This usually happens in scenario where you are running EIGRP on your PIX or ASA. You will not be able to ping the standby interface of the ASA because the EIGRP update will be sent only to Active ASA and will not be sent to Standby ASA.
This means that Primary ASA will have full EIGRP table, and secondary will not have it at all.
To solve this problem you must create STATIC route to the network you would like to ping secondary appliance from.
route inside 192.168.100.0 255.255.255.0 192.168.1.2 1
Then:
write memory
write standby
Now you will be able to ping standby ASA from 192.168.100.0/24 network.
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