Heat of combustion

The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The heating value (or energy value or calorific value) of a substance, usually a fuel or food (see food energy), is the amount of heat released during the combustion of a specified amount of it. The calorific value is the total energy released as heat when a substance undergoes complete combustion with oxygen under standard conditions. The chemical reaction is typically a hydrocarbon or other organic molecule reacting with oxygen to form carbon dioxide and water and release heat. It may be expressed with the quantities: There are two kinds of heat of combustion, called higher and lower heating value, depending on how much the products are allowed to cool and whether compounds like H2O are allowed to condense.The values are conventionally measured with a bomb calorimeter. They may also be calculated as the difference between the heat of formation ΔH⦵f of the products and reactants (though this approach is somewhat artificial since most heats of formation are calculated from measured heats of combustion). For a fuel of composition CcHhOoNn, the (higher) heat of combustion is 418 kJ/mol (c + 0.3 h – 0.5 o) usually to a good approximation (±3%), though it can be drastically wrong if o + n > c (for instance in the case of nitroglycerine (C3H5N3O9) this formula would predict a heat of combustion of 0). The value corresponds to an exothermic reaction (a negative change in enthalpy) because the double bond in molecular oxygen is much weaker than other double bonds or pairs of single bonds, particularly those in the combustion products carbon dioxide and water; conversion of the weak bonds in oxygen to the stronger bonds in carbon dioxide and water releases energy as heat. By convention, the heat of combustion is defined to be the heat released for the complete combustion of a compound in its standard state to form stable products in their standard states: hydrogen is converted to water (in its liquid state), carbon is converted to carbon dioxide gas, and nitrogen is converted to nitrogen gas. That is, the heat of combustion, ΔH°comb, is the heat of reaction of the following process: Chlorine and sulfur are not quite standardized; they are usually assumed to convert to hydrogen chloride gas and SO2 or SO3 gas, respectively, or to dilute aqueous hydrochloric and sulfuric acids, respectively, when the combustion is conducted in a bomb containing some water quantity of water. The quantity known as higher heating value (HHV) (or gross energy or upper heating value or gross calorific value (GCV) or higher calorific value (HCV)) is determined by bringing all the products of combustion back to the original pre-combustion temperature, and in particular condensing any vapor produced. Such measurements often use a standard temperature of 15 °C (59 °F; 288 K). 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 condensed to a liquid. The higher heating value takes into account the latent heat of vaporization of water in the combustion products, and is useful in calculating heating values for fuels where condensation of the reaction products is practical (e.g., in a gas-fired boiler used for space heat). In other words, HHV assumes all the water component is in liquid state at the end of combustion (in product of combustion) and that heat delivered at temperatures below 150 °C (302 °F) can be put to use The quantity known as lower heating value (LHV) (net calorific value (NCV) or lower calorific value (LCV)) is determined by subtracting the heat of vaporization of the water from the higher heating value. This treats any H2O formed as a vapor. The energy required to vaporize the water therefore is not released as heat. LHV calculations assume that the water component of a combustion process is in vapor state at the end of combustion, as opposed to the higher heating value (HHV) (a.k.a. gross calorific value or gross CV) which assumes that all of the water in a combustion process is in a liquid state after a combustion process. The LHV assumes that the latent heat of vaporization of water in the fuel and the reaction products is not recovered. It is useful in comparing fuels where condensation of the combustion products is impractical, or heat at a temperature below 150 °C (302 °F) cannot be put to use.