fuzzy logic models thus developed can be powerful tools for predicting the TSC grout flowability and mechanical properties and a useful aid for the design of TSC mixtures.

Transition-State Variation in the Solvolyses of para-Substiuted Phenyl Chloroformates in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;이익춘
    • Bulletin of the Korean Chemical Society
    • /
    • 제19권9호
    • /
    • pp.968-973
    • /
    • 1998
  • Solvolyses of para-substituted phenyl chloroformates in water, $D_2O,\;CH_3OD$, 50% $D_2O-CH_3OD$, and in aqueous binary mixtures of acetone, ethanol, methanol are investigated at 25.0 ℃. Product selectivities are reported for a wide range of ethanol-water and methanol-water solvent compositions. These data are interpreted using the Grunwald-Winstein relationship, Hammett equation, and quantum mechanical model. Grunwald-Winstein plots of the first-order rate constants for phenyl chloroformates with $Y_{Cl}$ (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. To account for these results, third-order rate constants, $k_{ww},\;k_{aw},\;k_{wa}$, and $k_{aa}$ were calculated from the observed $k_{ww}\;and\;k_{aa}$ values together with $k_{aw}\;and\;k_{wa}$ calculated from the computer fit. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination for para-substituted phenyl chloroformates solvolyses based on mass law and stoichiometric salvation effect studies. This study has shown that the quantum mechanical model predicts transition state variation correctly for $S_N2\;like\;S_AN$ reaction mechanism of para-substituted phenyl chloroformates.

Stoichiometric Solvation Effects. Product-Rate Correlation for Solvolyses of Phenyl Chloroformate in Alcohol-Water Mixtures

  • 구인선;양기율;강금덕;오혁근;이익춘
    • Bulletin of the Korean Chemical Society
    • /
    • 제17권6호
    • /
    • pp.520-524
    • /
    • 1996
  • Solvolyses of phenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for phenyl chloroformate with YCl (based on 2-adamantyl chloride) show marked dispersions into three separate lines for the three aqueous mixtures with a small m value (m< 0.2) and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed and/or carbonyl addition for phenyl chloroformate solvolyses based on mass law and stoichiometric solvation effect studies.

평판 표면에서 HFC32/HFC152a 혼합냉매의 풀 비등 열전달계수 (Pool Boiling Heat Transfer Coefficient of HFC32/HFC152a on a Plain Surface)

  • 강동규;이요한;정동수
    • 설비공학논문집
    • /
    • 제25권9호
    • /
    • pp.484-492
    • /
    • 2013
  • Nucleate pool boiling heat transfer coefficients (HTCs) are measured with HFC32/HFC152a mixture at several compositions. All data are taken at the liquid pool temperature of $7^{\circ}C$, on a horizontal plain square surface of $9.53{\times}9.53$ mm, with heat fluxes of 10 $kW/m^2$ to 100 $kW/m^2$ with an interval of 10 $kW/m^2$, in the increasing order of heat flux. Test results show that the HTCs of these mixtures are up to 45% lower than those of the ideal HTCs calculated by a linear mixing rule with pure fluids' HTCs, due to the mass transfer resistance associated with non-azeotropic refrigerant mixtures. Pool boiling data show the deduction in HTCs with an increase in GTD of the mixture. The present mixture data agree well with five well known correlations, within 20% deviation.