• Bulletin of the Korean Chemical Society
• /
• v.20 no.12
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.20 no.5
• /
• 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.

• Elastomers and Composites
• /
• v.38 no.1
• /
• 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.

• 한국정보디스플레이학회:학술대회논문집
• /
• 2005.07b
• /
• 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.

• Applied Chemistry for Engineering
• /
• v.7 no.6
• /
• pp.1087-1095
• /
• 1996

Pervaporation experiments of ternary ethanol/isopropanol/water mixtures were performed using poly(dimethyl siloxane)(PDMS) membrane at $45^{\circ}C$ and the mutual effects of ethanol and isopropanol on the permeation characteristics were studied. Compared to the case of the binary aqueous ethanol or isopropanol solutions, the existence of ethanol or isopropanol in the ternary mixtures resulted in the depression of each other's permeation rate. The depression effect of ethanol on the isopropanol permeation was more considerable than the depression effect of isopropanol on the ethanol permeation. These decreases in the permeation rate were thought to be due to the larger interactions between permeants than the plasticizing effects of ethanol or isopropanol on the polymer membrane. The strong interactions between permeants reduced the driving forces for both ethanol and isopropanol permeation in the ternary mixtures.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.10
• /
• 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

• Computers and Concrete
• /
• v.19 no.2
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.19 no.9
• /
• 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.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.6
• /
• 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.

• Korean Journal of Air-Conditioning and Refrigeration Engineering
• /
• v.25 no.9
• /
• 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.