A properly designed silencer will have the largest chamber nearest the muzzle, that is to say, the first one that receives the air, for the reason air-tech mentions.
I usually build mine with the smallest chamber at the other end.
The length of the chamber governs the frequency where the sound reduction will be at its maximum. Fm = C / (4L) where C is the speed of sound and L is the chamber length, in consistent units of course. The longer chambers give most effect at lower frequencies.
There is a frequency below which this length of chamber will be ineffective. This is the cut-off frequency, or Fc. You can calculate it with reasonable accuracy from the following formula:
Fc = Fm ( 0.003R2 – 0.09R + 1.03 ) where R = expansion ratio, ID divided by hole diameter.
There is also a higher frequency at which this length of chamber will be ineffective. That happens at twice the Fm frequency, ie., 2Fm
Using these formulae one can work out the optimum relationship of chamber lengths so that as one chamber tails off in effectiveness the next in size is ramping up to its peak. It turns out to be a Fibonacci sequence, nature's Golden Ratio.
Of course most folk prefer to make the bits and try them out rather than do the maths, it's more fun......