We report theoretical and experimental investigations of the flow instability responsible for the mushy-layer mode of convection and the formation of chimneys, drainage channels devoid of solid, during steady-state solidification of aqueous ammonium chloride. Under certain growth conditions a state of steady mushy-layer growth with no flow is unstable to the onset of convection, resulting in the formation of chimneys. We present regime diagrams to quantify the state of the flow as a function of the initial liquid concentration, the porous-medium Rayleigh number, and the sample width. For a given liquid concentration, increasing both the porous-medium Rayleigh number and the sample width caused the system to change from a stable state of no flow to a different state with the formation of chimneys. Decreasing the concentration ratio destabilized the system and promoted the formation of chimneys. As the initial liquid concentration increased, onset of convection and formation of chimneys occurred at larger values of the porous-medium Rayleigh number, but the critical cell widths for chimney formation are far less sensitive to the liquid concentration. At the highest liquid concentration, the mushy-layer mode of convection did not occur in the experiment. The formation of multiple chimneys and the morphological transitions between these states are discussed. The experimental results are interpreted in terms of a previous theoretical analysis of finite amplitude convection with chimneys, with a single value of the mushy-layer permeability consistent with the liquid concentrations considered in this study.