Natural gas at thermodynamic equilibrium Implications for the origin of natural gas

and isotopic compositions are also under equilibrium constraints:The functions [(CH4)*(C3H8)] and [(C2H6)2] exhibit a strong nonlinear correlation (R2 = 0.84) in which the quotient Q progresses to K as wet gas progresses to dry gas. There are striking similarities between natural gas and catalytic gas generated from marine shales. A Devonian/Mississippian New Albany shale generates gas with Q converging on K over time as wet gas progresses to dry gas at 200°C.The position that thermal cracking is the primary source of natural gas is no longer tenable. It is challenged by its inability to explain the composition of natural gas, natural gases at thermodynamic equilibrium, and by the existence of a catalytic path to gas that better explains gas compositions.The hydrocarbons in natural gas are believed to come from two sources, one biological ('biogenic gas'), and the other from thermal cracking, 'primary thermal gas' from kerogen cracking and 'secondary thermal gas' from oil cracking [1,2]. Although there is general agreement on the source of biogenic gas, disagreement persists over the origin of thermal gas. One point of controversy is that thermal cracking does not produce a gas resembling natural gas. Oil and kerogen pyrolysis typically give between 10 and 60% wt methane (C1–C4) [3-9] while natural gas contains between 60 and 95+% methane [10]. None of the explanations that have been offered to explain this [11-15] are satisfactory [16]. Catalysis by reduced transition metals can, in theory, explain high-methane in natural gas [17], and this hypothesis is supported by experimental results. Crude oils and n-alkanes decomposed over reduced nickel and cobalt oxides produce gas resembling natural gas in molecular and isotopic compositions [18]. There is, however, no evidence of metal activity in sedimentary rocks and therefore no compelling reason to question thermal cracking theory. Moreover, recent hydrous pyrolysis experiments with metal-rich Permian Kupferschiefer s