This paper deals with the optimization of biochemical reaction systems of rank one. Two optimization problems are solved: the problem of optimal operation for maximum productivity in steady state and the problem of the start-up to the optimal steady state. Application of Pontryagin's maximum principle shows that the controller is of the bang-bang type, with no singular intervals. The determination of the optimal switching surface involves the solution of a two point boundary value problem. Solving such a difficult problem is avoided by choosing candidate switching surfaces on a heuristic basis. This study shows that switching on the stability boundary of the nominal operating point corresponding to the maximum dilution rate is the best choice. Here the value of the cost index is minimum amongst the various switching surfaces considered and the stability boundary satisfies the conditions imposed on a candidate switching surface for proper operation. Simple, robust algorithms are formulated for accurately estimating the system's stability boundary. The obtained results display the influence of feedback control on the stability of the set point. The bang-bang controller substantially increases the set point's region of attraction in state space as compared to the uncontrolled bioreactor.