• Korean Chemical Engineering Research
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• 제56권5호
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• pp.767-772
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• 2018

전기유변(ER) 현상을 위해 제시된 메커니즘들이 중에서 정전기 분극 모델과 전도 모델이 이론적인 측면에서 적합한 것으로 알려져 있다. 그러나 이 모델들은 자체적인 제한들 때문에 효과적인 ER 액체의 개발에 적절한 도움이 되지 못했다. 이 문제를 해결하기 위해 Onsager 이론으로 확장한 Maxwell-Wagner 분극 모델을 개발하였다. 확장한 Maxwell-Wagner 분극 모델은 항복응력의 전기장 주파수 및 전기장 크기의 비제곱 의존성을 설명할 수 없는 정전기 분극 모델의 단점과 전기장 하에서의 입자의 미세 구조 변화를 예측할 수 없는 전도 모델의 단점을 해결할 수 있었다. 또한 이 모델은 정전기 분극 모델과 전도 모델에서 예측할 수 없었던 항복응력에의 입자 전도도 영향을 고려할 수 있는 장점도 있어 효과적인 ER 액체의 개발에 기여하리라 판단된다.

• Korean Chemical Engineering Research
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• 제58권3호
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• pp.480-485
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• 2020

Onsager 이론으로 확장된 Maxwell-Wagner 분극 모델을 이용하여 전도성 입자로 제조된 전기유변(Electrorheological, ER) 액체의 전기유변 현상에 대한 전산 모사를 수행하였다. 확장된 Maxwell-Wagner 분극 모델을 이용한 전산 모사는 전도성 입자로 제조된 전기유변 액체의 특성인 비제곱 전기유변 현상(Δτ∝Eⁿ, n≈1.5)을 확인하였다. 전단 흐름에서 전단응력이 정상상태에 도달하는 시점은 전기장 하에서 생성된 사슬 모양 구조가 전단 흐름에 의해 깨짐과 재생성이 정상상태에 도달하는 지점으로 나타났다. 또한, 전단 속도의 증가에 따라 전단응력이 최솟값을 보이는 전도성 입자를 기반으로 한 전기유변 액체의 현상도 관찰하였으며, 이것은 입자의 사슬 모양 구조가 무작위 배열로 바뀌는 순간에 발생하는 것임을 관찰하였다. 입자의 부피 분율 ϕ가 증가에 따라 전단응력은 증가하다가 일정해지는 경향도 관찰하였다.

• Bulletin of the Korean Chemical Society
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• 제21권5호
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• pp.503-509
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• 2000

The solvent effects on the relative free energies of solvation and the difference in partition coefficients (log P) for $Rb^+$ to $K^+$ mutation in several solvents have been investigated using Monte Carlo simulation (MCS) of statistical perturbation theory(SPT). In comparing the relative free energies for interconversion of one ion pair, $Rb^+$ to $K^+$, in $H_2O$(TIP4P) in this study with the relative free energies of the computer simulations and the experimental, we found that the figure in this study with the relative free energies of the computert simulations and the experimental, we found that the figure in this study is $-5.00\pm0.11$ kcal/mol and those of the computer simulations are $-5.40\pm1.9$, -5.5, and -5.4 kcal/mol. The experimental is -5.1 kcal/mol. There is good agreement among various studies, taking into account both methods used to obtain the hydration free energies and standard deviations. There is also good agreement between the calculated structural properties of this study and the simulations, ab initio and the experimental results. We have explained the deviation of the relationship between the free energy difference and the Onsager dielectric function of solvents by the electron pair donor properties of the solvents. For the $Rb^+$ and $K^+$ ion pair, the Onsager dielectric function of solvents (or solvent permittivity), donor number of solvent and the differences in solvation dominate the differences in the relative free energies of solvation and partition coefficients.

• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1347-1350
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• 1998

The equivalent conductances for tetraethylammonium perchlorate (TEAP), tetrabutylammonium perchlorate (TBAP), tetrahexylammonium perchlorate (THAP), and tetradodecylammonium perchlorate (TDDAP) were measured in pyridine (Py) at 25 ℃. The measured data have been analyzed by Onsager conductance theory. From Kohirausch's law of independent migration of ion, the limiting ionic conductances of tetraalkylammonium ions were determined using the limiting ionic conductance of perchlorate cited from reference. Using those and viscosity of pyridine, the Stokes and hydrodynamic radii of tetraethylammonium, tetrabutylammonium, tetrahexylammonium, and tetradodechylammonium ions were calculated. And, the salvation numbers of corresponding ions were also calculated using the hydrodynamic and crystallographic radii and the volume of one pyridine molecule. From those results, the model of salvation for those ions was extracted by comparison with the model for ion salvation. And the electrostatic Gibbs free energy (ΔGel) fitted for our salvation model was calculated. Those of corresponding ions in pyridine at 25 ℃ also increased with increasing radii of tetraalkylammonium ions. This trend of ΔGel was explained by the different ion-solvent interaction between tetraalkylammonium ion and pyridine.

• Bulletin of the Korean Chemical Society
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• 제32권2호
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• pp.673-680
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• 2011

The compound 3-(2-Mercaptopyridine)phthalonitrile has been synthesized and characterized by IR, UV-vis, and X-ray single-crystal determination. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock (HF) and density functional theory (DFT) with the 6-31G(d) basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound in solvent media was examined using the B3LYP method with the 6-31G(d) basis set by applying the Onsager and polarizable continuum model. Using the TD-DFT and TD-HF methods, electronic absorption spectra of the title compound have been predicted and good agreement with the TD-DFT method and the experimental determination was found. The predicted nonlinear optical properties of the title compound are much greater than those of urea. Besides, molecular electrostatic potential of the title compound were investigated by theoretical calculations. The thermodynamic properties of the compound at different temperatures have been calculated and corresponding relations between the properties and temperature have also been obtained.