I was thinking higher pressure due to tighter bore would equal higher velocity.
When all else is qual, the harder you push, the faster you go. But in this case, all else is not equal. The oversize bullet is a tighter fit, which means it takes more pressure to move it down the barrel, compared to the regular load.
Since the available pressure has to "work harder" to push the bullet down the barrel, it might not reach the same speed as the same load being fired in a barrel where the bullet fit isn't as tight.
Might not. That's the principle, but reality in guns is a bell curve, and while most things will fall in the middle of the possible range there are always some at each end.
One point about chrono data, its from individual guns. Testing a gun, or two of one make & model against others only really tells you about what those guns do, not about what ALL the examples of that make & model will do. For that' you'll have to test a lot of guns, to get a statistically valid sample.
you should test your Python against your S&Ws and anything else, not to "proove" anything about Pythons in general, but just to see what your guns do. They might do exactly what you expect, OR they might do something that surprises you.
As an example of what can happen (not what will, but what can) a some time back I tested 3 different 6" barrel .357s. The load was a hot 125gr JHP near the top of the listed data in the Speer manual current at the time.
A 6" S&W model 19, a 6" S&W model 28 and a 6" Desert Eagle.
The 19 belonged to a friend, and he shot it over my Chrony. Somehow, he doubled the gun. (fired two shots when only one was intended). At that point we stopped shooting that gun. The 4 unfired rounds fell out normally but the two fired cases had to be driven out of the cylinder with a rod and small hammer. That ammo might have been ok in a different K frame, but in his gun it was TOO HOT!. The Chrony read 1620fps. (this was above what the loading manual said)
Same ammo, fired by me, from the Model 28. 6 shots, one at a time. stout! Chrony avg was 1670fps. Cases ejected normally by hand.
Same ammo from the Desert Eagle, full mag, 9 shots, avg 1720fps. Function was flawless.
All three guns turned in velocities higher than the loading manual listed and the ammo was too hot in one, but fine in the other two. Doesn't mean anything about what other guns will do, only, that's what those guns did, that day.
A bit of an eye opener, that was...