You may consider not usin the 20GB at all as this could/would slow your system down.
the specs on 40gb is faster and better then the 20gb.
If you have master / slave setup on the same flat cable, then I garuantee you a slower performance.
Try setting up Two masters devices on two seperate cables. Place your DVD/CD devices as secondaries.
To join them. NO, NOT possible. I would not even look at a software mirror solution either. Must be identical drives.