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Volatiles in the Outer Solar System: I. Thermodynamics of Clathrate Hydrates. II. Ethane Ocean on Titan. III. Evolution of Primordial Titan Atmosphere


Lunine, Jonathan Irving (1985) Volatiles in the Outer Solar System: I. Thermodynamics of Clathrate Hydrates. II. Ethane Ocean on Titan. III. Evolution of Primordial Titan Atmosphere. Dissertation (Ph.D.), California Institute of Technology.


Three investigations are conducted into the physical chemistry of volatiles in the outer solar system and the role of volatiles in icy satellite evolution.

Part I:

The thermodynamic stability of clathrate hydrate is calculated under a wide range of temperature and pressure conditions applicable to solar system problems, using a statistical mechanical theory developed by Van der Waals and Platteeuw (1959) and existing experimental data on properties of clathrate hydrates and their components. At low pressure, dissociation pressures and partition functions (Langmuir constants) for CO clathrate (hydrate) have been predicted using the properties of clathrate containing, as guests, molecules similar to CO. The comparable or higher propensity of CO to incorporate in clathrate relative to N2 is used to argue for high CO to N2 ratios in primordial Titan if N2 were accreted as clathrate. The relative incorporation of noble gases in clathrate from a solar composition gas at low temperatures is calculated, and applied to the case of giant planet atmospheres and icy satellites. It is argued that non-solar but well-constrained noble gas abundances would be measured by Galileo in the Jovian atmosphere if the observed carbon enhancement were due to bombardment of the atmosphere by clathrate-bearing planetesimals sometime after planetary formation. The noble gas abundances of Titan's atmosphere are also predicted under the hypothesis that much of the satellite's methane accreted as clathrate. Double occupancy of clathrate cages by H2 and CH4 in contact with a solar composition gas is examined, and it is concluded that potentially important amounts of H2 may have incorporated in satellites as clathrate. The kinetics of clathrate formation is also examined, and it is suggested that, under thermodynamically appropriate conditions, essentially complete clathration of water ice could have occurred in high pressure nebulae around giant planets but probably not in the outer solar nebula; comets probably did not aggregate as clathrate. At moderate pressures, the phase diagram for methane clathrate hydrate in the presence of 15% ammonia (relative to water) is constructed, and application to the early Titan atmospheric composition is described. The high pressure stability of CH4, N2, and mixed CH4-N2 clathrate hydrate is calculated; conversion back to water and CH4 and/or N2 fluids or solids is predicted for pressures ≳12 kilobars and/or temperatures ≳320 K. The effect of ammonia is to shrink the T-P stability field of clathrate with increasing ammonia concentration. A preliminary phase diagram for the high pressure ammonia-water system is constructed using new data of Johnson et al. (1984). These results imply that 1) clathrate is stable throughout the interior of Oberon- and Rhea-sized icy satellites, and 2) clathrate incorporated in the inner-most icy regions of Titan would have decomposed, perhaps allowing buoyant methane to rise. Brief speculation on the implications of this conclusion for the origin of surficial methane on Titan is given. A list of suggested experiments and observations to test the theory and its predictions is presented.

Part II:

We propose a global Titanic ocean, one to several kilometers deep, the modern composition of which is predominantly ethane. If the ocean is in thermodynamic equilibrium with an atmosphere of 3' (mole fraction) methane then its composition is roughly 70% C2H6, 25% CH4, and 5% N2. Photochemical models predict that C2H6 is the dominant end-product of CH4 photolysis so that the evolving ocean is both the source and sink for ongoing photolysis. The coexisting atmosphere is compatible with Voyager data. Two consequences are pursued: the interaction of such an ocean with the underlying "bedrock" of Titan (assumed to be water-ice or ammonia hydrate) and with the primarily nitrogen atmosphere. It is concluded that although modest exchange of oceanic hydrocarbons with enclathrated methane in the bedrock can in principle occur, it is unlikely for reasonable regolith depths and probably physically inhibited by the presence of a layer of solid acetylene and complex polymeric hydrocarbons a couple of hundred meters thick at the base of the ocean. However, the surprisingly high solubility of water ice in liquid methane (Rebiai et al., 1983) implies that topographic features on Titan of order 100 meter in height can be eroded away on a time scale ≾109 years; "Karst" topography could be formed. Finally, the large solubility difference of N2 in methane versus ethane implies that the ocean composition is a strong determinant of atmospheric pressure; a simple radiative model of the Titan atmosphere is employed to demonstrate that significant surface pressure and temperature changes can occur as the oceanic composition evolves with time. The model suggests that the early methane-rich ocean may have been frozen; scenarios for evolution to the present liquid state are discussed.

Part III:

A simple convective cooling model of a primordial, CH4-NH3-N2 Titan atmosphere is constructed, in an effort to understand the fate of volatiles accreted from a gaseous disk ("nebula") surrounding Saturn and released from accreting planetesimals during the satellite's formation. Near-surface temperatures are initially ≳400 K consistent with the large amount of energy supplied to the atmosphere during accretion. As a consequence of accretional heating, the upper mantle of the satellite consists of an ammonia-water liquid, extending to the surface. This "magma ocean" is the primary buffer of atmospheric cooling because it is ≳10 times as massive as the atmosphere. The radiative properties of the atmosphere are assumed independent of frequency and the resulting temperature profile is found to be adiabatic; if the atmosphere contains dark particulates surface temperatures could be lower than calculated here. Three major processes drive the cooling: (1) hydrodynamic escape of gas from the top of the atmosphere, which determines the cooling time scales, (2) atmospheric ablation by high velocity impacts (not modeled in detail here), and (3) formation of clathrate hydrate at the ocean-atmosphere interface, at T ≤ 250 K. Cooling time scales driven by escape are sufficiently long (108-109 years) to allow ~10 bars of N2 to be produced photochemically from NH3 in the gas phase (Atreya et al., 1978); however, the abundance of NH3 at temperatures ≾150 K (where the intermediate photochemical products condense out) is optically thick to the dissociative UV photons. Thus, N2 formation may proceed primarily by shock heating of the atmosphere during large body impacts, as well as by photochemistry (1) at T < 150 K if intermediate products supersaturate, or (2) in a warm stratosphere, with NH3 abundance fixed by its tropopause value. The clathrate formed during late stages of cooling sequesters primarily CH4, with some N2, and forces surface temperatures and pressures to drop rapidly. The clathrate is only marginally buoyant relative to the coexisting ammonia-water liquid. If it sinks, the atmosphere is driven to an N2-rich state with most of the methane sequestered in clathrate when the ocean surface freezes over at ~180 K. Implications of this scenario for the present surface state of Titan are contrasted with those obtained if the clathrate forms a buoyant crust at the surface.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Planetary Science
Degree Grantor:California Institute of Technology
Division:Geological and Planetary Sciences
Major Option:Planetary Sciences
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Muhleman, Duane Owen
Thesis Committee:
  • Stevenson, David John (chair)
  • Yung, Yuk L.
  • Ingersoll, Andrew P.
  • Kamb, W. Barclay
  • Muhleman, Duane Owen
Defense Date:18 June 1984
Additional Information:Thesis title listed in 1985 Commencement Program varies from actual thesis: Volatiles in the Outer Solar System: I. Thermodynamics of Clathrate Hydrates. II. Ethane Ocean on Titan. III. Evolution of Titan Atmosphere.
Funding AgencyGrant Number
Record Number:CaltechTHESIS:02212013-144447105
Persistent URL:
Related URLs:
URLURL TypeDescription adapted for Part I. adapted for Part II. A. chapter adapted for Part II. B
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7490
Deposited By: Benjamin Perez
Deposited On:21 Feb 2013 23:11
Last Modified:18 Dec 2020 01:27

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