We know that IIS caches ConfigurationManager.AppSettings so it reads the disk only once until the web.config is changed. This is done for performance purposes.
Someone at:
http://forums.asp.net/p/1080926/1598469.aspx#1598469
stated that .NET Framework doesn't do the same for app.config, but it reads from the disk for every request. But I find it hard to believe, 'cause it would be slower. Please tell me that he is wrong or I'll have to fix every Console/Windows Forms/Windows Services I wrote.
Update I regret that I misinterpreted what people said in the linked forum above.