Experimental and Theoretical Determination of Henry’s Law Constant for Polychlorinated Biphenyls: Its Dependence on Solubility and Degree of Chlorination

  • R. C. Bhangare
  • P. Y. Ajmal
  • T. D. Rathod
  • M. Tiwari
  • S. K. SahuEmail author


The fate of a pollutant in the environment depends on its interaction with the surroundings. Henry’s law constant (HLC) is one of the important properties useful for assessment of environmental risk and estimation of mass transfer of the pollutant between water and air. Estimation of HLC is relatively a difficult task for many of the organic pollutants due to their very low aqueous solubility. People have attempted the measurement of HLC for persistent organic pollutants, such as polychlorinated biphenyls (PCBs), but due to the difficulty in estimation, there is a variation of approximately 2–3 orders of magnitude in reported values of HLC for PCBs in the literature. A study was performed for estimation of HLC for PCBs using the static method with a modification that eliminates any disturbance in equilibrium due to sampling and also avoids removal or addition of material in or out of the system unlike the conventional methods. The results were consistent with the literature values. The experimental values of HLC ranged from 0.004 to 0.08 for different congeners. All of the experimental values were in agreement with the literature values. The experimental data was further used for deriving a correlation equation for theoretical estimation of the HLC from aqueous solubility and chlorination number. The equation gave a very good estimation of HLC values for all the PCBs congeners except single- and double-chlorinated congeners. The theoretically predicted values were also found to be in close agreement with the reported HLC values.


  1. Abraham MH, Andonian HJ, Whiting GS, Leo A, Taft S (1994) Hydrogen bonding. Part 34. The factors that influence the solubility of gases and vapors in water at 298 K, a new method for its determination. J Chem Soc Perkins Trans 2(2):1777–1791CrossRefGoogle Scholar
  2. Altschuh J, Brüggemann R, Santl H, Eichinger G, Piringer OG (1999) Henry’s law constants for diverse organic chemicals: experimental determination and comparison of estimation methods. Chemosphere 39:1871–1887CrossRefGoogle Scholar
  3. Ashworth RA, Howe GB, Mullins ME, Rogers TN (1988) Air–water partitioning coefficients of organics in dilute aqueous solutions. J Hazard Mater 18:25–36CrossRefGoogle Scholar
  4. Bamford HA, Poster DL, Baker JE (2000) Henry’s law constants of polychlorinated biphenyl congeners and their variation with temperature. J Chem Eng Data 45:1069–1074CrossRefGoogle Scholar
  5. Bhangare RC, Ajmal PY, Tiwari M, Sahu SK, Pandit GG (2016) Rapid and solventless analysis of polychlorinated biphenyls in packaged milk using gas chromatography. Curr Chromatogr 3:64–72CrossRefGoogle Scholar
  6. Boddy R, Smith G (2009) Statistical methods in practice: for scientists and technologists. Wiley, HobokenCrossRefGoogle Scholar
  7. Bopp RF, Simpson HJ, Olsen CR, Kostyk N (1981) Polychlorinated biphenyls in sediments of the tidal Hudson River, New York. Environ Sci Technol 15:210–216CrossRefGoogle Scholar
  8. Brennan RA, Nirmalakhandan N, Speece RE (1998) Comparison of predictive methods for Henrys law coefficients of organic chemicals. Water Res 32:1901–1911CrossRefGoogle Scholar
  9. Brunner S, Hornung E, Santl S, Wolff E, Pringer OG, Altschuh J, Bruggemann R (1990) Henry’s law constant for polychlorinated biphenyls: experimental determination and structure-property relationships. Environ Sci Technol 24:1751–1754CrossRefGoogle Scholar
  10. Burkhard LP, Armstrong DE, Anders AW (1985a) Partitioning behavior of polychlorinated biphenyls. Chemosphere 14(11/12):1703–1716CrossRefGoogle Scholar
  11. Burkhard LP, Armstrong DE, Andren AW (1985b) Henry’s law constants for the PCBs. Environ Sci Technol 19:590–596CrossRefGoogle Scholar
  12. Chao HP, Lee JF, Chiou CT (2017) Determination of the Henry’s law constants of low-volatility compounds via the measured air-phase transfer coefficients. Water Res 120:238–244CrossRefGoogle Scholar
  13. Dewulf J, Drijvers D, Langenhove HV (1995) Measurement of Henry’s law constant as function of temperature and salinity for the low temperature range. Atmos Environ 29(3):323–331CrossRefGoogle Scholar
  14. Dewulf J, Langenhove HV, Everaert P (1999) Determination of Henry’s law coefficients by combination of the equilibrium partitioning in closed systems and solid-phase microextraction techniques. J Chromatogr A 830:353–363CrossRefGoogle Scholar
  15. Dunnivant FM, Coates JT, Elzerman AW (1988) Experimentally determined Henry’s law constants for 17 PCBs. Environ Sci Technol 22:448–453CrossRefGoogle Scholar
  16. Dunnivant FM, Elzerman AW, Jurs PC, Hasan MN (1992) Quantitative structure-property relationships for aqueous solubilities and Henry’s law constants of polychlorinated biphenyls. Environ Sci Technol 26:1567–1573CrossRefGoogle Scholar
  17. Eisert R, Levsen K (1996) Solid-phase microextraction coupled to gas chromatography: a new method for the analysis of organics in water. J Chromatogr A 733(1–2):143–157CrossRefGoogle Scholar
  18. Ettre L, Welter C, Kolb B (1993) Determination of gas–liquid partition coefficients by automatic equilibrium headspace-gas chromatography utilizing the phase ratio variation method. Chromatographia 35(1–2):73–84CrossRefGoogle Scholar
  19. Gharagheizi F, Eslamimanesh A, Mohammadi AH, Richon D (2012) Empirical method for estimation of Henry’s law constant of non-electrolyte organic compounds in water. J Chem Thermodyn 47:295–299CrossRefGoogle Scholar
  20. Goss KU (2006) Prediction of the temperature dependency of Henry’s law constant using poly-parameter linear free energy relationships. Chemosphere 64:1369–1374CrossRefGoogle Scholar
  21. Gossett JM (1987) Measurement of Henry’s law constants for C1 and C2 chlorinated hydrocarbons. Environ Sci Technol 21:202–208CrossRefGoogle Scholar
  22. Hansen KC, Zhou Z, Yaws CL, Aminabhavi TM (1993) Determination of Henry’s law constants of organics in dilute aqueous solutions. J Chem Eng Data 38:546–550CrossRefGoogle Scholar
  23. Helm PA, Jantunen LM, Ridal J, Bidleman TF (2003) Spatial distribution of polychlorinated naphthalenes in air over the Great Lakes and air and water gas exchange in Lake Ontario. Environ Toxicol Chem 22:1937–1944Google Scholar
  24. Kolb B, Welter C, Bichler C (1992) Determination of partition coefficients by automatic equilibrium headspace gas chromatography by vapor phase calibration. Chromatographia 34(5–8):235–240CrossRefGoogle Scholar
  25. Lincoff AH, Gossett JM (1984) Gas transfer at water surfaces. In: Brutsaert W, Jirka GH (eds) Reidel, DordrechtGoogle Scholar
  26. Lyman WJ (1985) Estimation of physical properties. In: Neely B, Blau GR (eds) Environmental exposure from chemicals. CRC Press, Boca Raton, pp 13–47Google Scholar
  27. Mackay D, Shiu WY (1981) A critical review of Henry’s law constants for chemicals of environmental interest. J Phys Chem Ref Data 10:1175–1199CrossRefGoogle Scholar
  28. Mackay D, Shiu WY, Sutherland RP (1979) Determination of air–water Henry’s law constants for hydrophobic pollutants. Environ Sci Technol 13:333–337CrossRefGoogle Scholar
  29. Makino M (1998) Prediction of aqueous solubility coefficients of polychlorinated biphenyls by use of computer-calculated molecular properties. Environ Int 24(5/6):653–663CrossRefGoogle Scholar
  30. McAuliffe C (1971) Gas chromatographic determination of solutes by multiple phase equilibrium. Chem Technol 1:46–51Google Scholar
  31. McVeety BD, Hites RA (1988) Atmospheric deposition of polycyclic aromatic-hydrocarbons to water surfaces: a mass balance approach. Atmos Environ 22(3):511–536CrossRefGoogle Scholar
  32. Meylan WM, Howard PH (1991) Bond contribution method for estimating Henry’s law constants. Environ Toxicol Chem 10:1283–1293CrossRefGoogle Scholar
  33. Michalski R (2016) Ion chromatography and related techniques. J Chromatogr Sep Tech 7:325CrossRefGoogle Scholar
  34. Motladiile S, Kwaambwa HM, Sichilongo K (2012) Development and validation of a gas chromatography-mass spectrometry method for the determination of PCBs in transformer oil samples-application on real samples from Botswana. J Chromatograph Sep Tech 2:116–124Google Scholar
  35. Motlagh S, Pawliszyn J (1993) On-line monitoring of flowing samples using solid phase microextraction-gas chromatography. Anal Chim Acta 284:265–273CrossRefGoogle Scholar
  36. Munz C, Roberts PV (1987) Air–water phase equilibria of volatile organic solutes. J Am Water Works Assoc 79(5):62–69CrossRefGoogle Scholar
  37. Murphy TJ, Pokojowczyk JC, Mullin MD (1983) Vapor exchange of PCBs with Lake Michigan: the atmosphere as a sink for PCBs. In: Mackay D, Patterson S, Eisenreich SJ, Simmons MS (eds) Physical behavior of PCBs in the Great Lakes. Ann Arbor Science, Ann Arbor, pp 49–58Google Scholar
  38. Murray MW, Andren AW (1992) Precipitation scavenging of polychlorinated biphenyl congeners in the great lakes region. Atmos Environ Part A 26(5):883–897CrossRefGoogle Scholar
  39. Nelson ED, McConnell LL, Baker JE (1998) Diffusive exchange of gaseous polycyclic aromatic hydrocarbons and polychlorinated biphenyls across the air water interface of the Chesapeake Bay. Environ Sci Technol 32:912–919CrossRefGoogle Scholar
  40. Nirmalakhandan NN, Speece RE (1988) QSAR model for predicting Henry’s constant. Environ Sci Technol 22:1349–1357CrossRefGoogle Scholar
  41. Odabasi TM, Adali M (2016) Determination of temperature dependent Henry’s law constants of polychlorinated naphthalenes: application to air-sea exchange in Izmir Bay. Atmos Environ 147:200–208CrossRefGoogle Scholar
  42. Page BD, Lacroix G (1993) Application of solid-phase microextraction to the headspace gas chromatographic analysis of halogenated volatiles in selected foods. J Chromatogr 648:199–211CrossRefGoogle Scholar
  43. Page BD, Lacroix G (1997) Application of solid-phase microextraction to the headspace gas chromatographic analysis of semi-volatile organochlorine contaminants in aqueous matrices. J Chromatogr A 757:173–182CrossRefGoogle Scholar
  44. Patil GS (1991) Correlation of aqueous solubility and octanol-water partition coefficient based on molecular structure. Chemosphere 22(8):723–738CrossRefGoogle Scholar
  45. Poland A, Knutson JC (1982) 2,3,7,8-tetrachlorodibenzo-p-dioxin and related halogenated aromatic hydrocarbons: examination of the mechanism of toxicity. Ann Rev Pharmacol Toxicol 22:517–554CrossRefGoogle Scholar
  46. Robertson LW, Hansen LG (eds) (2001) PCBs: recent advances in environmental toxicology and health effects. University Press of Kentucky, Lexington, p 11. ISBN 0813122260Google Scholar
  47. Sander R (2015) Compilation of Henry’s law constants (version 4.0) for water as solvent. Atmos Chem Phys 15:4399–4981CrossRefGoogle Scholar
  48. Santos FJ, Galceran MT, Fraisse D (1996) Application of solid-phase microextraction to the analysis of volatile organic compounds in water. J Chromatogr A 742:181–189CrossRefGoogle Scholar
  49. Staudinger J, Roberts PV (1996) A critical review of Henry’s law constants for environmental applications. Crit Rev Environ Sci Technol 26:205–297CrossRefGoogle Scholar
  50. Sundqvist KL, Wingfors H, Brorstöm LE, Wiberg K (2004) Air-sea gas exchange of HCHs and PCBs and enantiomers of a-HCH in the Kattegat Sea region. Environ Pollut 128:73–83CrossRefGoogle Scholar
  51. Thomas SP, Ranjan RS, Webster GRB, Sarna LP (1996) Protocol for the analysis of high concentrations of benzene, toluene, ethylbenzene, and xylene isomers in water using automated solid phase microextraction-GC-FID. Environ Sci Technol 30:1521–1526CrossRefGoogle Scholar
  52. Totten LA, Brunciak PA, Gigliotti CL, Dachs J, Glenn TR, Nelson ED, Eisenreich SJ (2001) Dynamic air-water exchange of polychlorinated biphenyls in the New York–New Jersey Harbor Estuary. Environ Sci Technol 35:3834–3840CrossRefGoogle Scholar
  53. Tülp HC, KeU Goss, Schwarzenbach RP, Fenner K (2008) Experimental determination of LSER parameters for a set of 76 diverse pesticides and pharmaceuticals. Environ Sci Technol 42:2034–2040CrossRefGoogle Scholar
  54. Zell M, Neu HJ, Ballschmiter K (1978) Single component analysis of polychlorinated biphenyl (PCB)—and chlorinated pesticide residues in marine fish samples. Fresenius Z Anal Chem 292:97–107CrossRefGoogle Scholar
  55. Zhang Z, Pawliszyn J (1993) Headspace solid-phase microextraction. Anal Chem 65(14):1843–1852CrossRefGoogle Scholar
  56. Zhang Z, Yang MJ, Pawliszyn J (1994) Solid-phase microextraction. A solvent-free alternative for sample preparation. Anal Chem 66(17):844–853CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • R. C. Bhangare
    • 1
  • P. Y. Ajmal
    • 1
  • T. D. Rathod
    • 1
  • M. Tiwari
    • 1
  • S. K. Sahu
    • 1
    Email author
  1. 1.Environmental Monitoring and Assessment Section, Health Safety and Environment GroupBhabha Atomic Research CentreMumbaiIndia

Personalised recommendations