When a UNIQUE constraint is added to an existing column or columns in the table, by default, the Database Engine examines the existing data in the columns to make sure all values are unique. If a UNIQUE constraint is added to a column that has duplicated values, the Database Engine returns an error and does not add the constraint.

When a UNIQUE constraint is added to an existing column or columns in the table, by default, the Database Engine examines the existing data in the columns to make sure all values are unique. If a UNIQUE constraint is added to a column that has duplicated values, the Database Engine returns an error and does not add the constraint.
The Database Engine automatically creates a UNIQUE index to enforce the uniqueness requirement of the UNIQUE constraint. Therefore, if an attempt to insert a duplicate row is made, the Database Engine returns an error message that states the UNIQUE constraint has been violated and does not add the row to the table. Unless a clustered index is explicitly specified, a unique, nonclustered index is created by default to enforce the UNIQUE constraint.