In both cases (“nachash” – serpent and “nawshaw” – deceived) the Hebrew letter shin is pronounced with the “sh” sound because you will notice that there is a tiny dot above and to the right of the letter shin. This dot is what tells you how it is to be pronounced. When the dot is above and to the left of the shin (as in שָׂטָן which is the Hebrew word for Satan), it is pronounced with the “s” sound. Interestingly enough, there is a Hebrew word that is pronounced “nasa” and it is spelled the same way as “nawshaw” but with the dot over the top left of the shin:

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