• Bulletin of the Korean Chemical Society
• /
• v.23 no.3
• /
• pp.459-468
• /
• 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.

• Journal of Korean Society for Atmospheric Environment
• /
• v.21 no.3
• /
• pp.285-293
• /
• 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.

• Journal of the Korean Chemical Society
• /
• v.46 no.6
• /
• pp.523-527
• /
• 2002

Partition coefficient related composition of LPG are studied. Analysed sulfur compounds are ethyl mer-captan,n-propyl mercaptan and n-butyl mercaptan. The composition of liquid phase and gas phase in LPG are deter-mined by gas chromatography. The partition coefficient to related the boiling point of sulfur compounds, the temperature and the compositions of solvents, determined by using MLR(multiple linear regression) of SAS is follows; Kpc= $0.61222({\pm}0.6578)-0.04670({\pm}0.000959)Bp+0.26984(\pm0.06504)C4+0.003803(^{\circ}ae0.0019993)Tk,$ N=24, F=14.851, $R^2_{adj}$=0.6437. The boiling points of sulfur compounds at atmospheric pressure and the compositions of LPG effect mostly on partition coefficients. It is presumed that the gas odor elevating effects should be increased, where being on high tem-perature and larger amounts of n-butane.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.8
• /
• pp.1207-1210
• /
• 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.