It's not uncommon to smell an "electrical" scent when you power up a brand new system for the first time. (Not saying you shouldn't be cautious, but it is a possibility). It's usually good to give a new system some "burn-in" time... that is, let it sit and run for a while. The system I'm using ran overnight before I shut it off and installed the hard drive and began installing the O/S. I also always buy a motherboard with built-in temperature sensors that can be checked from the BIOS... very handy when you want to keep an eye on things during "burn-in".
Definitely check your temps as posted above though, just in case.
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