If you are using the KDE desktop, do the following: Right click the file and select open with--> other, type kaffeine in the Open With box, then put a tick in Remember application assosciation for this type of file then click ok.
If you don't get the option to Remember application association, start your KDE Control Centre (kcontrol) then go to KDE Components--> File Associations, type ftv in the Find filename pattern box. Select the file when it is displayed in the Known Types box and on the right you will see a list of applications. If Kaffeine is in the list, click on it and move it up the order of preference, if it is not in the list then add it and make sure it is at the top of the preference list.
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