if you respond to an email sent through your POP account, it will reply through that account (not gmail), however, you cannot create a new email using your non-gmail account, through the gmail app. you can only do this by either using teh default email client, or using gmail.com (preferred).
if you set your default email app to never sync, you'll never send the mail. as soon as you sync, you'll have "double" emails (although in separate apps).

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