Can I use CLR (or something similar) to clean the chain of my bike?

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My bike chain is rather rusty and I was wondering what I can use to clean it. It's easy to take on and off I just want to know if it's worth it to clean it or buy something new. I was going to try soaking it in a solution of CLR and water but is that safe?

Also, I'm accumulating bike parts in an attempt to rebuild my other bike. As long as it still fits the frame, does tire width matter? ie: can I get thinner tires for my bike?
 
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