New messages will use whichever is designated the default account.
Replies will use the same account through which the message was
received. If you are replying to a message and it goes out using your
wife's account then it was received on your wife's account. Do you and
your wife actually have separate e-mail accounts, or do you share one
e-mail account and only get different aliases to the same account?
Use the Accounts button in the toolbar when composing a message to
change through which account the message gets sent.
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