Yes unpack is also byte aligned. unpack moves exactly like pack does given the same pattern, except it reads instead of writes. You did lose data with H5, that's why some chars were changed. One way to see that is to try "hehlo" or "hemlo" instead of hello. You'll see that you get the same result, because four bits in the byte are replaced by 0000 when pack was only given 5 hex digits for 3 bytes.
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