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Heat of combustion

The heating 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 enthalpy of combustion is the same value expressed as an enthalpy, where release of heat is described as negative number.

Definitions
Higher heating value The higher heating value (HHV; gross energy, upper heating value, gross calorific value GCV, or higher calorific value; HCV) indicates the upper limit of the available thermal energy produced by a complete combustion of fuel. It is measured as a unit of energy per unit mass or volume of substance. The HHV is determined by bringing all the products of combustion back to the original pre-combustion temperature, including condensing any vapor produced. Such measurements often use a standard temperature of . ; 150 °C LHV : This LHV is the amount of heat released when the products are cooled to . This means that the latent heat of vaporization of water (and many other potential products) is not recovered. It is useful in comparing fuels where condensation of the combustion products is impractical, or heat at a temperature below cannot be put to use. The definition in which the combustion products are all returned to the reference temperature is more easily calculated from the higher heating value than when using other definitions. It will in fact give a slightly different answer. Accounting for moisture 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. Gross heating value Gross heating value accounts for water in the exhaust leaving as vapor, as does LHV, but gross heating value also 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. End products for different elements Zwolinski and Wilhoit defined, in 1972, "gross" and "net" values for heats of combustion. In the gross definition the products are the most stable compounds, e.g. (l), (l), (s) and (l). In the net definition the products are the gases produced when the compound is burned in an open flame, e.g. (g), (g), (g) and (g). In both definitions the products for C, F, Cl and N are (g), (g), (g) and (g), respectively. There are many other definitions of "gross" and "net". == Estimating heating values ==
Estimating heating values
By elemental composition The heating value of a fuel can be estimated with the results of ultimate analysis of fuel, which provides for the percentages of each element by mass. By oxygen consumption For an organic fuel of composition CcHhOoNn, the (higher) heat of combustion is usually to a good approximation (±3% for more than 500 organic compounds). This corresponds to 418 kJ/mol for each mole of consumed. The accuracy of such a simplistic formula is due to the very high bond enthalpy of , which renders other bond enthalpies largely irrelevant. The API publishes its own Dulong-style formulas for petroleum liquids and synthetic fuels. == Measuring heating values ==
Measuring heating values
The higher heating value is experimentally determined in a bomb calorimeter. The combustion of a stoichiometric mixture of fuel and oxidizer (e.g. two moles of hydrogen and one mole of oxygen) in a steel container at is initiated by an ignition device and the reactions allowed to complete. When hydrogen and oxygen react during combustion, water vapor is produced. The vessel and its contents are then cooled to the original 25 °C and the higher heating value is determined as the heat released between identical initial and final temperatures. When the lower heating value (LHV) is determined, cooling is stopped at 150 °C and the reaction heat is only partially recovered. The limit of 150 °C is based on acid gas dew-point. Note: Higher heating value (HHV) is calculated with the product of water being in liquid form while lower heating value (LHV) is calculated with the product of water being in vapor form. == Relation between heating values ==
Relation between heating values
The difference between the two heating values depends on the chemical composition of the fuel. In the case of pure carbon or carbon monoxide, the two heating values are almost identical, the difference being the sensible heat content of carbon dioxide between 150 °C and 25 °C (sensible heat exchange causes a change of temperature, while latent heat is added or subtracted for phase transitions at constant temperature. Examples: heat of vaporization or heat of fusion). For hydrogen, the difference is much more significant as it includes the sensible heat of water vapor between 150 °C and 100 °C, the latent heat of condensation at 100 °C, and the sensible heat of the condensed water between 100 °C and 25 °C. In all, the higher heating value of hydrogen is 18.2% above its lower heating value (142MJ/kg vs. 120MJ/kg). For hydrocarbons, the difference depends on the hydrogen content of the fuel. For gasoline and diesel the higher heating value exceeds the lower heating value by about 10% and 7%, respectively, and for natural gas about 11%. A common method of relating HHV to LHV is: : \mathrm{HHV} = \mathrm{LHV} + H_\mathrm{v}\left(\frac{n_\mathrm{H_2O,out}}{n_\mathrm{fuel,in}}\right) where Hv is the heat of vaporization of water at the datum temperature (typically 25 °C), n,out is the number of moles of water vaporized and nfuel,in is the number of moles of fuel combusted. • Most applications that burn fuel produce water vapor, which is unused and thus wastes its heat content. In such applications, the lower heating value must be used to give a 'benchmark' for the process. • However, for true energy calculations in some specific cases, the higher heating value is correct. This is particularly relevant for natural gas, whose high hydrogen content produces much water, when it is burned in condensing boilers and power plants with flue-gas condensation that condense the water vapor produced by combustion, recovering heat which would otherwise be wasted. == Usage of terms ==
Usage of terms
Engine manufacturers typically rate their engines fuel consumption by the lower heating values since the exhaust is never condensed in the engine, and doing this allows them to publish more attractive numbers than are used in conventional power plant terms. The conventional power industry had used HHV (high heat value) exclusively for decades, even though virtually all of these plants did not condense exhaust either. American consumers should be aware that the corresponding fuel-consumption figure based on the higher heating value will be somewhat higher. The difference between HHV and LHV definitions causes endless confusion when quoters do not bother to state the convention being used. since there is typically a 10% difference between the two methods for a power plant burning natural gas. For simply benchmarking part of a reaction the LHV may be appropriate, but HHV should be used for overall energy efficiency calculations if only to avoid confusion, and in any case, the value or convention should be clearly stated. == Heat of combustion tables ==
Heat of combustion tables
; Note • There is no difference between the lower and higher heating values for the combustion of carbon, carbon monoxide and sulfur since no water is formed during the combustion of those substances. • BTU/lb values are calculated from MJ/kg (1 MJ/kg = 430 BTU/lb). Higher heating values of natural gases from various sources The International Energy Agency reports the following typical higher heating values per Standard cubic metre of gas: • Algeria: 39.57MJ/Sm3 • Bangladesh: 36.00MJ/Sm3 • Canada: 39.00MJ/Sm3 • China: 38.93MJ/Sm3 • Indonesia: 40.60MJ/Sm3 • Iran: 39.36MJ/Sm3 • Netherlands: 33.32MJ/Sm3 • Norway: 39.24MJ/Sm3 • Pakistan: 34.90MJ/Sm3 • Qatar: 41.40MJ/Sm3 • Russia: 38.23MJ/Sm3 • Saudi Arabia: 38.00MJ/Sm3 • Turkmenistan: 37.89MJ/Sm3 • United Kingdom: 39.71MJ/Sm3 • United States: 38.42MJ/Sm3 • Uzbekistan: 37.89MJ/Sm3 The lower heating value of natural gas is normally about 90% of its higher heating value. This table is in Standard cubic metres (1atm, 15°C), to convert to values per Normal cubic metre (1atm, 0°C), multiply above table by 1.0549. == See also ==
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