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2014 Annual Science Report

NASA Jet Propulsion Laboratory - Titan Reporting  |  SEP 2013 – DEC 2014

Co-Crystals on the Surface of Titan

Project Summary

We have discovered that benzene and ethane form a co-crystalline inclusion compound at Titan surface temperatures and pressures. Co-crystals of other organic compounds could be common on Titan’s surface. These results can help explain the release of ethane observed at the Huygens landing site, and point to a new type of surface material that may have significant impact on Titan surface chemistry and geology.

4 Institutions
3 Teams
10 Publications
0 Field Sites
Field Sites

Project Progress

Titan is the only body in the Solar System aside from Earth that has standing liquid on its surface. Due to the low surface temperatures (90-95 K), this liquid phase is comprised of hydrocarbons, mostly methane and ethane. Active photochemistry in the atmosphere due to solar radiation and energy from Saturn’s magnetosphere generates a plethora of organic molecules, from simple molecules to compounds >10,000 Da. These species are ultimately deposited onto the surface, including into the lakes. Evaporation or other processes could potentially induce precipitation of these organics, forming ‘bathtub rings’ similar to those observed by Cassini around some of the Northern lakes. These lake evaporites may play an important role in the surface chemistry of Titan.

We focus on benzene, which has been detected by Cassini in the Titan atmosphere and was tentatively identified on the surface by Huygens. Recent work in our laboratory shows that benzene has a very low solubility in liquid ethane (18.5 mg/L), meaning is a likely constituent of possible evaporites of Titan lakes.
We performed a series of experiments in which solid benzene and liquid ethane were allowed to interact under Titan surface conditions (1 bar N2, 94 K). The interaction was studied using confocal Raman microscopy. On the basis of optical microscopy and the Raman spectra, we identified the formation of a distinctive co-crystalline structure. New features in the Raman spectrum at 2873 cm-1 and 1455 cm-1 were characteristic of the new structure (Fig 1). Recrystallization of the solid benzene was observed during the co-crystal formation (Fig 2).

Additional experiments were performed in order to characterize the temperature stability and kinetics of formation of the benzene:ethane co-crystal. We find that the co-crystal is stable up to ~150 K, and would form rapidly (<18 hours) at temperatures representative of Titan’s surface (94 K).

In cooperation with Dr. Helen Maynard-Casely, we were awarded beam time at the Australian Synchrotron (Melbourne, Australia) in order to study the crystal structure of the benzene:ethane co-crystal on the powder diffraction (PD) beamline. The PD beamline at the Australian synchrotron is ideally suited for these experiments, as facilities for cooling of the sample to cryogenic temperatures and the ability to condense gasses onto the sample are already in place. These experiments were highly successful, and the we were able to obtain a powder diffraction patter of the co-crystal and solve the structure (Fig. 3.) A paper describing these results is in progress.

Our work suggests that the benzene:ethane co-crystal may be the dominant form of benzene on titan wherever crystalline benzene has been in contact with liquid ethane, as in evaporite basins around ethane/methane lakes and seas. The benzene:ethane co-crystal represents a new class of materials for Titan’s surface, analogous to hydrated minerals on Earth. This new structure may also influence evaporite characteristics such as particle size, dissolution rate, and infrared spectral properties. Future work will involve searching for new organic co-crystal structures and their characterization.

Figure 1.
High-resolution Raman spectra of crystalline benzene before (black) and after (blue) incorporation of ethane in its lattice at 90 K. Note the emergence of a shoulder at 2873 cm−1 upon ethane incorporation. In comparison to pure solid benzene at 90 K (red), the υ7 mode at 3040−3050 cm−1 undergoes a red shift, while the frequency of υ1 mode at 3063 cm−1 remains unchanged. The spectrum of solid ethane at 80 K (yellow) is also included for reference. All spectra are vertically offset for clarity.

Figure 2.
Microscope images of solid benzene before (left) and after (right) ethane incorporation, showing recrystallization during the formation of a new crystal structure.

Figure 3.
The benzene ethane co-crystal, viewed down the c-axis. The stoichiometry is 3:1 benzene:ethane.

Publications

  • Bennett, C. J., Pirim, C., & Orlando, T. M. (2013). Space-Weathering of Solar System Bodies: A Laboratory Perspective. Chem. Rev., 113(12), 9086–9150. doi:10.1021/cr400153k

  • Cable, M. L., Hörst, S. M., He, C., Stockton, A. M., Mora, M. F., Tolbert, M. A., … Willis, P. A. (2014). Identification of primary amines in Titan tholins using microchip nonaqueous capillary electrophoresis. Earth and Planetary Science Letters, 403, 99–107. doi:10.1016/j.epsl.2014.06.028

  • Cable, M. L., Vu, T. H., Hodyss, R., Choukroun, M., Malaska, M. J., & Beauchamp, P. (2014). Experimental determination of the kinetics of formation of the benzene-ethane co-crystal and implications for Titan. Geophysical Research Letters, 41(15), 5396–5401. doi:10.1002/2014gl060531

  • Dawley, M. M., Pirim, C., & Orlando, T. M. (2014). Radiation Processing of Formamide and Formamide:Water Ices on Silicate Grain Analogue. The Journal of Physical Chemistry A, 118(7), 1228–1236. doi:10.1021/jp4042815

  • Dawley, M. M., Pirim, C., & Orlando, T. M. (2014). Thermal Processing of Formamide Ices on Silicate Grain Analogue. The Journal of Physical Chemistry A, 118(7), 1220–1227. doi:10.1021/jp404026s

  • He, C., & Smith, M. A. (2014). A comprehensive NMR structural study of Titan aerosol analogs: Implications for Titan’s atmospheric chemistry. Icarus, 243, 31–38. doi:10.1016/j.icarus.2014.09.021

  • He, C., & Smith, M. A. (2014). Solubility and stability investigation of Titan aerosol analogs: New insight from NMR analysis. Icarus, 232, 54–59. doi:10.1016/j.icarus.2014.01.007

  • Jeilani, Y. A., Orlando, T. M., Pope, A., Pirim, C., & Nguyen, M. T. (2014). Prebiotic synthesis of triazines from urea: a theoretical study of free radical routes to melamine, ammeline, ammelide and cyanuric acid. RSC Adv., 4(61), 32375. doi:10.1039/c4ra03717k

  • Malaska, M. J., & Hodyss, R. (2014). Dissolution of benzene, naphthalene, and biphenyl in a simulated Titan lake. Icarus, 242, 74–81. doi:10.1016/j.icarus.2014.07.022

  • Vu, T. H., Cable, M. L., Choukroun, M., Hodyss, R., & Beauchamp, P. (2014). Formation of a New Benzene–Ethane Co-Crystalline Structure Under Cryogenic Conditions. The Journal of Physical Chemistry A, 118(23), 4087–4094. doi:10.1021/jp501698j

  • PROJECT INVESTIGATORS:
  • PROJECT MEMBERS:
    Robert Hodyss
    Project Investigator

    Morgan Cable
    Co-Investigator

    Mathieu Choukroun
    Co-Investigator

    Tuan Vu
    Co-Investigator

    Patricia Beauchamp
    Collaborator

    Michael Malaska
    Collaborator

  • RELATED OBJECTIVES:
    Objective 1.1
    Formation and evolution of habitable planets.

    Objective 2.2
    Outer Solar System exploration

    Objective 3.1
    Sources of prebiotic materials and catalysts

    Objective 3.2
    Origins and evolution of functional biomolecules