Visual Studio - Locating exe.config file

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C#

C#4.0

BACKGROUND

I've decided to try using the Visual Studio support for configuration files for the first time.

In Project->Properties->Settings I have created a bunch of application settings with the "User" scope so that I can change them at run-time.

This is working OK, but I notice that when I run the program within the Visual Studio environment, it uses a different config file than when it runs as an executable outside of VS. I can't locate either of the files responsible for this!

Example:
One of the settings is called "EngineerPassword".
If I debug the application in Visual Studio and then, at run time, I change the EngineerPassword to "hello", this setting persists when I stop debugging and start debugging again.
If I then stop debugging, and I run the executable directly, I find that the password is not "hello". I can set it to something: let's say I set it to "world". Now, when I run the application inside Visual Studio the EngineerPassword is still "hello", and when I run the executable it is "world". So clearly it is using separate config files in these scenarios.

Inside the application folder structure there is a file called app.config, but this contains the default settings which were in place when I initially created the Settings. It does not change when I change the settings at runtime.
Additionally there is an exe.config file located in the same folder as the executable. This does not change when I change the settings either.

THE QUESTION:

Which files are changing when I set new settings? Where are they located?