You cannot tell by looking at the JID. You have to keep enough context in a given protocol exchange to know what you are talking to.
Typically on startup, a client will send a disco#items
query to the server:
<iq type='get'
to='shakespeare.lit'
id='items1'>
<query xmlns='http://jabber.org/protocol/disco#items'/>
</iq>
to find all of the local services, then send a disco#info
query to each of those services to find out more about the service. Once you find a MUC server:
<iq from='chat.shakespeare.lit'
type='result'>
<query xmlns='http://jabber.org/protocol/disco#info'>
<identity
category='conference'
name='Shakespearean Chat Service'
type='text'/>
<feature var='http://jabber.org/protocol/muc'/>
</query>
</iq>
you know that all of the JIDs that include this domain name (chat.shakespeare.lit
in the above example) are associated with MUC rooms.