in windows your new drive need to a) be partitioned b) formatted and in this last step you can assign, or let windows assign the drive letter automatically (suggest you do unless you have a reason for it.)
UNPLUG the external drive in system, then in your windows search box type " compmgmt.msc " and open the Computer Management windows, bottom left of the left column you will see Disk management click on that
BE CAREFULL WHAT YOU DO HERE!!! IF YOU SELECT TEH WRONG DRIVE YOU CAN MESS THINGS UP BAD.
I am showing using a thumb drive, but the principal is the same...Below you will see drives numerated
Before I plug drive in: (only have 4 drives)
After I plug my drive in (now a 5th shows.)...