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In this study, an efficient ghost cell‐based immersed boundary method is used to perform direct numerical simulations of mass‐transfer processes in bidisperse arrays. Stationary spherical particles, with a size ratio of 1.5, are homogeneously distributed in a periodic domain in the spanwise directions. Simulations are performed over a range of solids volume fractions, volume fraction ratios of small‐to‐large particles, and Reynolds numbers. Through our studies, we find that large particles have a negative influence on the overall mass‐transfer performance; however, the performance of individual particle species is independent on the relative volume fraction ratios. We propose two correlations: (a) a refitted Gunn correlation for a better description of the interfacial transfer performance based on individual particle species; (b) a fractional calculation for a simple estimation of the overall performance in bidisperse systems using characteristics of individual particle species. We also investigate how well the overall mass‐transfer coefficient can be predicted by defining an appropriate equivalent diameter. [ABSTRACT FROM AUTHOR]