The solidification of melts can be profoundly influenced by convection. In alloys, compositional convection can be driven by solute gradients generated as one component of the alloy is preferentially incorporated within the solid, even when the thermal field is stabilizing. In this paper, two modes of compositional convection during solidification from below are uncovered using a linear-stability analysis: one, which we shall call the ‘mushy-layer mode’, is driven by buoyant residual fluid within a mushy layer, or porous medium, of dendritic crystals; the other, which we shall call the ‘boundary-layer mode’ is associated with a narrow compositional boundary layer in the melt just above the mush-liquid interface. Either mode can be the first to become unstable depending on the thermodynamical and physical properties of the alloy. The marginally stable eigenfunctions suggest that the boundary-layer mode results in fine-scale convection in the melt above the mushy layer and leaves the interstitial fluid of the mushy layer virtually stagnant. In contrast, the mushy-layer mode causes perturbations to the solid fraction of the mushy layer that are indicative of a tendency to form chimneys, which are vertical channels of reduced or zero solid fraction that have been observed experimentally. Particular attention is focused on the mushy-layer mode and its dependence upon the thermodynamical properties of the alloy. The results of this analysis are used to make a number of interpretations of earlier experimental studies such as the observations that some systems are less prone to form chimneys and that the regions of melt in these systems evolve to supersaturated conditions, while the melt evolves to unsaturated conditions once chimneys have formed. In addition, good quantitative agreement is found between the results of the linear-stability analysis and the experimental results of Tait & Jaupart (1992) for the onset of the mushy-layer mode of convection.