The objective of this investigation was to study how different concentration profiles of sodium ions influence the delignification rate, hexenuronic acid formation/degradation and xylan retention under kraft cooking conditions. The concentration of sodium ions was varied in time between 0.52 and 3.00 mol/kg solvent, taking two different routes by the controlled addition of sodium carbonate. The reaction rates of hexenuronic acid were found to increase when the sodium ion concentration was at the higher level. Furthermore, the results implied that the kinetics of hexenuronic acid reactions responds rapidly to changes in sodium ion concentration. Delignification and the removal rates of xylan decreased rapidly after the sodium ion concentration was increased. However, when the sodium ion concentration was decreased, the response to the change was delayed. These findings indicate that effects of ionic strength on the rate of delignification and removal of xylan arise as a consequence of changes in solubility and on mass transport phenomena rather than from the rates of chemical reaction. Furthermore, the results suggest that non-dissolved xylan located in the fibre wall matrix may also sorb on cellulose surfaces relatively early on in the cook if the concentration of sodium ions is at high level.