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When sales order is created with account assignment or when Profitability analysis is activated account assignment happens with KOFK .
In all other cased standard system uses KOFI , unless modified using a routine in the account determination procedure.
When profit center is maintained in sales order KOFI is used.
Reference
http://scn.sap.com/thread/926013
The difference between KOFI and KOFK is
KOFI — Account determination without CO
KOFK — Account determination with CO
You can control through Routine, which you can placed in Requirement Column of the account determination procedure.
Routine 2 – With CO acct.assignt
Routine 3 – With out CO acct.assignt
If you have both when ever the costing related transfer system will take KOFK,if there is no costing related tranfer system will take KOFI