It depends on the item.
Some are usable by all in the inventory, some are usable only by the classes that can equip in the inventory, and some you have to equip to click it.
Just look the item up on wiki - if it says "Any slot", you can click it from inventory; if it says "Any slot/Can equip" then it is only clickable by equip-able classes, and if it says "Must equip" then it is required you equip it to click it.
Also, if it says "Combat" then it is a proc item.
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