I am using a Debian 8 virtual machine for testing purposes with Xfce as a DE. I noticed that clicking the WebBrowser button on the default panel does not do anything visible. In fact, typing exo-open --launch WebBrowser in a terminal does not seem to work either. xdg-settings get default-web-browser gives firefox.desktop locate firefox.desktop gives /usr/share/xfce4/helpers/firefox.desktop /usr/share/xfce4/helpers/firefox.desktop contains X-XFCE-Binaries=firefox;firefox-gtk2;firefox-gtk;mozilla-firefox; and running "firefox" correctly opens the Firefox browser. The Preferred application dialog also states Mozilla Firefox as the default web browser. exo-open --launch TerminalEmulator and FileManager correctly open a new terminal/manager window. exo-open --launch MailReader correctly prompts for the choice of a default application.
Note : after running firefox once and closing it, exo-open --launch WebBrowser correctly opens it again. This is still a problem because we are deploying this setup to inexperienced students and the standard WebBrowser is proeminent in the interface, and does not work the first time one logs into the computer.
It's a crude workaround, albeit one that I would use on newly deployed machines anyway, so here it is: Set up a firefox profile with bookmarks, extensions, etcetera that you want to be common to all users, then copy that profile dir (and its parents all the way up to $HOME/.config/) and place it in /etc/skel/ (change ownership to root:root). Any new accounts added to the machine will then get a fully configured firefox that has (as far as the system is concerned) already been launched once.
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