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When the system is under constant pressure, this equation gives you the work done by the expansion or compression of the gases. Think of a piston changing the volume of enclosed gases, as it can be derived using PV=nRT so change in moles of gas*n*R*T can also be used accordingly.
you use it for irreverible reactions. usually youre given the external pressure pushing onto the system and you need to find the work of the systemm pushing out against the external pressure. and its w = -pdeltav
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