UPDATE table SET new_field = 'default_value'and they'll all be set.
One thing when pulling MySQL values into PHP, if you fetch the results into an array and do
if( $results['new_field'] ){ ... }you won't get anything for null or empty values. But the query in MySQL will return different results if you use
SELECT * WHERE new_field IS NULLand
SELECT * WHERE new_field = ''