Yes that should work if the drive is brand new and never used and in working condition. this would be the best way to do it remove your existing hard drive and fit a new one then install the windows CD on the new hard drive once the PC is all up and going you can change the jumper on you existing hard drive and set it as a slave drive(Setting ussually on the top of the hard drive) put it back in the PC. Done

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P.S or if you like you can leave the second hard drive and not install it