Is separate sound from motherboard possible?

The title might be a bit confusing but basically my question is whether or not I can have the sound from two programs come out at different points. I have a 42inch tv and a 24inch monitor hooked up through my GTX660. The tv is mostly for playing movies and the monitor is for everything else. I know I can get sound to come throught the GTX660 to the tv if no other headphones or speakers are plugged in but is it possible to have a movie playing on the tv with its sound coming through the tv speakers only, while playing a game on the monitor and having it's sound come through my headphones only without the need for an extra sound card? 

I'm hoping in this day and age it isn't impossible to do but I'm not really looking to spend much if any money as although it's inconvienient it's not a huge deal yet

My rig is posted in my profile but I'm using a ASUS P8Z77-V LE PLUS motherboard with it's built-in audio and as mentioned an ASUS GTX660 video card.

Thank you for any help or ideas!

HDMI supports audio; you should be getting sound from the speakers on the TV.

If a program has a selection of audio output devices, it's possible. Which is not the case for games.

What I can imagine working is that you set the default audio output to your headphones so that games automatically use it and in your video player (at least MPC-HC can do it) you set your second audio card for output so that it outputs sound to your TV.

i do that now with a usb headset you just have to change the default device

right click the speaker icon in your tray and select playback devices.