You have to add an entry.
- Right Click on about:config page
- New -> String
- Preference Name: "general.useragent.override" -> OK
- Add the value you want -> OK
- You are ready, test your new user agent!
If you want to reset this value
- Go to about:config
- Right click on the preference "general.useragent.override"
- Reset
- You are ready (Note that the preference will stay empty, but the next time you will visit about:config will not be there)
If you want an easier way to change/toggle user agent I suggest you use an addon.