• 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.

• Bulletin of the Korean Chemical Society
• /
• 제11권6호
• /
• pp.497-505
• /
• 1990

The function exp$(x^2)$erfc(x), which is often encountered in studies of electrode kinetics, is evaluated to an extended precision with 32 significant decimal digits in order to find theoretical relationships used in derivative polarography/voltammetry for a chemically-coupled electrode process. Computations with a lower precision are not successful. Evaluation of the function is accomplished by using three types of expansions for the function. Best ranges of arguments are selected for each equation for particular precisions for efficiencies. The method is successfully applied to calculate higher-order derivatives of the current-potential curves in all potential ranges for a reversible electron transfer reaction coupled with a prior chemical equilibrium (i.e., a CE type process). Various parameters that characterize the peak asymmetry (such as ratios of peak-heights, ratios of half-peak-widths, and separations in peak-potentials) are analyzed to find how kinetic and thermodynamic parameters influence shapes of the derivatives. The results from the CE process is compared with those from an EC process in which a reversible electron transfer is coupled with a follow-up homogeneous chemical reaction. The two processes exibit quite contrasting differences for values of the parameters.

• 공업화학
• /
• 제32권5호
• /
• pp.581-588
• /
• 2021

In this study, soil slurry bioreactors were used to treat soils containing 16 polycyclic aromatic hydrocarbons (PAHs) for 35 days. Five different soil samples were taken from manufactured gas plant (MGP) and coal tar disposal sites. Soil properties, such as carbon content and particle distribution, were measured. These properties were significantly correlated with percent biodegradation and degradation rate. The cumulative amount of PAH degraded (P), degradation rate (K_m), and lag phase (𝜆) constants of PAHs in different MGP soils for 16 PAHs were successfully obtained from nonlinear regression analysis using the Gompertz equation, but only those of naphthalene, anthracene, acenaphthene, fluoranthene, chrysene, benzo[k]fluoranthene, benzo(a)pyrene, and benzo(g,h,i)perylene are presented in this study. A comparison between total non-carcinogenic and carcinogenic PAHs indicated higher maximum amounts of PAH degraded in the former than that in the latter owing to lower partition coefficients and higher water solubilities (S). The degradation rates of total non-carcinogenic compounds for all soils were more than four times higher than those of total carcinogenic compounds. Carcinogenic PAHs have the highest partitioning coefficients (K_oc), resulting in lower bioavailability as the molecular weight (MW) increases. Good linear relationships of K_m, 𝜆, and P with the octanol-water partitioning coefficient (K_ow), MW, and S were used to estimate PAH remaining, lag time, and biodegradation rate for other PAHs.

• 한국환경과학회지
• /
• 제27권11호
• /
• pp.975-982
• /
• 2018

In this study, zeolite (Z-C1) was synthesized using a fusion/hydrothermal method from coal fly ash. The morphological structures of Z-C1 were confirmed to be highly crystalline with a cubic crystal structure. Exchange capacities of $Ca^{2+}$ and $Mg^{2+}$ ions in a single and a mixed solution reached equilibrium within 120 min. The exchange kinetics of these ions were well predicted by the pseudo-second-order rate equation. The exchange isotherms of the $Ca^{2+}$ and $Mg^{2+}$ ions matched the Langmuir isotherm better than the Freundlich isotherm. The maximum cation exchange capacities ($q_m$) obtained by the Langmuir isotherm model were 2.11 mmol/g (84.52 mg/L) and 1.13 mmol/g (27.39 mg/L) for the $Ca^{2+}$ and $Mg^{2+}$ ions, respectively.

• Structural Engineering and Mechanics
• /
• 제70권5호
• /
• pp.623-637
• /
• 2019

This paper analyzes the non-stationary vibration and super-harmonic resonances in nonlinear dynamic motion of viscoelastic nano-resonators. For this purpose, a new coupled size-dependent model is developed for a plate-shape nano-resonator made of nonlinear viscoelastic material based on modified coupled stress theory. The virtual work induced by viscous forces obtained in the framework of the Leaderman integral for the size-independent and size-dependent stress tensors. With incorporating the size-dependent potential energy, kinetic energy, and an external excitation force work based on Hamilton's principle, the viscous work equation is balanced. The resulting size-dependent viscoelastically coupled equations are solved using the expansion theory, Galerkin method and the fourth-order Runge-Kutta technique. The Hilbert-Huang transform is performed to examine the effects of the viscoelastic parameter and initial excitation values on the nanosystem free vibration. Furthermore, the secondary resonance due to the super-harmonic motions are examined in the form of frequency response, force response, Poincare map, phase portrait and fast Fourier transforms. The results show that the vibration of viscoelastic nanosystem is non-stationary at higher excitation values unlike the elastic ones. In addition, ignoring the small-size effects shifts the secondary resonance, significantly.

• Bulletin of the Korean Chemical Society
• /
• 제16권3호
• /
• pp.265-269
• /
• 1995

Complexation of ortho-xylyl-17-crown-5 (X17C5) with alkali metal ions in acetonitrile was studied by 7Li and 23Na NMR spectroscopy. The complex formation constants of X17C5 with LiI, LiSCN, NaI, and NaSCN were determined by investigating the changes in the chemical shifts as a function of the concentration ratio of X17C5 to metal ion. It was found that X17C5 forms 1:1 complex with Li+ and Na+ ions and the log Kf's for the complexation with LiI, LiSCN, NaI, and NaSCN were determined to be 2.88, 2.43, 2.53, and 2.30, respectively. In particular, the kinetics of complexation of X17C5 with Na+ was investigated by the method of 23Na NMR lineshape analysis. Activation energies were determined from Arrhenius plot of the resultant rate constant data to be 25.4 kJ/mol for NaI and 15.1 kJ/mol for NaSCN. Other kinetic parameters were also calculated by employing the Eyring equation. The decomplexation rates measured were 1.82 × 104 M-1s-1 for NaI and 1.50 × 104 M-1s-1 for NaSCN. It is concluded that the decomplexation mechanism is predominantly a bimolecular cation exchange for both cases.

• 대한금속재료학회지
• /
• 제49권1호
• /
• pp.52-57
• /
• 2011

Nickel ferrite ($NiFe_2O_4$) powder was prepared through the ceramic route by calcination of a stoichiometric mixture of nickel oxide (NiO) and iron oxide ($Fe_2O_3$). The pressed pellets of $NiFe_2O_4$ were isothermally reduced in pure hydrogen at 800, 900, 1000 and $1100^{\circ}C$. Based on thermogravimetric analysis, the reduction behavior and the kinetic reaction mechanisms of the synthesized ferrite were studied. The initial ferrite powder and various reduction products were characterized by XRD, SEM, reflected light microscope and VSM to reveal the effect of hydrogen reduction on the composition, microstructure, magnetic properties and reaction kinetics of the produced Fe-Ni alloy. Complete reduction of the $NiFe_2O_4$ was achieved with synthesis of homogeneous nanocrystalline Fe-Ni alloys. Arrhenius equation with the approved mathematical formulations for a gas-solid reaction was applied for calculating the activation energy ($E_a$) values and detecting the controlling reaction mechanism.

• Nuclear Engineering and Technology
• /
• 제54권8호
• /
• pp.2771-2782
• /
• 2022

When assessing the radiological consequences of postulated accident scenarios, it is of primary interest to determine the amount of radioactive fission gas accumulated in the fuel rod free volume. The state-of-the-art semi-empirical approach (ANS 5.4-2010) is reviewed and compared with a mechanistic approach to evaluate the release of radioactive fission gases. At the intra-granular level, the diffusion-decay equation is handled by a spectral diffusion algorithm. At the inter-granular level, a mechanistic description of the grain boundary is considered: bubble growth and coalescence are treated as interrelated phenomena, resulting in the grain-boundary venting as the onset for the release from the fuel pellets. The outcome is a kinetic description of the release of radioactive fission gases, of interest when assessing normal and off-normal conditions. We implement the model in SCIANTIX and reproduce the release of short-lived fission gases, during the CONTACT 1 experiments. The results show a satisfactory agreement with the measurement and with the state-of-the-art methodology, demonstrating the model soundness. A second work will follow, providing integral fuel rod analysis by coupling the code SCIANTIX with the thermo-mechanical code TRANSURANUS.

• Computers and Concrete
• /
• 제30권1호
• /
• pp.19-32
• /
• 2022

This paper presents an investigation into the failure of RC columns under impact loadings. A numerical simulation of 19 identical RC columns subjected to single and repeated impact loadings was performed. A free-falling hammer was dropped at midspan with the same total kinetic energy input but varying mass and momentum. The specimens under the repeated impact test were struck two times at the same location. The colliding index, defined as the impact energy-momentum ratio, was proposed to explain the different impact responses under equal-energy impacts. The increase of colliding index from low to high indicates the transition of the impact response from static to dynamic and failure mode from flexure to shear. This phenomenon was more evident when the column had a greater axial load and was impacted with a high colliding index. The existence of the axial load had an inhibitory effect on the crack development and increased the shear resistance. The second impact changes the failure mode from flexural to brittle shear as found in the specimen with 20% axial load subjected to high a colliding index. Moreover, a deflection prediction equation based on the impact energy and force was limited to the low colliding index impact.

• 한국분말재료학회지
• /
• 제29권6호
• /
• pp.517-522
• /
• 2022

We investigate the austenite stability in nanocrystalline Fe-7%Mn-X%Mo (X = 0, 1, and 2) alloys fabricated by spark plasma sintering. Mo is known as a ferrite stabilizing element, whereas Mn is an austenite stabilizing element, and many studies have focused on the effect of Mn addition on austenite stability. Herein, the volume fraction of austenite in nanocrystalline Fe-7%Mn alloys with different Mo contents is measured using X-ray diffraction. Using a disk compressive test, austenite in Fe-Mn-Mo alloys is confirmed to transform into strain-induced martensite during plastic deformation by a disk d. The variation in austenite stability in response to the addition of Mo is quantitatively evaluated by comparing the k-parameters of the kinetic equation for the strain-induced martensite transformation.