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Is there any rule for pronunciation of the vowel in words like "approximate" or "appropriate"? Why is one pronounced as /ɑ/ and one as /o/? I have searched threads but can't seem to find an answer.

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    Once again, I hate to be the one to tell you, but English spelling does not represent English pronunciation very well. English spelling is a very good fit to Middle English pronunciation, but it hasn't changed much since printing hit England around 1500, right in the middle of the Great Vowel Shift. When that ended, English was Modern; but English spelling wasn't. Consequently the answer to all such questions has to be, "no, there isn't any rule; they have to be learned individually". Sorry about that, but it's a painful truth. – John Lawler Jun 29 '17 at 15:00
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The pronunciation of the "o" in "approximate" follows the rule that in a stressed syllable, a vowel letter before the letter "x" represents its associated "short vowel" pronunciation. This is similar to how a "short" pronunciation is regular before "ct" which represents the consonant cluster /kt/. In general, when a single vowel letter is used to represent a vowel sound before a consonant cluster that can't occur at the start of a word in English, the vowel sound is "short" rather than "long". Since the letter "x" after a vowel letter represents the consonant cluster /ks/ (or sometimes /gz/, /kʃ/ or /gʒ/), which cannot occur at the start of an English word, the letters "a" "e" "i" "o" "u" "y" are regularly pronounced as /æ ɛ ɪ ɒ ʌ ɪ/ (or /æ ɛ ɪ ɑ ʌ ɪ/ in American English) before the letter "x".

The pronunciation of the "o" in "appropriate" is explained by two rules: the one described in Why is "salient" pronounced with a "long a" sound? and a rule that certain consonant clusters that can occur at the start of words, like "tr", "pr", "cr" and "cl", act the same as single consonant letters for the purposes of vowel letter pronunciation.

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