• Bulletin of the Korean Chemical Society
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• 제23권3호
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• pp.459-468
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• 2002

Literature data measured by the author have been processed to report on the effect of solute structure on gas liquid partition coefficients of eleven normal, branched and cyclic alkanes ranging in carbon number from five to nine in sixty nine low molecular weight liquids. The alkane solutes are n-pentane(p), n-hexane(hx), n-heptane(hp), n-octane(o), n-nonane(n), 2-methylpentane(mp), 2,5-dimethylpentane(dp), 2,5-dimethylhexane(dh), 2,3,4-trimethylpentane(tp), cyclohexane(ch), and ethylcyclohexane(ec). The solvent set encompasses most of those studied by Rohrschneider as well as three homologous series of solvents (n-alkanes, 1-alcohols and 1-nitriles) and several perfluorinated alkanes and highly fluorinated alcohols. An excellent linear relationship was observed between lnK and the carbon number of n-alkanes. The effective carbon numbers of branched and cyclic alkanes were determined in a similar fashion to the method of Kovats index. We found that the logarithm of solute vapor pressure multiplied by solute molar volume was a perfect descriptor for the linear relationship with the median effective carbon number.

• 한국대기환경학회지
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• 제21권3호
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• pp.285-293
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• 2005

This study was aimed at estimation of gas-particle partitioning of polychlorinated biphenyls (PCBs) in ambient air. The samples were collected at urban site in Japan from March 2002 to January 2003. The concentration of total PCBs (from 4 CB to 10 CB) and TEQ (Toxic equivalent) ranged from 62 to $247\;pg/m^3$ and from 2 to $14\;fgTEQ/m^3 $, respectively. The average contribution $(\%)$ of gas phase to total PCBs concentration was above $80\%$, which suggests that in the atmosphere PCBs predominantly existed in the gas phase. The weak correlations between total PCBs concentration and temperature was found. However this result was due to a typhoon during summer and raining during sampling period. The gas-particle partition coefficient (Kp) was obtained as a function of temperature. The partition ratio of gaseous and particulate phase PCBs can be estimated for an arbitrary temperature. The plot of gas/particle partition coefficient (log Kp) vs. sub-cooled liquid vapor pressure $(log\;P_L)$ had reasonable correlations for individual samples but the slope varied among the samples (coefficients of determination for log Kp versus log $P_L$ plot were> 0.76 $(p<0.0001)$, except for 3 samples). As a result, the variations in the slope among the sampling period may be due to change of temperature, raining during sampling period and wind in this study.

• 대한화학회지
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• 제46권6호
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• pp.523-527
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• 2002

LPG에서 황화합물의 분배계수에 미치는 영향에 관하여 연구하였다. 분석 대상 물질은 알칸계통에 사슬형머캡탄이었다. LPG의 액체상 및 기체상의 조성을 기체크로마토그래피로 분석하였다. SAS를 사용한 다중회귀분석방법(MLR)으로 황화합물의 끓는점(Bp), 온도(Tk), 용매의 조성(C4)과 관련되 분배계수를 다음과 같이 구할 수 있었다. Kpc=0.61222(${\pm}$0.000959)Bp+0.26984(${\pm}$0.06504)C40.003803(${\pm}$0.0019993)Tk, N=24, F=14.851, $R^2_{adj}$=0.6437. 분배계수에 미치는 중요 인자는 황화합물의 대기압에서 끓는점과 LPG의 조성이었다. n-부탄의 높은 조성 및 높은 온도에는 분배계수가 증가하여 가스의 취기 상승효과가 클 것으로 추측된다.

• Bulletin of the Korean Chemical Society
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• 제24권8호
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• pp.1207-1210
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• 2003

The effect of solvent structure on the slope in the plot of ln K vs. solute carbon number was examined. It was found that the free energy of methylene group transfer from the gas phase into a solvent was always negative and that the absolute magnitude of interaction free energy between the methylene group and the solvent was always larger than the absolute magnitude of cavity formation free energy of the methylene group in the solvent. Thus, the slope in the plot of ln K vs. solute carbon number was always positive and its value decreases with increase of solvent polarity since the cavity formation energy of the CH₂ unit increases with increase of solvent polarity while the dispersive interaction energy of the CH₂ unit is virtually invariant. We also examined the effect of sequential addition of CH₂ unit to a solvent molecule upon ln K for three homologous series of solvents: n-alkanes, n-alcohols, and n-nitriles. Characteristic trends in the plots of ln K vs. solvent carbon number were observed for individual solvent groups. A decrease of ln K with solvent carbon number was observed for n-alkanes. An abrupt increase in ln K followed by levelling off was observed for n-alcohols while a final slight decrease in ln K after an abrupt increase followed by rapid levelling off was noted for n-nitriles. All of theses phenomena were found related to variation in cavity formation energy. It was clearly shown that a structural change of a polar solvent by sequential addition of CH₂ units causes an abrupt polarity decrease initially, then gradual levelling off, and finally, conversion to a virtually nonpolar solvent if enough CH₂ units are added.