View More View Less
  • 1 Division of Engineering, Brown University, 182 Hope Street, Providence, RI, 02912, USA Indrek_Kulaots@brown.edu
Restricted access

Abstract

Anthracene is a common byproduct of incomplete combustion of fossil fuels and other anthropogenic sources. Its heteroatomic counterparts, including 9-bromoanthracene, 1,5-dibromoanthracene, 9,10-dibromoanthracene, 2-chloroanthracene, 9,10-dichloroanthracene, 9-anthraldehyde, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, and anthraquinone, are formed through various mechanistic pathways during the combustion process. We use a differential scanning calorimeter to measure the melting points and enthalpies of fusion of these compounds. As expected, we find no correlation between molecular mass and melting point and enthalpy of fusion—rather the type, number and position of the heteroatoms substituted on the parent molecule all influence its fusion thermodynamics. A wide range of melting points is noted for the same substituents(s) at different carbon positions. This suggests that intermolecular forces, such as hydrogen bonding and steric repulsion, are significantly impacted by the position of the substituents on the linear anthracene parent molecular. In addition, different substituents at the same position further suggest that the electronegativity/polarity of a given atom strongly influences the observed fusion behavior.

  • 1. Peters, CA, Mukherji, S, Knightes, CD WJ Weber Jr Phase stability of multicomponent NAPLs containing PAHs. Environ Sci Technol 1997 31:25402546 .

  • 2. Hu, J, Jin, X, Kunikane, S, Terao, Y, Aizawa, T 2006 Transformation of pyrene in aqueous chlorination in the presence and absence of bromide ion: kinetics, products, and their aryl hydrocarbon receptor-mediated activities. Environ Sci Technol 40:487493 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 3. Huang, J, Senkan, SM 1996 Polycyclic aromatic hydrocarbon and soot formation in premixed flames of CH3Cl/CH4 and CH4. Proc Comb Inst 26:23352341.

    • Search Google Scholar
    • Export Citation
  • 4. Rogge, WF, Hildemann, LM, Mazurek, MA, Cass, GR, Simoneit, BRT 1997 Sources of fine organic aerosol. 8. Boilers burning no. 2 distillate fuel oil. Environ Sci Technol 31:27312737 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Barbas, JT, Sigman, ME, Dabestani, R 1996 Photochemical Oxidation of Phenanthrene Sorbed on Silica Gel. Environ Sci Technol 30:17761780 .

  • 6. Sweeting, LM, Rheingold, AL, Gingerich, JM, Rutter, AW, Spence, RA, Cox, CD, Kim, TJ 1997 Crystal structure and triboluminescence. II. 9-Anthracencecarboxylic acid and its esters. Chem Mater 9:11031115 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Desiraju, GR, Gavezzotti, A 1989 Crystal structures of polynuclear aromatic hydrocarbons, classification, rationalization and prediction from molecular structure. Acta Cryst B45:473482.

    • Search Google Scholar
    • Export Citation
  • 8. Klebe, G, Diederich, F 1993 A comparison of the crystal packing in benzene with the geometry seen in crystalline cyclophane-benzene complexes: guidelines for rational receptor design. Phil Trans R Soc Lond A 345:3748 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Cammenga, HK, Eysel, W, Gmelin, E, Hemminger, W, Höhne, GWH, Sarge, SM 1993 The temperature calibration of scanning calorimeters: part 2. Calibration substances. Thermochim Acta 219:333342 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Drozdzewska, K, Kestens, V, Held, A, Roebben, G, Linsinger, T 2007 Differential scanning calorimetry to measure the purity of polycyclic aromatic hydrocarbons. J Therm Anal Calorim 88:757762 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 11. Goldfarb, JL, Suuberg, EM 2008 Vapor pressures and thermodynamics of oxygen-containing polycyclic aromatic hydrocarbons measured using Knudsen effusion. Environ Toxicol Chem 27:12441249 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Goldfarb, JL, Suuberg, EM 2010 Vapor pressures and sublimation enthalpies of seven heteroatomic aromatic compounds measured via the Knudsen effusion technique. J Chem Thermodyn 42:781786 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Coutsikos, P, Voutsas, E, Magoulas, K, Tassios, DP 2003 Prediction of vapor pressures of solid organic compounds with a group-contribution method. Fluid Phase Equilib 207:263281 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Tanimoto, I, Kushioka, K, Kitagawa, T, Maruyama, K 1979 Binary phase chlorination of aromatic hydrocarbons with solid copper(II) chloride: reaction mechanism. Bull Chem Soc Jpn 52:35863591 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Goldfarb, JL, Suuberg, EM 2008 Vapor pressures and enthalpies of sublimation of ten polycyclic aromatic hydrocarbons determined via the Knudsen effusion method. J Chem Eng Data 53:670676 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Barnett, EB, Cook, JW, Matthews, MA 1926 The mechanism of substitution reactions in the aromatic nucleus. Part VI. Recl Trav Chim Pays-Bas 45:6879 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. Barnett, EB, Matthews, MA, Wiltshire, JL 1926 The mechanism of substitution reactions in the aromatic nucleus. Part VII. Recl Trav Chim Pays-Bas 45:558563 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 18. Goldfarb, JL, Suuberg, EM 2008 The effects of halogen heteroatoms on the vapor pressures and thermodynamics of polycyclic aromatic compounds measured via the Knudsen effusion technique. J Chem Thermodyn 40:460466 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 19. Clark, JM Solubilities, separation, and purification of anthracene, carbazol, and phenanthrene. J Ind Eng Chem 1919 11:204209 .

  • 20. Hildebrand, JH, Duschak, AC, Foster, AH, Beebe, CW 1917 The specific heats and heats of fusion of triphenylmethane, anthraquinone and anthracene. J Am Chem Soc 39:22932297 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Mortimer, FS, Murphy, RV 1923 The vapor pressures of some substances found in coal tar. Ind Eng Chem 15:11401142 .

  • 22. Jones, RC, Neuworth, MB 1944 The ultraviolet absorption spectra of hydrocarbon-trinitrobenzene complexes. J Am Chem Soc 66:14971499 .

  • 23. Sears, GW, Hopke, ER 1949 Vapor pressures of naphthalene, anthracene, and hexachlorobenzene in a low pressure region. J Am Chem Soc 71:16321634 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Schmitt, WJ, Reid, RC 1986 Solubility of monofunctional organic solids in chemically diverse supercritical fluids. J Chem Eng Data 31:204212 .

  • 25. Goursot, P, Girdhar, HL EF Westrum Jr Thermodynamics of polynuclear aromatic molecules. III. Heat capacities and enthalpies of fusion of anthracene. J Phys Chem 1970 74:25382541 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Spotswood, TM 1962 Charge-transfer complexes of brominated polycyclic aromatic hydrocarbons. Aust J Chem 15:278289 .

  • 27. Li, Z, Werner, A, Schlögl, K 1993 Syntheses and absolute stereochemistry of chiral 9,10-dihydro-9,10-ethanoanthracenes and their tricarbonylchromium complexes. Chem Mon 124:441452 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 28. Heilbron, IM, Heaton, JS 1923 9,10-Dibromoanthracene. Org Synth Coll 1:207.

  • 29. Sampey, JR, McCuen, AK, Cox, JM 1950 Bromination of 9,10-dihydroanthracene. J Am Chem Soc 72:1854 .

Manuscript Submission: HERE

  • Impact Factor (2019): 2.731
  • Scimago Journal Rank (2019): 0.415
  • SJR Hirsch-Index (2019): 87
  • SJR Quartile Score (2019): Q3 Condensed Matter Physics
  • SJR Quartile Score (2019): Q3 Physical and Theoretical Chemistry
  • Impact Factor (2018): 2.471
  • Scimago Journal Rank (2018): 0.634
  • SJR Hirsch-Index (2018): 78
  • SJR Quartile Score (2018): Q2 Condensed Matter Physics
  • SJR Quartile Score (2018): Q2 Physical and Theoretical Chemistry

For subscription options, please visit the website of Springer.

Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation
1969
Volumes
per Year
4
Issues
per Year
24
Founder Akadémiai Kiadó
Founder's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address
H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher
Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)