Past exam of the mathematics course of the University of Cambridge / 2018 / iii / Paper 315 / 3 / b / iv

At fixed temperature and pressure, the atmospheric carbon-to-oxygen ratio controls the division of the elemental inventory among carbon monoxide, methane, water and other molecules. For an oxygen-rich mixture, water can remain after carbon monoxide consumes its share of oxygen. Increasing the atmospheric carbon-to-oxygen ratio reduces the oxygen available for water, particularly in the hotter layers where carbon monoxide is stable. Near or above unity there, water can become strongly depleted while excess carbon feeds methane, hydrogen cyanide and acetylene. This familiar hot carbon-rich behavior should not be applied unchanged to every cool layer: at $500\mathrm{K}$, methane formation can leave substantial water even at high atmospheric carbon-to-oxygen ratio.

Increasing the atmospheric metallicity of a giant planet at fixed elemental ratios increases the heavy-element inventory relative to molecular hydrogen and helium. Abundances of water and the major carbon-bearing molecules generally rise while molecular hydrogen remains dominant. In that regime, the law of mass action for $\mathrm{CO}+{\mathrm{H}}_2\mathrm{O}\rightleftharpoons {\mathrm{CO}}_2+{\mathrm{H}}_2$ givesWhere carbon monoxide and water each scale roughly linearly with enrichment $Z$, carbon dioxide consequently scales approximately as $Z^2$. This scaling changes when molecular hydrogen ceases to dominate or chemical partitioning changes. Higher enrichment can also favor carbon monoxide over methane at fixed conditions, increase mean molecular weight, and reduce the atmospheric scale height and transmission-feature amplitudes. Cloud formation and atmospheric condensate rainout alter the observable elemental ratios relative to the bulk ones.