Posted from a website I found...
What is Port 25?
Each and every Internet application, such as web, mail or ftp is assigned a unique port number by the Internet Assigned Names Authority (IANA). When a computer running mail server software starts up, it attaches to that port and uses it to listen for incoming requests. Because the port numbers are standardised across the Internet, clients can make reasonable assumptions about which port is the proper destination for a given service. When your computer needs to deliver an email to another person for example, it connects to a server on port 25 and sends the email to it. This server then sends it on to its destination. Because of the standard, you can always assume that port 25 is the SMTP mail server, not the HTTP (web) server which is port 80, or some other service.
So, why block on port 25?
Mail servers are probably the most complex piece of Internet software to configure correctly. By default these are "open" services and will happily send an email out to anywhere if one is sent to it. You can often be unaware that you are even running a mail server, therefore we block port 25 connections by default. This stops the spammers dead in their tracks from using your connection to send out spam.