The idea that one may calculate the proper amount of powder to use in a particular gun, shooting black powder, do not take into account the actual differences in how different powders burn in the bore. There is a big difference between what works best if you compare a very fast and hot burning power like the Swiss powder versus a rifle burn rate powder such as GOEX.
Shooters think of powder burn rates only in terms of grain sizing when the real burn rate is a point of powder combustion reactions determined by the chemistry of the powder.
Old writings talked about the "expansive force" of a powder. That involves how much total volume of gases produced, at a certain rate and at a certain temperature.
For instance. Maximum gas temperatures. A musket burn rate powder will give about 1800 degrees gas temperature. A rifle powder around 1900 degrees and a fast burning sporting powder about 2,000 degrees.
In the gun. A point is reached in pressure development where the projectile can no longer respond, or accelerate, to an increase in this expansive force. That is in effect the point of diminishing returns. That may be looked at using chronograph data with uniform incremental increases in the powder charge. One may also look at this in terms of how tight the resulting groups are. Generally. As you go above this point of diminishing returns the groups will open up.
Mad Monk