Session start event is fired only when a new session for a user starts. Once “Session_Start” for a user is fired then if the user makes subsequent request to any resource within the application this event is not at all triggered. The event is triggered only when the user’s session expires and then the user tries to access any resource in the application again.
This event can be used when you want to do something when the user visits you site/application for the first time or when his session starts. This event doesn’t get triggered if you are not using sessions which can be disabled in the web.config.
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--Amit