You're doing something a tad unconventional in having multiple apps share an app.config. As its name implies, app.config is intended to be per app. There are methods in System.Configuration
that allow an app to write to the app.config (thus write-locking it for a moment. Another app trying to write at the same moment will receive an error.) I personally tend to put shared config in the database.
Yet if you have a strong case for this, you should be OK. Apps reads app.config upon startup and cache the settings. I'd suggest making a documented convention among your developers that apps sharing config shouldn't write to the app.config.
Note that ASP.NET web.config
has some extra behavior in that it gets monitored for changes. But I think this is specific to IIS; and I don't think you're dealing with web.config.