How do HEX codes affect CMYK Process colors?

I just received a banner for a client and their logo had two different blacks utilized within different letters of the text.
Basically, the logo has the word Barn in it and the "B" looks more brown in comparison, with the rest of the letters ("arn") as black.
Under closer examination, I discovered the "B" in the word Barn had a different HEX code than the rest of the letters even though all of the letters are all 100K black.
Color of the B: Hex #231F20
Color of ARN: Hex #010101
What really throws me off is that the black used in the letter "B" is a default process swatch in Illustrator in the Greys folder.
I'm not sure how the colors changed in my design process, but I have never taken hex code into account when designing. I view it as 100k black should print 100k no matter what. In trying to decipher what happened, as well as prevent this from occuring in the future, I would very much appreciate any explaination on this occurance.
Obviously I intended all of the blacks to print the same shade of black (again, I am not sure how the B was changed while designing the banners), but why would hex code affect anything at all? Shouldn't a color (especially a process color) print at 100k?
Also, why would the Illustrator process color swatch that is included within the defaults and listed in the grey folder print more brown than my other letters?
THANK YOU!

First before anything make sure you are in the correct file >> document color mode
RGB - Web or DIgitial Banners
CMYK - Printed Banners
There is not one CMYK value for every one RGB value, so therefore you have three 100k screenshots, with different RGB values. If you file is in document color mode CMYK you should be good for getting 100k to print. If you are in doucemtn colro mode RGB, then you will have 3 differetn values for the screenshots shown.
You ask a very good question, as this is often overlooked, and can get confusing. Remember that whatever document color mode your color panel should always match when entering numbers. Having a doucument color mode of CMYK, and entering values in RGB is useless and really should not even be allowed.

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How do HEX codes affect CMYK Process colors?

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