A two-dimensional 51 V homonuclear NMR exchange experiment (2D-EXSY) has been used to study the oligomerization reactions vanadate undergoes in aqueous solutions. This manuscript describes the first quantitative measurement of complex intermolecular chemical exchange rates by using 51 V (I=7/2) in a 2D-EXSY experiment. Microscopic rate constants for intermolecular exchange were obtained by using a numerical procedure to solve the 2D exchange matrix. The 2D exchange matrix was converted to a rate matrix that could be used in a kinetic analysis of the four exchanging vanadium species