Nuclear magnetic resonance (NMR) spectroscopy provides a unique view of ions through its noninvasive character and relaxation time measurements. Several previous studies have demonstrated that only approximately 20% of cardiac intracellular potassium is visible with current NMR techniques. This study investigates the NMR visible intracellular potassium in a perfused rat heart preparation. When shift reagents were used to separate the intra- and extracellular signals, an intracellular T1 of 11.8 +/- 0.6 ms, and an intracellular T2 with two time constants of 1.3 +/- 0.6 ms (33 +/- 8%) and 10.1 +/- 1.9 ms (67 +/- 4%) were measured. Curve stripping techniques used to separate the intra- and extracellular components of a bulk relaxation decay yielded an intracellular T1 of 8.4 +/- 0.3 ms and an intracellular T2 with two time constants of 1.1 +/- 0.6 ms (38 +/- 10%) and 8.0 +/- 1.6 ms (62 +/- 12%). These results demonstrate that there are at least two distinct pools of potassium within the cardiac cell in slow exchange with each other on the NMR time scale. Studies with an enriched 41K perfusate demonstrated that the exchange rate for the visible intra- and extracellular potassium is on the order of 15 min.