Yes we can add a column using withColumn with the function as shown below for your reference.
val sqlContext = new SQLContext(sc)
import sqlContext.implicits._ // for `toDF` and $""
import org.apache.spark.sql.functions._ // for `when`
val df = sc.parallelize(Seq((4, "blah", 2), (2, "", 3), (56, "foo", 3), (100, null, 5)))
.toDF("A", "B", "C")
val newDf = df.withColumn("D", when($"B".isNull or $"B" === "", 0).otherwise(1))
newDf.show() shows
+---+----+---+---+
| A| B| C| D|
+---+----+---+---+
| 4|blah| 2| 1|
| 2| | 3| 0|
| 56| foo| 3| 1|
|100|null| 5| 0|
+---+----+---+---+