Experimental study is conducted to investigate the heat/mass transfer and flow characteristics for the flow over backward-facing step and cavities. A naphthalene sublimation method has been employed to measure the mass transfer coefficients on the duct wall and LDV system has been used to obtain mean velocity profiles and turbulence intensities. Reynolds number based on the step height and free stream velocity is 20,000 and St numbers of acoustic excitations given to separated flow are 0.2 to 0.4. The spectra of streamwise velocity fluctuation show a sharp peak forcing frequency for an acoustically excited flow. The results reveal that the vortex pairing and overall turbulence level are enhanced by the acoustic excitation and a significant decrease in the reattachment length and the increased turbulence intensity are observed with the excitation. A certain acoustic excitation increases considerably the heat/mass transfer coefficient at the reattachment point and in the recirculation region. For the cavities, heat/mass transfer is enhanced by the acoustic excitation due to the elevated turbulence intensity. For the 10H cavity, the flow pattern is significantly changed with the acoustic excitation. However, for the 5H cavity, the acoustic excitation has little effect on the flow pattern in the cavity.