If the bolt drops into the notch in the cylinder and locks it there the alignment is correct.
Sorry, but that's not correct.
It's entirely possible to have the chambers, or even just one or two chambers, out of position in the cylinder, such that they do not line up with the barrel bore when in battery. I've seen this on a number of replica bp revolvers.
You check this by putting the chamber in battery, putting a strong light on the cylinder face at the forcing cone and looking down the bore. If you see a crescent of light the chamber is misaligned. If you see a full circle of light, the chamber is smaller than the bore, which is just as bad for accuracy as the swaged ball will be loose in the bore and not engage the rifling.