Particulate matter (PM) generated from pulverized coal combustion is influenced by a process of vaporization, nucleation and condensation/reaction of semi-volatile minerals. The objective of the work is to identify the controlling mechanism of the enrichment of volatile sodium (Na). Three representative kinds of coal with different rank and mineral content, Zhundong lignite, Hami lignite and high-ash-fusion (HAF) bituminous, were burned in a 25 kW self-sustained pulverized coal combustor. Zhundong lignite, possessing medium rank among the three coal samples, exhibits the highest formation ability of ultra fine PM0.2, indicating a prominent effect of mineral content over that of coal rank on PM formation. The size partitioning behavior of sodium is affected by the molar ratio Na2O/(SiO2+A1(2)O(3)) instead of the absolute Na content. With this ratio increasing from 0.27 (HAF bituminous) to 20 (Zhundong lignite), the gas-to-particle conversion of Na transits from a surface-reaction controlled process to a nucleationcondensation/coagulation dominated pathway. The Na partitioning behavior of Zhundong lignite is then quantitatively interpreted by a population-balance-based theoretical approach. The model reveals the details on the competing processes of homogeneous nucleation and vapor condensation, resulting in that the simulated final particle mass size distribution exhibits reasonable agreement with the experimental result. The model has also successfully reproduced the d(p)(0) dependence of Na fraction in the ultrafine size regime from a process of homogeneous nucleation under the decreasing gas temperature from 1420 to 1270 K. (C) 2017 Published by Elsevier Inc. on behalf of The Combustion Institute.