Which profile and device name is this for? I can see some of the profiles allow VPN's
FreeVPN is blocked by the VPN category, but if you are allowing VPN's and limiting time, yes the schedule still applies when using a VPN.
If you think VPN's should be blocked for that profile and time limits are not being enforced that sounds like the device maybe in the wrong/profile or the wrong device has the wrong name.
Can you visit http://warez.com on your daughters device this should be met with a blocked page and will tell you the profile name and device name of the device being used.