the 5-digit e-file PIN is arbitrary and assigned by the user, it doesn't matter if it matches old values or not and won't cause a rejected file.
the 6-digit IRS IP PIN needs to match what IRS has generated for the current calendar year, again prior years' PIN values are useless, it changes every calendar year for all filings regardless of tax year. Your ex-wife should check her account at IRS for the latest IP PIN if getting rejected e-files due to this.