Just to clarify my understanding:

On a server with two network interfaces, the first interface has one public IP, 
the seconds interface has one private (192.168.x.x) IP.

    inet_interfaces = all
    inet_protocols = all
    #smtp_bind_address = 
    #smtp_bind_address6 = 

With the following configuration it binds as such

    tcp   0  0 0.0.0.0:25  0.0.0.0:*  LISTEN  21067/master
    tcp6  0  0 :::25       :::*       LISTEN  21067/master

The docs say

    when inet_interfaces specifies no more than one IPv4 address, and that 
address is a non-loopback address, it is automatically used as the 
smtp_bind_address

Is the second interface with the private IP being considered? With the above 
config is there a risk of postfix trying to use the 192.168.x.x (or IPv6 
equivalent) for outbound connections? Should the bind addresses be specified 
when using a private network on second interface?

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