hey, fella, you haven't heard this yet as far as I could see.
The key is acceleration, acceleration is provided by ongoing high pressure. A chamber pressure doesn't mean squat for velocity. Your sustained pressure as the bullet goes down the bore is what matters. In fact, some really extremely weird loads will actually slow down in the trip down the bore because of friction and extreme pressure drop.
When you use a slow burning powder such as 4831, your pressure is sustained all throughout the run down the barrel, and yes, a lot of that fire is wasted outside of the barrel. You use a slow powder to generate sustained high pressures all the way down the barrel. It generates thrust. It increases the rate of speed buildup or acceleration.
A faster burning powder will fizzle out, so to speak, and the pressure peaks early and fails to provide further acceleration.your velocity is limited because your pressure peaks early and it kills acceleration.
There are so many factors involved. Resistance of the bullet because of the weight is important. so many others, like case capacity. All of this change the way a charge ignites and burns, how acceleration builds.
For example, a .30-30 is a tiny case that must use a relatively quick burning powder to get up to speed because there is no room in the case for a slow burning powder, and a slow burning powder in a small case cant really generate the needed thrust and pressure.
A 30-06 is a larger case. it can support a larger charge. Since there is more room, we can pack in more, and slower powder, and that entire charge will be effectively used to move the bullet. just that one thing, bigger case, larger, slower charge will cause a longer high pressure period.
A .300 ultra magnum is going to have so much capacity that it is hard to actually find a proper load. using a fast powder, a small charge of something that will fizzle out halfway down the barrel with an extremely high chamber pressure is a waste. it will not generate even a fraction of the power and velocity that the full load of extremely slow powder will.
There are many, dozens and more, factors that decide what powder will be effective in any given case. Generally speaking, choose the load data that gives the higher velocity range and test them. The slowest powders will generally give the greatest velocities but what does that mean? it means that MAYBE your loads will shoot faster. Does it mean that it will work well? No. High velocity may be a poor decision in your individul rifle. Accuracy may be terrible.
It used to be that when you looked for load data you had over a dozen, sometimes every possible powder offered. Many if not most of them were just useless, written only to put words on the paper. Now, the makers have gotten smarter, they have limited the suggested loads to the ones that are most appropriate, and best capable of generating safe, accurate, powerful loads.
The perfect situation would be that a cartridge maintains the same pressure from chamber to bore, accelerating every MM of the way. A powder that allows that to work will generate the highest possible velocity from any given cartridge.
This exact effect is why we have coatings on powders to slow ignition a bit. We have powders in larger granules to slow down the buildup of pressure. we have powders that are pierced, since under high pressure that also ignites them and they burn from the inside out. granule shape and size, ranging from small ball powder to sticks all have different amounts of surface exposed to the flame.
Have you noticed that certain "ball" powders are actually flakes? "ball" powder is the description of how it is made, not the shape. Many ball powders are rolled flat, this exposes more surface area, accelerating the burn.
Nobody but an engineer or a very well educated person can fully understand or predict what a powder will do. What this means to you is that you should never deviate from the professionally generated data.
Keep in mind that if you are crazy enough to load something like nitroglycerin into a cartridge, count on the rifle to explode, but in all honesty, you may not be able to find actual acceptable signs of "overpressure".