<p>Did you set the <code>Icon</code> field in the desktop entry files to different icons? If that doesn't work, I'd file a bug against whichever part of Xfce is showing the wrong icon (ex. if it's in the window titlebar, xfwm4, if it's in the panel, the "window buttons" (or whatever it's called) plugin for xfce4-panel, if it's in the virtual desktop switcher, against that panel plugin, etc.)</p>

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