I am trying to make postfix run with tls in chroot mode, but I am not able to send the messages with tls on. I am using postfix 2.2.10 on centos 4.0 and I had compiled the postfix from sources with tls & cyrus-sasl support. I copied the certificates from /usr/share/ssl to /etc/postfix.
While maybe not directly related to your problem, please consider running 'yum update' once in a while. CentOS 4.0 is about a year out of date, and with bug fixes and security updates is now 4.3. Please verify that you're not running code with security holes and or other problems.