Chemistry, Physics and Technology of Surface, 2010, 1 (4), 401-414.

Partitioning of Volatile Halocarbons between Surrogates for Atmospheric Solid Aerosols and Gas Phase as Examined by TPD MS and Inverse Gas Chromatography



V. I. Bogillo, M. S. Bazylevska, B. G. Mischanchuk, V. A. Pokrovskiy

Abstract


The desorption non-isothermal kinetics of preliminary adsorbed Cl, Br, and I-containing volatile halocarbons  from the surface of surrogates for atmospheric solid aerosols (fumed silica and alumina, silica gel and H-mordenite) was studied by TPD MS. The TPD spectra demonstrate high heterogeneity of the surface studied. The average desorption activation energies and half-widths of the halocarbons desorption energy rectangular distribution were calculated. The relationships between the average desorption activation energies and molecular descriptors for the halocarbons were derived for the solids. The partitioning of the halocarbons and additional volatile organics between surrogates for mineral and carbonaceous atmospheric aerosols (silica gel, Carbopack S, Carbosil) was examined by using the inverse gas chromatography method. These data indicate to the energetic heterogeneity of the solid surfaces. The average adsorption energies and variances of the adsorption energy rectangular distribution were calculated and connected with molecular descriptors of the volatiles. A relationship is observed between average desorption activation energies of halocarbons on the silica gel surface from TPD MS data and average adsorption energies in these systems determined using inverse gas chromatography method at finite concentrations.

Full Text:

PDF

References


The Handbook of Environmental Chemistry / Ed. P. Fabian, O.N. Singh. – V. 4, Part E. Reactive Halogen Compounds in the Atmosphere – Heidelberg, Germany: Springer, 1999. – 221 p.

Solomon S. Stratospheric ozone depletion: a review of concept and history // Rev. Geophys. – 1999. – V. 37, N 3. – P. 275–316.

Robinson G.N., Freedman A., Kolb C.E., Worsnop D.R. Decomposition of halomethanes on α-alumina at stratospheric temperature // Geophys. Res. Lett. – 1994. – V. 21. – P. 377–380.

Kutsuna S., Takeuchi K., Ibusuki T. Laboratory study on heterogeneous degradation of methyl chloroform (CH3CCl3) on aluminosilica clay minerals as its potential tropospheric sink // J. Geophys. Res. – 2000. – v. 105. – P. 6611–6620.

Zakharenko V.S., Parmon V.N. Remediation of the Earth’s atmosphere throgh photoinitiated destruction of freons on the alkaline earth oxide components of tropospheric aerosols // Colloid. Surf. A. – 1999. – V. 151. – P. 367–376.

Isidorov V.A. Organic chemistry of the Atmosphere. – St. Petersburg: Khimizdat, 2001. – 351 p.

Bogillo V.I. Impact of mineral aerosols composition on the kinetics of the heterogeneous fate of trace volatiles from atmosphere // Chem. Phys. Technol. Surf. – 2010. – V. 1. – N 1. – P. 36–47.

Bogillo V.I., Bazylevska M.S., Borchers R. Past and future for ozone-depleting halocarbons in Antarctic environment // Role of Interfaces in Environmental Protection NATO Sci. Ser. (IV. Earth Environ. Sci. V. 24) / ed. S. Barany. – Dordrecht: Kluwer Acad. Publ., 2003. – P. 161–168.

Bogillo V.I., Borchers R., Bazylevska M.S. Formation and sinks of volatile trace compounds in coastal Antarctica // Terra Nostra. – 2004. – V. 4. – P. 109–110.

Keppler F., Eiden R., Nirdan V. et al. Halocarbons produced by natural oxidation processes during degradation of organic matter // Nature. – 2000. – V. 403. – P. 298–301.

Carpenter L.J., Hopkins J.R., Jones C.E. et al. Abiotic source of reactive organic halogens in the Sub-Arctic atmosphere? // Environ. Sci. Technol. – 2005. – V. 39, N 22. – P. 8812–8816.

Stroebe M., Scheringer M., Held H., Hungerbühler K. Inter-comparison of multimedia modelling approaches: modes of transport, measures of long range transport potential and the spatial remote state // Sci. Total Environ. – 2004. – V. 321. – P. 1–20.

Kawasaki N., Tanada S., Nakamura T., Abe I. The recovery of chlorofluorocarbons and chlorofluorocarbon replacements by surface modified activated carbon // J. Colloid. Interface Sci. – 1995. – V. 172. – P. 368–373.

Kovalchuk V.I., d’Itri J.L. Catalytic chemistry of chloro- and chlorofluorocarbon dehalogenation: from macroscopic observations to molecular level understanding // Appl. Catal. A. – 2004. – V. 271. – P. 13–25.

Howe R.F. Zeolite catalysts for dehalogenation processes // Appl. Catal. A. – 2004. – V. 271. – P. 3–11.

Bogillo V.I., Shkilev V.P., Voelkel A. Determination of surface free energy components for heterogeneous solids by means of inverse gas chromatography at finite concentrations // J. Mat. Chem. – 1998. – V. 8, N 9. – P. 1953–1961.

Pokrovskiy V.A. Temperature-programmed desorption mass spectrometry (TPD MS) of dispersed oxides // Adsorpt. Sci. Technol. – 1997. – V. 14, N 5. – Р. 301–317.

Reid R., Prausnitz J.M., Sherwood T. The Properties of Gases and Liquids / 3rd ed. – New Tork: McGraw-Hill, 1977. – 576 p.

Pokrovskiy V.A., Bogillo V.I., Dabrowski A. Adsorption and chemisorption of organic pollutants on the solid aerosols surface // Adsorption and its Application in Industry and Environmental Protection / Ed. A. Dabrowski. – Amsterdam: Elsevier, 1999. – P. 571–634.

Turov V.V., Leboda R., Bogillo V.I., Skubishewska-Zieba J. Adsorption of water on the surface of mesoporous silicas and carbosils as examined by 1H nuclear magnetic resonance spectroscopy // Langmuir. – 1997. – V. 13, N 5. – P. 1237–1244.

Conder J.D., Young C.L. Physicochemical Measurements by Gas Chromatography. – New York: Wiley, 1979. – 267 p.

Balard H. Estimation of the surface energetic heterogeneity of a solid by inverse gas chromatography // Langmuir. – 1997. – V. 13, N 5. – P. 1260–1269.

Zhdanov V.P. Elementary Physicochemical Processes on the Surface. – Novosibirsk: Nauka, 1988. – 319 p. (in Russian).

Bogillo V.I., Pirnach L.S., Dabrowski A. Monte Carlo simulation of silica surface dehydroxylation under nonisothermal conditions // Langmuir. – 1997. – V. 13, N 5. – P. 928–935.

Bogillo V I., Staszczuk P. Characterization of the structural and energetic heterogeneity of mesoporous solid surfaces from Q-DTG data // J. Therm. Anal. Calorim. – 1999. – V. 55, N 2. – P. 493–510.

deJong A.M., Niemantsverdriet J.W. Thermal desorption analysis: comparative test of ten commonly applied procedures // Surf. Sci. – 1990. – V. 233. – P. 355–365.

Rudzinski W., Borowiecki T., Panczyk T., Dominko A. On the applicability of Arrhenius plot methods to determine surface energetic heterogeneity of adsorbents and catalysts surfaces from experimental TPD spectra // Adv. Colloid Interfaces Sci. – 2000. – V. 84. – P. 1–26.

Bazylevska M.S., Bogillo V.I. Description of air/surface partitioning for volatile organic pollutants in Antarctic environment // Role of Interfaces in Environmental Protection NATO Sci. Ser. (IV. Earth Environ. Sci. V. 24) / ed. S. Barany. – Dordrecht: Kluwer Acad. Publ., 2003. – P. 153–160.

CRC Handbook of Chemistry and Physics / 77th ed. – Boca Raton: CRC. – 1996. – 1539 p.

Abraham M.H., Andonian-Haftvan J., Whiting G.S., Leo A. Hydrogen bonding. Part 34. The factors that influence the solubility of gases and vapours in water at 298 K, and a new method for its determination // J. Chem. Soc. Perkin Trans. II. – 1994. – P. 1777–1791.

Su B.-L., Norberg V. Quantitative characterization of H-mordenite zeolite structure by infrared spectroscopy using benzene adsorption // Colloids Surf. – 2001. – V. 187–188. – P. 311–318.

Jaroniec M., Madey R. Physical Adsorption on Heterogeneous Solids. – Amsterdam: Elsevier, 1988. – 351 P.

Bogillo V.I., Shkilev V.P. Evaluation of desorption energy distributions from TPD spectra on a heterogeneous solid surface // J. Therm. Anal. Calorim. – 1999. – V. 55, N 2. – P. 483–492.

Bogillo V.I. Kinetics of organic compounds chemisorption from gas phase on oxide surfaces // Adsorption on New and Modified Inorganic Sorbents / Ed. A. Dabrowski, V.A. Tertykh. – Amsterdam: Elsevier, 1996. – P. 135–184.

Liu L., Guo O.-X. Isokinetic relationship, isoequilibrium relationship, and enthalpy-entropy compensation // Chem. Rev. – 2001. – V. 101. – P. 673–695.

Bogillo V.I., Bazylevska M.S. Compensation effect in adsorption on heterogeneous solid surface // Ukr. Khim. Zh. – 2006. – V. 72, N 8. – P. 78–84.

Crowley J.N., Ammann M., Cox R.A. et al. Evaluated kinetic and photochemical data for atmospheric chemistry: Volume V – heterogeneous reactions on solid substrates // Atmos. Chem. Phys. Discuss. – 2010. – V. 10. – P. 5233–5564.

Bogillo V.I. The particle morphology effect of atmospheric aerosols on the interaction kinetics with volatile impurities // Chem. Phys. Technol. Surf. – 2010. – V. 1. N. 2. – P. 148–165. (in Russian).




Copyright (©) 2010 V. I. Bogillo, M. S. Bazylevska, B. G. Mischanchuk, V. A. Pokrovskiy

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.