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No, the pronunciation of "when" does not rhyme with "sin." "When" is pronounced /wɛn/ while "sin" is pronounced /sɪn/.
It's pronounced Sin-Wall or Sin-Wool.
In the poem by Dowson, it's pronounced SIN-a-ra.
The phrase is "sin alcohol." (pronounced seen, sin= without)
Sinews is pronounced "sin-yoos," with the emphasis on the first syllable.
Cinco, which is pronounced SIN-cu.
Well theirs cyn pronounced sin
Capsaicin is pronounced; cap-SAY-sin.
It is pronounced "kruh-vo-SIN-ski."
It is pronounced "sin-nath-ih-day."
The word "Squaxin" is pronounced as skwak-sin.
The word "synecdoche" is pronounced "sin-eck-doe-key."