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On the webmail, I have both addresses listed and can choose the default.
Go to Options at the top, then mail options. Click on Mail Accounts on the left, then in the middle column it should list the two accounts, I have Mail and Mail Extra Address. If you click on the BTInternet account there should be a box there to tick to make it the default sending account. Then click the yellow save button.
Hope that helps!
Andy
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