The energy levels of the hydrogen atom are given by:
\[
E_n = - \frac{13.6}{n^2} \, \text{eV}
\]
where \( n \) is the principal quantum number. The energy ratio for the first and second excited states is:
\[
\frac{E_2}{E_3} = \frac{\left( -\frac{13.6}{2^2} \right)}{\left( -\frac{13.6}{3^2} \right)} = \frac{4}{9}
\]
Final Answer:
\[
\boxed{\frac{4}{9}}
\]