The only way I know how to change a pst password is to go to Control Panel, Mail(or Mail and Fax). Check the properties for the PST. file (if it is listed). But you do have to know the old password. Otherwise I don't think you can change it.
I am not sure if this would work but you could try deleting the users profile. Then create a new one and either use the import/export wizard (and import the .pst file) or rename the pst file the same one that the new one is called (it is probably named Outlook.pst) and replace it in the same location.
Just My 2 Cents
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