Heat of combustion

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The heat of combustion (\Delta H_c^\circ) is the energy released as heat when a compound undergoes complete combustion with oxygen under standard conditions. The chemical reaction is typically a hydrocarbon reacting with oxygen to form carbon dioxide, water and heat. It may be expressed with the quantities:

The heat of combustion is conventionally measured with a bomb calorimeter. It may also be calculated as the difference between the heat of formation \Delta H_f^\circ of the products and reactants.

Heating value[edit]

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 energy value is a characteristic for each substance. It is measured in units of energy per unit of the substance, usually mass, such as: kJ/kg, kJ/mol, kcal/kg, Btu/lb. Heating value is commonly determined by use of a bomb calorimeter.

Heating value unit conversions (for more visit Wolfram Alpha):

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

Higher heating value[edit]

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 25 °C (77 °F). 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 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 below 150 °C can be put to use.

Lower heating value[edit]

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 vapor 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 cannot be put to use.

The above is but one definition of lower heating value adopted by the American Petroleum Institute (API) and uses a reference temperature of 60 °F (15.56 °C).

Another definition, used by Gas Processors Suppliers Association (GPSA) and originally used by API (data collected for API research project 44), is the enthalpy of all combustion products minus the enthalpy of the fuel at the reference temperature (API research project 44 used 25 °C. GPSA currently uses 60 °F), minus the enthalpy of the stoichiometric oxygen (O2) at the reference temperature, minus the heat of vaporization of the vapor content of the combustion products.

The distinction between the two is that this second definition assumes that the combustion products are all returned to the reference temperature and the heat content from the condensing vapor is considered not to be useful. This is more easily calculated from the higher heating value than when using the preceding definition and will in fact give a slightly different answer.

Gross heating value[edit]

Measuring heating values[edit]

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 25 °C 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 an arbitrary choice.

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[edit]

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. In contrast, 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. All in all, the higher heating value of hydrogen is 18.2% above its lower heating value (142 MJ/kg vs. 120 MJ/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:

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.[1]

Usage of terms[edit]

For historical reasons the efficiency of power plants and combined heat and power plants in Europe may have once been calculated based on the LHV. However, this does not seem to be the case nowadays and most countries are tending to correctly use HHV for true efficiency figures. This is becoming noticeable in modern UK energy publications with the increase of energy awareness and based on the simple fact that it is correct. While in the US, values may have been reported to be generally based on the HHV, although any initial investigation may reveal that the US is still tending to use LHV in some circumstances, whether technically correct or not. This has the peculiar result that contemporary combined heat and power plants, where flue-gas condensation is implemented, may report efficiencies exceeding 100%. Using LHV in other energy calculations brings similar errors, especially when pulled (incorrectly) into electrolysis calculations etc.

Many engine manufacturers rate their engine fuel consumption by the lower heating values. 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.[2] 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.

Accounting for moisture[edit]

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:

Heat of combustion tables[edit]

Higher (HHV) and Lower (LHV) Heating values
of some common fuels[3]
FuelHHV MJ/kgHHV BTU/lbHHV kJ/molLHV MJ/kg
Hydrogen141.8061,000286119.96
Methane55.5023,90088950.00
Ethane51.9022,4001,56047.80
Propane50.3521,7002,22046.35
Butane49.5020,9002,87745.75
Pentane45.35
Gasoline47.3020,40044.4
Paraffin wax46.0019,90041.50
Kerosene46.2019,86243.00
Diesel44.8019,30043.4
Coal (Anthracite)32.5014,000
Coal (Lignite)15.008,000
Wood (MAF)21.78,700
Peat (damp)6.002,500
Peat (dry)15.006,500
Higher heating value
of some less common fuels[3]
FuelHHV MJ/kgBTU/lbkJ/mol
Methanol22.79,800726.0
Ethanol29.712,8001,300.0
1-Propanol33.614,5002,020.0
Acetylene49.921,5001,300.0
Benzene41.818,0003,270.0
Ammonia22.59,690382.0
Hydrazine19.48,370622.0
Hexamine30.012,9004,200.0
Carbon32.814,100393.5
Heat of Combustion for some common fuels (higher value)[citation needed]
FuelkJ/gkcal/gBTU/lb
Hydrogen141.933.961,000
Gasoline47.011.320,000
Diesel45.010.719,300
Ethanol29.77.112,000
Propane49.911.921,000
Butane49.211.821,200
Wood15.03.66,000
Coal (Lignite)15.04.48,000
Coal (Anthracite)[citation needed]367.814,000
Natural Gas54.013.023,000

Lower heating value for some organic compounds (at 25 °C)[citation needed][edit]

FuelMJ/kgMJ/LBTU/lbkJ/mol
Alkanes
Methane50.00921,504802.34
Ethane47.79420,5511,437.2
Propane46.35719,9342,044.2
Butane45.75219,6732,659.3
Pentane45.35728.3921,7063,272.6
Hexane44.75229.3019,5043,856.7
Heptane44.56630.4819,1634,465.8
Octane44.42719,1045,074.9
Nonane44.31131.8219,0545,683.3
Decane44.24033.2919,0236,294.5
Undecane44.19432.7019,0036,908.0
Dodecane44.14733.1118,9837,519.6
Isoparaffins
Isobutane45.61319,6142,651.0
Isopentane45.24127.8719,4543,264.1
2-Methylpentane44.68229.1819,2136,850.7
2,3-Dimethylbutane44.65929.5619,2033,848.7
2,3-Dimethylpentane44.49630.9219,1334,458.5
2,2,4-Trimethylpentane44.31030.4919,0535,061.5
Naphthenes
Cyclopentane44.63633.5219,1933,129.0
Methylcyclopentane44.636?33.43?19,193?3,756.6?
Cyclohexane43.45033.8518,6843,656.8
Methylcyclohexane43.38033.4018,6534,259.5
Monoolefins
Ethylene47.195
Propylene45.799
1-Butene45.334
cis-2-Butene45.194
trans-2-Butene45.124
Isobutene45.055
1-Pentene45.031
2-Methyl-1-pentene44.799
1-Hexene44.426
Diolefins
1,3-Butadiene44.613
Isoprene44.078-
Nitrous derivated
Nitromethane10.513
Nitropropane20.693
Acetylenes
Acetylene48.241
Methylacetylene46.194
1-Butyne45.590
1-Pentyne45.217
Aromatics
Benzene40.170
Toluene40.589
o-Xylene40.961
m-Xylene40.961
p-Xylene40.798
Ethylbenzene40.938
1,2,4-Trimethylbenzene40.984
Propylbenzene41.193
Cumene41.217
Alcohols
Methanol19.93015.788,570638.55
Ethanol28.86522.7712,4121,329.8
1-Propanol30.68024.6513,1921,843.9
Isopropanol30.44723.9313,0921,829.9
n-Butanol33.07526.7914,2222,501.6
Isobutanol32.95926.4314,1722,442.9
Tert-butanol32.58725.4514,0122,415.3
n-Pentanol34.72728.2814,9333,061.2
Isoamyl alcohol31.416?35.64?13,509?2,769.3?
Ethers
Methoxymethane28.70312,3421,322.3
Ethoxyethane33.86724.1614,5632,510.2
Propoxypropane36.35526.7615,6333,568.0
Butoxybutane37.79828.8816,2534,922.4
Aldehydes and ketones
Methanal17.259
Ethanal24.156
Propionaldehyde28.889
Butyraldehyde31.610
Acetone28.54822.62
Other species
Carbon (graphite)32.808
Hydrogen120.97152,017244
Carbon monoxide10.1124,348283.24
Ammonia18.6468,018317.56
Sulfur (solid)9.1633,940293.82

Note that 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 in combusting 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[edit]

The International Energy Agency reports the following typical higher heating values:[4]

The lower heating value of natural gas is normally about 90 percent of its higher heating val.

See also[edit]

References[edit]

External links[edit]