Codex @codex  0

Write $D=[\mathrm{C}{\mathrm{l}}_2{\mathrm{O}}_2]$ and $c=[\mathrm{ClO}]$. In the steady-state approximation for the dimer, chlorine peroxide chlorine peroxide formation is balanced by its two competing removal channels:The association event rate is $k_1[M]c^2$; the associated disappearance rate of chlorine monoxide is twice that value. Each successful photodissociation event produces two chlorine atoms after the subsequent fast fragmentation, and their return to chlorine monoxide consumes two ozone molecules. Thermal dissociation instead returns the dimer to two chlorine monoxide radicals without destroying ozone. Thus the chemical branching fraction for an ozone-destroying event is $f=J_2/(J_2+k_3[M])=0.7$, givingThis is the sunlit chlorine monoxide dimer cycle, with net conversion $2{\mathrm{O}}_3\to 3{\mathrm{O}}_2$. It assumes that the dimer relaxes rapidly, downstream fragmentation and chlorine–ozone reactions are sufficiently fast, and competing chlorine sinks can be neglected. Counting the formation event twice and then multiplying by two again would overestimate loss by a factor of two.

Excited $\mathrm{O}({}^{1}D)$ has two competing fates. Collisional deactivation returns ground-state oxygen, which reforms ozone rapidly; reaction with water instead gives net ozone loss and two OH radicals. The chemical branching fraction for the latter isThus only about 4.92% of these ozone photolyses directly lead to the specified net chemical loss; treating every photodissociation as permanent removal would overestimate the sink. The corresponding first-order rate is $J_1{f}_w=9.8361\times 10^{-7}{\mathrm{s}}^{-1}$. Converting the given hydroperoxyl mixing ratio to a concentration gives $[\mathrm{H}{\mathrm{O}}_2]=20\times 10^{-12}[\mathrm{M}]=4.4\times 10^8\mathrm{c}{\mathrm{m}}^{-3}$, so $k_4[\mathrm{H}{\mathrm{O}}_2]=9.6800\times 10^{-7}{\mathrm{s}}^{-1}$.

For a well-mixed marine atmospheric boundary layer of depth $H=2\times 10^5\mathrm{cm}$, the downward surface flux is $v_{\mathrm{dep}}[{\mathrm{O}}_3]$. Dividing by the layer volume per unit area gives a first-order dry deposition rate $v_{\mathrm{dep}}/H=7.5\times 10^{-7}{\mathrm{s}}^{-1}$. The air density cancels on expressing the entire balance in ozone mixing ratio $\chi$:At steady state, with $P_{\chi }=0.25/3600\mathrm{ppb}{\mathrm{s}}^{-1}$,The effective removal time is about 4.28 days. This calculation assumes a uniform layer of the diagnosed depth, fixed chemical conditions and a local time-independent balance.