The tendency for irreversible processes to generate entropy is the ultimate driving force for structure evolution in nature. In engineering, entropy production is often used as an indicator for loss of usable energy. In this study, we show that the analysis of entropy production patterns can provide insight into the diverse observations from experiments that investigate porous medium dissolution in imposed flow field. We first present a numerical scheme for the analysis of entropy production in dissolving porous media. Our scheme uses a greyscale digital model for chalk (an extremely fine grained rock), that was obtained using X-ray nanotomography. Greyscale models preserve structural heterogeneities with very high fidelity. We focussed on the coupling between two types of entropy production: the percolative entropy, generated by dissipating the kinetic energy of fluid flow, and the reactive entropy, originating from the consumption of chemical free energy. Their temporal patterns pinpoint three stages of microstructural evolution. We then showed that local mixing deteriorates fluid channelisation by reducing local variations of reactant concentration. We also showed that microstructural evolution can be sensitive to the initial transport heterogeneities, when the macroscopic flowrate is low. This dependence on flowrate indicates the need to resolve the structural features of a porous system when fluid residence time is long.