Assume a hydrogen-rich gas with approximately solar elemental ratios and local thermochemical equilibrium when identifying the limiting compositions. At , a representative set of dominant molecules is . In the deeper regime, it is . Helium is an abundant atom, not a molecule. The carbon and nitrogen switches, carbon monoxide–methane quenching and nitrogen–ammonia quenching when frozen by mixing, are represented by
Low temperature and high pressure favor the right-hand sides, while hotter gas favors carbon monoxide and . Exact boundaries depend on pressure and composition; can become important at high metallicity. If mixing is strong, the cool upper atmosphere need not retain its local-equilibrium four-species ordering.
To preserve the hot-region reactant aloft, require transport to beat its conversion at the quench region. With a mixing length and vertical eddy diffusivity ,
For the simplest use of the supplied atmospheric scale height reference, assume the same temperature and mean molecular weight as the reference atmosphere and take . Since , , giving .
The hotter quench layer requires a temperature correction if the reference is ordinary Jupiter; the temperature of that scale-height reference was not specified. An explicit estimate using , dimensionless mean molecular weight , and gives
Thus a scale-height-based estimate using the hot layer is of order . Both estimates state their assumptions: the reference scaling alone does not include the temperature ratio. Choosing lowers the threshold by a factor of , and a full quench calculation needs the reaction timescale along the profile. The dependence of a quench diffusivity on mixing length shows why the stated reaction timescale supplies a mixing constraint, not a unique measured coefficient.
Convection mixes material vertically where the Schwarzschild criterion or Ledoux criterion allows it. Its chemical effect is controlled by competition between transport and reaction, rather than by a direct alteration of the equilibrium constant. Parametrize vertical transport by a vertical eddy diffusion coefficient ; the eddy mixing time over a scale height is
Let be the chemical relaxation time of the relevant interconversion. If reactions are faster, the gas follows local thermochemical equilibrium. If transport becomes faster, composition can be carried upward faster than it re-equilibrates. A chemical quench level is approximately where the two times match:
For example, hot deep gas may contain abundant carbon monoxide. Strong mixing can maintain it in cooler layers where equilibrium would favour methane; this is carbon monoxide–methane quenching. Similar reasoning applies to nitrogen–ammonia quenching. The cooler nightside commonly has slower reaction rates and can preserve such quenched composition more readily, whereas sufficiently rapid dayside chemistry can restore local equilibrium. Neither statement is universal without the actual reaction network and temperature.
The observable atmosphere of a strongly irradiated hot Jupiter may be radiative and stable even if the deeper interior is convective. Deep convection influences the photosphere only if some mixing crosses the intervening radiative region, for example through overshoot or other dynamical transport. Moreover, transport from day to night is horizontal circulation, not vertical convection; its relevant competition is atmospheric advection time versus chemical relaxation time, giving horizontal chemical quenching. Convection can affect either hemisphere indirectly through connected vertical transport; strong deep convection alone does not guarantee a quenched observable composition.
The first two signatures can be consequences of the same process and are not independent evidence for two mechanisms. Changes in atmospheric carbon-to-oxygen ratio, atmospheric metallicity of a giant planet, exoplanet cloud coverage, and the atmospheric pressure-temperature profile can mimic abundance changes. A convincing inference compares several molecular bands with a chemically consistent equilibrium model rather than identifying one unusual band alone.
Assume a hydrogen-helium perfect gas with mean particle mass , Jupiter gravity , and mixing over one atmospheric scale height. At ,
The eddy mixing time is . A chemical quench level at one bar requires , hence the vertical eddy diffusion coefficient must be of order
The number depends quadratically on the assumed mixing length; using a fraction of reduces it accordingly.
Above the chemical quench level, neglect photochemistry, condensation, and molecular diffusion. The quenched atmospheric mixing ratio is approximately constant, while the number density is
Thus the abundance fraction is frozen, but the absolute number density falls with pressure and altitude. Examples are carbon monoxide–methane quenching, through , and nitrogen–ammonia quenching, through .
Approximate the atmosphere above as isothermal with constant gravity and atmospheric scale height , so
Vertical transport over one scale height has eddy mixing time
The chemical quench level satisfies . Since ,
Above this level, mixing is faster than reaction and freezes the deeper abundance of A. Larger moves the quench level deeper and raises . Important examples are carbon monoxide–methane quenching and nitrogen–ammonia quenching; phosphine destruction is another tracer of vertical quenching.