In which of the following reactions Markovnikov’s rule is not observed ?

Markovnikov’s rule is not followed when free radical addition of HBr takes place to an unsymmetrical alkene
$$\begin{gathered} {\mathrm{CH}}_3-\mathrm{CH}={\mathrm{CH}}_2+\mathrm{HBr}\underset{\mathrm{hv}}{\overset{\mathrm{organic}peroxide}{\to }}{\mathrm{CH}}_3-{\mathrm{CH}}_2-{\mathrm{CH}}_2-\mathrm{Br} \\ {\mathrm{CH}}_3-\mathrm{CH}={\mathrm{CH}}_2+\mathrm{HBr}\stackrel{{\mathrm{H}}_2{\mathrm{O}}_2,\mathrm{hv}}{\to }{\mathrm{CH}}_3-{\mathrm{CH}}_2-{\mathrm{CH}}_2-\mathrm{Br} \end{gathered}$$
Both these reactions follow free radical mechanism and hence Markovnikov’s addition is not observed.