Rick,
I just found out the same - Bibit changed the way its payments are processed, but didn't provide new php-examples... Had to work it all out for myself. Since your post is from November last year, I guess you already figured it out as well; I hope, however, that is post is still useful for anyone else who needs to use Bibit and php for online payments.
$url = "https://secure-test.bibit.com/jsp/merchant/xml/paymentService.jsp";
$xml = "The full xml-string you want to send";
$ch=curl_init();
curl_setopt($ch,CURLOPT_VERBOSE,1);
// Let curl report anything that happens
curl_setopt($ch,CURLOPT_FOLLOWLOCATION,1);
// Set this option to a non-zero value to follow any "Location: " header that the server sends as a part of the HTTP header (note this is recursive, PHP will follow as many "Location: " headers that it is sent.)
curl_setopt($ch,CURLOPT_URL,$url);
// This is the URL that you want PHP to fetch. You can also set this option when initializing a session with the curl_init() function
curl_setopt($ch,CURLOPT_POST,1);
// Set this option to a non-zero value if you want PHP to do a regular HTTP POST. This POST is a normal application/x-www-form-urlencoded kind, most commonly used by HTML forms
curl_setopt($ch,CURLOPT_HTTPHEADER,array('Content-Type: text/xml'));
// Pass an array of HTTP header fields to set - in this case a Content-Type-header to tell curl it's an XML-post.
curl_setopt($ch,CURLOPT_USERPWD,"MERCHANTCODE😛ASSWORD");
// Pass a string formatted in the [username]:[password] manner, for PHP to use for the connection
curl_setopt($ch,CURLOPT_POSTFIELDS,$xml);
// Pass a string containing the full data to post in an HTTP "POST" operation - the xml-string, in this case
curl_setopt($ch,CURLOPT_RETURNTRANSFER,1);
// Pass a non-zero value if you want CURL to directly return the transfer instead of printing it out directly
$xmlresponse = curl_exec($ch);
curl_close($ch);
After this, Bibit's response to your xml-post is in the variable $xmlresponse, which you can then parse using an XML-parser, e.g. Expat (http://www.php.net/manual/en/ref.xml.php). For me (I know nothing of XML-parsing) the article by Justin Grant on phpbuilder was very useful (http://www.phpbuilder.com/columns/justin20000428.php3).
Good luck,
Bas