In today's competitive environment, the low-tonnage chemicals industry (fine and effect chemicals) is under increasing pressure to deliver more products to the market quicker and more cost effectively. Process development is a critical phase in bringing a fine chemical product from discovery to the market and requires the provision of an efficient framework for the capture of process knowledge and understanding. This is traditionally done by somewhat indirect means-either through building understanding in individuals or the construction of a mathematical or physical model of the process. Such approaches suffer from two defects: first they do not collect understanding in a form that is readily shared by all the technologists involved, and second they do not collect understanding early enough in design. For example, the data required for the detailed modelling of a process is often only available well after the process configuration is fixed and properties can be measured under relevant conditions. Considering a liquid biphase reaction system, this paper demonstrates the interaction of targeted experimentation and qualitative/semiquantitative reaction evaluation to allow capture, testing, and sharing of understanding much earlier in design. The resultant qualitative predictions are tested against experimental observations to identify aspects where the qualitative model needs refinement. Recommendations for using more rigorous process analysis tools to explain these so-called anomalous observations are thus made. © 2006 American Chemical Society.