• Bulletin of the Korean Chemical Society
• /
• v.26 no.11
• /
• pp.1761-1766
• /
• 2005

Solvolysis rates of isopropenyl chloroformate (3) in water, $D_2O$, $CH_3OD$ and in aqueous methanol, ethanol, 2,2,2-trifluoroethanol (TFE), acetone, 1,4-dioxane as well as TFE-ethanol at 10 ${^{\circ}C}$ are reported. Additional kinetic data for pure water, pure ethanol and 80%(w/w) 2,2,2-trifuoroethanol (T)-water (W) at various temperatures are also reported. These rates show the phenomena of maximum rates in specific solvents (30% (v/v) methanol-water and 20% (v/v) ethanol-water) and, variations in relative rates are small in aqueous alcohols. The kinetic data are analyzed in terms of GW correlations, steric effect, kinetic solvent isotope effects (KSIE), and a third order model based on general base catalysis (GBC). Solvolyses based on predominately stoichiometric solvation effect relative to medium solvation are proceeding in 3 and the results are remarkably similar to those for p-nitrobenzoyl chloride (4) in mechanism and reactivity.

• Transactions of the Korean Society of Mechanical Engineers
• /
• v.11 no.3
• /
• pp.444-453
• /
• 1987

In the present study, a new computational closure model is proposed in order to contain physical models in the k- and .epsilon.- equations. The time scale of the third-order diffusive transport of turbulent kinetic energy in a curved streamline flow field is assumed as a function of a velocity time scale and a curvature time scale, the latter being derived from the analogy between buoyancy and streamline curvature effects on turbulence. The curvature time scale is represented by a combination of Brunt-Vaisala frequency of the curvature instability and the velocity time scale. Besides the modification of diffusive transport time scale, the destruction term in the dissipation rate equation is modeled to incorporate the streamline curvature effect on the dissipation rate of turbulent kinetic energy as a function of the ratio between velocity time scale and curvature time scale. The new curvature dependent 2-equation model is found to yield very good prediction accuracy for the various turbulent recirculating flows. Particurarly, the recovery of the mean velocity profile in the redeveloping region after the reattachment is correctly simulated by the present model.

• Bulletin of the Korean Chemical Society
• /
• v.25 no.9
• /
• pp.1346-1350
• /
• 2004

Pseudo-first order rate constants $(k_{obs})$ are reported for the following solvolyses in approximately isodielectric mixtures: 3- and 4-methoxybenzyl chloride, bromo- and chlorodiphenylmethane, and 4-chloro-, 4,4'-dichloro and 4-methyl-chlorodiphenylmethane in 0-80% v/v nitromethane-methanol mixtures; and bromo- and chlorodiphenylmethane and 4-methyl-chlorodiphenylmethane in various acetonitrile-methanol mixtures (in the range 0-50% v/v) at$25^{\circ}C.$ These data, and literature data for t-butyl halides (Cl, Br, and I), and for p-methoxybenzoyl chloride, show rate maxima in solvent compositions of ca. 30% aprotic cosolvent, explained by a stoichiometric solvent effect on electrophilic solvation. Linear relationships are observed between $(k_{obs})/[MeOH]^2$ and [AP]/[MeOH], where [AP] refers to the molar concentration of aprotic cosolvent. The results are consistent with competing third order contributions to $k_{obs}$, $k_{MM}[MeOH]^2$ with hydrogen-bonded methanol as electrophile, and $k_{MAP}[MeOH][AP]$ with hydrogen-bonding disrupted by the aprotic solvent.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.8
• /
• pp.1089-1096
• /
• 2002

Solvolyses rate constants of trimethylacetyl chloride (2), isobutyryl chloride (3), diphenylacetyl chloride (4) and p-methoxyphenylacetyl chloride (5) in 2,2,2-trifluoroethanol (TFE)-water, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water and TFE-et hanol solvent systems at $10^{\circ}C$ are determined by a conductimetric method. Kinetic solvent isotope effects (KSIE) are reported from additional kinetic data for methanolyses of various substituted acetylchlorides in methanol According to the results of those reactions analyzed in terms of rate-rate profiles,extended Grunwald-Winstein type correlations, application of a third order reaction model based a general base catalyzed (GBC) and KSIE values. Regardless of the kind of neighboring groups (CH3- or Ph-groups) of reaction center, for aqueous fluorinated alcohol systems, solvolyses of 2, 3, 4, and 5 were exposed to the reaction with the same mechanism (a loose SN2 type mechanism by electrophilic solvation) controlled by a similarity of solvation of the transition sate (TS). Whereas, for TFE-ethanol solvent systems, the reactivity depended on whether substituted acetyl chloride have aromatic rings (Ph-) or alkyl groups (CH3-); the solvations by the predominant stoichiometric effect (third order reaction mechanism by GBC and/or by push-pull type) for Ph- groups (4 and 5) and the same solvation effects as those shown in TFE-water solvent systems for CH3- groups (2 and 3) were exhibited Such phenomena can be interpreted as having relevance to the inductive effect ( $\sigmaI)$ of substituted groups; the plot of log (KSIE) vs. ${\sigma}I$ parameter give an acceptable the linear correlation with r = 0.970 (slope = 0.44 $\pm$ 0.06, n = 5).

• The Korean Journal of Food & Health Convergence
• /
• v.8 no.5
• /
• pp.11-20
• /
• 2022

Honey was diluted with different percentages of water and was analysed rheologically at room temperature of 27℃. The rheological profiles of pure and impure honey samples were measured at low shear rates (0.01-4.16s^-1). This work developed a structural kinetic model, which correlated well with the rheological data. The new model was used to categorise honey samples using their average molecular weights as one of the distinctive properties. Also, the kinetics order in the new model predicts the number of active components in the "honey" undergoing deformation. Honey produced third order kinetics to depict the monomers, oligomers and water content in honey. Pure honey exhibits peculiar non-Newtonian rheological behaviour. The behaviour of water is Newtonian. Dilution of honey with different percentages of water turns the resulting fluid Newtonian from 10% dilution with water. This study analysed the antibacterial activities of honey and serially adulterated samples against Staphylococcus aureus and Pseudomonas aeruginosa. The antibacterial analyses of honey were conducted using Kirby Bauer's well diffusion method. The results indicated that pure honey exhibited a zone of inhibition against both organisms. Also, the diameter of the zone of inhibition decreased with increasing dilution of honey, suggesting a correlation with the rheological method.

• 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.

• Journal of Korean Society of Water and Wastewater
• /
• v.25 no.5
• /
• pp.725-730
• /
• 2011

In this study, it was investigated that the feasibility of utilizing inorganic mesostructures for removal of phosphate in water. The comparison of the efficiency for phosphate adsorption between inorganic mesostructures was conducted. X-ray diffraction(XRD) and Brunauer-Emmett-Teller(BET) methods were used to characterize these mesostructures. The efficiencies of silica and titanium mesostructures for the removal of phosphate from aqueous solution were investigated. Equilibrium data were analyzed using the Langmuir isotherm. The maximum adsorption capacities of mesostructure adsorbents were found to be 49.3 and 19.5 mg $g^{-1}$ for the titanium and silica mesostructures, respectively. The adsorption kinetics was described by a pseudo third-order kinetic model. The results from this study indicated that the titanium mesostructure has the potential to be utilized for the cost-effective removal of phosphate from wastewater.

• Advances in aircraft and spacecraft science
• /
• v.8 no.4
• /
• pp.345-372
• /
• 2021

The analysis of nonlinear vibrations, buckling, post-buckling, flutter boundary determination and post-flutter behavior of a homogeneous curved plate assuming cylindrical bending is conducted in this article. Other assumptions include simply-supported boundary conditions, supersonic aerodynamic flow at the top of the plate, constant pressure conditions below the plate, non-viscous flow model (using first- and third-order piston theory), nonlinear structural model with large deformations, and application of mechanical and thermal loads on the curved plate. The analysis is performed with constant environmental indicators (flow density, heat, Reynolds number and Mach number). The material properties (i.e., coefficient of thermal expansion and modulus of elasticity) are temperature-dependent. The equations are derived using the principle of virtual displacement. Furthermore, based on the definitions of virtual work, the potential and kinetic energy of the final relations in the integral form, and the governing nonlinear differential equations are obtained after fractional integration. This problem is solved using two approaches. The frequency analysis and flutter are studied in the first approach by transferring the handle of ordinary differential equations to the state space, calculating the system Jacobin matrix and analyzing the eigenvalue to determine the instability conditions. The second approach discusses the nonlinear frequency analysis and nonlinear flutter using the semi-analytical solution of governing differential equations based on the weighted residual method. The partial differential equations are converted to ordinary differential equations, after which they are solved based on the Runge-Kutta fourth- and fifth-order methods. The comparison between the results of frequency and flutter analysis of curved plate is linearly and nonlinearly performed for the first time. The results show that the plate curvature has a profound impact on the instability boundary of the plate under supersonic aerodynamic loading. The flutter boundary decreases with growing thermal load and increases with growing curvature.

• Bulletin of the Korean Chemical Society
• /
• v.23 no.1
• /
• pp.123-131
• /
• 2002

Solvolyses rate constant of 1- and 2- naphthoyl chlorides (1 and 2) are reported for aqueous binary mixtures with methanol, ethanol, fluorinated alcohol, acetonitrile and dioxane. Kinetic solvent isotope effects (KISE) in methanol and product selectivities (S) of 2-naphthoyl chloride (2) in alcohol-water are also reported. Dispersions in Grunwald-Winstein correlations $(r{\leq}0.901)$ are discussed by multiple regression analysis incorporating ionizing power $(Y_{Cl})$ scale and rate-rate profiles. Major causes for these phenomena are investigated as an aromatic ring solvation effects, in conjunction with weakly nucleophilic solvation effects ($S_N2$ character), for solvolyses of 1 and for solvolyses of 2, as dual reaction channels, described as $S_N1$-$S_N2$ and $S_AN$-$S_N2$ processes. Distinct border lines between the two pathways are derived from solvolyses rates of 2 in 18 solvent using the results of $log(k/k_o)=mY_{Cl}+lN_T+hI$ plot with values of 1.13 for m, 0.37 for l and 0.15 for h value in 5 aqueous fluorinated alcohol mixtures. Using rate-product correlation, the validity of a third order model based on a general base catalyzed by solvent and contribution from these rate constants, $k_{aa},\;k_{aw}$ and $k_{aw}$, are investigated for $S_AN$-$S_N2$ solvolyses of 2 favored in more rich alcohol media and gradual addition of water to alcohol solvent shows a great shift away from stoichiometric solvation to predominantly medium effects. Rate-rate correlation between solvolyses of 2 and trimethyl acetylchloride (5) with alkyl group in the 29 aqueous solvent mixtures shows appreciable linearity (slope = 0.84, r = 0.987), caused by the same pathway ($S_N1$-$S_N2$ process), even if this correlation coincides with appreciable dispersion (different solvation effect).