We determine the energy splitting of the conduction-band valleys in two-dimensional electrons confined to low-disorder Si quantum wells. We probe the valley splitting dependence on both perpendicular magnetic field B and Hall density by performing activation energy measurements in the quantum Hall regime over a large range of filling factors. The mobility gap of the valley-split levels increases linearly with B and is strikingly independent of Hall density. The data are consistent with a transport model in which valley splitting depends on the incremental changes in density eB/h across quantum Hall edge strips, rather than the bulk density. Based on these results, we estimate that the valley splitting increases with density at a rate of 116 μeV/1011 cm-2, which is consistent with theoretical predictions for near-perfect quantum well top interfaces.