From The MySQL Manual: http://www.mysql.com/doc/en/JOIN.html
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;
This example finds all rows in table1 with an id value that is not present in table2 (that is, all rows in table1 with no corresponding row in table2).