How to convert all columns data to two columns in SQL Server?

Try this

  SELECT empcode, 
	     starttime, 
		 endtime
    FROM [dbo].[yourTableName] 
   CROSS APPLY
   (
	 VALUES 
	 (timein1, timeout1),
	 (timein2, timeout2),
	 (timein3, timeout3),
	 (timein4, timeout4),
	 (timein5, timeout5)
   ) c (starttime, endtime)
   WHERE logdate = '2022-08-24' 
	 AND starttime <> ''
ORDER BY empcode;