You cannot use web based web services through outlook express. It is a server based system via your service provider and works on the pop3 system. I don't know of any way to get outlook express to access your hotmail accounts.
You can log onto your hotmail account from any computer (with web access) in the world as long as you have your password with you. The best you can do is create a little shortcut to the log in page and dump it on your desktop for easy access to it, but thats a bout it. One in hotmail you can forward recieved emails to your standard email adress, then you will have access to them in outlook express.
+Not sure you follow what I mean. Will try to explain. When I am on internet and viewing a certain site like Bt and I wish to contact them via email from their site It brings up outlook express. On my old pc when I I contacted site it used my hotmail emails. I was able to to do this by setting my hotmail email to do this but cannot remember how it was done