Domain Structure of Liguid Water According to the Theory of Intermolecular Forces

전무식,조웅인,Mu Shik Jhon,Ung In Cho Korean Chemical Society 1972 대한화학회지 Vol.16 No.3

In the past years, a number of theories have been published to elucidate the structure of liquid water. common to most of these theories is that water mainly consist of several different kinds of clusters and also hydrogen bonds in water may be bent to some degree. Recentrly, in a series of paper, Jhon and Eyring successfully explained thermodynamic, dielectric, surface and transport properites of water, assuming that it contains small domains of about 46 molecules. According to the theory, the cluster size does not change with temperature, but the cluster concentration changes. In this paper, the potential function for the hydrogen bond, the dispersion energy and dipole-dipole interaction terms. The calculated results show that the domain of nearly 46 molecules is energetically most probable, and its size is independent of temperature. And also, we evaluated the effect of angel variation of the bent hydrogen bond. In addition, the relaxation energy different for ice and water is also explained by this method.

The Significant Structures of Liquid Fluorine

전무식,장세헌,Jhon, Mu-Shik,Chang, Sei-Hun Korean Chemical Society 1964 대한화학회지 Vol.8 No.2

H. Eyring등에 의하여 제안된 액체구조에 관한 이론에 따라서 액체의 partition function을 정하였다. parameter $E_S$, $V_S$, ${\theta}$, a는 앞서 저자들에 의해 제안된 방법에 의하여 정하였고, 이렇게 정해진 partition function을 써서 액체의 몰부피, 증기압, 한계점. 증발엔트로피 및 표면장력등을 계산한 결과 실측치와 잘 맞는 값을 얻었다. The partition function of liquid fluorine were developed by applying the theory of significant structures in liquids. The molar volume, vapor pressure, entropy of vaporization and surface tension of the liquid were calculated over a wide temperature range. The critical properties for the liquid were also calculated. The results show good agreement with experimental observations.

Theoretical Calculation of Hydration Number and Activity Coefficients of Salts in Concentrated Electrolyte Solutions

성용길,전무식,Yong Kil Sung,Mu Shik Jhon Korean Chemical Society 1970 대한화학회지 Vol.14 No.2

The extension of the theory of the electrolyte solution to the calculation of the hydration number and the mean activity coefficient of some 1:1 electrolytes in the concentrated solutions has been made. In this derivation, the hydration number has been calculated from the equation of the dielectric constant proposed by Hobbs, Jhon, and Eyring, and the mean activity coefficient from the theoretical formula developed by Jhon and Eyring. The agreement between theory and experiment over a.wide concentration range is quite satisfactory.

Thermodynamic Properties of Aliphatic and Aromatic Hydrocarbons in Liquid Water

성용길,김은식,전무식,Sung Yong Kiel,Kim Un Shik,Jhon Mu Shik Korean Chemical Society 1972 대한화학회지 Vol.16 No.5

지방족 및 방향족 탄화수소의 수용액을 Jhon 등이 제창한 liquid water의 significant structure theory 를 이용하여 연구하였으며 Helmholtz free energy, internal energy, entropy, heat capacity 등의 열역학적 성질을 계산하였다. 계산결과는 문헌에 발표된 실험치와 잘 일치됨을 볼 수 있다 The aqueous solutions of aliphatic and aromatic hydrocarbons have been studied on the basis of the significant structure theory of liquid water proposed by Jhon, et al. The thermodynamic properties such as Helmholtz free energy, internal energy entropy, and heat capacity have been calculated. The results show good agreements with the experiments in the literature.

Theoretical Calculation of Activity Coefficients of Liquid Mixtures

문대원,전무식,이태규,Moon Dae-Won,Jhon Mu Shik,Lee Taikyue Korean Chemical Society 1977 대한화학회지 Vol.21 No.6

액체이론(Significant Structure Theory)를 단원자 분자로부터 다원자 분자에 이르는 여러 액체혼합물에 적용하여 전 농도 범위에서 액체 혼합물의 활동도 계수를 계산했다. 단원자 분자계(Ar-Kr, Kr-Xe)와 이원자 분자계$(Ar-O_2,\;N_2-CO)$와 메탄-크립톤계의 액체혼합물의 활동도 계수는 ${\delta}E_s$ 수정 변수에 의해 좋은 결과를 얻었다. 아르곤-질소, 산소-질소, 그리고 메탄-프로판계에 대해서는 이 외에 ${\delta}$V, ${\delta}$n 수정 변수가 더 필요했다. Significant structure theory was applied to some liquid mixture systems ranging from simple monatomic molecule systems to polyatomic molecule systems, and the activity coefficients ${\gamma}$ of the liquid mixture systems were calculated over whole mole fractions using the following thermodynamic relation $RTln_{{\gamma}i} = (\frac{{\partial A}^E}{{\partial N}_i})_{T,V,N_i} $ where $A^E$ represents the excess Helmholtz free energy, and $N_i$ is the number of molecules of component i. The activity coefficients of the solutions such as monatomic molecule systems (Ar-Kr, Kr-Xe) and diatomic molecule systems $(Ar-O_2,\;N_2-CO)$ and $CH_4-Kr$ systems whose components have similar shapes for intermolecular potential curves were calculated successfully only with the ${\delta}E_s$, correction parameter for energy $E_s$, for mixture systems. For other systems such as $Ar-N_2,\;O_2-N_2\;and\;CH_4-C_3H_8$ whose components have dissimilar intermolecular potential curve shapes an additional correction parameters ${\delta}$V and even one more parameter ${\delta}$n were necessary [see Eqs.(10)∼(12)].

Theoretical Study of Hydration of Zeolite NaA

노경태,전무식,Kyoung Tai No,Mu Shik Jhon Korean Chemical Society 1979 대한화학회지 Vol.23 No.6

Zeolite NaA의 ${\alpha}$ cage에 있어서의 수화에너지와 그 위치를 결정하였다. Na(1)과 Na(2)사이의 site selectivity를 에너지 계산으로부터 결정하였는데 Na(1)이 Na(2)보다 선택성이 있는 것을 알 수 있었다. ${\alpha}$-Cage에 수화된 물들은 일그러진 정 12면체를 형성함을 알 수 있었다. Water(1), Water(2), Water(3)의 평균수화에너지는 각각 -29.847, -25.344, -15.888kcal/mole이다. 이 에너지 계산으로부터 얻어진 수화된 물들의 산소원자의 위치는 X선값과 잘 일치함을 보여준다. 또 수화된 정도에 따른 수화에너지의 그래프를 얻었다. 이 결과는 실험으로부터 얻어진 differential heat of sorption curve와 잘 일치함을 보여준다. ${\alpha}$ Cage 속에서의 유전상수는 3.5가 적합함을 알 수 있었다. Hydration scheme and hydration energy are determined in ${\alpha}$ cage of zeolite NaA. The selectivity between Na(1) and Na(2) is determined from energy calculation. The waters in ${\alpha}$ cage form a distorted dodecahedral cage. The average binding energies of water(1), water(2) and water(3) are -29.847, -25.344 and -15.888 kcal/mole respectively. The positions of oxygens of hydrated waters are in good agreement with the X-ray data. The heat of immersion curve is also obtained. This result is in good agreement with the differential heat of sorption curve obtained from differential thermal analysis. It is concluded that theoretical method provides considerable uses in the determination and understanding of the hydration and interaction energy of zeolites sorbate binding.

Theoretical Estimation of Interfacial Tension between Molten Polymers

오영기,전무식,Youngie Oh,Joseph D. Andrade,Mu Shik Jhon Korean Chemical Society 1979 대한화학회지 Vol.23 No.4

특성구조액체이론(significant structure theory of liquids)에 입각하여, 섞이지 않는 두 용융 고분자중에서의 계면장력을 예측하는 간단한 계산방법을 연구하였다. 접착에너지는 응집에너지들의 기하평균과 보정항의 곱으로 표시되며, 응집에너지는 고분자 사슬의 격자상을 가정하므로써 계산된다. 계면장력올 계산함에 있어서 고분자사슬의 구성요소간 분산력(dispersion force) 외에 극성력(poIar force)를 포함시켜야 함이 확인되었다. A simple method to calculate the interfacial tension between two immiscible molten polymers has been developed. The theory is based on the significant structure theory of liquids. The energy of adhesion is expressed as a geometric mean of the cohesion energies multiplied by correction factor $({\Phi}12)$, ${\Delta}E_{12}={\Phi}_{12}\sqrt{{\Delta}E_{11}{\Delta}E_{22^{\circ}}$. In the calculation of ${\Delta}E_{11}\;and\;{\Delta}E_{22}$, a quasilattice of polymer chains has been assumed. It is assured that, besides the dispersion force, the polar force interactions between polymer constituent groups should be considered in the calculation of the interfacial tensions.

Isotope Effects on Vapor Pressure

오영기,전무식,Youngie Oh,Mu Shik Jhon Korean Chemical Society 1977 대한화학회지 Vol.21 No.2

순수한 액체의 증가압에 미치는 동위원소 효과를 연구하였고, 증기압 비를 계산하였다. Significant Structure Theory of Liquid를 사용한 계산결과에 의하면, $C_2H_4/C_2H_2D_2$(trans)계 에서는 분자량과 관성능률에 의한 효과가 현저하고, $C_2H_2D_2(trans)/C_2H_2D_2(cis)$계에서는 분자 회전이 자유롭지 못한 데서 오는 영점에너지 효과가 현저했다. 그리고, $CH_3OH/CH_3OD$계에서는 분자간 인력이 동위원소에 따라 다르기 때문임이 밝혀졌다. $CH_4/CD_4,\;SiH_4/SiD_4,\;GeH_4/GeD_4$ 동위원소계에서는 분자량에 의한 효과가 $CH_4/CD_4 >SiH_4/SiD_4 >GeH_4/GeD_4$의 순서로 감소함을 알 수 있었다. The isotope effect of pure liquid on vapor pressure is examined, and the vapor pressure ratios of two different isotopes are calculated. Based on the Significant Structure Theory of Liquids, the effect of molecular weight and the effect of moments of inertia are dominant in ordinary/trans-$d_2$ ethylene isotopes; the effect of hindered rotational zero-point energy is dominant in trans-$d_2$/cis-$d_2$ ethylene isotopes; and the effect of intermolecular potential difference is found in $CH_3OH/CH_3OD$ isotopes. In the isotopes of $CH_4/CD_4,\;SiH_4/SiD_4\;and\;GeH_4/GeD_4$, the weight effect decrease in the order of $CH_4/CD_4 >SiH_4/SiD_4 >GeH_4/GeD_4$.

Significant Structure of Liquid Ammonia

이해방,전무식,장세헌,Lee, Hai-Bang,Jhon, Mu-Shik,Chang, Sei-Hun Korean Chemical Society 1964 대한화학회지 Vol.8 No.4

Modified significant structure theory of liquid를 써서 액체 암모니아의 partition function을 정하여 액체 암모니아의 몰부피, 증기압, 한계점, 증발엔트로피, 표면장력을 계산한 결과 실측치와 잘 맞는 값을 얻었다. The partition function of liquid ammonia was developed by applying the modified significant structure theory of liquid.$^5$ The molar volume, vapor pressure, vaporization entropy were calculated over a wide temperature range. The critical properties for the liquid were also calculated. And surface tensions of the liquid were calculated in a similar manner developed for water by Chang and Pak.$^{10}$ The results show good agreement with experimental observations.

Sweet Taste Mechanism of 1-Alkoxy-4-nitroaniline

김의락,전무식,채영복,U. R. Kim,M. S. Jhon,Y. B. Chae Korean Chemical Society 1973 대한화학회지 Vol.17 No.6

반실험적인 양자역학 이론인 extended Huckel theory를 nitroaniline, 1-methoxy-4-nitroaniline과 1-ethoxy-4-nitroaniline에 적용하여 정량적으로 변화하는 sweetness기구를 구명코져 nitroaniline을 coplanar로 두고 ortho치환체의 geometrical rotation을 시켰을 때 charge density와 sweetness와의 상관관계를 설명하였다. A semiempirical molecular orbital theory which is known as extended H ckel theory is applied to explain the sweet taste mechanism of nitroaniline, 1-methoxy-4-nitroaniline, and 1-ethoxy-4-nitroaniline which has different sweetness respectively. In this paper, the assumption is made that the nitroaniline is coplanar. The relationship between charge density and sweetness has been calculated according to the geometrical rotation of the orthosubstitute of nitroanilines. It has been shown that the calculated results are consistent with the experimental order of the relative sweetness.