I think she just needs to register with social Welfare as unemployed, and then with FAS. But depending on your earnings she may not get a SW payment. Also, there might be a stamp issue - ie. being in paid employment and paying tax.
Best asking directly in your closest Social Welfare office, or citizens information office because you have to be a certain length unemployed before you can do CE. Fas course I think is ok to do, if you can get one you want to do, and are willing to wait a while as waiting lists are long.
Sorry if i'm a bit vague - but I seem to recall hearing a similar story recently.
Alli