Both are correct but mean something different.
First means maybe I’ll be free but I don’t know. If so, I’ll go with you.
Second means I’m not free,but if I were I would go.
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Both statements are grammatically correct but they apply to different situations.
Read Phil's excellent article.
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Both are correct.
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You can find a short summary of all you need to know in my brief mini-article:
Grammar boost: Conditionals cheat sheet PART 1
https://www.italki.com/discussion/164505
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The second sentence:
"If I were free, I would go with you".
The first one would be correct without "if":
"I am free, I will go with you."