It is a file, you can put it where you want.
You can add it through the hibernate.cfg.xml (section <mapping>); using the xsd to write the hibernate.cfg.xml you can see this help:
There are 3 possible combinations of mapping attributes
1 - resource & assembly: NHibernate will read the mapping resource from the specified assembly
2 - file only: NHibernate will read the mapping from the file.
3 - assembly only: NHibernate will find all the resources ending in hbm.xml from the assembly.
or through the Configuration. methods:
AddFile(FileInfo xmlFile)
AddXmlFile(string xmlFile)
AddUrl(string url)
AddUrl(Uri url)