The mass transfer behavior of oxygen and ferricyanide in dilute aqueous solutions was investigated using a rotating cylinder electrode under bulk boiling condition. A correlation was developed for predicting the mass transfer behavior using the reaction of dissolved oxygen below boiling condition. This correlation was used to predict the mass transfer behavior for ferricyanide reaction from room temperature to just below boiling point (i.e. 99 degrees C) for the rotating speeds between 100 and 3300 rpm. These results indicated that the ferricyanide reaction could be used as a model to predict the electrochemical behavior of dissolved oxygen at the elevated electrolyte temperatures. However, the correlation could not predict the experimental data obtained under boiling conditions very well. The experimentally determined mass transfer coefficients under boiling condition were on the average 38% higher than those obtained just below boiling point due to the generation and rupture of boiling bubbles in bulk solution. (C) 2013 Elsevier Ltd. All rights reserved.