This is from the manual, I think it may help:
If there is no matching record for the right table in the ON or USING part in a LEFT JOIN, a row with all columns set to NULL is used for the right table. You can use this fact to find records in a table that have no counterpart in another table:
mysql> SELECT table1.* FROM table1
-> LEFT JOIN table2 ON table1.id=table2.id
-> WHERE table2.id IS NULL;