The ultrathin precursor film surrounding droplets of liquid on a solid surface is used here as a confined reaction medium in order to drive a reaction that would not occur in bulk fluid. Sodium carbonate and calcium chloride mixed together in the presence of the organic thiol dithiothreitol (DTT) produced crystals of gypsum, or calcium sulfate, instead of the otherwise expected calcium carbonate. The possible sources of sulfate in the system are contaminants in the DTT or the oxidation product of the DTT sulfhydryl. The amount of gypsum produced implies that contaminants do not account for the total sulfate present in the system, suggesting that the DTT could be oxidized. The reaction quotient may be skewed in favor of this unexpected reaction by a combination of efficient removal of sulfate by precipitation and the concentration of DTT at the leading edge of the precursor film through the coffee-ring effect during a brief drying step.