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I want to group some unnecessary items such as explorer into a group so that I can close them once and for all. But this grouping option also group Firefox (for some reason I always use two separate Firefox windows at the office). This leads to an extra mouse click to open up one of the instances of Firefox. Can we group some items while don't group others?
This is on Windows XP.

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No. This isn't possible. The taskbar allows you to group windows that are from the same application. So having two instances of Firefox will be grouped by the OS automatically when space runs out on the taskbar.

However, instead of having the same web browser opened twice, you could perhaps use two different web browsers (say firefox and chrome) to overcome this issue.

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