The heat content of a system is equal to the enthalpy only for a system that is at constant what?

1 Answer
Jun 14, 2017

Only for a system at constant pressure... By definition, q = nDeltabarH = DeltaH at constant pressure, where DeltabarH is the molar enthalpy in "J/mol".


We can begin from the first law of thermodynamics

DeltaU = q + w,

where q and w are the heat flow and work, respectively,

and the relation of the internal energy U to the enthalpy H,

DeltaH = DeltaU + Delta(PV)

where P and V are pressure and volume.

When one plugs in the expression for DeltaU:

DeltaH = q + w + Delta(PV)

The common convention is that the work is defined by w = -PDeltaV when work is with respect to the system (i.e. negatively-signed when the system does work on the surroundings by expanding, with DeltaV > 0).

Furthermore, we apply the product rule from calculus (plus a bit extra) to see that Delta(PV) = PDeltaV + VDeltaP + DeltaPDeltaV. Therefore:

DeltaH = q - cancel(PDeltaV + PDeltaV) + VDeltaP + DeltaPDeltaV

As a result, the change in enthalpy is related to the heat flow as:

color(blue)(DeltaH = q + VDeltaP + DeltaPDeltaV)

Clearly, when the pressure is constant, we can see that VDeltaP = 0. We designate this as

DeltaH = q_P,

if both quantities are in "J". Multiplying the left by n/n, where n is the mols, gives the first equation presented,

color(blue)(nDeltabarH = q_P)