CyberFort- Actually there is the ability to Block. Place the Firewall in Custom Ruleset and you can block on a application by application basis as you will get a Firewall popup to do just that.
If you choose not to do the above, one can Block individual applications like so- while keeping the Firewall in Safe Mode, one can change how the firewall will handle any already existing specific application in the Application Rules section of the Firewall settings (Choose the application, double click it, change to "Use Ruleset", then change the dropdown box to "Blocked Application".