As far as I know, you use Mrs. when you're talking about or talking to a woman who you know is married. And you use Ms.
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As far as I know, you use Mrs. when you're talking about or talking to a woman who you know is married.
And you use Ms. when you're not sure if she's married or not.
"Ms. Janet Jones" OR "Mrs. Ian Jones" BUT NOT "Mrs. Janet Jones"