Y como complemento, te recuerdo que '00:00:00' es diferente de NULL (lo mismo que una cadena vacía ('')), mucho ojo con eso:
Código MySQL:
Ver original+----+----------+
| id | hora |
+----+----------+
| 1 | 00:04:33 |
| 3 | 00:00:00 |
+----+----------+
+----+------+
| id | hora |
+----+------+
+----+------+
+----+----------+
| id | hora |
+----+----------+
| 1 | 00:04:33 |
| 3 | 00:00:00 |
+----+----------+
+----+----------+
| id | hora |
+----+----------+
| 3 | 00:00:00 |
+----+----------+
+----+----------+
| id | hora |
+----+----------+
| 1 | 00:04:33 |
+----+----------+
Saludos
Leo.