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The longest word starting with E is Electroencephalographically.
Floccinaucinihilipilification is the longest word starting with F; it means the act of estimating something as worthless.
Pneumonoultramicroscopicsilicovolcanoconiosis (also happens to be the longest word in the English language)
Extraterritoriality is the longest word in the English language beginning with "ex."
The longest word starting with a "P" is pneumonoultramicroscopicsilicovolcanoconiosis, which has 45 letters and is in the Guinness Book of Records. It was, however, coined for the specific purpose of becoming the longest word, and is not a specifically recognized form of silicosis.