Systematic studies of mass transfer interactions with intrinsic reaction kinetics were performed for the three-phase selective hydrogenation of 2-methyl-3-butyn-2-ol (MBY) to 2-methyl-3-buten-2-ol (MBE) over a modified Pd/CaCO3 catalyst under solvent free conditions. Hydrogen concentration in the liquid phase (CH2,b) was monitored in situ during the catalytic reaction by means of the "Fugatron" analyzer. Reactions were carried out in an autoclave at different stirring rates at two concentrations of hydrogen (5 and 13 mol .m(-3)). For stirring speeds higher than 1500 rpm no influence of gas-liquid mass transfer was observed. Hydrogen liquid-solid (L-S) mass transfer was found to be negligible, whereas the MBY mass L-S transfer becomes important at high MBY conversions at high hydrogen concentration. Low stiffer speed caused the reaction rate and MBE selectivity to decrease. No internal mass transfer limitations were observed, and conditions for the kinetic regime were found. The kinetics modeled followed the Langmuir-Hinshelwood mechanism and was consistent with the experimental data.