The impact of steady-state multiplicities on the control of a simulated industrial scale methyl acetate reactive distillation (RD) column is studied. At a fixed reflux rate, output multiplicity, with multiple output values for the same reboiler duty, causes the column to drift to an undesirable steady-state under open loop operation. The same is avoided for a fixed reflux ratio policy. Input multiplicity, where multiple input values give the same output, leads to "wrong" control action under feedback control severely compromising control system robustness. A new metric, rangeability, is defined to quantify the severity of input multiplicity in a steady-state input-output (10) relation. Rangeability is used in conjunction with conventional sensitivity analysis for the design of robust control structures for the RD column. Results for the two synthesized control structures show that controlling the most sensitive reactive tray temperature results in poor robustness due to low rangeability causing "wrong" control action for large disturbances. Controlling a reactive tray temperature with acceptable sensitivity but larger rangeability gives better robustness. It is also shown that controlling the difference in the temperature of two suitably chosen reactive trays further improves robustness of both the structures as input multiplicity is avoided. The article brings out the importance of IO relations for control system design and understanding the complex dynamic behavior of RD systems. (c) 2007 Elsevier Ltd. All rights reserved.