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Question

In the photochemical decomposition of acetaldehyde, one photon of absorbed light decomposes one molecule of CH3CHO into CH3 and CHO. If Iabs is the intensity of light absorbed in the reaction. Write the rate equation for this photochemical decomposition. (Note: the first step in the photochemical reaction is temperature independent)
Calculate [CH3]andd[CO]dt assuming steps (ii) to (iv) given are same and [CH3],[CH3CO] are under steady state.

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Solution

i)d[CH3]dt=k1[CH3CHO]k2[CH3CHO][CH3]+k3[CH3CO]2k4[CH3]2=0ii)d[CH3CO]dt=k2[CH3CHO][CH3]kc[CH3CO]=0CH3CHO+hvCH3+CHO[CH3]=k12k4[CH3CHO]1/2=(Iabs/2k4)1/2[CH3CHO]1/2d[CO]dt=k3[CH3CHO]3/2=k2k12k4[CH3CHO]3/2=k2(Iabs/2k4)1/2[CH3CHO]3/2

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