 Adiabatic work in a comoving volume

For a homogeneous cosmic fluid, the physical volume bounded by fixed comoving coordinates obeys $V\propto a^3$. The cosmological continuity equation therefore gives $d(\rho c^{2}V)=-PdV$. This is the first law of thermodynamics with conserved entropy and no additional chemical work. The internal energy of that volume need not be constant: a component with negative pressure gains internal energy as the universe expands. Local stress-energy conservation does not imply a global conserved energy for an arbitrary expanding spacetime.