From page 108 of user guide:
For consistency, the HEAT_OF_COMBUSTION(i,j) can also be specified for each species, i, in each reaction, j. These values are used only if the corresponding heats of combustion for the gaseous species are greater than zero. Note that HEAT_OF_COMBUSTION(i,j) discussed here is not necessarily the same as the HEAT_OF_COMBUSTION of the surrogate FUEL used for gas phase combustion (e.g., ’PROPANE’). When the heats of combustion differ, the mass flux of the surrogate FUEL in the gas phase is adjusted so that the correct heat release rate is attained. This is further discussed in the next section.