apache and php strangeness

I have a strange problem that I haven't been able to solve:  

We have 2 internal web sites (developed using PHP) running on a RHEL5 server. Each and every time, without fail, when the server is rebooted, you browse to those sites and get a 500 Internal Server Error message. The only way I've found that "fixes" it on the short term is to do:  

killall httpd
apachectl -k restart  

A regular "service httpd restart" doesn't do the trick.  

Can anyone perhaps give me a clue as why this might be? It's not a huge problem and those sites aren't mission-critical, but it would be nice to know why I'm getting this behaviour.  

Thanks very much.

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