The mass transfer kinetics of thiourea, phenol, ethylbenzene, propylbenzene, butylbenzene, and amylbenzene were studied on a Gemini-C-18 (5 mu m, 110 angstrom, 375 m(2)/g) column (150 mm x 4.6 mm) eluted with methanol/water solutions (100, 90, and 20% v/v). Each of the successive steps of the mass transfer of these solutes (axial diffusion, eddy dispersion, film mass transfer resistance, and transparticle mass transfer resistance) was unambiguously measured, using a combination of the peak parking method, the total pore blocking method, and moment analysis, in a wide range of reduced linear velocities. The results obtained offer new insights on the mass transfer kinetics in chromatographic columns. They show first that the eddy dispersion A-term is strongly correlated with the particle porosity. The complex, anastomosed transcolumn flow pattern causes extra band broadening. This transcolumn effect was found to be markedly smaller with porous particles than with nonporous particles of the same size. Second, the film mass transfer coefficient of retained compounds is smaller for porous than for nonporous particles, a result consistent with concentration gradients being steeper at the wall of solid particles than across the entrance surface of pores. The external mass transfer coefficient decreases with increasing fraction of the surface area of the particles that is open to pores, e. g., with increasing particle porosity. (C) 2010 American Institute of Chemical Engineers AIChE J, 57: 333-345, 2011