Heat of Combustion

Heat of combustion (ΔH) is the energy released as heat when one mol of a compound undergoes complete combustion with oxygen. The chemical reaction is typically a hydrocarbon reacting with oxygen to form carbon dioxide, water and heat. It may be expressed with the quantities:
energy/mole of fuel (J/mol)
energy/mass of fuel
energy/volume of fuel
The heat of combustion is traditionally measured with a bomb calorimeter. It may also be calculated as the difference between the heat of formation (ΔfH0) of the products and reactants.

Heating value
The heating value or calorific value of a substance, usually a fuel or food, is the amount of heat released during the combustion of a specified amount of it. The calorific value is a characteristic for each substance. It is measured in units of energy per unit of the substance, usually mass, such as: kcal/kg, kJ/kg, J/mol, Btu/m³. Heating value is commonly determined by use of a bomb calorimeter.

The heat of combustion for fuels is expressed as the HHV, LHV, or GHV:

The quantity known as higher heating value (HHV) (or gross calorific value or gross energy or upper heating value) is determined by bringing all the products of combustion back to the original pre-combustion temperature, and in particular condensing any vapor produced. This is the same as the thermodynamic heat of combustion since the enthalpy change for the reaction assumes a common temperature of the compounds before and after combustion, in which case the water produced by combustion is liquid.

The quantity known as lower heating value (LHV) (or net calorific value) is determined by subtracting the heat of vaporization of the water vapor from the higher heating value. This treats any H2O formed as a vapor. The energy required to vaporize the water therefore is not realized as heat.

Gross heating value accounts for water in the exhaust leaving as vapor, and includes liquid water in the fuel prior to combustion. This value is important for fuels like wood or coal, which will usually contain some amount of water prior to burning.
A common method of relating HHV to LHV is:

HHV = LHV + hv x (nH2O,out/nfuel,in)

where hv is the heat of vaporization of water, nH2O,out is the moles of water vaporized and nfuel,in is the number of moles of fuel combusted.

Most applications which burn fuel produce water vapor which is not used, and thus wasting its heat content. In such applications, the lower heating value is the applicable measure. This is particularly relevant for natural gas, whose high hydrogen content produces much water. The gross calorific value is relevant for gas burnt in condensing boilers which condense the water vapor produced by combustion, recovering heat which would otherwise be wasted.

Both HHV and LHV can be expressed in terms of AR (all moisture counted), MF and MAF (only water from combustion of hydrogen). AR, MF, and MAF are commonly used for indicating the heating values of coal:

AR (As Received) indicates that the fuel heating value has been measured with all moisture and ash forming minerals present.
MF (Moisture Free) or Dry indicates that the fuel heating value has been measured after the fuel has been dried of all inherent moisture but still retaining its ash forming minerals.
MAF (Moisture and Ash Free) or DAF (Dry and Ash Free) indicates that the fuel heating value has been measured in the absence of inherent moisture and ash forming minerals.

Higher heating value of some less common fuels
Fuel HHV MJ/kg BTU/lb kJ/mol

Methanol 22.7 9,800 726.0
Ethanol 29.7 12,800 1,300.0
Propanol 33.6 14,500 2,020.0
Acetylene 49.9 21,500 1,300.0
Benzene 41.8 18,000 3,270.0
Ammonia 22.5 9,690 382.0
Hydrazine 19.4 8,370 622.0
Hexamine 30.0 12,900 4,200.0
Carbon 32.8 14,100 393.5