Applications -> Utilities -> System Information -> Memory
DIMM0's should be equal in size
DIMM1's should be equal in size
That is to say
BANK 0/DIMM0 16GB
BANK 1/DIMM0 16GB
BANK 0/DIMM1 4GB
BANK 1/DIMM1 4GB
Or if you prefer put the 16's in DIMM1 and the 4's in DIMM0.
If you have the DIMM0's matching and the DIMM1's matching you get memory interleaving.
Reading RAM is destructive, so after reading a value, it has to be written back to the memory cells. This re-write takes an extra cycle, during which the DIMM is unavailble.
Interleaving means the CPU alternates DIMMs when reading consecutive memory locations. So while BANK 0 is rewriting the value just read, BANK 1 can be fetching the next memory value. And while BANK 1 is rewriting the value it just fetched, BANK 0 will be ready to read another value.
NOTE: The Mac will still work if you do not properly match RAM sizes, it will just take twice as long to read consecutive memory locations as interleaving will not be used, so the CPU must wait 2 memory cycles for each memory access.