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I'm not too sure about how the whole process works, but from what I know, there are 100 witnesses chosen at random. So does that mean if you're not one of them at the time, then you can't mine?

Well, there are 19 permanent witnesses plus one randomly chosen from the upvoted witness list and 1 miner. The miners are put in the waiting queue after they mine a block, after your miner mined a block you're in the waiting queue and you can't mine with the same miner until the block is validated. This is what i figured out from the white paper and post on #steemhelp and #mining .

I appreciate all the help! I'll definitely keep learning more about the process. Just have a ton of questions like how long is a miner typically in the waiting queue and after you mine a block and it gets validated what happens then? Do you go back in the waiting queue or are you never able to mine another block with the same account? Sorry, tons of questions hahaa

@bitcoiner Every round of mining consists on 21 blocks mined at every 3 seconds. That means every miner is in queue for 36 seconds till his time pass. Being at the end of the queue (let say 100 in queue) makes you wait 3600 seconds for the block to be validated. After you get validated you're returning to mining the next block with the same account of course.